TW202321150A

TW202321150A - Sic volumetric shapes and methods of forming boules

Info

Publication number: TW202321150A
Application number: TW112104365A
Authority: TW
Inventors: 道格拉斯Ｍ杜克斯; 格蘭森德葛倫; 安德魯Ｒ哈波金斯; 伊莎貝爾柏林翰; 馬克Ｓ蘭德
Original assignee: 美商佩利達斯股份有限公司
Priority date: 2017-08-14
Filing date: 2018-08-10
Publication date: 2023-06-01
Also published as: TW201919995A

Abstract

Volumetric shapes of SiC starting materials for boule growth. Methods of controlling vapor deposition growth of SiC boules, and providing directional flux. Methods of increase the number of wafers, the number of electronic components and the number of operable devices from a single boule growth cycle.

Description

碳化矽空間形體及形成胚晶之方法Silicon carbide space shape and method for forming embryo crystal

本申請案：(ii)根據專利法主張2017年8月14日申請的美國臨時申請案第62/545,367號之權益，其每一者之全部揭示內容以引用方式併入本文中。This application: (ii) asserts the benefit under the patent law of U.S. Provisional Application No. 62/545,367, filed August 14, 2017, the entire disclosure of each of which is incorporated herein by reference.

本發明係關於用於製造碳化矽(SiC)及SiC組合物、結構、部件、材料之方法及用於製造該些物品之設備；用於製造碳化矽(SiC)及SiOC組合物、結構、部件、材料之方法及用於製造該些物品之設備；且詳言之，係關於SiC空間形體、該些空間形體在氣相沉積製程中形成胚晶之用途、及相關方法。The present invention relates to methods for the manufacture of silicon carbide (SiC) and SiC compositions, structures, parts, materials and equipment for the manufacture of these articles; for the manufacture of silicon carbide (SiC) and SiOC compositions, structures, parts , methods of materials and equipment used to manufacture these articles; and in particular, relate to SiC spacers, use of these spacers to form embryo crystals in a vapor deposition process, and related methods.

在美國專利第9,815,952號及第9,815,943號以及美國專利公開案第2015/0175750號中揭示並教示多晶碳氧矽材料(polysilocarb material)及製造彼等材料之方法，該等專利案中每一者之全部揭示內容以引用方式併入本文中。Polysilocarb materials and methods of making them are disclosed and taught in U.S. Patent Nos. 9,815,952 and 9,815,943 and U.S. Patent Publication No. 2015/0175750, each of which The entire disclosure is incorporated herein by reference.

如本文所使用，除非另外指定，「氣相沉積」(Vapor Deposition; VD)、「氣相沉積技術」、氣相沉積製程及類似的此類術語意欲給出其最廣含義，且將包括例如其中固體或液體起始材料轉變成氣體或蒸汽狀態，且隨後該氣體或蒸汽經沉積以形成，例如，生長固體材料之製程。如本文所使用，氣相沉積技術將包括藉由磊晶術之生長，其中該層係自蒸汽或氣相提供。其他類型之氣相沉積技術包括：化學氣相沉積(Chemical Vapor Deposition; CVD)；物理氣相沉積(Physical Vapor Deposition; PVD)、電漿增強CVD、物理氣相傳輸(Physical Vapor Transport; PVT)及其他技術。氣相沉積裝置之實例將包括熱壁反應器、多晶圓反應器、煙囪反應器、RF熔爐、及胚晶生長熔爐。As used herein, unless otherwise specified, "Vapor Deposition" (Vapor Deposition; VD), "Vapor Deposition Technology", "Vapor Deposition Process" and similar such terms are intended to be given their broadest meaning and shall include, for example A process in which a solid or liquid starting material is transformed into a gas or vapor state, and the gas or vapor is subsequently deposited to form, eg, grow, a solid material. As used herein, vapor deposition techniques shall include growth by epitaxy, wherein the layer is provided from the vapor or gas phase. Other types of vapor deposition techniques include: chemical vapor deposition (Chemical Vapor Deposition; CVD); physical vapor deposition (Physical Vapor Deposition; PVD), plasma enhanced CVD, physical vapor transport (Physical Vapor Transport; PVT) and other technologies. Examples of vapor deposition apparatus would include hot wall reactors, multi-wafer reactors, chimney reactors, RF furnaces, and embryonic crystal growth furnaces.

如本文所使用，除非另外指定，術語「汽化溫度」意欲給出其最廣可能的含義且包括材料自液體轉變成氣態、自固體轉變成氣態、或兩種情況下的溫度(例如，固體至液體至氣體轉變在極小的溫度範圍上發生，例如，小於約20℃、小於約10℃、及小於約5℃之範圍)。除非另外具體地陳述，汽化溫度將為相應於其中此種轉變發生所處的任何特定壓力之溫度，該特定壓力例如一個大氣壓、0.5個大氣壓。當論述材料在特定應用、方法中或用於諸如PVT裝置之特定裝置之汽化溫度時，汽化溫度將處於用於或典型地用於彼應用、方法或裝置中之壓力，除非另外明確地陳述。As used herein, unless otherwise specified, the term "vaporization temperature" is intended to be given its broadest possible meaning and includes the temperature at which a material transitions from a liquid to a gaseous state, from a solid to a gaseous state, or both (e.g., solid to The liquid-to-gas transition occurs over a very small temperature range, eg, ranges less than about 20°C, less than about 10°C, and less than about 5°C). Unless specifically stated otherwise, the vaporization temperature will be the temperature corresponding to any particular pressure at which this transformation occurs, eg, one atmosphere, 0.5 atmospheres. When discussing the vaporization temperature of a material in a particular application, method or use in a particular device such as a PVT device, the vaporization temperature will be at the pressure used or typically used in that application, method or device, unless expressly stated otherwise.

碳化矽通常在真空下，在高於約1,700℃之溫度下不具有液相而替代地其昇華。轉向第17圖，提供SiC之分壓曲線之圖表。典型地，在工業及商業應用中，建立各種條件以便在約2,500℃及高於此之溫度下發生昇華。當碳化矽昇華時，其典型地形成由矽及碳之各種物質組成的蒸汽，該等物質例如，Si、C、SiC、Si ₂C及SiC ₂。通常，咸信溫度決定碳化矽蒸汽中的該些不同組分之比率。然而，本發明尤其提供除溫度之外或連同溫度一起預選並控制該些組分之比率的能力。 Silicon carbide generally does not have a liquid phase but instead sublimes it under vacuum at temperatures above about 1,700°C. Turning to Figure 17, a graph of the partial pressure curve for SiC is provided. Typically, in industrial and commercial applications, conditions are established so that sublimation occurs at temperatures of about 2,500°C and above. When silicon carbide sublimes, it typically forms a vapor composed of various species of silicon and carbon, such as Si, C, SiC, _Si2C , and _SiC2 . In general, it is believed that temperature determines the ratio of these different components in the silicon carbide vapor. However, the present invention specifically provides the ability to preselect and control the ratios of these components in addition to or in conjunction with temperature.

如本文所使用，除非另外指定，術語比重，亦稱為表觀密度，應給出其最廣可能的含義，且通常意指每單位體積之結構，例如，材料之空間形體的重量。此性質將包括作為粒子體積之部分的粒子之內部孔隙率。其可利用潤濕粒子表面之低黏度流體以及其他技術來量測。As used herein, unless otherwise specified, the term specific gravity, also known as apparent density, shall be given its broadest possible meaning and generally means the weight per unit volume of structure, eg, a spatial form of a material. This property will include the internal porosity of the particle as a fraction of the particle volume. It can be measured using low viscosity fluids that wet particle surfaces, among other techniques.

如本文所使用，除非另外指定，術語實際密度，亦可稱為真密度，應給出其最廣可能的含義，且一般意指在彼材料中不存在空隙時，每單位體積之材料的重量。此量測及性質本質上自材料消除任何內部孔隙率，例如，其不包括材料中之任何空隙。As used herein, unless otherwise specified, the term actual density, which may also be called true density, shall be given its broadest possible meaning and generally means the weight of a material per unit volume when no voids are present in that material . This measurement and property essentially eliminates any internal porosity from the material, eg, it does not include any voids in the material.

因此，多孔泡沫球(例如，Nerf®球)集合可用於說明三種密度性質之間的關係。填充容器之球的重量將為球之體密度：Thus, a collection of porous foam spheres (eg, Nerf® spheres) can be used to illustrate the relationship between the three density properties. The weight of the ball filling the container will be the bulk density of the ball:

每球之球形體積的單一球的重量將為其表觀密度：The weight of a single ball per spherical volume of the ball will be its apparent density:

每構成球，亦即，移除所有空隙體積的球之骨架的材料之剩餘體積的彼材料的重量將為實際密度：The weight of that material per remaining volume of the material making up the ball, i.e., the skeleton of the ball with all void volume removed, will be the actual density:

如本文所使用，除非另有說明，室溫為25℃。此外，標準環境溫度及壓力為25℃及1個大氣壓。除非另外明確地陳述，否則為溫度依賴性、壓力依賴性、或兩者的所有測試、測試結果、物理性質、及值係在標準環境溫度及壓力下提供，此將包括黏度。As used herein, unless otherwise stated, room temperature is 25°C. In addition, the standard ambient temperature and pressure are 25° C. and 1 atmosphere. Unless expressly stated otherwise, all tests, test results, physical properties, and values given for temperature dependence, pressure dependence, or both are at standard ambient temperature and pressure, which will include viscosity.

一般而言，除非另有說明，如本文所使用的術語「約」及符號「~」意欲涵蓋±10%之差異或範圍、與獲得所述值相關聯的實驗或儀器誤差、且較佳地該些值中較大者。Generally, unless otherwise stated, the term "about" and the symbol "~" as used herein are intended to cover a variance or range of ±10%, experimental or instrumental error associated with obtaining the stated value, and preferably The larger of these values.

如本文所使用，除非另外指定，術語%、重量%及質量%可互換地使用且係指作為總物質重量之百分比的第一組分之重量，該總物質例如調配物、混合物、預成型件、材料、結構或產物。除非另外明確地提供，否則使用X/Y或XY指示調配物中X之重量%及Y之重量%。除非另外明確地提供，否則使用X/Y/Z或XYZ指示調配物中X之重量%、Y之重量%及Z之重量%。As used herein, unless otherwise specified, the terms %, weight % and mass % are used interchangeably and refer to the weight of the first component as a percentage of the weight of the total substance, such as a formulation, mixture, preform , material, structure or product. X/Y or XY is used to indicate weight % of X and weight % of Y in the formulation unless expressly provided otherwise. X/Y/Z or XYZ are used to indicate weight % of X, weight % of Y and weight % of Z in the formulation unless expressly provided otherwise.

如本文所使用，除非另外指定，術語「體積%」及「%體積」及類似的此種術語係指作為總物質體積之百分比的第一組分之體積，該總物質例如調配物、混合物、預成型件、材料、結構或產物。As used herein, unless otherwise specified, the terms "volume %" and "% volume" and similar such terms refer to the volume of the first component as a percentage of the volume of the total substance, such as a formulation, mixture, Preform, material, structure or product.

如本文所使用，除非另外明確地陳述，術語「源材料」及「起始材料」為同義的，且如在胚晶生長、氣相沉積設備、磊晶術、及晶體成長及沉積製程之上下文中所使用的，應給出其最廣可能的定義，且係指材料、空間形體、及兩者，其係置放於生長腔室中，或在其他情況下置放於用於晶體成長、胚晶生長、磊晶術、或SiC沉積之設備中，且形成通量。As used herein, unless expressly stated otherwise, the terms "source material" and "starting material" are synonymous, and as in the context of embryonic crystal growth, vapor deposition equipment, epitaxy, and crystal growth and deposition processes As used in , the broadest possible definition shall be given and shall refer to materials, spatial forms, and both, which are placed in a growth chamber or otherwise placed in a chamber for crystal growth, Embryo crystal growth, epitaxy, or SiC deposition equipment, and form flux.

如本文所使用，除非另外明確地陳述，術語「現有材料」、「先前材料」、「當前材料」、「當前可利用的材料」、「現存氣相沉積設備」、「當前氣相沉積設備」及類似的此種術語係指在本發明之前存在或已存在的源材料及設備。此術語之使用不欲視為且不為對先前技術之承認。其僅僅描述此項技術之當前狀態以作為基線或參考點，藉以可評估、對比及量測本發明之實施例的顯著及突破性改良。As used herein, unless expressly stated otherwise, the terms "existing material", "previous material", "current material", "currently available material", "existing vapor deposition equipment", "current vapor deposition equipment" and similar terms refer to source materials and equipment that existed or existed prior to the present invention. Use of this term is not intended to be and does not constitute an admission of prior art. It merely describes the current state of the art to serve as a baseline or reference point by which significant and breakthrough improvements of embodiments of the present invention may be evaluated, compared and measured.

此發明背景部分意欲介紹此項技術之各種態樣，其可與本發明之實施例相關聯。因此，此部分中的前述論述提供用於較好理解本發明之框架，且不意欲視為承認先前技術。This Background of the Invention section is intended to introduce various aspects of the art, which may be associated with embodiments of the present invention. Accordingly, the foregoing discussion in this section provides a framework for a better understanding of the present invention and is not intended to be taken as an admission of prior art.

對以成本有效方式製造SiC胚晶以尤其提供用於製造供裝置、設備及裝備用的SiC電子部件的高品質單晶SiC胚晶存在長期且未得到滿足的需要。本發明尤其藉由提供本文教示、揭示及主張的組合物、材料、製品、裝置及製程來解決該些需要。There is a longstanding and unmet need to fabricate SiC embryos in a cost effective manner to provide, inter alia, high quality single crystal SiC embryos for use in the manufacture of SiC electronic components for devices, equipment and equipment. The present invention addresses these needs, inter alia, by providing compositions, materials, articles of manufacture, devices and processes taught, disclosed and claimed herein.

提供使用黏合劑製造包括聚合物衍生SiC之SiC的空間形體的方法，其中聚合物衍生SiC粒子係與黏合劑材料混合，黏合劑及SiC粒子係成形成空間結構，其較佳地具有預定形狀及大小(及因此體積)且隨後加以固化。空間形體及黏合劑可隨後例如用於氣相沉積製程以形成材料、層及結構，諸如胚晶，可使用本發明的此種設備及製程之實例在美國專利公開案第2017/0204532號中揭示並教示。Provided is a method for producing spatial shapes of SiC including polymer-derived SiC using a binder, wherein polymer-derived SiC particles are mixed with a binder material, the binder and SiC particles are formed into a spatial structure, which preferably has a predetermined shape and size (and thus volume) and is subsequently solidified. The spacers and binders can then be used, for example, in a vapor deposition process to form materials, layers and structures, such as embryonic crystals, an example of such an apparatus and process that can use the present invention is disclosed in U.S. Patent Publication No. 2017/0204532 And teach.

因此，提供SiC之空間形體，該空間形體具有：約100 g至約12,000 g之SiC顆粒，其具有約0.1 μm至約100 μm之粒子大小；該等SiC顆粒界定具有結構完整性之空間形體；黏合劑，其中該黏合劑結合該等SiC顆粒，藉以該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時維持該結構完整性；該空間形體界定空隙；且，該空間形體具有多孔性，其中該空間形體具有小於3.0 g/cc之表觀密度。Accordingly, there is provided a spatial body of SiC having: from about 100 g to about 12,000 g of SiC particles having a particle size from about 0.1 μm to about 100 μm; the SiC particles defining a spatial body with structural integrity; a binder, wherein the binder binds the SiC particles whereby the spatial form is capable of maintaining the structural integrity when placed in a vapor deposition apparatus during a growth cycle of an embryo crystal; the spatial form defines a void; and, the space The bodies are porous, wherein the space bodies have an apparent density of less than 3.0 g/cc.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：其中SiC顆粒之重量為約1000 g至約9000 g；其中SiC顆粒之重量為約2500 g至約8000 g；其中SiC顆粒之重量為約5000 g至約11000 g；其中該等顆粒具有約0.1 μm至約20.0 μm之初級粒子D ₅₀大小；其中該等顆粒具有約0.5 μm至約10.0 μm、約0.5 μm至約2.0 μm之初級粒子D ₅₀大小；其中該等顆粒具有約1 μm至約5 μm之初級粒子D ₅₀大小；其中該等顆粒具有約0.5 μm至約3 μm之初級粒子D50大小；其中該空隙界定該空間形體之頂部中的通道；其中在該通道中的為成角度環形通道；其中該空隙係位於該空間形體之頂部中；其中該空隙係位於該空間形體之底部中；其中該空隙具有位於該空間形體之頂部及底部中的空隙；其中該空隙界定延伸穿過該空間形體的圓柱形通道；其中該形體為圓片(puck)；其中形體具有平坦頂部、平坦底部及錐形側面；其中該表觀密度為小於2.5 g/cc；其中該表觀密度為小於2.5 g/cc；其中該表觀密度為小於2.5 g/cc；其中該表觀密度為小於2.5 g/cc；其中該表觀密度為約1.5 g/cc至2.8 g/cc；其中該表觀密度為約1.5 g/cc至2.8 g/cc；其中該等SiC顆粒為聚合物衍生SiC且具有至少99.999%之純度；其中該等SiC顆粒為聚合物衍生SiC且具有至少99.9999%之純度；具有0.5:2的Si:C之莫耳比率；具有2:0.5的Si:C之莫耳比率；具有在約1:1至約0.5:2範圍內的Si:C之莫耳比率；具有在約1:1至約2:0.5範圍內的Si:C之莫耳比率；及具有在約0.5:2至約2:0.5範圍內的Si:C之莫耳比率。 In addition, the methods, spatial bodies, wafers and embryos are provided with one or more of the following features: wherein the weight of SiC particles is from about 1000 g to about 9000 g; wherein the weight of SiC particles is from about 2500 g to about 8000 g; wherein the weight of SiC particles is about 5000 g to about 11000 g; wherein the particles have a primary particle D ₅₀ size of about 0.1 μm to about 20.0 μm; wherein the particles have a size of about 0.5 μm to about 10.0 μm, about A primary particle _D50 size of 0.5 μm to about 2.0 μm; wherein the particles have a primary particle D50 size of about 1 μm to about 5 μm; wherein the particles have a primary particle _D50 size of about 0.5 μm to about 3 μm; wherein the void defines a passage in the top of the spatial form; wherein in the passage is an angled annular passage; wherein the void is located in the top of the spatial form; wherein the void is located in the bottom of the spatial form; wherein The void has a void in the top and bottom of the spatial form; wherein the void defines a cylindrical channel extending through the spatial form; wherein the form is a puck; wherein the form has a flat top, a flat bottom, and a cone shaped side; wherein the apparent density is less than 2.5 g/cc; wherein the apparent density is less than 2.5 g/cc; wherein the apparent density is less than 2.5 g/cc; wherein the apparent density is less than 2.5 g/cc wherein the apparent density is from about 1.5 g/cc to 2.8 g/cc; wherein the apparent density is from about 1.5 g/cc to 2.8 g/cc; wherein the SiC particles are polymer derived SiC and have at least 99.999% wherein the SiC particles are polymer derived SiC and have a purity of at least 99.9999%; have a molar ratio of Si:C of 0.5:2; have a molar ratio of Si:C of 2:0.5; A Si:C molar ratio in the range of 1:1 to about 0.5:2; having a Si:C molar ratio in the range of about 1:1 to about 2:0.5; and having a Si:C molar ratio in the range of about 0.5:2 to about Molar ratio of Si:C in the range of 2:0.5.

更進一步，提供SiC之空間形體，該空間形體具有：約100 g至約12,000 g之SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該等SiC顆粒界定具有結構完整性之空間形體，其中該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時維持該結構完整性；該空間形體界定空隙；及，該空間形體具有多孔性，其中該空間形體具有小於3.0 g/cc之表觀密度。Still further, there is provided a spatial body of SiC having: from about 100 g to about 12,000 g of SiC particles having a particle size from about 0.1 μm to about 100 μm; the SiC particles defining a spatial body with structural integrity, wherein the space body is capable of maintaining the structural integrity when placed in a vapor deposition apparatus during a growth cycle of an embryo crystal; the space body defines voids; and, the space body has porosity, wherein the space body has a mass of less than 3.0 g /cc apparent density.

又進一步，提供SiC之空間形體，該空間形體具有：約100 g至約12,000 g之SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該SiC顆粒界定具有結構完整性之空間形體；黏合劑，其中該黏合劑結合該等SiC顆粒，藉以該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時維持該結構完整性；及，該空間形體界定空隙。Still further, there is provided a spatial body of SiC having: about 100 g to about 12,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles defining a spatial body with structural integrity; adhesive an agent, wherein the binder binds the SiC particles, whereby the spatial form is capable of maintaining the structural integrity when placed in a vapor deposition apparatus during a growth cycle of an embryo crystal; and, the spatial form defines a void.

另外，提供SiC之空間形體，該空間形體具有：SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該SiC顆粒界定具有結構完整性之空間形體；黏合劑，其中該黏合劑結合該等SiC顆粒，藉以該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時維持該結構完整性；該空間形體界定空隙；及，該空間形體具有多孔性，其中該空間形體具有小於3.1 g/cc之表觀密度；其中該空間形體能夠在該胚晶之該生長循環期間提供預定通量。Additionally, there is provided a space body of SiC having: SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles defining a space body with structural integrity; a binder, wherein the binder binds the SiC particles, whereby the spatial body is capable of maintaining the structural integrity when placed in a vapor deposition apparatus during a growth cycle of an embryo crystal; the spatial body defines voids; and, the spatial body has porosity, wherein the spatial body has An apparent density of less than 3.1 g/cc; wherein the steric body is capable of providing a predetermined flux during the growth cycle of the embryo crystal.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：其中該預定通量為均勻及一致的通量；其中該預定通量在生長循環之最後20%期間在胚晶之生長面的外區域附近具有增加的通量密度；其中該預定通量在生長循環之最後30%期間在胚晶之生長面的外區域附近具有增加的通量密度；且其中該預定通量在生長循環之最後40%期間在胚晶之生長面的外區域附近具有增加的通量密度。In addition, the methods, spatial shapes, wafers, and embryos are provided having one or more of the following features: wherein the predetermined flux is a uniform and consistent flux; wherein the predetermined flux is within the last 20% of a growth cycle During the period, there is an increased flux density near the outer region of the growth face of the embryo crystal; wherein the predetermined flux has an increased flux density near the outer region of the growth face of the embryo crystal during the last 30% of the growth cycle; and wherein The predetermined flux has an increased flux density near the outer region of the growth face of the embryo crystal during the last 40% of the growth cycle.

此外，提供SiC之空間形體，該空間形體具有：SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該SiC顆粒界定具有結構完整性之空間形體；該空間形體界定空隙；及，該空間形體具有多孔性，其中該空間形體具有小於3.1 g/cc之表觀密度；其中該空間形體能夠在生長循環期間提供預定通量。Additionally, a space body of SiC is provided, the space body having: SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles defining a space body having structural integrity; the space body defining a void; and, the space The body has porosity, wherein the space body has an apparent density of less than 3.1 g/cc; wherein the space body is capable of providing a predetermined flux during a growth cycle.

更進一步，提供SiC之空間形體，該空間形體具有：SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該SiC顆粒界定具有結構完整性之空間形體；黏合劑，其中該黏合劑結合該等SiC顆粒，藉以該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時維持該結構完整性；及，該空間形體界定空隙；其中該空間形體能夠提供預定通量。Still further, there is provided a spatial body of SiC having: SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles defining a spatial body with structural integrity; a binder, wherein the binder binds the SiC particles, whereby the spatial form is capable of maintaining the structural integrity when placed in a vapor deposition apparatus during a growth cycle of an embryo crystal; and, the spatial form defines a void; wherein the spatial form is capable of providing a predetermined flux.

此外，提供SiC之空間形體，該空間形體具有：約100 g至約12,000 g之SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該等SiC顆粒界定空間形體；該空間形體具有多孔性，其中該空間形體具有小於2.9 g/cc之表觀密度；其中該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時提供在該生長循環期間的通量形成之一致速率。In addition, a spatial body of SiC is provided, the spatial body having: about 100 g to about 12,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles define the spatial body; the spatial body has porosity , wherein the steric body has an apparent density of less than 2.9 g/cc; wherein the steric body is capable of providing a consistent rate of flux formation during a growth cycle of an embryo crystal when placed in a vapor deposition apparatus during the growth cycle of the embryo .

又進一步，提供SiC之空間形體，該空間形體具有：約100 g至約12,000 g之SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該等SiC顆粒界定空間形體；及，該空間形體界定空隙；其中該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時提供在該生長循環期間的通量形成之一致速率。Still further, there is provided a spatial body of SiC, the spatial body having: about 100 g to about 12,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles defining the spatial body; and, the spatial body A void is defined; wherein the spatial form is capable of providing a consistent rate of flux formation during a growth cycle of an embryo crystal when placed in a vapor deposition apparatus during the growth cycle.

此外，提供SiC之空間形體，該空間形體具有：約100 g至約12,000 g之SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該等SiC顆粒界定空間形體；黏合劑，其中該黏合劑結合該等SiC顆粒；及，其中該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時提供在該生長循環期間的通量形成之預定速率。In addition, there is provided a spatial body of SiC having: about 100 g to about 12,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles delimiting the spatial body; an adhesive, wherein the adhesive An agent binds the SiC particles; and, wherein the steric body is capable of providing a predetermined rate of flux formation during a growth cycle of an embryo crystal when placed in a vapor deposition apparatus during the growth cycle.

又進一步，提供SiC之空間形體，該空間形體具有：約100 g至約12,000 g之SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該等SiC顆粒界定空間形體；黏合劑，其中該黏合劑結合該等SiC顆粒，進而界定該空間形體；該空間形體具有多孔性，其中該空間形體具有小於2.9 g/cc之表觀密度；其中該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時提供在該生長循環期間的均勻通量形成。Still further, there is provided a spatial body of SiC having: about 100 g to about 12,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles defining the spatial body; a binder, wherein the The binder binds the SiC particles, thereby defining the space body; the space body has porosity, wherein the space body has an apparent density of less than 2.9 g/cc; wherein the space body can be placed during a growth cycle of an embryo crystal Uniform flux formation during the growth cycle is provided when in a vapor deposition apparatus.

另外，提供SiC之空間形體，該空間形體具有：約100 g至約12,000 g之SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該等SiC顆粒界定空間形體；及，該空間形體界定空隙；其中該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時提供在該生長循環期間的均勻通量形成。Additionally, there is provided a space body of SiC having: about 100 g to about 12,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles defining a space body; and, the space body defining Void; wherein the spatial form is capable of providing uniform flux formation during a growth cycle of an embryo crystal when placed in a vapor deposition apparatus during the growth cycle.

此外，提供SiC之空間形體，該空間形體具有：約100 g至約5,000 g之SiC顆粒，具有約0.1 μm至約100 μm之粒子大小；該等SiC顆粒界定空間形體；黏合劑，其中該黏合劑結合該等SiC顆粒；及，其中該空間形體能夠在胚晶之生長循環期間置放於氣相沉積設備中時提供在該生長循環期間的均勻通量形成。In addition, there is provided a spatial body of SiC having: about 100 g to about 5,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm; the SiC particles delimiting the spatial body; an adhesive, wherein the adhesive An agent binds the SiC particles; and, wherein the steric body is capable of providing uniform flux formation during a growth cycle of an embryo crystal when placed in a vapor deposition apparatus during the growth cycle.

進一步提供生長SiC胚晶之方法，該方法包括：將具有SiC之起始材料置放於氣相沉積設備中；將該起始材料加熱至藉以該SiC昇華之溫度從而形成具有Si及C之物質的通量；該通量跨於直接相鄰於胚晶之該生長面的區域流動；其中該區域與該胚晶之該生長面相同且重合；其中該通量經預定跨於該區域之整體；及，將該通量沉積在該胚晶之該生長面上以使該胚晶在長度上生長。Further provided is a method for growing an SiC embryo, the method comprising: placing a starting material having SiC in a vapor deposition device; heating the starting material to a temperature at which the SiC is sublimated to form a substance having Si and C the flux; the flux flows across the region immediately adjacent to the growth face of the embryo crystal; wherein the region is identical to and coincident with the growth face of the embryo crystal; wherein the flux is predetermined to span the entirety of the region and, depositing the flux on the growth face of the embryo crystal to grow the embryo crystal in length.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：其中該通量在胚晶生長期間跨於該區域之整體為均勻的；其中該通量在該胚晶之該生長期間在該胚晶之該長度之至少一半已生長時的一時間期間在該胚晶面之外區域附近較大；其中該胚晶之該生長面為晶種；其中該胚晶之該生長面為該胚晶之一面；其中剛生長的該胚晶為單一結晶的；其中剛生長的該胚晶為單一多型體；藉以剛生長的該胚晶藉由約3吋至約6吋之直徑、約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少2倍；藉以剛生長的該胚晶藉由約3吋至約6吋之直徑、約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少5倍；藉以剛生長的該胚晶藉由約3吋至約6吋之直徑、約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少10倍；藉以剛生長的該胚晶藉由約3吋至約6吋之直徑、約2吋至約8吋之長度、及為無限的該生長面的曲率半徑表徵；藉以剛生長的該胚晶藉由約3吋至約6吋之直徑、約2吋至約8吋之長度、及為至少約50吋的該生長面的曲率半徑表徵；藉以剛生長的該胚晶藉由約6吋至約8吋之直徑、約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少2倍；藉以剛生長的該胚晶藉由約6吋至約8吋之直徑、約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少5倍；藉以剛生長的該胚晶藉由約6吋至約8吋之直徑、約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少10倍；藉以剛生長的該胚晶藉由約6吋至約8吋之直徑、約2吋至約8吋之長度、及為無限的該生長面的曲率半徑表徵；藉以剛生長的該胚晶藉由約6吋至約8吋之直徑、約2吋至約8吋之長度、及為至少約50吋的該生長面的曲率半徑表徵；藉以剛生長的該胚晶藉由約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少2倍；藉以剛生長的該胚晶藉由約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少5倍；藉以剛生長的該胚晶藉由約2吋至約8吋之長度表徵，且該胚晶之該生長面的曲率半徑為該長度的至少10倍；藉以剛生長的該胚晶藉由約2吋至約8吋之長度、及為無限的該生長面之曲率半徑表徵；及藉以剛生長的該胚晶藉由約2吋至約8吋之長度、及為至少約50吋的該生長面之曲率半徑表徵；及，其中該通量係以恆定速率維持。Additionally, the methods, spatial bodies, wafers, and embryos are provided having one or more of the following features: wherein the flux is uniform across the entirety of the region during embryo crystal growth; wherein the flux is uniform across the region during growth of the embryo; The growth period of the embryo crystal is greater near a region outside the embryo crystal face during a period of time when at least half of the length of the embryo crystal has grown; wherein the growth face of the embryo crystal is a seed crystal; wherein the embryo crystal The growth face of the crystal is one side of the embryo crystal; wherein the embryo crystal just grown is monocrystalline; wherein the embryo crystal just grown is a single polytype; whereby the embryo crystal grown just grows by about 3 inches Characterized by a diameter of about 6 inches, a length of about 2 inches to about 8 inches, and the radius of curvature of the growth face of the embryo crystal is at least 2 times the length; Characterized by a diameter of about 6 inches, a length of about 2 inches to about 8 inches, and the radius of curvature of the growth face of the embryo crystal is at least 5 times the length; whereby the newly grown embryo crystal is by about 3 inches to about Characterized by a diameter of 6 inches, a length of about 2 inches to about 8 inches, and the radius of curvature of the growth face of the embryo crystal is at least 10 times the length; whereby the embryo crystal has just grown by about 3 inches to about 6 inches. Inch diameter, length from about 2 inches to about 8 inches, and the radius of curvature of the growth surface being infinite; whereby the newly grown embryo crystal is characterized by a diameter from about 3 inches to about 6 inches, from about 2 inches to about 8 inches in length, and a radius of curvature of the growth surface that is at least about 50 inches; whereby the as-grown embryo crystal is characterized by a diameter of about 6 inches to about 8 inches, a length of about 2 inches to about 8 inches, and the radius of curvature of the growth face of the embryocrystal is at least 2 times the length; whereby the as-grown embryocrystal is characterized by a diameter of about 6 inches to about 8 inches, a length of about 2 inches to about 8 inches, and The radius of curvature of the growth face of the embryocrystal is at least 5 times the length; whereby the as-grown embryocrystal is characterized by a diameter of about 6 inches to about 8 inches, a length of about 2 inches to about 8 inches, and the The radius of curvature of the growth face of the embryocrystal is at least 10 times the length; whereby the as-grown embryocrystal has a diameter of about 6 inches to about 8 inches, a length of about 2 inches to about 8 inches, and is infinite The radius of curvature of the growth face is characterized by the embryo crystal as-grown by a diameter of about 6 inches to about 8 inches, a length of about 2 inches to about 8 inches, and a radius of curvature of the growth face of at least about 50 inches Characterization; whereby the as-grown embryo is characterized by a length of about 2 inches to about 8 inches, and the radius of curvature of the growth face of the embryo is at least 2 times that length; whereby the as-grown embryo is characterized by characterized by a length of about 2 inches to about 8 inches, and the radius of curvature of the growth face of the embryocrystal is at least 5 times that length; whereby the as-grown embryocrystal is characterized by a length of about 2 inches to about 8 inches, and the radius of curvature of the growth face of the embryocrystal is at least 10 times the length; whereby the as-grown embryocrystal is characterized by a length of about 2 inches to about 8 inches, and a radius of curvature of the growth face that is infinite; and whereby the newly grown embryo crystal is characterized by a length of about 2 inches to about 8 inches, and a radius of curvature of the growth face of at least about 50 inches; and, wherein the flux is maintained at a constant rate.

進一步提供生長SiC胚晶之方法，該方法具有：將具有SiC之起始材料置放於氣相沉積設備中；加熱該起始材料以產生通量且開始生長循環；在該生長循環期間使該通量跨於直接相鄰於胚晶之生長面的區域流動；其中該通量流動在該生長循環期間以一預定速率維持；及，將該通量沉積在該胚晶之該生長面上以使該胚晶在長度上生長。Further provided is a method of growing a SiC embryo, the method having: placing a starting material having SiC in a vapor deposition apparatus; heating the starting material to generate a flux and starting a growth cycle; during the growth cycle causing the flux flows across the region immediately adjacent to the growth face of the embryo crystal; wherein the flux flow is maintained at a predetermined rate during the growth cycle; and, the flux is deposited on the growth face of the embryo crystal to The embryo crystal is allowed to grow in length.

另外，提供生長SiC胚晶之方法，該方法包括：將具有SiC之起始材料之空間形體置放於氣相沉積設備中；加熱該空間形體以在胚晶之生長循環期間提供方向性通量；及，將該方向性通量沉積在該胚晶之生長面上以使該胚晶在長度上生長。Additionally, a method of growing a SiC embryo is provided, the method comprising: placing a spacer having a starting material of SiC in a vapor deposition apparatus; heating the spacer to provide a directional flux during a growth cycle of the embryo and, depositing the directional flux on the growth surface of the embryo crystal to grow the embryo crystal in length.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：其中該方向性通量為該生長面之該外區域提供增加的通量密度，藉以該胚晶具有平坦面持續時間；及其中該胚晶不含缺陷；Additionally, the methods, spatial shapes, wafers, and embryos are provided having one or more of the following features: wherein the directional flux provides an increased flux density to the outer region of the growth surface, whereby the embryo having flat face duration; and wherein the embryo crystal is free of defects;

又另外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：藉以該胚晶係藉由本說明書中揭示的方法生長；製造電子部件之該方法，包括獲得藉由本說明書中揭示的方法製造的晶圓；在藉由本說明書中揭示的方法製造的晶圓上提供印製電路；及製造具有藉由本說明書之方法獲得的電子部件之系統；將電子部件組裝成系統，其中部件係基於或含有藉由本說明書中揭示的方法製造的晶圓。Still further, there are provided the methods, spatial bodies, wafers, and embryos that have one or more of the following features: whereby the embryos are grown by the method disclosed in this specification; the method of manufacturing electronic components includes obtaining the Wafers produced by the methods disclosed in this specification; providing printed circuits on wafers produced by the methods disclosed in this specification; and producing systems with electronic components obtained by the methods of this specification; assembling electronic components into systems , wherein the components are based on or contain wafers fabricated by the methods disclosed in this specification.

進一步提供自胚晶之單一生長循環提供大量裝置之方法，該方法包括：將具有SiC之起始材料之空間形體置放於氣相沉積設備中；加熱該空間形體以在胚晶之生長循環期間提供方向性通量；及，將該方向性通量沉積在該胚晶之生長面上以使該胚晶在長度上生長；其中胚晶係形成為能夠提供顯著大量的晶圓、電子電路及系統。There is further provided a method of providing a large number of devices from a single growth cycle of an embryo, the method comprising: placing a spacer having a starting material of SiC in a vapor deposition apparatus; heating the spacer so that during the growth cycle of the embryo providing directional flux; and, depositing the directional flux on the growth surface of the embryo to grow the embryo in length; wherein the embryo is formed to provide a significant amount of wafers, electronic circuits, and system.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：其中該胚晶之該長度的約80%能夠經切割來提供無缺陷晶圓；其中該胚晶之該長度的約90%能夠經切割來提供無缺陷晶圓；其中該胚晶之該長度的約95%能夠經切割來提供無缺陷晶圓；其中該胚晶之該長度的約99%能夠經切割來提供無缺陷晶圓；其中晶圓具有MPD (≤ 0.1 cm-2)、TSD (≤ 300 cm-2)及BPD (≤ 500 cm-2)；具有在20℃下大於約10,000 ohm-cm之電阻率；及具有在20℃下不小於約10,000 ohm-cm之電阻率。In addition, the methods, spatial shapes, wafers, and embryos are provided having one or more of the following features: wherein about 80% of the length of the embryo can be cut to provide a defect-free wafer; wherein the embryo About 90% of the length of the embryo can be cut to provide a defect-free wafer; wherein about 95% of the length of the embryo can be cut to provide a defect-free wafer; wherein about 99% of the length of the embryo can be Sliced to provide defect-free wafers; wherein the wafers have MPD (≤ 0.1 cm-2), TSD (≤ 300 cm-2) and BPD (≤ 500 cm-2); have greater than approximately 10,000 ohm-2 at 20°C have a resistivity in cm; and have a resistivity of not less than about 10,000 ohm-cm at 20°C.

更進一步提供用於碳化矽胚晶之氣相沉積生長的超純碳化矽粒子及黏合劑之複合材料的空間形體，該空間形體具有：碳化矽粒子，其中該等粒子為至少99.999%純；黏合劑，其將該等碳化矽粒子接合在一起且進而界定空間形體；該黏合劑具有由碳及矽組成的交聯聚合材料；及，其中該黏合劑具有在約300℃與700℃之間的揮發溫度(volitization temperature)；藉以該黏合劑不能干擾SiC胚晶生長且不能不利地影響SiC胚晶品質。Still further provided is a spatial form of a composite material of ultrapure silicon carbide particles and a binder for vapor deposition growth of silicon carbide embryo crystals, the spatial form having: silicon carbide particles, wherein the particles are at least 99.999% pure; an agent that joins the silicon carbide particles together and thereby defines a spatial form; the binder has a cross-linked polymeric material composed of carbon and silicon; and, wherein the binder has a temperature between about 300°C and 700°C Volatization temperature; whereby the binder cannot interfere with SiC embryo crystal growth and cannot adversely affect SiC embryo crystal quality.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：具有約1 g/cc至約3 g/cc之密度；其中該黏合劑小於該空間形體之重量的5%；其中該黏合劑小於該空間形體之重量的10%；其中該黏合劑小於該空間形體之重量的20%；其中該黏合劑小於該空間形體之重量的35%；其中該黏合劑小於該空間形體之重量的5%；其中該黏合劑小於該空間形體之重量的10%；其中該黏合劑小於該空間形體之重量的20%；其中該黏合劑小於該空間形體之重量的35%；具有小於約3.1 g/cc之密度；具有小於約3 g/cc之密度；具有小於約2.5 g/cc之密度；具有小於約2 g/cc之密度。Additionally, the methods, spaceforms, wafers, and embryos are provided having one or more of the following features: having a density of about 1 g/cc to about 3 g/cc; wherein the binder is less than the weight of the spaceform 5% of the weight of the spatial body; wherein the adhesive is less than 10% of the weight of the spatial body; wherein the adhesive is less than 20% of the weight of the spatial body; wherein the adhesive is less than 35% of the weight of the spatial body; wherein the adhesive Less than 5% of the weight of the spatial body; wherein the adhesive is less than 10% of the weight of the spatial body; wherein the adhesive is less than 20% of the weight of the spatial body; wherein the adhesive is less than 35% of the weight of the spatial body %; having a density of less than about 3.1 g/cc; having a density of less than about 3 g/cc; having a density of less than about 2.5 g/cc; having a density of less than about 2 g/cc.

另外，提供用於碳化矽胚晶之氣相沉積生長的超純碳化矽粒子及黏合劑之複合材料的空間形體，該空間形體具有：聚合物衍生碳化矽粒子，其具有非氧化物成形表面；其中該等粒子為至少99.9999%純；黏合劑，其將該等碳化矽粒子接合在一起且進而界定空間形體；及，其中該黏合劑具有低於該等聚合物衍生碳化矽粒子之該揮發溫度的揮發溫度；藉以該黏合劑不能干擾SiC胚晶生長且不能不利地影響SiC胚晶品質。In addition, there is provided a spatial form of a composite material of ultrapure silicon carbide particles and a binder for vapor deposition growth of silicon carbide embryo crystals, the spatial form having: polymer-derived silicon carbide particles having a non-oxide shaped surface; wherein the particles are at least 99.9999% pure; a binder that binds the silicon carbide particles together and thereby defines a spatial form; and wherein the binder has a volatilization temperature lower than the volatilization temperature of the polymer-derived silicon carbide particles The volatilization temperature; whereby the binder cannot interfere with the growth of SiC embryo crystals and cannot adversely affect the quality of SiC embryo crystals.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：具有約10%至約30%空隙體積之多孔性；具有約5%至約40%空隙體積之多孔性；具有約10%至約30%空隙體積之多孔性；具有約5%至約40%空隙體積之多孔性；具有約1 g/cc至約3 g/cc之密度；其中該黏合劑小於該空間形體之重量的5%；其中該黏合劑小於該空間形體之重量的10%；其中該黏合劑小於該空間形體之重量的20%；及，其中該黏合劑小於該空間形體之重量的35%。In addition, the methods, spatial bodies, wafers, and embryos are provided having one or more of the following features: porosity with about 10% to about 30% void volume; porosity with about 5% to about 40% void volume Porosity; porosity having from about 10% to about 30% void volume; porosity having from about 5% to about 40% void volume; having a density from about 1 g/cc to about 3 g/cc; wherein the binder less than 5% of the weight of the space-form; wherein the adhesive is less than 10% of the weight of the space-form; wherein the adhesive is less than 20% of the weight of the space-form; and, wherein the adhesive is less than the weight of the space-form 35%.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：其中該黏合劑之該揮發溫度低於該等碳化矽粒子之該揮發溫度至少500℃；其中該黏合劑之該揮發溫度低於該等碳化矽粒子之該揮發溫度至少550℃；其中該黏合劑之該揮發溫度低於該等碳化矽粒子之該揮發溫度至少600℃；其中該黏合劑之該揮發溫度低於該等碳化矽粒子之該揮發溫度至少650℃；及其中該黏合劑之該揮發溫度低於該等碳化矽粒子之該揮發溫度至少700℃；其中該黏合劑之該揮發溫度低於該等碳化矽粒子之該揮發溫度至少800℃；其中該黏合劑之該揮發溫度低於該等碳化矽粒子之該揮發溫度至少900℃；其中該黏合劑之該揮發溫度低於該等碳化矽粒子之該揮發溫度至少1,000℃。In addition, the methods, spatial bodies, wafers, and embryos are provided with one or more of the following features: wherein the volatilization temperature of the binder is at least 500° C. lower than the volatilization temperature of the silicon carbide particles; wherein the The volatilization temperature of the binder is at least 550°C lower than the volatilization temperature of the silicon carbide particles; wherein the volatilization temperature of the binder is at least 600°C lower than the volatilization temperature of the silicon carbide particles; The volatilization temperature is at least 650°C lower than the volatilization temperature of the silicon carbide particles; and wherein the volatilization temperature of the binder is at least 700°C lower than the volatilization temperature of the silicon carbide particles; wherein the volatilization temperature of the binder is lower The volatilization temperature of the silicon carbide particles is at least 800°C; wherein the volatilization temperature of the binder is at least 900°C lower than the volatilization temperature of the silicon carbide particles; The volatilization temperature of silicon particles is at least 1,000°C.

更進一步提供用於碳化矽胚晶之氣相沉積生長的超純碳化矽粒子及黏合劑之複合材料的空間形體，該空間形體具有：碳化矽粒子，其中該等粒子為至少99.999%純，其中該等粒子具有約0.1 μm至約20.0 μm之 D ₅₀粒子大小；黏合劑，其將該等碳化矽粒子接合在一起且進而界定空間形體；該黏合劑具有具碳及矽的交聯聚合材料；及，其中該黏合劑具有在約300℃與900℃之間的揮發溫度；藉以該黏合劑不能干擾胚晶生長且不能不利地影響胚晶品質。 There is further provided a spatial form of a composite material of ultrapure silicon carbide particles and a binder for vapor deposition growth of silicon carbide embryo crystals, the spatial form having: silicon carbide particles, wherein the particles are at least 99.999% pure, wherein The particles have a _D50 particle size of about 0.1 μm to about 20.0 μm; a binder that joins the silicon carbide particles together and thereby defines a spatial form; the binder has a cross-linked polymeric material comprising carbon and silicon; And, wherein the binder has a volatilization temperature between about 300° C. and 900° C.; whereby the binder cannot interfere with the growth of the embryo crystal and cannot adversely affect the quality of the embryo crystal.

此外，提供具有以下特徵之一或多者的該些方法、空間形體、晶圓及胚晶：具有約10 GPa至約300 GPa之彈性模數；具有約300 Kg/mm ²至約2,000 Kg/mm ²之硬度；具有約50 MPa至約3,000 MPa之壓縮強度；具有約300 Kg/mm ²至約2,000 Kg/mm ²之硬度，且具有約50 MPa至約3,000 MPa之壓縮強度；及；其中該等粒子具有約0.5 μm至約10 μm之D ₅₀粒子大小；其中該等粒子具有約1 μm至約15 μm之D ₅₀粒子大小；其中該等粒子具有約1 μm之D ₅₀粒子大小；及其中該等粒子具有約3 μm之D ₅₀粒子大小。 Additionally, the methods, steric bodies, wafers, and embryos are provided having one or more of the following features: having an elastic modulus of about 10 GPa to about 300 GPa; having an elastic modulus of about 300 Kg/mm ² to about 2,000 Kg/mm having a hardness of from about 50 MPa to about 3,000 MPa; having a hardness of from about 300 Kg ^/ ^mm to about 2,000 Kg/ ^mm and having a compressive strength of from about 50 MPa to about 3,000 MPa; and; wherein the particles have a D 50 particle size of about 0.5 μm to about 10 μm; wherein the particles have a D ₅₀ particle size _{of about 1 μm to about 15 μm; wherein the particles have a D 50} _particle size of about 1 μm; and wherein the particles have a _D50 particle size of about 3 μm.

進一步，提供用於碳化矽胚晶之氣相沉積生長的超純碳化矽粒子及黏合劑之複合材料的空間形體，該空間形體具有：碳化矽粒子，其中該等粒子為至少99.999%純，其中該等粒子具有等於或小於5 μm之平均粒子大小且不超過10%之粒子大於10 μm；黏合劑，其將該等碳化矽粒子接合在一起且進而界定空間形體；該黏合劑具有具碳及矽的交聯聚合材料；及，其中該黏合劑具有在約300℃與900℃之間的揮發溫度；藉以該黏合劑不能干擾胚晶生長且不能不利地影響胚晶品質。Further, there is provided a spatial form of a composite material of ultrapure silicon carbide particles and a binder for vapor deposition growth of silicon carbide embryo crystals, the spatial form has: silicon carbide particles, wherein the particles are at least 99.999% pure, wherein The particles have an average particle size equal to or smaller than 5 μm and not more than 10% of the particles are larger than 10 μm; binders which bind the silicon carbide particles together and thereby define spatial shapes; the binders have carbon and A cross-linked polymeric material of silicon; and, wherein the binder has a volatilization temperature between about 300°C and 900°C; whereby the binder does not interfere with embryonic growth and does not adversely affect embryonic quality.

更進一步，提供在氣相沉積設備中生長胚晶之方法，該方法包括：將本發明之空間形體置放於氣相沉積設備中；在時間上將該黏合劑首先汽化且其次將該等碳化矽粒子汽化；及自該等汽化碳化矽粒子形成胚晶，其不含該汽化黏合劑。Furthermore, there is provided a method for growing embryo crystals in a vapor deposition device, the method comprising: placing the spatial body of the present invention in a vapor deposition device; first vaporizing the binder and secondly carbonizing the binders in time vaporizing silicon particles; and forming embryo crystals from the vaporized silicon carbide particles, which do not contain the vaporized binder.

又另外，提供在氣相沉積設備中生長胚晶之方法，該方法包括：將超純碳化矽粒子及黏合劑之複合材料之空間形體置放於氣相沉積設備中；該空間形體具有：聚合物衍生碳化矽粒子，具有非氧化物成形表面；其中該等粒子為至少99.9999%純；黏合劑，其將該等碳化矽粒子接合在一起且進而界定空間形體；該黏合劑具有矽、碳及添加劑以用於向胚晶提供官能性；其中該黏合劑具有處於或低於該等聚合物衍生碳化矽粒子之該揮發溫度的揮發溫度，且該添加劑具有處於該等聚合物衍生陶瓷粒子之約該揮發溫度的揮發溫度；汽化該空間形體以形成蒸汽；將該等蒸汽沉積在基板上以形成胚晶；藉以該黏合劑不能為該胚晶提供預定官能性，且該添加劑能夠提供部分地基於該添加劑的官能性。In addition, there is provided a method for growing an embryo in a vapor deposition device, the method comprising: placing a space body of a composite material of ultrapure silicon carbide particles and a binder in a vapor deposition device; the space body has: polymerization Derived silicon carbide particles having a non-oxide shaped surface; wherein the particles are at least 99.9999% pure; a binder which joins the silicon carbide particles together and thereby defines a spatial form; the binder has silicon, carbon and An additive for providing functionality to the embryonic crystal; wherein the binder has a volatilization temperature at or below the volatilization temperature of the polymer-derived silicon carbide particles, and the additive has a volatilization temperature at or below the volatilization temperature of the polymer-derived ceramic particles The volatilization temperature of the volatilization temperature; vaporize the steric body to form vapors; deposit the vapors on the substrate to form embryo crystals; whereby the binder cannot provide the embryo crystals with predetermined functionality and the additive can provide based in part The functionality of the additive.

又另外，提供用於碳化矽胚晶之氣相沉積生長的超純碳化矽粒子及黏合劑之複合材料的空間形體，該空間形體具有：碳化矽粒子，其中該等粒子為至少99.999%純；黏合劑，其將該等碳化矽粒子接合在一起且進而界定空間形體；該黏合劑具有不具有氧且具有碳及矽的交聯聚合材料；及，其中該黏合劑具有在約300℃與800℃之間的揮發溫度；藉以該黏合劑不能干擾SiC胚晶生長且不能不利地影響SiC胚晶品質。Still further, there is provided a spatial form of a composite material of ultrapure silicon carbide particles and a binder for vapor deposition growth of silicon carbide embryo crystals, the spatial form having: silicon carbide particles, wherein the particles are at least 99.999% pure; A binder that joins the silicon carbide particles together and thereby defines a spatial form; the binder has a cross-linked polymeric material that does not have oxygen but has carbon and silicon; and, wherein the binder has a temperature between about 300° C. The volatilization temperature between °C; whereby the binder cannot interfere with SiC embryo crystal growth and cannot adversely affect SiC embryo crystal quality.

又此外，提供用於碳化矽胚晶之氣相沉積生長的超純碳化矽粒子及黏合劑之複合材料的空間形體，該空間形體具有：碳化矽粒子，其中該等粒子為至少99.999%純；黏合劑，其將該等碳化矽粒子接合在一起且進而界定空間形體；該黏合劑具有不具有氧、不具有矽且具有碳的交聯聚合材料；及，其中該黏合劑具有在約300℃與800℃之間的揮發溫度；藉以該黏合劑不能干擾SiC胚晶生長且不能不利地影響SiC胚晶品質。Still further, there is provided a spatial form of a composite material of ultrapure silicon carbide particles and a binder for vapor deposition growth of silicon carbide embryo crystals, the spatial form having: silicon carbide particles, wherein the particles are at least 99.999% pure; A binder that joins the silicon carbide particles together and thereby defines a spatial form; the binder has a cross-linked polymeric material that has no oxygen, no silicon, and carbon; and, wherein the binder has a temperature of about 300° C. and a volatilization temperature between 800° C.; whereby the binder cannot interfere with SiC embryo crystal growth and cannot adversely affect SiC embryo crystal quality.

大體而言，本發明係關於碳化矽(SiC)粒子之空間形體；及來自該些空間形體之生長結構。在實施例中，粒子以及空間形體具有良好、高的、及超高純度。本發明進一步係關於在氣相沉積技術中使用SiC粒子之該些空間形體以形成SiC胚晶之設備及方法，該等胚晶例如用於製造用於電子學應用的晶圓及裝置。In general, the present invention relates to spatial shapes of silicon carbide (SiC) particles; and growth structures derived from these spatial shapes. In embodiments, the particles and spatial features are of good, high, and ultrahigh purity. The invention further relates to apparatus and methods for using these spatial configurations of SiC particles in vapor deposition techniques to form SiC embryos, such as those used in the manufacture of wafers and devices for electronics applications.

雖然本說明書集中在SiC氣相沉積技術上，但應理解本發明不因此受限，且可在其他SiC結晶生長製程、接合製程、以及其他應用中有適用性。Although this description focuses on SiC vapor deposition technology, it should be understood that the present invention is not limited thereby and may have applicability in other SiC crystal growth processes, bonding processes, and other applications.

實施例可包括大體上使用、基於、或構成PDC之聚合物衍生陶瓷(polymer derived ceramic;「PDC」)材料、產品及應用。Embodiments may include polymer derived ceramic ("PDC") materials, products, and applications that generally use, be based on, or constitute PDC.

本發明之實施例較佳地使用、基於或構成PDC，其為「多晶碳氧矽」材料，例如，含有矽(Si)、氧(O)及碳(C)之材料，及已固化的此種材料之實施例，及已熱解的此種材料之實施例及已轉化成SiC的此種材料之實施例。多晶碳氧矽材料可具有高的及異常高的純度。多晶碳氧矽材料亦可含有其他元素。多晶碳氧矽材料由一或多種多晶碳氧矽前驅物調配物或前驅物調配物製成。多晶碳氧矽前驅物調配物含有一或多種官能化矽聚合物、或單體、非基於矽的交聯劑、以及潛在地其他成分，諸如例如，抑制劑、觸媒、填料、摻雜劑、改質劑、起始劑、增強劑、纖維、粒子、著色劑、顏料、染料、相同或其他PDC、陶瓷、金屬、金屬錯合物、及該些及其他材料及添加劑之組合及變化。除非另外具體陳述，碳氧化矽材料、SiOC組合物、及類似的此種術語係指多晶碳氧矽材料，且將包括液體材料、固體未固化材料、固化材料、陶瓷材料、及該些者之組合及變化。Embodiments of the present invention preferably use, be based on, or form PDCs, which are "polycrystalline silicon oxycarbide" materials, for example, materials containing silicon (Si), oxygen (O) and carbon (C), and cured Examples of such materials, and examples of such materials that have been pyrolyzed and examples of such materials that have been converted to SiC. Polycrystalline silicon oxycarbide materials can be of high and unusually high purity. The polycrystalline silicon oxycarbide material may also contain other elements. The polycrystalline silicon oxycarbide material is made from one or more polycrystalline silicon oxycarbide precursor formulations or precursor formulations. The polycrystalline silicon oxycarbide precursor formulation contains one or more functionalized silicon polymers, or monomers, non-silicon-based crosslinkers, and potentially other ingredients such as, for example, inhibitors, catalysts, fillers, dopants Agents, modifiers, initiators, reinforcing agents, fibers, particles, colorants, pigments, dyes, the same or other PDC, ceramics, metals, metal complexes, and combinations and changes of these and other materials and additives . Unless specifically stated otherwise, silicon oxycarbide materials, SiOC compositions, and similar such terms refer to polycrystalline silicon oxycarbide materials and shall include liquid materials, solid uncured materials, cured materials, ceramic materials, and the like Combinations and changes.

在本發明之實施例中在利用待使用的本說明書之教示時可使用，或改編及改良的PDC、PDC調配物、潛在前驅物、起始材料、及用於製造該些材料之設備及方法的實例見於例如以下美國專利公開案號：2014/0274658、2014/0323364、2015/0175750、2016/0207782、2016/0280607、2017/0050337、2008/0095942、2008/0093185、2007/0292690、2006/0069176、2006/0004169、及2005/0276961，及以下美國專利號：9,499,677、9,481,781、8,742,008、8,119,057、7,714,092、7,087,656、5,153,295、及4,657,991，且其每一者之全部揭示內容係以引用方式併入本文中。PDCs, PDC formulations, potential precursors, starting materials, and equipment and methods for making these materials that can be used, or adapted and improved, in embodiments of the invention utilizing the teachings of this specification to be used Examples of ® are found, for example, in the following U.S. Patent Publication Nos.: 2014/0274658, 2014/0323364, 2015/0175750, 2016/0207782, 2016/0280607, 2017/0050337, 2008/0095942, 2008/0093185, 2007/ 0292690, 2006/0069176 , 2006/0004169, and 2005/0276961, and the following U.S. Patent Nos.: 9,499,677, 9,481,781, 8,742,008, 8,119,057, 7,714,092, 7,087,656, 5,153,295, and 4,657,991, and the entirety of each The disclosure is incorporated herein by reference .

製造各種多晶碳氧矽之調配物、製程、方法及用於其之組合物係教示及揭示在以下美國專利號：9,499,677、9,481,781，及以下美國專利公開案號：2014/0274658、2014/0323364、2015/0175750、2016/0207782、2016/0280607、2017/0050337中，其每一者之全部揭示內容係以引用方式併入本文中。Formulations, processes, methods and compositions for making various polycrystalline silicon oxycarbides are taught and disclosed in the following U.S. Patent Nos.: 9,499,677, 9,481,781, and the following U.S. Patent Publication Nos.: 2014/0274658, 2014/0323364 , 2015/0175750, 2016/0207782, 2016/0280607, 2017/0050337, the entire disclosure of each of which is incorporated herein by reference.

典型地及較佳地，多晶碳氧矽前驅物調配物最初為液體。液體前驅物經固化成固體或半固體SiOC。固體或半固體SiOC隨後熱解成陶瓷SiOC，其隨後轉化成SiC。Typically and preferably, the polycrystalline silicon oxycarbide precursor formulation is initially a liquid. The liquid precursor is cured into solid or semi-solid SiOC. The solid or semi-solid SiOC is then pyrolyzed to ceramic SiOC, which is then converted to SiC.

碳化矽通常在真空下，在高於約1,700℃至1,800℃之溫度下不具有液相而替代地其昇華。轉向第17圖，提供SiC之分壓曲線之圖表。典型地，在工業及商業應用中，建立各種條件以便在約2,500℃及高於此之溫度下發生昇華。當碳化矽昇華時，其典型地形成由矽及碳之若干不同物質組成的蒸汽。通常，咸信溫度決定矽碳蒸汽中的該些不同組分之比率。Silicon carbide generally does not have a liquid phase but instead sublimates it under vacuum at temperatures above about 1,700°C to 1,800°C. Turning to Figure 17, a graph of the partial pressure curve for SiC is provided. Typically, in industrial and commercial applications, conditions are established so that sublimation occurs at temperatures of about 2,500°C and above. When silicon carbide sublimes, it typically forms a vapor consisting of several different species of silicon and carbon. In general, it is believed that the temperature determines the ratio of these different components in the silicon carbide vapor.

然而，本發明尤其提供預選及控制存在於矽碳蒸汽中的例如Si、C、SiC、Si ₂C及SiC ₂之不同物質之比率的能力。因此，除溫度之外，本發明允許控制起始材料(例如SiC之圓片)中及其中矽碳蒸汽作為例如晶體之固體沉積以生長例如胚晶的表面中及該起始材料與該表面之間的蒸汽中之矽碳物質。氣相沉積製程中的此矽碳蒸汽可稱為「通量」。 In particular, however, the present invention provides the ability to preselect and control the ratios of different species such as Si, C, SiC, _Si2C and _SiC2 present in the silicon carbon vapor. Thus, in addition to the temperature, the present invention allows the control of the starting material (e.g. a wafer of SiC) and in the surface in which the silicon carbon vapor is deposited as a solid such as a crystal to grow, e.g. Silicon carbon substances in the steam between. This SiC vapor in the vapor deposition process may be referred to as "flux".

胚晶之較佳實施例為單晶且僅具有單一多型體。應理解，本說明書亦設想具有多個多型體、具有多個晶體、及兩者兼有的胚晶之實施例。A preferred embodiment of an embryo crystal is single crystal and has only a single polytype. It should be understood that this description also contemplates embodiments having multiple polytypes, having multiple crystals, and embryocrystals of both.

理論上，例如，藉由相對於多晶碳氧矽衍生SiC中或用作起始材料之空間形體中存在的矽之量控制存在的碳之量，通量中存在的Si及C之量及物質可得以預定及控制。另外，及例如，藉由以受控方式使多晶碳氧矽衍生SiC之多孔性、空間形體之多孔性及兩者變化，通量之量、通量形成之速率、及通量中存在的矽及碳之物質可得以預定及控制。Theoretically, the amount of Si and C present in the flux and Substances can be predetermined and controlled. Additionally, and for example, by varying the porosity of polycrystalline silicon oxycarbide-derived SiC, the porosity of the spatial form, and both in a controlled manner, the amount of flux, the rate of flux formation, and the presence of flux in the flux The substances of silicon and carbon can be predetermined and controlled.

起始材料或起始圓片中存在的，例如，過量(比化學計量更多的碳，該化學計量亦即，1比1、矽比碳)、欠缺(比化學計量更少的碳)及化學計量的碳之量可得以預定。以此方式，起始材料或空間形體，例如，圓片中的碳之量可得以設定或建立。此量可例如藉由以下方式建立：(i)使用不同的黏合劑來形成空間形體；(ii)具有SiC材料之層，該SiC材料具有存在的不同預定量之碳；(iii)在SiC之空間形體中具有區帶，該SiC具有存在的不同預定量之碳；及(iv)該些方式之組合及變化，以及以預定方式控制起始材料中存在的碳之量。進一步，藉由控制及預定起始材料中碳對矽之比率，可在通量中控制及預定該些比率。Excess (more carbon than stoichiometric, i.e., 1 to 1, silicon to carbon), deficiency (less carbon than stoichiometric) present in the starting material or starting wafer, for example, The stoichiometric amount of carbon can be predetermined. In this way, a starting material or spatial form, eg, the amount of carbon in a wafer can be set or established. This amount can be established, for example, by: (i) using different binders to form the spatial features; (ii) having a layer of SiC material with a different predetermined amount of carbon present; (iii) between the SiC having zones in the spatial form, the SiC having different predetermined amounts of carbon present; and (iv) combinations and variations of these, and controlling the amount of carbon present in the starting material in a predetermined manner. Further, by controlling and pre-determining the ratio of carbon to silicon in the starting material, these ratios can be controlled and pre-determined in throughput.

本發明提供用於胚晶之生長，例如，SiC之氣相沉積以形成SiC之單晶胚晶的方法及製程之實施例，該單晶胚晶在該胚晶之面處提供極平坦，例如，具有有限量之曲率或弧度。胚晶之極平坦輪廓係主要地藉由使用置放於氣相沉積設備中的SiC圓片之預選形體來達成。預選形體係配置來以便在氣相沉積製程期間，通量之區域及彼區域中之流動在整個胚晶生長製程期間保持恆定。以此方式，在SiC生長時沉積在胚晶之面上的SiC之速率及量在胚晶生長製程期間保持一致及均勻。因此，例如，在生長6吋直徑胚晶中，通量流動之面積將為28.27吋 ²，且跨於彼區域流動的SiC之流動速率及量將在胚晶之生長期間跨於彼整個區域為均勻的，例如，3吋長度胚晶、4吋長度胚晶等等。正如在製程期間在圓片內的可利用於昇華改變之SiC之量及位置，圓片之形體以保持通量之流動跨於直接相鄰於胚晶之面的區域均勻的方式導引通量，例如，「方向性通量」。提供方向性通量的形體之實例將為第4A圖-第4F圖、及第5A圖-第5F圖之實施例。 The present invention provides embodiments of methods and processes for the growth of an embryo, e.g., vapor deposition of SiC to form a single crystal embryo of SiC that provides an extremely flat surface at the face of the embryo, such as , has a finite amount of curvature or arc. The extremely flat profile of the embryo crystal is mainly achieved by using a preselected shape of the SiC wafer placed in the vapor deposition equipment. The pre-shape system is configured so that during the vapor deposition process, the region of flux and the flow in that region remains constant throughout the embryonic crystal growth process. In this way, the rate and amount of SiC deposited on the face of the embryo crystal as SiC grows remains consistent and uniform during the embryo crystal growth process. Thus, for example, in growing a 6 inch diameter embryo crystal, the area of flux flow would be 28.27 ^inches , and the flow rate and amount of SiC flowing across that area would be Uniform, eg, 3 inch length embryo crystals, 4 inch length embryo crystals, etc. As the amount and location of SiC available for sublimation changes within the wafer during processing, the shape of the wafer directs the flux in a manner that keeps the flow of flux uniform across the region immediately adjacent to the face of the embryo crystal. , for example, Directional Flux. Examples of features that provide directional flux would be the embodiments of Figures 4A-4F, and Figures 5A-5F.

在實施例中，通量遍及生長製程不維持恆定。因此，在此等實施例中，通量跨於生長面之分佈以預定方式管理，例如，控制來提供胚晶或生長面之區域的預定生長。因此，例如，在生長之稍後階段，通量可以預定方式經導引以補償已在胚晶之生長中發生的不均勻性。在此實例中，其中通量在生長之較早階段中較多的區域在生長之稍後階段中具有較少的通量；類似地，其中通量在生長之較早階段中較少的區域在生長之稍後階段中具有較多的通量。以此方式，最終胚晶生長面最小化胚晶面之曲率或最大化胚晶面之曲率半徑。In an embodiment, the flux is not maintained constant throughout the growth process. Thus, in such embodiments, the distribution of flux across the growth surface is managed in a predetermined manner, eg, controlled to provide a predetermined growth of the embryonic crystal or region of the growth surface. Thus, for example, at a later stage of growth, the flux can be directed in a predetermined manner to compensate for inhomogeneities that have occurred in the growth of the embryo crystal. In this example, regions where flux is more in earlier stages of growth have less flux in later stages of growth; similarly, regions where flux is less in earlier stages of growth There is more flux in later stages of growth. In this way, the final embryo crystal growth plane minimizes the curvature of the embryo crystal face or maximizes the radius of curvature of the embryo crystal face.

在實施例中，受控通量及更佳地方向通量之使用可提供4吋胚晶，其具有將為至少約6吋、至少約8吋、至少約20吋、至少約60吋、及接近無限(亦即，平坦)，以及該些值範圍內之所有值的曲率半徑(亦即，曲率之倒數)。在6吋胚晶之實施例中，曲率半徑(亦即，曲率之倒數)將為至少約10吋、至少約15吋、至少約25吋、至少約60吋、及接近無限(亦即，平坦)，以及該些值範圍內之所有值。在實施例中，胚晶面之曲率半徑為胚晶之長度的至少2倍、胚晶之長度的至少5倍、胚晶之長度的至少10倍、及胚晶之長度的至少25倍，多至且包括其中胚晶面為平坦之情況，以及此範圍內之所有值。轉向第21圖，為胚晶2100之示意圖。胚晶2100具有藉由箭頭2102展示的長度及藉由箭頭2103展示的寬度或直徑。胚晶具有面(例如生長面) 2101，其具有彎曲表面2101a。彼表面2101a之曲率半徑係藉由虛線2104展示。因此，將為胚晶2100之曲率半徑的表面2101a之曲率半徑等於圓弧之半徑2104，該圓弧最佳地近似面2101之曲線。In an embodiment, the use of controlled flux and more preferably directional flux can provide a 4 inch embryo crystal having a size that will be at least about 6 inches, at least about 8 inches, at least about 20 inches, at least about 60 inches, and near infinity (ie, flat), and the radius of curvature (ie, the reciprocal of curvature) for all values within these ranges of values. In embodiments of a 6 inch embryo, the radius of curvature (i.e., the inverse of curvature) will be at least about 10 inches, at least about 15 inches, at least about 25 inches, at least about 60 inches, and nearly infinite (i.e., flat ), and all values within those values. In an embodiment, the radius of curvature of the embryo crystal face is at least 2 times the length of the embryo crystal, at least 5 times the length of the embryo crystal, at least 10 times the length of the embryo crystal, and at least 25 times the length of the embryo crystal, at least Up to and including the case where the embryonic plane is flat, and all values within this range. Turning to FIG. 21 , it is a schematic diagram of an embryo crystal 2100 . Embryocrystal 2100 has a length shown by arrow 2102 and a width or diameter shown by arrow 2103 . The embryo crystal has a face (eg, growth face) 2101 with a curved surface 2101a. The radius of curvature of the surface 2101 a is shown by dashed line 2104 . Thus, the radius of curvature of the surface 2101a which will be the radius of curvature of the embryonic crystal 2100 is equal to the radius 2104 of the arc which best approximates the curve of the surface 2101 .

在實施例中，通量可以壓力以及溫度操縱。對於給定生長溫度，生長可藉由增加腔室壓力減慢。最快速率係典型地處於「完全」真空下(例如，真空泵開啟且保持腔室壓力盡可能低)。因此，例如，為以400 μm/hr生長胚晶，該生長可在完全真空之P1下處於溫度T1，或可處於溫度T2＞T1，並具有幾mBar至幾十mBar之氬分壓(P2＞P1)。以此方式，通量及生長速率可經「調諧」。In an embodiment, the flux can be manipulated by pressure as well as temperature. For a given growth temperature, growth can be slowed by increasing the chamber pressure. The fastest rates are typically at "full" vacuum (eg, vacuum pump on and chamber pressure kept as low as possible). Thus, for example, to grow an embryo at 400 μm/hr, the growth can be at temperature T1 under P1 in full vacuum, or can be at temperature T2>T1 with an argon partial pressure of a few mBar to tens of mBar (P2> P1). In this way, flux and growth rate can be "tuned."

在實施例中，聚合物衍生SiC在胚晶中賦予較好的多型體穩定性，此歸因於隨時間更一致的通量組成。此實施例，亦即，受控多型體穩定性對胚晶製造商而言有價值且為重要的，因為多型體變換中等生長僅意指胚晶之一部分為原始多型體，其典型地不利地影響電子性質，從而影響由其構建的晶片之裝置效能。In an embodiment, polymer derived SiC confers better polytype stability in the embryo due to a more consistent flux composition over time. This embodiment, i.e., controlled polytype stability is valuable and important to the embryo crystal manufacturer, because the polytype transformation medium growth only means that a part of the embryo crystal is the original polytype, which typically It can adversely affect the electronic properties, thereby affecting the device performance of chips built therefrom.

本發明提供「調諧」通量之能力，且因此提供經由使用本發明的聚合物衍生SiC及預定圓片形體來賦能有效性較小的氣相沉積設備以產生處於實質上改良品質、數量、生產率及該些者之組合及變化的能力。以此方式，較低品質氣相沉積設備之效能可顯著地改良，且經改良至其中其滿足或超過較高品質氣相沉積設備之點。因此，例如，本發明之形體及其調諧通量之能力提供不具有任何機械修改的現存氣相沉積設備生產胚晶之能力，該等胚晶具有：少10%之缺陷，具有少20%之缺陷，具有少50%之缺陷，具有少100%之缺陷，及甚至更少缺陷；生產胚晶之能力，該等胚晶係以2倍速率、以3倍速率、及以4倍速率及更大速率生產；且生產胚晶之能力，該等胚晶具有較平的面，亦即，更平坦的，平至少2倍、平至少3倍、平至少4倍、及更平的，以及該些值範圍內之全部；及該些改良之組合及變化，包括該些一般改良中之所有三者，亦即，較少缺陷、增加的速率、及增加的平坦度。調諧通量提供不具有任何機械修改的氣相沉積設備對給定時間段而言生產1.5倍、2倍、3倍、或更多倍胚晶之能力，且更佳地具有本文闡述的改良品質特徵之一或多者，包括實質上較少的缺陷及大體上較高的品質。The present invention provides the ability to "tune" the flux and thus provide the ability to enable less effective vapor deposition equipment by using the polymer-derived SiC of the present invention and predetermined wafer shapes to produce substantially improved quality, quantity, Productivity and the ability to combine and vary these. In this way, the performance of lower quality vapor deposition equipment can be significantly improved, and improved to the point where it meets or exceeds higher quality vapor deposition equipment. Thus, for example, the morphology of the present invention and its ability to tune flux provides the ability, without any mechanical modification, of existing vapor deposition equipment to produce embryo crystals with: 10% fewer defects, with 20% fewer Defects, with 50% fewer defects, with 100% fewer defects, and even fewer defects; the ability to produce embryo crystals at 2 times the rate, at 3 times the rate, and at 4 times the rate and more High rate production; and the ability to produce embryo crystals that have a flatter face, i.e., flatter, at least 2 times flatter, at least 3 times flatter, at least 4 times flatter, and flatter, and the all within these ranges of values; and combinations and variations of such improvements, including all three of these general improvements, namely, fewer defects, increased speed, and increased flatness. Tuned throughput provides the ability of a vapor deposition apparatus without any mechanical modifications to produce 1.5x, 2x, 3x, or more embryo crystals for a given time period, and preferably with the improved qualities set forth herein One or more of the characteristics, including substantially fewer defects and generally higher quality.

轉向第18圖，展示用於生長SiC晶體、結晶結構及胚晶的設備之示意橫截面表示。氣相沉積裝置1800為具有側壁1808、底部或底部壁1809、及頂部或頂部壁1810之容器。壁1808、1809、1810可具有埠1806、1807、1805，其可為開口、噴嘴、閥，其可控制或允許氣體流入及流出裝置1800。裝置1800與其加熱元件1804相關聯。加熱元件可經配置及操作以在裝置1800內部提供單一溫度區帶，或多個溫度區帶。在裝置1800內部，存在圓片1801，其係由已成形在一起成為空間形體之SiC粒子製成。Turning to Figure 18, there is shown a schematic cross-sectional representation of an apparatus for growing SiC crystals, crystalline structures and embryo crystals. Vapor deposition apparatus 1800 is a container having sidewalls 1808 , a bottom or bottom wall 1809 , and a top or top wall 1810 . Walls 1808 , 1809 , 1810 may have ports 1806 , 1807 , 1805 , which may be openings, nozzles, valves, which may control or allow gas to flow into and out of device 1800 . The device 1800 is associated with its heating element 1804 . The heating element may be configured and operated to provide a single temperature zone, or multiple temperature zones, within device 1800 . Inside the device 1800 there is a wafer 1801 made of SiC particles that have been shaped together into a spatial form.

圓片1801可具有預定多孔性及密度。SiC粒子可具有預定多孔性及密度。SiC粒子係保持在一起，較佳地藉由黏合劑保持在一起。圓片1801可為富碳、貧碳、或化學計量的。圓片1801可具有為富碳、貧碳、或化學計量的區帶或層。較佳地，SiC粒子為SiOC聚合物衍生SiC。非聚合物衍生SiC亦可用作圓片之部分或全部。圓片1801具有藉由箭頭1821展示的高度及橫截面或直徑1820。圓片1801具有上表面或頂表面1823及底表面1824。在此實施例中，圓片1801係展示為平坦頂部及底部圓柱體；應瞭解，藉由本說明書涵蓋的任何空間形體可用於裝置1800。The wafer 1801 may have a predetermined porosity and density. The SiC particles may have a predetermined porosity and density. The SiC particles are held together, preferably by a binder. Wafer 1801 may be carbon rich, carbon lean, or stoichiometric. Wafer 1801 may have zones or layers that are carbon rich, carbon lean, or stoichiometric. Preferably, the SiC particles are SiOC polymer derived SiC. Non-polymer derived SiC can also be used as part or all of the wafer. Wafer 1801 has a height and a cross-section or diameter 1820 shown by arrow 1821 . Wafer 1801 has an upper or top surface 1823 and a bottom surface 1824 . In this embodiment, wafer 1801 is shown as a flat top and bottom cylinder; it should be understood that any spatial shape encompassed by this description may be used for device 1800 .

在裝置1800之頂部1810處，存在晶種1802，其具有表面1802a。晶種1802具有橫截面或直徑1822及高度1823。在一些實施例中，晶種可安裝在可移動平臺1803上以調整表面1802a與表面1823之間的距離。At the top 1810 of the device 1800, there is a seed crystal 1802, which has a surface 1802a. Seed 1802 has a cross-section or diameter 1822 and a height 1823 . In some embodiments, seeds can be mounted on movable platform 1803 to adjust the distance between surface 1802a and surface 1823 .

圓片1801之直徑1820可大於、小於、或與晶種1802之直徑1822相同。The diameter 1820 of the wafer 1801 may be larger, smaller, or the same as the diameter 1822 of the seed crystal 1802 .

在操作中，加熱元件1804升高圓片1801之溫度至SiC昇華之點。此昇華引起具有矽及碳之各種物質的氣體之形成。此氣體，亦即，通量存在於表面1802a與1823之間的區域1850。取決於多孔性或其他因素，通量亦可存在於圓片1801內。通量在裝置1800中上升穿過區域1850，其中通量將SiC沉積在表面1802a上。表面1802a必須保持在一溫度下，該溫度足夠冷以引起氣態矽碳物質沉積出其表面以形成SiC晶體。以此方式，晶種1802係藉由連續地在其表面上在多型體匹配定向上添加已生長的SiC來生長成胚晶。因此，除非藉由裝置1803 (其以完全收縮位置展示)調整，否則在胚晶之生長期間，表面1803將朝向底部1809生長，且因此，減少表面1802a與底部1809之間的距離。通量之形體可用於在氣相沉積製程期間在圓片內產生預定溫度差。此預定溫度差可解決、減少且消除鈍化之有害效應，此為其中物質在減少或防止Si-C蒸汽形成之製程期間堆積在圓片中的狀況。In operation, heating element 1804 raises the temperature of wafer 1801 to the point where SiC sublimates. This sublimation causes the formation of gases with various species of silicon and carbon. This gas, ie flux, exists in region 1850 between surfaces 1802a and 1823 . Flux may also exist within the wafer 1801 depending on porosity or other factors. Flux rises in device 1800 through region 1850, where the flux deposits SiC on surface 1802a. Surface 1802a must be maintained at a temperature that is cold enough to cause gaseous silicon carbon species to deposit out of its surface to form SiC crystals. In this way, the seed crystal 1802 is grown into an embryo crystal by successively adding grown SiC on its surface in a polytype-matched orientation. Therefore, unless adjusted by means 1803 (shown in a fully retracted position), during growth of the embryo, surface 1803 will grow towards bottom 1809, and thus, reduce the distance between surface 1802a and bottom 1809. Flux profiles can be used to create predetermined temperature differentials within a wafer during a vapor deposition process. This predetermined temperature difference can address, reduce and eliminate the deleterious effects of passivation, a condition in which species build up in the wafer during a process that reduces or prevents Si—C vapor formation.

理論上，昇華及沉積之製程在源材料自身之空間形體內部發生且遵循源材料中自然產生之熱梯度，或該熱梯度可藉由圓片之形體決定。在實施例中，黏合材料可較佳地保持存在且在昇華溫度期間維持圓片之形體及完整性，並因此在SiC之昇華溫度下或低於該昇華溫度不會昇華。此熱梯度典型地自外部朝向內部且向上。理論上，材料持續地昇華且再沉積在相鄰粒子上且以此方式經歷Si-C物質之回流或固態「分餾」或「分昇華」。Theoretically, the processes of sublimation and deposition take place within the spatial shape of the source material itself and follow the thermal gradients naturally occurring in the source material, or this thermal gradient can be determined by the shape of the wafer. In embodiments, the adhesive material may preferably remain present and maintain the shape and integrity of the wafer during the sublimation temperature, and thus will not sublime at or below the sublimation temperature of SiC. This thermal gradient is typically from the outside towards the inside and upwards. Theoretically, the material is continuously sublimated and redeposited on adjacent particles and in this way undergoes reflux or solid state "fractionation" or "subsublimation" of the Si-C species.

進一步在理論上，在實施例中，空間形體及其預定梯度可允許一些較重雜質俘獲在生長腔室之底部中於圓片內，而較輕元素連同Si-C蒸汽一起昇華且運送至晶種。此理論上提供在製程中的預定時間具有摻雜劑或其他添加劑釋放；以及緩和雜質之潛在不利效應的能力。應瞭解，較佳地將超純材料用於圓片中。Further in theory, in embodiments, the spatial shape and its predetermined gradient may allow some heavier impurities to be trapped within the wafer in the bottom of the growth chamber, while lighter elements are sublimated and transported to the wafer along with the Si—C vapor. kind. This theoretically provides the ability to have dopants or other additives released at predetermined times in the process; and to mitigate the potential adverse effects of impurities. It will be appreciated that ultrapure materials are preferably used in the wafers.

在實施例中，圓片提供針對給定溫度更一致的通量形成速率。形體可經特製以提供遍及形體之更均勻溫度，從而允許該形體之較高體積分數一次性昇華，在晶種/蒸汽界面處在給定溫度下比標準粉末堆或粉末之圓柱形形體驅動更高速率之通量。因此，需要較低溫度生長製程之多型體之生長將因而不受限於減慢的生長速率。In an embodiment, the wafer provides a more consistent rate of flux formation for a given temperature. A body can be tailored to provide a more uniform temperature throughout the body, allowing a higher volume fraction of the body to sublime at once, driving more at a given temperature at the seed/vapor interface than a standard powder stack or cylindrical body of powder. High rate throughput. Thus, the growth of polytypes requiring lower temperature growth processes will thus not be limited by a reduced growth rate.

昇華速率係以公克/小時來量測。通量係以公克/cm ²-hr (亦即，材料通過區域之速率)給出。因此，關鍵面積為相應於胚晶生長面之即時表面面積的通量面積，例如，其中SiC正在沉積的胚晶之面。典型地，通量面積及胚晶面之面積約相同的，且該些面積典型地稍微小於氣相沉積設備之生長腔室之橫截面積。 Sublimation rate is measured in grams per hour. Flux is given in grams/cm2 ^- hr (ie, the rate at which material passes through a region). Thus, the critical area is the flux area corresponding to the immediate surface area of the embryonic growth face, eg, the face of the embryonic crystal where SiC is being deposited. Typically, the flux area and the area of the embryo plane are about the same, and these areas are typically slightly smaller than the cross-sectional area of the growth chamber of the vapor deposition apparatus.

出於計算及此分析之目的，出於計算方便，假定生長腔室之橫截面積與通量面積及胚晶面之面積相同。因此，胚晶之生長速率(μm/hr)可亦等於穿過胚晶表面之區域(cm ²)的蒸汽通量—μm/hr—g/hr (完全緻密SiC之密度為3.21 g/cc)。現場量測可經由X射線成像或X射線電腦斷層攝影(computed tomography; CT)來進行。另外，平均生長速率可藉由在生長之前/之後稱重胚晶來測定。 For the purposes of the calculations and this analysis, for computational convenience, it is assumed that the cross-sectional area of the growth chamber is the same as the flux area and the area of the embryo face. Therefore, the growth rate of the embryo crystal (μm/hr) can also be equal to the vapor flux through the area (cm ² ) of the surface of the embryo crystal—μm/hr—g/hr (the density of fully dense SiC is 3.21 g/cc) . The on-site measurement can be performed by X-ray imaging or X-ray computed tomography (CT). Alternatively, the average growth rate can be determined by weighing the embryo crystals before/after growth.

典型的商業生長速率在200-500 μm/hr範圍。本發明之製程及空間形體之實施例遠超過該些現存的商業速率，而同時提供相等及優越品質之胚晶。例如，本發明之實施例可具有在高溫及低壓下的約550至約1,1000 μm/hr、約800至約1,000 μm/hr、約900至約1,100 μm/hr、約700 μm/hr、約 800 μm/hr、約 900 μm/hr、約 1,000 μm/hr、1,100 μm/hr之生長速率。涵蓋較高速率且亦可使用較慢速率，以及該些範圍內的所有速率。Typical commercial growth rates are in the range of 200-500 μm/hr. The process and spatial form embodiments of the present invention far exceed these existing commercial rates while providing embryo crystals of equal and superior quality. For example, embodiments of the present invention may have about 550 to about 1,1000 μm/hr, about 800 to about 1,000 μm/hr, about 900 to about 1,100 μm/hr, about 700 μm/hr, Growth rates of about 800 μm/hr, about 900 μm/hr, about 1,000 μm/hr, and 1,100 μm/hr. Higher rates are contemplated, and slower rates may also be used, and all rates within these ranges.

通常，生長速率係藉由1)溫度及2)供氣壓力(Ar、N ₂等等)來驅動。更大氣體壓力稀釋在晶種處及胚晶之面處的矽碳物質之蒸汽壓，且針對任何給定溫度減慢生長速率。因此，壓力可用於「撥入(dial-in)」生長速率。第19圖之圖表展示本發明之多晶碳氧矽衍生SiC之實施例(具有1.4-1.45 g/cc填積密度之圓片)的生長速率。 Typically, the growth rate is driven by 1) temperature and 2) gas supply pressure (Ar, _N2, etc.). Greater gas pressure dilutes the vapor pressure of the silicon carbon species at the seed and at the face of the embryo crystal and slows the growth rate for any given temperature. Thus, pressure can be used to "dial-in" the growth rate. Figure 19 is a graph showing the growth rate for embodiments of polycrystalline silicon oxycarbide derived SiC of the present invention (wafers with a packing density of 1.4-1.45 g/cc).

根據第19圖之圖表，可見本發明之實施例不展現鈍化。其不為自我限制的，且其為無鈍化的。該些實施例提供超過氣相沉積製程中SiC起始材料之現存來源的顯著改良及優點。SiC之該些現存來源具有自我限制效應，其中通量產生之速率隨時間推移降低，因為起始材料上之表面效應約束或抑制昇華。此自我限制效應通常稱為鈍化，但亦可稱為來源耗盡、石墨化、或碳化。From the graph of Figure 19, it can be seen that the embodiments of the present invention do not exhibit passivation. It is not self-limiting, and it is non-passivating. These embodiments provide significant improvements and advantages over existing sources of SiC starting material in vapor deposition processes. These existing sources of SiC have a self-limiting effect, where the rate of flux generation decreases over time because surface effects on the starting material confine or inhibit sublimation. This self-limiting effect is commonly referred to as passivation, but may also be referred to as source depletion, graphitization, or carbonization.

因此，給定恆定溫度，空間形體之實施例，例如，圓片可在胚晶生長之整個操作期間維持一致的通量產生速率，例如，恆定通量產生速率，該胚晶包括具有約4吋至約10吋直徑、約6吋至約8吋直徑、約4吋直徑、約6吋直徑、約8吋直徑及較大及較小直徑，以及該些值之範圍內的所有直徑之胚晶。給定用於整個胚晶生長製程之恆定溫度，空間形體之實施例可將通量產生速率，及因此胚晶生長速率維持在恆定速率、恆定速率、具有小於約0.001%改變之速率、具有小於約0.01%改變之速率、具有小於約1%改變之速率、具有小於約5%改變之速率、具有小於約20%改變之速率、具有約0.001%改變至約15%改變之速率、具有約0.01%改變至約5%改變之速率、及在胚晶之生長期間該些者之組合及變化，以及該些值之範圍內的所有值。在實施例中，在恆定溫度下通量形成速率保持在：其最大速率之約99.999%至約60%；其最大速率之約99%至約95%；其最大速率之約99.99%至約80%；其最大速率之約99%至約70%；其最大速率之約95%至約70%；其最大速率之約99%至約95%；及在胚晶之生長期間該些者之組合及變化，以及該些百分比範圍內之所有值。Thus, given a constant temperature, an embodiment of a spatial body, e.g., a wafer, can maintain a consistent rate of flux generation, e.g., a constant rate of flux generation, during the entire operation of the growth of an embryonic crystal comprising about 4 inches of Embryocrystals to about 10 inches in diameter, about 6 inches to about 8 inches in diameter, about 4 inches in diameter, about 6 inches in diameter, about 8 inches in diameter and larger and smaller diameters, and all diameters within the range of these values . Given a constant temperature for the entire embryo crystal growth process, embodiments of the space form can maintain the rate of flux generation, and thus the rate of embryo crystal growth, at a constant rate, a constant rate, a rate with less than about 0.001% variation, with a rate of less than A rate of change of about 0.01%, a rate of change of less than about 1%, a rate of change of less than about 5%, a rate of change of less than about 20%, a rate of change of about 0.001% to about 15%, a rate of change of about 0.01 % change to about 5% change rate, and combinations and changes of these during the growth of the embryocrystal, and all values within the range of these values. In an embodiment, the rate of flux formation at a constant temperature is maintained at: about 99.999% to about 60% of its maximum rate; about 99% to about 95% of its maximum rate; about 99.99% to about 80% of its maximum rate %; about 99% to about 70% of its maximum rate; about 95% to about 70% of its maximum rate; about 99% to about 95% of its maximum rate; and combinations of these during the growth of the embryo crystal and changes, and all values within those percentage ranges.

實施例具有獨特體密度。在實施例中，空間形體，例如，圓片係在模製製程中製成，且因此，粉末可經壓實至多至2.0 g/cc (2.0/3.21 = 62%填積分數或38%多孔性)之極高體密度。所得形體仍具有相同的起始材料粒子之高表面面積，仍允許更大重量之源材料佔據生長腔室之底部。以此方式，較大胚晶可自較高密度源材料生長。在整個生長製程期間亦保持活性的更多源材料產生較長的生長時間及因此較長、較寬、及兩者的胚晶。該些益處不管生長界面之最終形狀而存在。此亦可延長生長循環以進一步生長較大的胚晶。Embodiments have unique bulk densities. In an embodiment, a spatial form, such as a disc, is made in a molding process, and thus, the powder can be compacted up to 2.0 g/cc (2.0/3.21 = 62% fill fraction or 38% porosity ) extremely high body density. The resulting shape still has the same high surface area of the starting material particles, still allowing a greater weight of source material to occupy the bottom of the growth chamber. In this way, larger embryo crystals can be grown from higher density source materials. More source material that also remains active throughout the growth process results in longer growth times and thus longer, wider, and both embryonic crystals. These benefits exist regardless of the final shape of the growth interface. This can also extend the growth cycle to further grow larger embryo crystals.

以此方式，氣相沉積製程之循環的生長部分之容量利用可得以最大化。因此，本發明之實施例提供大大地增加現存氣相沉積設備之生長循環的容量利用之能力。典型地，在現存氣相沉積設備中，需要約10-30 hr之加熱時間(其不為生長循環之一部分)及約30-50 hr之冷卻時間(其不為生長循環之一部分)。該些非生長循環時間將僅隨較大胚晶大小(腔室及胚晶不可熱震或其可破裂)而增加。因此，若生長循環(亦即，在加熱循環期間在昇華及沉積以生長胚晶發生時的時間)延長10-20 hr之生長，則該生長循環可增加400 μm/hr之胚晶生長。此舉又顯著地賦能每一胚晶生長循環更多晶圓得以生產且減小可消耗物之成本及最終每一晶圓之製造成本。因此，本發明之實施例為實質上增加熔爐之生長持續時間容量利用之能力。In this way, capacity utilization for the growth portion of the cycle of the vapor deposition process can be maximized. Accordingly, embodiments of the present invention provide the ability to greatly increase the capacity utilization of growth cycles of existing vapor deposition equipment. Typically, in existing vapor deposition equipment, about 10-30 hr of heating time (which is not part of the growth cycle) and about 30-50 hr of cooling time (which is not part of the growth cycle) are required. These non-growth cycle times will only increase with larger embryo crystal size (the chamber and the embryo crystal cannot be thermally shocked or they can be broken). Thus, if the growth cycle (ie, the time during the heating cycle when sublimation and deposition to grow the embryo crystal occurs) is extended by 10-20 hrs of growth, the growth cycle can increase the growth of the embryo crystal by 400 μm/hr. This in turn enables significantly more wafers to be produced per embryonic growth cycle and reduces the cost of consumables and ultimately the manufacturing cost per wafer. Accordingly, embodiments of the present invention are capable of substantially increasing the growth duration capacity utilization of a furnace.

因此，在實施例中，相較於使用當前可利用的SiC源材料而言，用於具有相同直徑之胚晶的氣相沉積設備之生長循環可藉由使用本發明之聚合物衍生SiC及空間形體之實施例來增加達：約10%至約100%、約10%至約60%、約20%至約60%、約33%至約70%、至少約30%、至少約50%、至少約70%及更大，以及該些百分比範圍內之所有值。在實施例中，對於可最終自單一生長循環獲得(生長胚晶且隨後切割成具有相同厚度之晶圓)的具有相同厚度及直徑之晶圓，相較於使用當前可利用的SiC源材料而言，晶圓之數量可使用本發明之聚合物衍生SiC及空間形體之實施例增加達：約10%至約500%、約100%至約300%、約10%至約70%、約30%至約70%、至少約20%、至少約50%、至少約100%、至少約200%、至少2個晶圓、至少10個晶圓、至少20個晶圓、至少100個晶圓、至少1,000個晶圓、至少約2個至100個晶圓、至少約10個至100個晶圓、至少約50個至200個晶圓、約100個至500個晶圓、及更個，以及該些值範圍內之所有值。亦獲得自單一生長循環獲得更多晶圓之能力且得以進一步增加，因為本發明之胚晶之實施例將具有實質上比自習知SiC源材料生長的胚晶更少的缺陷，且因此將在胚晶中存在實質上更多的可使用材料來製造晶圓。此增加的晶圓生產量、及增加的胚晶生長效率、及增加的胚晶品質可進一步具有來自單一生長循環的裝置之增加產量之效應。因此，裝置之數量可增加達至少約100個、至少約200個、至少約1,000個、至少約10,000個、至少約100,000個及更多個，約100個至約10,000個、約1,000個至約30,000個、約500個至約20,000個及約20,000個至約50,000個，以及該些值範圍內之所有值。Thus, in an embodiment, the growth cycle of a vapor deposition apparatus for an embryo having the same diameter as compared to using currently available SiC source materials can be achieved by using the polymer-derived SiC and spacers of the present invention. Embodiments of the shape increase up to: about 10% to about 100%, about 10% to about 60%, about 20% to about 60%, about 33% to about 70%, at least about 30%, at least about 50%, At least about 70% and greater, and all values within those percentage ranges. In an embodiment, for wafers of the same thickness and diameter that can ultimately be obtained from a single growth cycle (growing embryo crystals and then dicing into wafers of the same thickness), compared to using currently available SiC source material In other words, the number of wafers can be increased by about 10% to about 500%, about 100% to about 300%, about 10% to about 70%, about 30% using embodiments of the polymer-derived SiC and spatial features of the present invention. % to about 70%, at least about 20%, at least about 50%, at least about 100%, at least about 200%, at least 2 wafers, at least 10 wafers, at least 20 wafers, at least 100 wafers, at least 1,000 wafers, at least about 2 to 100 wafers, at least about 10 to 100 wafers, at least about 50 to 200 wafers, about 100 to 500 wafers, and more, and All values within these ranges. The ability to obtain more wafers from a single growth cycle is also obtained and further increased because embodiments of the embryos of the present invention will have substantially fewer defects than embryos grown from conventional SiC source materials, and will therefore There is substantially more usable material in the embryonic crystal to make the wafer. This increased wafer throughput, and increased embryo crystal growth efficiency, and increased embryo crystal quality may further have the effect of increased yield of devices from a single growth cycle. Thus, the number of devices can be increased to at least about 100, at least about 200, at least about 1,000, at least about 10,000, at least about 100,000, and more, from about 100 to about 10,000, from about 1,000 to about 30,000, about 500 to about 20,000, and about 20,000 to about 50,000, and all values within these ranges.

實施例提供在預定形體中具有形體控制的能力，咸信該等形體中許多者尚未知曉，且對大型部件而言，使用現存起始材料不可獲得。置放於氣相沉積設備中作為用於胚晶生長之源材料的空間形體，例如，圓片之形體可驅動或正面地影響生長製程之許多參數以相較於習知源材料獲得較大胚晶、較高品質胚晶、較高品質晶圓、更多晶圓，及該些者之組合及變化。該些改良生長參數包括：減少來源之軸向熱梯度；來源之徑向熱梯度；增加來源之軸向熱梯度；正在昇華的源材料之表面面積，防止通量限制；較熱的內部來源溫度以提供遍及源材料之更均勻昇華；穿過源材料之快速通量及引導通量路徑(將蒸汽導引至所要位置—中心或邊緣或兩者，此尤其提供較平坦胚晶生長面)。在稍後生長階段期間將通量朝向胚晶之邊緣導引的能力賦能邊緣與中心一樣快地生長，不管來源在邊緣附近更完全地消耗。因此，最終幾何形狀不為典型的凸狀胚晶，其係藉由使用當前源材料獲得，且具有不可用於自其製造晶圓的廢胚晶材料。替代地，源材料之本發明實施例提供具有平坦面之胚晶，因此大大地增加可用於製造晶圓的胚晶之量。Embodiments provide the ability to have shape control in predetermined shapes, many of which are believed to be unknown and, for large parts, not achievable using existing starting materials. Placement in vapor deposition equipment as a spatial shape of source material for embryo growth, for example, the shape of a wafer can drive or positively affect many parameters of the growth process to obtain larger embryos compared to conventional source materials, Higher quality embryos, higher quality wafers, more wafers, and combinations and variations of these. These modified growth parameters include: reduced axial thermal gradient of the source; radial thermal gradient of the source; increased axial thermal gradient of the source; surface area of the source material being sublimated to prevent flux limitation; hotter internal source temperature To provide more uniform sublimation throughout the source material; fast flux through the source material and directing the flux path (directing the vapor to the desired location - center or edge or both, this especially provides a flatter embryonic growth surface). The ability to direct flux towards the edge of the embryonic crystal during later growth stages enables the edge to grow as fast as the center, despite sources being more completely consumed near the edge. Therefore, the final geometry is not the typical convex embryo obtained by using the current source material and having spent embryo material that is not available for making wafers from it. Alternatively, the inventive embodiments of the source material provide embryo crystals with planar faces, thereby greatly increasing the amount of embryo crystals available for wafer fabrication.

除上述之外，自具有起始材料之預定形體獲得的額外益處包括：賦能穿過視線至坩堝底部的生長面之中心之輻射加熱，從而尤其減少晶種中之徑向熱梯度且進一步咸信賦能較大胚晶(8"、10"及超過此)的生長，以及阻尼冷卻循環以減少晶體中之應力且防止開裂；相較於在相同氣相沉積設備中使用現存起始材料而言，經由更均勻的胚晶溫度及結果在胚晶上較少的熱應力而改良多型體穩定性且減少線缺陷/錯位；由於預選或決定在製程結束時不具有其從未完全地得到昇華的起始材料之能力，賦能源材料之更完全利用；藉由使大量源材料昇華以形成胚晶，且因此改良來源至胚晶產率及成本效率而減少浪費源材料。In addition to the above, additional benefits obtained from having a pre-shaped body of starting material include: enabling radiative heating across the line of sight to the center of the growth face at the bottom of the crucible, thereby reducing inter alia radial thermal gradients in the seed and further Facilitates the growth of larger embryo crystals (8", 10" and beyond), and dampens cooling cycles to reduce stress in the crystal and prevent cracking; compared to using existing starting materials in the same vapor deposition equipment In other words, improved polytype stability and reduced line defects/dislocations through more uniform embryo temperature and consequently less thermal stress on the embryo; this has never been fully achieved due to preselection or decision not to have at the end of the process The ability to sublimate starting materials enables more complete utilization of source materials; reducing waste of source materials by sublimating large quantities of source materials to form embryos, and thus improving source-to-embryo yields and cost-efficiency.

在生長前沿的胚晶之中心典型地比邊緣更冷，從而使得其更像是用於材料沉積之「槽坑(sink)」(彙集蒸汽通量之來源)。因此，理論上，若視線係穿過源材料自底部通向頂部，則自坩堝之底部的輻射將到達球狀面之中心且將其稍微升溫—甚至一至數十℃左右—從而使得中心較不像「槽坑」且允許整個晶種之更均勻溫度，從而在沿晶體的所有位置處產生更均勻通量且賦能較平坦胚晶。進一步在理論上，此開放視線形體實施例亦將允許在源材料之中心處的材料更有效地昇華且轉變成胚晶—此通常為昇華的最後地方，因為其為源材料之最冷部分且生長在其未曾耗盡之前停止。開放視線形體圓片之實施例之實例係展示在第9圖及第10圖。The center of the embryonic crystal at the growth front is typically cooler than the edges, making it more like a "sink" (a source of concentrating vapor flux) for material deposition. Therefore, in theory, if the line of sight goes from the bottom to the top through the source material, the radiation from the bottom of the crucible will reach the center of the spherical surface and heat it up slightly—even by one to tens of degrees Celsius—so that the center is less dense. Acts like a "well" and allows for a more uniform temperature across the seed, resulting in a more uniform flux and energization of a flatter embryo at all locations along the crystal. Further in theory, this open line-of-sight form embodiment would also allow the material at the center of the source material to sublimate more efficiently and transform into the embryo crystal - this is usually the last place to sublimate since it is the coldest part of the source material and Growth stops before it is depleted. Examples of embodiments of open line of sight shape wafers are shown in FIGS. 9 and 10 .

實施例提供源材料遍及空間形體之密度分佈，該空間形體係用作氣相沉積設備中之起始材料。密度之此預定分配提供超過現存源材料之若干優點及改良，包括：向形體之特定部分或區域的預定及受控熱傳導，諸如向某些區域之改良熱傳導，有限的熱傳導，以使得在生長循環之持續時間期間來源全程更均勻地消耗，且具有以受控方式維持的熱傳導，較佳地均勻熱傳導。昇華組成(亦即，由起始材料之昇華形成的蒸汽之組成，例如，通量組成)亦可改變，具有遍及循環更持續或均勻的組成，或在生長開始時更增強的組成，從而尤其提供歸因於穩定組成的較好多型體穩定性。Embodiments provide a density distribution of source materials throughout a spatial form used as a starting material in a vapor deposition apparatus. This predetermined distribution of density provides several advantages and improvements over existing source materials, including: predetermined and controlled heat conduction to specific parts or regions of a feature, such as improved heat conduction to certain regions, limited heat conduction such that during growth cycles The source is consumed more evenly throughout the duration of the source and has heat conduction maintained in a controlled manner, preferably uniform heat conduction. The sublimation composition (i.e., the composition of the vapor formed by the sublimation of the starting material, e.g., the flux composition) can also vary, with a composition that is more consistent or uniform throughout the cycle, or a composition that is more enhanced at the onset of growth, thereby particularly Provides better polytype stability due to stable composition.

實施例提供不同化學計量之粉末遍及形體，例如，具有不同類型之粉末起始材料、不同黏合劑之層、區帶、區域及該些者之組合及變化的分佈。不同化學計量之此預定分配提供若干優點，包括：作為源材料之昇華組合物之客製係自外部向內消耗，從而賦能自生長循環之開始至結束的組合物之較少變換。不同化學計量之此預定分配亦可由於蒸汽之一致組成而增進多型體穩定性。Embodiments provide different stoichiometric powders throughout the form, eg, layers, zones, regions, and combinations and variations of these with different types of powder starting materials, different binders. This predetermined distribution of different stoichiometries offers several advantages, including: customization of the sublimation composition as source material is consumed from the outside in, enabling less change in composition from the beginning to the end of the growth cycle. This predetermined distribution of different stoichiometries may also enhance polytype stability due to the consistent composition of the vapors.

實施例提供來源或起始材料粉末之特製化學計量、空間形體黏合劑、空間形體之添加劑、起始材料粉末之添加劑之特製化學計量、及該些者之組合及變化。例如，使用多至20%液相黏合劑及粒子意指化學計量可自1:1 Si:C，例如，自1.5:1 Si:C變換至1:1.5 Si:C，以及該些比率範圍內之所有值。涵蓋較大及較小變換。化學計量使用PDC前驅物、水、或蒸發性溶劑或非Si或非C化合物(例如，硼酸、氧化鋁、氮化鋁、硝酸鋁、硝酸鈣、磷酸鈉)來維持。化學計量係使用LDPE、炭黑、石墨粉末、碳化硼、PAN、蠟、聚乳酸、纖維素、蔗糖/糖、碳酸氫鈉、澱粉等等變換成富C的。化學計量係使用Si粉末、以富Si之SiC開始、二氧化矽、鈉鈣玻璃、硼矽酸鹽玻璃、氮化矽來變換。The examples provide tailored stoichiometry of sources or starting material powders, steric body binders, additives to steric bodies, tailored stoichiometry of additives to starting material powders, and combinations and variations of these. For example, using up to 20% liquid phase binder and particles means that the stoichiometry can be shifted from 1:1 Si:C, for example, from 1.5:1 Si:C to 1:1.5 Si:C, and within these ratios of all values. Covers both major and minor transformations. Stoichiometry is maintained using PDC precursors, water, or evaporative solvents or non-Si or non-C compounds (eg, boric acid, alumina, aluminum nitride, aluminum nitrate, calcium nitrate, sodium phosphate). Stoichiometry is converted to C-rich using LDPE, carbon black, graphite powder, boron carbide, PAN, wax, polylactic acid, cellulose, sucrose/sugar, sodium bicarbonate, starch, etc. The stoichiometry is transformed using Si powder, starting with Si-rich SiC, silicon dioxide, soda lime glass, borosilicate glass, silicon nitride.

富矽或富碳化學計量物質將在生長開始時，在蒸氣通量中分別具有較高矽或碳含量且影響生長之多型體穩定性。因此，例如，具有提供富碳氣相的源材料化學計量可增加4H多型體穩定性。在空間形體、氣體流動或兩者中具有氮摻雜可類似地增加4H多型體穩定性。同樣地，具有在2,100至2,500℃之生長溫度可增加4H多型體穩定性。Silicon-rich or carbon-rich stoichiometric species will have higher silicon or carbon content, respectively, in the vapor flux at the onset of growth and affect the polytype stability of growth. Thus, for example, having a source material stoichiometry that provides a carbon-rich gas phase can increase 4H polytype stability. Having nitrogen doping in the steric body, gas flow, or both can similarly increase 4H polytype stability. Likewise, having a growth temperature between 2,100 and 2,500°C increases 4H polytype stability.

特製粉末之化學計量的此能力可與特製富矽相之幾何位置之能力組合。以此方式，富矽相之位置可使得所耗盡SiC之「石墨化」現象可在現場反應來形成用於昇華之另外的SiC。替代地，富Si區域可在稍後生長階段期間補償汽相中減少的Si含量，從而隨後將允許遍及生長持續時間、尤其在稍後生長階段期間的更一致的矽-碳物質通量。This ability to tailor the stoichiometry of powders can be combined with the ability to tailor the geometry of the silicon-rich phase. In this way, the location of the silicon-rich phase can allow "graphitization" of depleted SiC to react in situ to form additional SiC for sublimation. Alternatively, the Si-rich region can compensate for the reduced Si content in the vapor phase during later growth stages, which will then allow for a more consistent flux of silicon-carbon species throughout the duration of growth, especially during later growth stages.

通常，用於獲得SiC之製程自液體前驅物調配物轉變成固化材料、熱解SiOC材料，其轉化為SiC材料(α、β、或兩者)。在該些製程—固化、熱解及轉化期間，各種建構塊中之一些損失，典型地為C及O。Si亦可損失，但較佳地製程及前驅物使得Si損失為最少至無損失。例如，建構成前驅物或自外部來源，例如，烘箱中建構的過量C將驅動CO超過SiO之形成，從而產生較少的Si損失。發生固化材料中之交聯度越大，在熱解及轉化期間損失的Si越低，且因此，SiC之產率越大。Typically, the process for obtaining SiC changes from a liquid precursor formulation to a cured material, pyrolyzing the SiOC material, which converts to a SiC material (alpha, beta, or both). During these processes - curing, pyrolysis and conversion, some of the various building blocks are lost, typically C and O. Si can also be lost, but preferred processes and precursors result in minimal to no Si loss. For example, excess C built up as a precursor or from an external source, eg, in an oven, will drive CO over SiO formation, resulting in less Si loss. The greater the degree of crosslinking in the cured material, the lower the Si loss during pyrolysis and conversion, and therefore, the greater the yield of SiC.

用於製造高純度及超高純度SiC及SiOC之製程、調配物及系統揭示且教示於美國公開案第2016/0207782號中，該案係以引用方式併入本文中。Processes, formulations, and systems for making high- and ultra-high-purity SiC and SiOC are disclosed and taught in US Publication No. 2016/0207782, which is incorporated herein by reference.

在實施例中，固化SiOC可呈空間形體，例如圓片、彈丸、團塊、板、珠粒或圓盤，隨後直接轉化成SiC之易碎質塊，而無需中間處理步驟，且研磨最少至無研磨。在實施例中，將固化SiOC研磨成粒狀SiOC且隨後轉化成粒狀SiC，隨後藉助於黏合劑形成為空間形體。在實施例中，SiOC(固化或熱解)係形成為SiC粒子。粒子可隨後形成，例如，壓製為空間形體或SiC之質塊。較佳地，SiC粒子之大小及大小分佈係預定且無需進一步研磨。在實施例中，若需要，則該些粒子可隨後磨小成較小、更均勻顆粒或兩者兼有的顆粒。顆粒可隨後形成，例如，壓製為空間形體或SiC之質塊。在該些以及其他實施例中，當製造高純度及超高純度SiC時，較佳地具有系統之所有組分而不含在用於SiC之後續用途或製程中視為雜質的物質；或令該些組分屏蔽、包封或在其他其他情況下實施緩和步驟來避免將雜質引入至製程及SiC中。In an embodiment, solidified SiOC may be in the form of a spacer, such as a disc, pellet, agglomerate, plate, bead, or disc, which is then directly converted into a friable mass of SiC without intermediate processing steps and with minimal grinding to No grinding. In an embodiment, the solidified SiOC is ground into granular SiOC and subsequently converted into granular SiC, which is then formed into a spatial form by means of a binder. In an embodiment, the SiOC (cured or pyrolyzed) system is formed into SiC particles. The particles can then be formed, for example, pressed into a spacer or a mass of SiC. Preferably, the size and size distribution of the SiC particles are predetermined and no further grinding is required. In embodiments, the particles can then be ground down to smaller, more uniform particles, or both, if desired. The particles can then be formed, for example, pressed into spatial bodies or masses of SiC. In these and other embodiments, when manufacturing high-purity and ultra-high-purity SiC, it is preferable to have all components of the system free of substances that would be considered impurities in subsequent uses or processes for SiC; or to have the These components are shielded, encapsulated, or otherwise mitigated to avoid introducing impurities into the process and into the SiC.

轉向第16圖，提供用於製造來源於SiOC之SiC之空間形體、及用於製造較佳地呈較高純度之此種空間形體(例如，3個九、4個九、5個九及更多九，且較佳6個九或更多)之系統及方法之實施例的示意透視流程圖。含有前驅物及其他材料之系統的管線、閥及內表面係由不污染SiOC、SiC之衍生SiC及空間形體，例如，不提供雜質來源之材料製程或由該等材料塗佈。儲存槽150a、150b保持液體多晶碳氧矽前驅物。在此實施例中，前驅物中之一或兩者或無一者可經攜帶穿過蒸餾設備151a及蒸餾設備151b，以移除來自液體前驅物之任何雜質。液體前驅物隨後轉移至混合容器152，其中其混合以形成前驅物批料且加以催化。在清潔室環境157a中，前驅物批料經包裝至容器153中以供置放於熔爐154中。熔爐154具有掃掠氣進口161及廢氣去除管線162。經包裝及固化之材料隨後在清潔室條件下轉移至若干熱解爐155a、155b、155c，其中材料自SiOC轉變成SiC。熔爐分別具有掃掠氣進口管線158a、158b、158c，且分別具有兩個廢氣去除管線159a及160a、159b及160b、159c及160c。廢氣可經處理，清潔且將起始材料回收在具有進口管線164之廢氣處理總成163中，該廢氣處理總成163自系統中之各種單元收集廢氣。Turning to FIG. 16, space features for making SiC derived from SiOC, and for making such space features, preferably at higher purity (e.g., 3 nines, 4 nines, 5 nines, and more) are provided. More than nine, and preferably six nine or more) schematic perspective flow diagram of an embodiment of the system and method. Pipelines, valves and internal surfaces of systems containing precursors and other materials are made of SiOC, SiC derivatives of SiC and space bodies that do not contaminate, eg, process or coat from materials that do not provide a source of impurities. The storage tanks 150a, 150b hold liquid polycrystalline silicon oxycarbide precursors. In this embodiment, one or both or neither of the precursors may be carried through distillation apparatus 151a and distillation apparatus 151b to remove any impurities from the liquid precursors. The liquid precursors are then transferred to mixing vessel 152 where they are mixed to form a precursor batch and catalyzed. In the clean room environment 157a, the precursor batches are packaged into containers 153 for placement in the furnace 154 . The furnace 154 has a sweep gas inlet 161 and a waste gas removal line 162 . The packaged and cured material is then transferred under clean room conditions to several pyrolysis furnaces 155a, 155b, 155c where the material is converted from SiOC to SiC. The furnace has sweep gas inlet lines 158a, 158b, 158c, respectively, and two exhaust gas removal lines 159a and 160a, 159b and 160b, 159c, and 160c, respectively. The exhaust gas can be treated, cleaned and the starting materials recovered in an exhaust gas treatment assembly 163 having an inlet line 164 which collects exhaust gas from various units in the system.

所得SiC隨後轉移至空間形體形成區域190，其較佳地處於清潔室條件下。在區域190中，SiC係提供至具有混合裝置173(例如，槳片、葉片、攪拌器等等)之混合容器172。來自黏合劑槽170之黏合劑係經由管線171添加至容器172。在混合容器172，將SiC與黏合劑混合以形成漿料或摻合物。漿料之稠度應使得促進稍後的造粒操作。SiC-黏合劑漿料隨後轉移至成形設備175，其中漿料係形成為空間形體，例如，團塊、圓盤、塊體等等，且進料至烘箱177中，其中黏合劑係固化來得到具有所要強度之空間形體。固化空間形體隨後轉移至包裝裝置180，其中將固化空間形體包裝。較佳地，該些操作係在清潔室條件下執行，且更佳地，該等操作係在單獨清潔室或清潔室之區域190a、190b、190c中執行。The resulting SiC is then transferred to the spatial feature formation area 190, which is preferably under clean room conditions. In zone 190, SiC is provided to a mixing vessel 172 having a mixing device 173 (eg, paddle, blade, stirrer, etc.). Adhesive from adhesive tank 170 is added to container 172 via line 171 . In mixing vessel 172, the SiC is mixed with a binder to form a slurry or blend. The consistency of the slurry should be such that the later granulation operation is facilitated. The SiC-binder slurry is then transferred to a forming device 175, where the slurry is formed into spatial shapes, e.g., clumps, discs, blocks, etc., and fed into an oven 177, where the binder is cured to obtain Spatial form with desired strength. The cured spatial form is then transferred to the packaging device 180, wherein the cured spatial form is packaged. Preferably, the operations are performed under clean room conditions, and more preferably, the operations are performed in individual clean rooms or areas 190a, 190b, 190c of clean rooms.

較佳地，在製造SiC中及用於製造SiC之材料中，在較佳實施例中，多晶碳氧矽前驅物可在約1個大氣壓下、在清潔空氣中混合。Preferably, in the manufacture of SiC and the materials used in the manufacture of SiC, the polycrystalline silicon oxycarbide precursors can be mixed in clean air at about 1 atmosphere in a preferred embodiment.

較佳地，在製造SiC中及用於製造SiC之材料中，固化發生在約20℃至約150℃、約75℃至約125℃及約80℃至90℃範圍內及該些溫度之變化及組合，以及該些溫度範圍內之所有值的溫度下。固化係在較佳地產生硬固化材料之時間段內進行。固化可發生在空氣或惰性氣氛中，且較佳地，固化在環境壓力下在氬氣氛中發生。最佳地，對於高純度材料，熔爐、容器、操縱儀器、及固化設備之其他部件為清潔的，本質上不含且不貢獻將認為是固化材料之雜質或污染物的任何元素或材料。Preferably, in the manufacture of SiC and in the materials used for the manufacture of SiC, curing occurs in the range of about 20°C to about 150°C, about 75°C to about 125°C, and about 80°C to 90°C and variations of these temperatures and combinations, and at temperatures of all values within these temperature ranges. Curing is carried out over a period of time which preferably results in a hard cured material. Curing can occur in air or an inert atmosphere, and preferably, curing occurs in an argon atmosphere at ambient pressure. Optimally, for high purity materials, the furnaces, vessels, manipulators, and other parts of the solidification apparatus are clean, essentially free of and do not contribute any elements or materials that would be considered impurities or contaminants of the solidified material.

較佳地，在製造SiC中及用於製造SiC之材料中，熱解發生在約800℃至約1300℃、約900℃至約1200℃及約950℃至1150℃範圍內以及該些溫度範圍內之所有值的溫度下。熱解在較佳地產生預成形件之完全熱解的時間段內進行。較佳地，熱解發生在惰性氣體中，例如，氬中，且更佳地在或約在大氣壓力下在流動氬氣中發生。氣體可以約1,200 cc/min至約200 cc/min、約800 cc/min至約400 cc/min，且以約500 cc/min，以及該些流量範圍內之所有值流動。較佳地，完成處理爐之初始真空抽空至至少低於1E-3托之減壓，且用例如氬之惰性氣體再加壓至大於或等於100托。更佳地，在用惰性氣體再加壓之前完成真空抽空至低於1E-5托之壓力。真空抽空製程可在處理之前完成零次至＞4次中的任何次數。最佳地，對於高純度材料，熔爐、容器、操縱儀器、及固化設備之其他部件為清潔的，本質上不含且不貢獻將認為是固化材料之雜質或污染物的任何元素或材料。Preferably, in the manufacture of SiC and in the materials used for the manufacture of SiC, pyrolysis occurs in the ranges of about 800°C to about 1300°C, about 900°C to about 1200°C, and about 950°C to 1150°C and these temperature ranges at all values within the temperature. The pyrolysis is carried out over a period of time which preferably results in complete pyrolysis of the preform. Preferably, pyrolysis occurs in an inert gas, eg, argon, and more preferably in flowing argon at or about atmospheric pressure. The gas may flow from about 1,200 cc/min to about 200 cc/min, from about 800 cc/min to about 400 cc/min, and at about 500 cc/min, and all values within these flow ranges. Preferably, initial vacuum evacuation of the processing furnace to a reduced pressure of at least less than 1E-3 Torr and repressurization with an inert gas such as argon to greater than or equal to 100 Torr is accomplished. More preferably, vacuum evacuation to a pressure below 1E-5 Torr is accomplished prior to repressurization with an inert gas. The vacuum evacuation process can be done any number of times from zero to >4 times prior to processing. Optimally, for high purity materials, the furnaces, vessels, manipulators, and other parts of the curing apparatus are clean, essentially free of and not contributing to any element or material that would be considered an impurity or contamination of the solidified material.

熱解可在維持要求溫度及環境控制之任何加熱設備中進行。因此，例如，熱解可利用以下各項來進行：高壓爐、箱式爐、管式爐、晶體生長熔爐、石墨箱式爐、電弧熔化熔爐、感應爐、窯爐、MoSi2加熱元件熔爐、碳熔爐、真空爐、氣體燃爐、電爐、直接加熱、間接加熱、流體化床、RF熔爐、窯爐、隧道式窯爐、箱式窯爐、梭動窯爐、焦炭型設備、雷射器、微波、其他電磁輻射、及可獲得用於熱解之要求溫度的該些及其他加熱設備及系統之組合及變化。Pyrolysis can be performed in any heating apparatus that maintains the required temperature and environmental controls. Thus, for example, pyrolysis can be performed using: high pressure furnaces, box furnaces, tube furnaces, crystal growth furnaces, graphite box furnaces, arc melting furnaces, induction furnaces, kilns, MoSi2 heating element furnaces, carbon Furnace, vacuum furnace, gas furnace, electric furnace, direct heating, indirect heating, fluidized bed, RF furnace, furnace, tunnel furnace, box furnace, shuttle furnace, coke type equipment, laser, Combinations and variations of microwaves, other electromagnetic radiation, and these and other heating devices and systems to obtain the desired temperature for pyrolysis.

在其中需要低N及O位準之實施例中，使用真空、較佳地渦輪泵來達成10E-6托並利用惰性氣體回填係更佳的。此純化製程可進行一次或多次以達成低位準。「掃掠」氣體之恆定流率可幫助在揮發性物質產生期間沖洗熔爐。In embodiments where low N and O levels are required, it is better to use a vacuum, preferably a turbo pump to achieve 10E-6 Torr and backfill with an inert gas. This purification process can be performed one or more times to achieve a low level. A constant flow rate of "sweep" gas assists in flushing the furnace during periods of volatile generation.

較佳地，在製造SiC中，陶瓷SiOC係在後續或延續熱解或轉化步驟中轉化成SiC。自SiOC之轉化步驟可為SiOC預成形件之熱解的一部分，例如與該熱解相連，或其可在時間上、位置上所及兩者上為完全獨立的步驟。取決於所要SiC之類型，可在約1,200℃至約2,550℃及約1,300℃至1,700℃，以及該些溫度範圍內之所有值下進行慣例步驟。通常，在約1,600℃至1900℃之溫度下，隨時間推移有利於β類型之形成。在高於1900℃之溫度下，隨時間推移有利於α類型之形成。較佳地，轉化發生在惰性氣體中，例如，氬中，且更佳地在或約在大氣壓力下在流動氬氣中發生。氣體可以約600 cc/min至約10 cc/min、約300 cc/min至約50 cc/min，且以約80 cc/min至約40 cc/min，以及該些流量範圍內之所有值流動。最佳地，對於高純度材料，熔爐、容器、操縱儀器、及固化設備之其他部件為清潔的，本質上不含且不貢獻將認為是SiC之雜質或污染物的任何元素或材料。Preferably, in the manufacture of SiC, the ceramic SiOC is converted to SiC in a subsequent or continuing pyrolysis or conversion step. The conversion step from SiOC may be part of, for example connected to, the pyrolysis of the SiOC preform, or it may be a completely independent step both in time and in location. Conventional steps may be performed at about 1,200°C to about 2,550°C and about 1,300°C to 1,700°C, and all values within these temperature ranges, depending on the type of SiC desired. Generally, the formation of the beta form is favored over time at temperatures of about 1,600°C to 1900°C. At temperatures above 1900°C, the formation of the alpha form is favored over time. Preferably, the conversion takes place under an inert gas, such as argon, and more preferably under flowing argon at or about atmospheric pressure. Gas can flow from about 600 cc/min to about 10 cc/min, from about 300 cc/min to about 50 cc/min, and at about 80 cc/min to about 40 cc/min, and all values within these flow ranges . Optimally, for high purity materials, the furnaces, vessels, manipulators, and other parts of the curing equipment are clean, essentially free of and not contributing to any elements or materials that would be considered impurities or contaminants of SiC.

SiOC衍生SiC之後續產率通常為約10%至50%，典型地30%至40%，雖然可獲得較高及較低範圍，以及該些百分比範圍內之所有值。The subsequent yield of SiOC derived SiC is typically about 10% to 50%, typically 30% to 40%, although higher and lower ranges are available, and all values within these percentage ranges.

最佳地，當製造高純度SiC時，與製造、固化、熱解及轉化材料相關聯的活動係在清潔室條件中、清潔室條件下，例如，在至少ISO 5、至少ISO 4、至少ISO 3、至少ISO 2、及至少ISO 1之ISO 14644-1清潔室標準下進行。在實施例中，材料操縱步驟係在至少ISO 5之清潔室中進行，而次清潔區域(ISO ＞5)係用於熱解及轉化步驟。Optimally, when manufacturing high purity SiC, the activities associated with manufacturing, curing, pyrolyzing and converting the material are in clean room conditions, under clean room conditions, e.g., at least ISO 5, at least ISO 4, at least ISO 3. At least ISO 2, and at least ISO 1 ISO 14644-1 clean room standard. In an embodiment, the material handling steps are performed in a clean room of at least ISO 5, while a less clean area (ISO > 5) is used for the pyrolysis and conversion steps.

SiC或SiOC及超純SiC或SiOC之空間形體可為任何預定空間形體，包括例如球體、圓片、團塊、環、透鏡、圓盤、面板、圓錐體、截錐形體、正方形體、矩形體、桁架、有角體(angle)、通道、中空密封室、中空球體、塊體、片材、塗層、膜、外皮、微粒、束、棒、有角體、平板、管柱、纖維、切斷纖維、管、杯、管道、及該些及其他更複雜形狀之組合及各種形體，皆可為工程化及建築學的。The spatial shape of SiC or SiOC and ultrapure SiC or SiOC can be any predetermined spatial shape, including, for example, spheres, disks, agglomerates, rings, lenses, disks, panels, cones, frustums, squares, rectangles , Truss, Angle, Channel, Hollow Sealed Chamber, Hollow Sphere, Block, Sheet, Coating, Membrane, Skin, Particle, Bundle, Rod, Angle, Flat Plate, Column, Fiber, Cut Broken fibers, tubes, cups, pipes, and combinations of these and other more complex shapes and shapes can be engineered and architectural.

在製造空間形體中，添加至SiC之黏合劑的量可與SiC粒子之輕塗層相差達形成類似漿料之糊狀物的充分量。因此，取決於成形設備要求、空間形體及黏合劑自身之強度要求，將約0.1%至約65%、約0.1%至約45%、約0.5%至約40%、約20%至約40%、約1%至約15%、及約2%至約7%、約1%及更多、約2%及更多、及約3%及更多的黏合劑添加至SiC以形成漿料或摻合物，以及添加該些百分比範圍內之所有量。取決於在固化期間的黏合劑損失之量，此可產生空間形體，在該空間形體中具有約0.05%至約25%、約0.75%至約12%、1%至約5%、約1%及更多、約2%及更多、約4%及更多、約6%及更多的固化黏合劑，以及該些百分比範圍內之所有量。In the fabrication of spatial shapes, the amount of binder added to SiC can differ from a light coating of SiC particles by a sufficient amount to form a slurry-like paste. Therefore, about 0.1% to about 65%, about 0.1% to about 45%, about 0.5% to about 40%, about 20% to about 40% , about 1% to about 15%, and about 2% to about 7%, about 1% and more, about 2% and more, and about 3% and more binder added to SiC to form a slurry or Blends, and all amounts within these percentage ranges are added. Depending on the amount of binder loss during curing, this can result in a space feature in which there is about 0.05% to about 25%, about 0.75% to about 12%, 1% to about 5%, about 1% and more, about 2% and more, about 4% and more, about 6% and more of cured adhesive, and all amounts within those percentage ranges.

與黏合劑混合以形成空間形體之SiC顆粒之大小可為約0.1 μm(微米)至約100 μm、約0.5 μm至約50 μm、約 0.3 μm至約20 μm、約0.3 μm至約10 μm、及較大及較小大小，以及不同大小之組合，以及該些大小範圍內之所有值。因此，顆粒可具有以下初級粒子D ₅₀大小：約0.1 μm至約20.0 μm、約0.5 μm至約10.0 μm、約 0.5 μm至約2.0 μm、約0.5 μm至約1.0 μm、約 1 μm至約5 μm、約1 μm、約2 μm、約3 μm、及較大及較小D ₅₀大小，以及該些大小範圍內之所有值。 The size of the SiC particles mixed with the binder to form the spatial shape can be from about 0.1 μm (micrometer) to about 100 μm, from about 0.5 μm to about 50 μm, from about 0.3 μm to about 20 μm, from about 0.3 μm to about 10 μm, and larger and smaller sizes, and combinations of different sizes, and all values within those size ranges. Thus, the particles may have the following primary particle _D50 sizes: about 0.1 μm to about 20.0 μm, about 0.5 μm to about 10.0 μm, about 0.5 μm to about 2.0 μm, about 0.5 μm to about 1.0 μm, about 1 μm to about 5 μm, about 1 μm, about 2 μm, about 3 μm, and larger and smaller D ₅₀ sizes, and all values within those size ranges.

黏合劑可為用於在處理、固化及空間形體之稍後使用期間保持預定形體中之SiC的任何黏合劑。黏合劑之實施例可較佳為無氧的。黏合劑之實施例可較佳地由僅具有碳及氫之材料製成。黏合劑之實施例可由具有氧之材料製成。黏合劑之實施例可為用於燒結SiC之任何燒結助劑。黏合劑之實施例可為熔融二氧化矽。黏合劑之實施例可為多晶碳氧矽前驅物材料，包括本說明書中闡述的所有液體前驅物。該些及其他材料之組合及變化亦可用作黏合劑。The binder may be any binder used to retain the SiC in the preform during handling, curing and later use of the spatial form. Embodiments of the binder may preferably be oxygen-free. Embodiments of the adhesive may preferably be made of materials having only carbon and hydrogen. Embodiments of the adhesive may be made from materials that have oxygen. An example of a binder can be any sintering aid used for sintering SiC. An example of a binder may be fused silica. Examples of binders may be polycrystalline silicon oxycarbide precursor materials, including all liquid precursors described in this specification. Combinations and variations of these and other materials can also be used as adhesives.

黏合劑可在用於固化多晶碳氧矽前驅物之條件下，或在需要將黏合劑轉變成足夠硬(例如，堅韌)材料以維持空間形體之形狀所需的條件下固化至所需程度。因此，視情況，固化、硬化、成形、或定型應基於黏合劑之特性來進行。應作未來考慮以防止黏合劑之固化或硬化或定型引入雜質或其他非所欲物質至空間形體中。The binder can be cured to the desired extent under the conditions used to cure the polycrystalline silicon oxycarbide precursor, or under the conditions needed to convert the binder into a sufficiently hard (eg, tough) material to maintain the shape of the spatial form . Therefore, curing, hardening, shaping, or setting, as the case may be, should be performed based on the properties of the adhesive. Future considerations should be taken to prevent the curing or hardening or setting of the adhesive from introducing impurities or other undesirable substances into the spatial form.

不具有氧的黏合劑之實施例之實例將包括聚乙烯、矽金屬、烴蠟、聚苯乙烯、及聚丙烯及該些者之組合及變化。Examples of embodiments of the oxygen-free binder would include polyethylene, silicon metal, hydrocarbon wax, polystyrene, and polypropylene and combinations and variations of these.

僅含有碳及氫的黏合劑之實施例之實例將包括聚乙烯、烴蠟、碳或石墨粉末、炭黑、HDPE、LDPE、UHDPE、及PP及該些者之組合及變化。Examples of embodiments of binders containing only carbon and hydrogen would include polyethylene, hydrocarbon wax, carbon or graphite powder, carbon black, HDPE, LDPE, UHDPE, and PP and combinations and variations of these.

含有氧的黏合劑之實施例之實例將包括硼酸、氧化硼、二氧化矽、多元醇、聚乳酸、纖維素材料、糖及醣、聚酯、環氧化物、矽氧烷、矽酸鹽、矽烷、矽倍半氧烷、諸如乙酸乙烯乙酯(ethylvinylacetate; EVA)之乙酸酯、諸如PMMA之聚丙烯酸酯、及聚合物衍生陶瓷前驅物及該些者之組合及變化。Examples of embodiments of oxygen-containing binders would include boric acid, boron oxide, silicon dioxide, polyols, polylactic acid, cellulosic materials, sugars and sugars, polyesters, epoxides, siloxanes, silicates, Silanes, silsesquioxanes, acetates such as ethylvinylacetate (EVA), polyacrylates such as PMMA, and polymer derived ceramic precursors and combinations and variations of these.

為燒結助劑的黏合劑之實施例之實例將包括矽、氧化硼、硼酸、碳化硼、矽及碳粉末、二氧化矽、矽酸鹽及聚合物衍生陶瓷前驅物及該些者之組合及變化。Examples of embodiments of binders that are sintering aids would include silicon, boron oxide, boric acid, boron carbide, silicon and carbon powders, silicon dioxide, silicates and polymer derived ceramic precursors and combinations of these and changes.

對於用於諸如生長胚晶及用於製造晶圓之應用的純及超純SiC材料而言，黏合劑材料較佳不含認為是污染物的所有材料。因此，在實施例中，黏合劑材料為至少5個九、至少6個九、至少7個九、及至少8個九純的，例如，為不含認為是污染物之材料。For pure and ultrapure SiC materials for applications such as growing embryonic crystals and for manufacturing wafers, the binder material is preferably free of all materials considered to be contaminants. Thus, in embodiments, the binder material is at least 5 nines, at least 6 nines, at least 7 nines, and at least 8 nines pure, eg, free of materials considered contaminants.

較佳地，黏合劑之使用不向SiC或SiOC添加污染物及可偵測量之污染物。在實施例中，黏合劑亦維持Si:C之適當化學計量以在處理之後維持接近矽原子對碳原子之1:1比率。在實施例中，黏合劑具有Si:C之預定比率，其為富碳、貧碳、或化學計量的以提供具有預定SiC比率之空間形體。Preferably, the use of the binder does not add contaminants and detectable amounts of contaminants to the SiC or SiOC. In an embodiment, the binder also maintains a proper stoichiometry of Si:C to maintain a near 1:1 ratio of silicon atoms to carbon atoms after processing. In an embodiment, the binder has a predetermined ratio of Si:C that is carbon-rich, carbon-poor, or stoichiometric to provide a steric form with a predetermined SiC ratio.

對於純及超純SiC應用及材料而言，黏合劑可較佳地為化妝等級、電子學等級、及外科等級材料。For pure and ultrapure SiC applications and materials, the binder may preferably be cosmetic grade, electronics grade, and surgical grade materials.

黏合劑之實施例將包括催化及未催化的前驅物調配物，如美國專利第9,499,677號、第9,481,781號及美國專利公開案第2014/0274658號、第2014/0323364號、第2015/0175750號、第2016/0207782號、第2016/0280607號、第2017/0050337號中所揭示及教示，其中每一者之全部揭示內容係以引用方式併入本文中。固化該些黏合劑之方法係揭示及教示於該些專利及公開的申請案中，其中每一者之全部揭示內容係以引用方式併入本文中。Examples of binders would include catalyzed and uncatalyzed precursor formulations such as U.S. Patent Nos. 9,499,677, 9,481,781 and U.S. Patent Publication Nos. 2014/0274658, 2014/0323364, 2015/0175750, Disclosed and taught in Nos. 2016/0207782, 2016/0280607, 2017/0050337, the entire disclosure of each of which is incorporated herein by reference. Methods of curing the adhesives are disclosed and taught in these patents and published applications, the entire disclosure of each of which is incorporated herein by reference.

在較佳實施例中，SiC空間形體係使用聚合物衍生、及較佳地多晶碳氧矽聚合物衍生SiC (例如，如美國公開案第2016/0207782號中所教示及揭示，其係以引用方式併入本文中)、及多晶碳氧矽黏合劑來製成。在實施例中，SiC係來自習知來源。此實施例為次較佳的，如咸信慣例SiC具有不同的結構，例如，形態學及表面性質，從而在諸如氣相沉積之應用中產生比聚合物衍生SiC差的效能。在實施例中，空間形體為聚合物衍生SiC及習知SiC之混合物。In a preferred embodiment, the SiC space-shape system uses polymer-derived, and preferably polycrystalline silicon oxycarbide polymer-derived SiC (for example, as taught and disclosed in U.S. Publication No. 2016/0207782, which is based on Incorporated herein by reference), and polycrystalline silicon oxycarbide adhesive to make. In an embodiment, the SiC system is from a known source. This embodiment is less preferred, as conventional SiC is believed to have different structures, eg, morphology and surface properties, resulting in poorer performance than polymer derived SiC in applications such as vapor deposition. In an embodiment, the spatial form is a mixture of polymer derived SiC and conventional SiC.

在實施例中，黏合劑係用於為小片、珠粒或空間形體提供傳導性。因此，黏合劑可為碳、矽，或可現場分解成導電物質，諸如碳—實例包括多醣、PE、烴油及蠟等等或多晶碳氧矽調配物，其具有大的碳過量且因此遠不能達成Si:C化學計量且替代地現場形成C-SiC複合物，或可具有添加至其的碳及矽。以此方式，空間形體，例如，圓盤、圓片、團塊、珠粒、小片、彈丸、等等具有在20℃下低於10,000 ohm-cm、在20℃下低於8,000 ohm-cm、在20℃下低於5,000 ohm-cm、及在20℃下低於2,000 ohm-cm，以及該些電阻率範圍內之所有值之電阻率。In an embodiment, a binder is used to provide conductivity to the platelets, beads or spatial features. Thus, the binder can be carbon, silicon, or decomposable in situ into conductive species such as carbon - examples include polysaccharides, PE, hydrocarbon oils and waxes, etc. Si:C stoichiometry is far from being achieved and instead a C-SiC composite is formed in situ, or may have carbon and silicon added to it. In this way, spatial features such as discs, discs, agglomerates, beads, flakes, pellets, etc. have an Resistivity below 5,000 ohm-cm at 20°C, and below 2,000 ohm-cm at 20°C, and all values within these resistivity ranges.

通常，在實施例中，黏合劑材料在700℃下完全揮發、在600℃下完全揮發、及在500℃下完全揮發，以及在該些溫度範圍內之所有值下完全揮發。當使用不同類型之PDC作為黏合劑材料時，揮發範圍可變化，且因此用於黏合劑之揮發的溫度範圍可在約900℃至約300℃範圍變化，以及該些溫度範圍內之所有值。亦較佳的是，黏合劑之揮發組分不沉積於，或以其他方式形成於、結垢或污染設備之內部部件，該設備係用於自SiC製造結構，例如，氣相沉積裝置。Typically, in embodiments, the binder material is fully volatile at 700°C, fully volatile at 600°C, and fully volatile at 500°C, and at all values within these temperature ranges. When different types of PDC are used as the binder material, the volatilization range can vary, and thus the temperature range for volatilization of the binder can vary from about 900°C to about 300°C, and all values within these temperature ranges. It is also preferred that volatile components of the adhesive do not deposit on, or otherwise form on, foul or contaminate internal components of equipment used to fabricate structures from SiC, eg, vapor deposition devices.

與超純SiC一起使用以形成空間形體，例如，小片、圓盤、圓片、彈丸、團塊、珠粒的在20℃下具有低於8,000 ohm-cm之電阻率及至少約5個九之純度(空間形體之純度)的黏合劑材料之較佳實施例為矽金屬、碳粉末、烴蠟、純聚乙烯、及主要含有矽及碳及氫之可蒸餾化合物及聚合物衍生陶瓷前驅物及該些者之組合及變化。Use with ultrapure SiC to form spatial features such as pellets, disks, discs, pellets, pellets, beads having a resistivity of less than 8,000 ohm-cm and at least about 5 nines at 20°C Preferred examples of binder materials for purity (stereomorphic purity) are silicon metals, carbon powders, hydrocarbon waxes, pure polyethylene, and distillable compounds and polymer-derived ceramic precursors mainly containing silicon and carbon and hydrogen and combinations and variations thereof.

用於形成空間形體之設備及製程將包括例如冷壓機、冷等靜壓機、熱壓機、熱等靜壓機、擠壓機、模鑄、及模製製程及該些者之組合及變化。Equipment and processes for forming spatial shapes will include, for example, cold presses, cold isostatic presses, hot presses, hot isostatic presses, extruders, die casting, and molding processes and combinations thereof and Variety.

在利用直接通量、回流、分餾或分昇華的實施例及其中預定形體將要在生長循環之大部分及較佳地全部期間保持其結構完整性的其他實施例中，黏合劑必須使得其不昇華或以其他方式損失維持空間形體之結構完整性之能力。該些類型之黏合劑之實例將包括PDC前驅物作為黏合劑。用於維持空間形體之結構完整性例如以便用作回流結構的較佳實施例將為10重量%-15重量%純的PDC前驅物材料。In embodiments utilizing direct flux, reflux, fractional distillation, or subsublimation, and other embodiments where the predetermined shape is to retain its structural integrity during most, and preferably all, of the growth cycle, the binder must be such that it does not sublime Or otherwise lose the ability to maintain the structural integrity of the spatial form. Examples of these types of binders would include PDC precursors as binders. A preferred embodiment for maintaining the structural integrity of the spatial form, eg, for use as a reflow structure, would be 10 wt% - 15 wt% pure PDC precursor material.

以本質上具有製造SiC所需的例如Si及C之所有建構塊的例如前驅物批料之液體材料開始的能力在控制雜質、污染，及在製造高純度SiOC中提供顯著優勢，該高純度SiOC又可轉化成高純度SiC或可直接在單一組合製程或步驟中製成。亦在理論上，部分地基於氣相沉積設備及生長胚晶中的本發明之聚合物衍生SiC之效能，聚合物衍生SiC顯著地不同於非聚合物衍生SiC。因此，胚晶生長及純度、晶圓產率及裝置產率中之協同益處進一步由本發明之個別益處產生，該等益處為體密度、粒子大小、SiC之相(β相對α)、化學計量、氧含量(極低至無，及缺少氧化物層)、高及超高純度。The ability to start with a liquid material, such as a precursor batch, that essentially has all the building blocks needed to make SiC, such as Si and C, provides significant advantages in controlling impurities, contamination, and in the production of high-purity SiOC that It can in turn be converted to high-purity SiC or can be made directly in a single combined process or step. It is also theoretical, based in part on the performance of the polymer-derived SiC of the present invention in vapor deposition equipment and growing embryos, that polymer-derived SiC differs significantly from non-polymer-derived SiC. Thus, synergistic benefits in embryonic growth and purity, wafer yield, and device yield result further from the individual benefits of the present invention, which are bulk density, particle size, phase of SiC (beta vs. alpha), stoichiometry, Oxygen content (very low to none, and lack of oxide layer), high and ultra-high purity.

因此，本發明之實施例提供SiOC及SiOC空間形體之使用，該等空間形體為至少約99.9% (3個九)、至少約99.99% (4個九)、至少約99.999% (5個九)、及至少約99.9999% (6個九)及至少約99.99999% (7個九)或更大純度，以及該些純度範圍內之所有值。類似地，本發明之實施例提供SiC及SiC空間形體之使用，該等空間形體為至少約99.9%(3個九)、至少約99.99% (4個九)、至少約99.999% (5個九)、及至少約99.9999% (6個九)及至少約99.99999% (7個九)或更大純度，以及該些純度範圍內之所有值。該些純度值係視情況基於SiOC或SiC相對存在或含在SiOC或SiC產品之給定樣本內的所有材料之量。如本文所使用，SiOC或SiC產品將係指粉末SiOC或SiC，以及，該些材料之空間形體。具有適當黏合劑選擇的SiC及SiOC之空間形體之實施例具有相同純度位準。Accordingly, embodiments of the present invention provide for the use of SiOC and SiOC spatial shapes that are at least about 99.9% (3 nines), at least about 99.99% (4 nines), at least about 99.999% (5 nines) , and at least about 99.9999% (6 nines) and at least about 99.99999% (7 nines) or greater purity, and all values within such purity ranges. Similarly, embodiments of the present invention provide for the use of SiC and SiC spatial features that are at least about 99.9% (3 nines), at least about 99.99% (4 nines), at least about 99.999% (5 nines) ), and at least about 99.9999% (6 nines) and at least about 99.99999% (7 nines) or greater purity, and all values within such purity ranges. These purity values are based on the SiOC or SiC relative to the amount of all materials present or contained within a given sample of SiOC or SiC product, as the case may be. As used herein, SiOC or SiC products shall refer to powdered SiOC or SiC, and the spatial forms of these materials. Embodiments of spatial features of SiC and SiOC with proper binder selection have the same purity level.

亦注意，若污染物係以不會不利地影響SiC及SiOC在其所欲製造製程或最終用途中之使用；及不會不利地影響由SiC及SiOC起始材料製成的最終產品的方式揮發(或以其他方式移除)，則空間形體之較低純度位準可為可接受的。因此，例如，其中SiC為7個九純的SiC之4個九純圓盤及降低該圓盤之總體純度的黏合劑係在胚晶成形氣相沉積製程中的達到700℃之圓盤可為可接受的之前加以移除。另外，過重(較高AMU)之雜質可俘獲在圓片內，且因此，得以緩和。Note also that if the contaminants are volatilized in a manner that does not adversely affect the use of SiC and SiOC in their intended manufacturing process or end use; and does not adversely affect the final product made from the SiC and SiOC starting materials (or otherwise removed), a lower purity level of the spatial form may be acceptable. Thus, for example, 4 nine-pure discs of SiC in which SiC is 7 nine-pure and a binder that reduces the overall purity of the pucks can be used for disks up to 700°C in an embryonic crystal forming vapor deposition process. Removed before acceptable. Additionally, impurities that are too heavy (higher AMU) can be trapped within the wafer and, therefore, moderated.

在本發明之實施例中，高純度SiC空間形體具有低、極低及低於偵測極限的量之引起顯著問題或在物件之稍後處理及製造中視為雜質的材料，該等物件例如，胚晶、晶圓、電子部件、光學部件及其他基於SiC的中間物及最終產品。In embodiments of the present invention, the high purity SiC spacers have low, very low, and below detection limit amounts of materials that cause significant problems or are considered impurities in later processing and fabrication of objects such as, Embryos, wafers, electronic components, optical components and other SiC-based intermediates and final products.

因此，聚合物衍生高純度SiC、及尤其多晶碳氧矽衍生高純度SiOC，以及SiOC所轉化成的高純度SiC具有至少約99.9%、至少約99.99%、至少約99.999%、及至少約99.9999%及至少約99.99999%或更大之純度。進一步，應注意，本發明之實施例包括具有任何純度位準之聚合物衍生SiC及SiOC，包括較低位準之純度，諸如99.0%、95%、90%及更低。咸信該些較低，例如，非高純度實施例具有及將得到實質使用及應用。類似地，咸信高純度SiC之實施例將得到應用、使用，且為應用提供新的及令人驚訝的益處，該等益處在本發明之前係限於Si或不同於SiC之材料。具有適當黏合劑選擇的SiC之空間形體之實施例具有相同純度位準。Thus, polymer-derived high-purity SiC, and particularly polycrystalline silicon oxycarbide-derived high-purity SiOC, and SiOC converted to high-purity SiC have at least about 99.9%, at least about 99.99%, at least about 99.999%, and at least about 99.9999% % and at least about 99.99999% or greater in purity. Further, it should be noted that embodiments of the present invention include polymer derived SiC and SiOC having any level of purity, including lower levels of purity, such as 99.0%, 95%, 90% and lower. It is believed that these lower, eg, non-high purity embodiments have and will find substantial use and application. Similarly, it is believed that embodiments of high purity SiC will find application, use, and provide new and surprising benefits for applications that prior to the present invention were limited to Si or materials other than SiC. Embodiments of SiC spatial features with proper binder selection have the same purity level.

本發明之實施例包括高純度SiC在製造用於電子學及半導體應用中之應用的晶圓中的用途。在產生胚晶及晶圓用於稍後使用的氣相沉積設備及製程兩者中，需要高純度SiC。詳言之，如表1所闡述，高純度SiC之實施例可較佳地具有低位準的表1中之一種、多於一種、及所有要素，其在某些氣相沉積設備、電子學應用、及半導體應用中被認為是雜質。因此，SiC粒子及空間形體之實施例可不含雜質，實質上不含雜質，且含有一些但具有不超過表1陳述的量及量之組合。Embodiments of the present invention include the use of high purity SiC in the manufacture of wafers for applications in electronics and semiconductor applications. High purity SiC is required both in the vapor deposition equipment and in the process to create embryos and wafers for later use. In particular, as set forth in Table 1, embodiments of high-purity SiC may preferably have low levels of one, more than one, and all of the elements in Table 1, which are useful in certain vapor deposition equipment, electronics applications , and semiconductor applications are considered impurities. Thus, embodiments of SiC particles and spatial features may be free of impurities, substantially free of impurities, and contain some but not exceeding the amounts and combinations of amounts stated in Table 1.

表1 元素小於 ppm 小於 ppm 小於 ppm 小於 ppm 小於 ppm Al 1,000 100 10 1 0.1 Fe 1,000 100 10 1 0.1 B 1,000 100 10 1 0.1 P 1,000 100 10 1 0.1 Pt 1,000 100 10 1 0.1 Ca 1,000 100 10 1 0.1 Mg 1,000 100 10 1 0.1 Li 1,000 100 10 1 0.1 Na 1,000 100 10 1 0.1 Ni 1,000 100 10 1 0.1 V 1,000 100 10 1 0.1 Ti 1,000 100 10 1 0.1 Ce 1,000 100 10 1 0.1 Cr 1,000 100 10 1 0.1 S 1,000 100 10 1 0.1 As 1,000 100 10 1 0.1 上述一或多者之總和 3,000 500 50 10 1 Table 1 element less than ppm less than ppm less than ppm less than ppm less than ppm Al 1,000 100 10 1 0.1 Fe 1,000 100 10 1 0.1 B 1,000 100 10 1 0.1 P 1,000 100 10 1 0.1 Pt 1,000 100 10 1 0.1 Ca 1,000 100 10 1 0.1 Mg 1,000 100 10 1 0.1 Li 1,000 100 10 1 0.1 Na 1,000 100 10 1 0.1 Ni 1,000 100 10 1 0.1 V 1,000 100 10 1 0.1 Ti 1,000 100 10 1 0.1 Ce 1,000 100 10 1 0.1 Cr 1,000 100 10 1 0.1 S 1,000 100 10 1 0.1 As 1,000 100 10 1 0.1 the sum of one or more of the above 3,000 500 50 10 1

在實施例，Pr亦可在一些應用中認為是雜質，且若如此認為，則表1之極限及量可適用於Pr。In an example, Pr may also be considered an impurity in some applications, and if so considered, the limits and amounts in Table 1 may apply to Pr.

除非另外指定，否則如本文所使用，當提及純度位準、高純度、純度%、雜質%、及類似的此種術語時，在材料之計算或表徵中不包括、提及、認為、或使用過量碳，亦即，超過化學計量的SiC。在一些應用中，過量碳可對應用或產品具有小的效應至不具有效應，且因此，將不認為是雜質。在其他應用中，過量的碳可為有益的，例如，碳可充當燒結助劑；過量碳可用於解決且補償氣相沉積設備及製程中之不規則性，且可用於控制或實現氣相沉積製程。Unless otherwise specified, as used herein, when referring to purity level, high purity, % purity, % impurity, and similar such terms, calculations or characterizations of materials do not include, refer to, assume, or Excess carbon is used, that is, SiC over stoichiometric. In some applications, excess carbon may have little to no effect on the application or product, and therefore, would not be considered an impurity. In other applications, excess carbon can be beneficial, for example, carbon can act as a sintering aid; excess carbon can be used to address and compensate for irregularities in vapor deposition equipment and processes, and can be used to control or enable vapor deposition Process.

在其中氮係視為污染物之應用中，多晶碳氧矽衍生SiC及SiOC之實施例可具有小於約10,000 ppm、小於1000 ppm、小於約100 ppm、小於約10 ppm、小於約1 ppm及小於約0.1 ppm及更低的氮，及約1000 ppm至約0.01 ppm的氮、約100 ppm至約0.001 ppm的氮。SiC之空間形體之實施例具有相同純度位準。Embodiments of polycrystalline silicon oxycarbide derived SiC and SiOC may have less than about 10,000 ppm, less than 1000 ppm, less than about 100 ppm, less than about 10 ppm, less than about 1 ppm and Less than about 0.1 ppm nitrogen and lower, and about 1000 ppm to about 0.01 ppm nitrogen, about 100 ppm to about 0.001 ppm nitrogen. Embodiments of spatial features of SiC have the same purity level.

在多晶碳氧矽衍生SiC之實施例中，其本質上不含及不含呈任何形式的氧之存在，該形式為結合至Si或C或作為氧化物層。因此，多晶碳氧矽衍生SiC及SiC之空間形體的實施例可具有小於約10,000 ppm、小於1000 ppm、小於約100 ppm、小於約10 ppm、小於約1 ppm及小於約0.1 ppm及更低的氧，及約1000 ppm至約0.01 ppm的氧、約100 ppm至約0.001 ppm的氧。多晶碳氧矽衍生SiC具有在標準溫度及壓力下暴露於空氣時抵抗且不形成氧化物層之能力。在環境條件下儲存時不存在氧化物層，亦即，無氧化物層之SiC在稍後製造製程中提供優點，其中氧化物層可視為雜質，或另外視為對製造製程之有害物。SiC之空間形體之實施例具有相同純度位準。In the embodiment of polycrystalline silicon oxycarbide derived SiC, it is essentially free and free of the presence of oxygen in any form, either bound to Si or C or as an oxide layer. Thus, embodiments of polycrystalline silicon oxycarbide derived SiC and SiC steric features can have less than about 10,000 ppm, less than 1000 ppm, less than about 100 ppm, less than about 10 ppm, less than about 1 ppm, and less than about 0.1 ppm and lower oxygen, and oxygen from about 1000 ppm to about 0.01 ppm, and oxygen from about 100 ppm to about 0.001 ppm. Polycrystalline silicon oxycarbide derived SiC has the ability to resist and not form an oxide layer when exposed to air at standard temperature and pressure. The absence of an oxide layer when stored under ambient conditions, ie SiC without an oxide layer provides advantages later in the manufacturing process where the oxide layer may be considered an impurity, or otherwise detrimental to the manufacturing process. Embodiments of spatial features of SiC have the same purity level.

本發明之多晶碳氧矽SiC及SiC胚晶、晶圓及由多晶碳氧矽衍生SiC製成的其他結構之實施例展現多形性，且通常展現稱為多型性之一維多形性。因此，多晶碳氧矽衍生SiC可在許多、理論上無限的不同多型體中存在。如本文所使用，除非另外明確地提供，否則術語多型性、多型體及類似的此種術語應給定其最廣可能的含義，且將包括各種不同的碳化矽四面體(SiC ₄)藉由得以配置的框架、結構、或排列。通常，該些多型體分成兩個種類-阿爾法(α)及貝他β)。 Embodiments of polycrystalline silicon oxycarbide SiC and SiC embryos, wafers, and other structures made from polycrystalline silicon oxycarbide derived SiC of the present invention exhibit polymorphism, and often exhibit a multi-dimensional nature known as polymorphism. Formality. Thus, polycrystalline silicon oxycarbide derived SiC can exist in many, theoretically infinite, different polytypes. As used herein, unless expressly provided otherwise, the terms polymorphism, polytype and similar such terms shall be given their broadest possible meaning and shall include the various silicon carbide tetrahedra (SiC ₄ ) By a frame, structure, or arrangement to be configured. Generally, these polytypes are divided into two classes - alpha (α) and beta (β).

多晶碳氧矽衍生SiC之α種類之實施例典型地含有六邊形(H)、菱面體(R)、三角形(T)結構且可含有該些者之組合。β種類典型地含有立方體(C)或閃鋅礦結構。因此，例如，多晶碳氧矽衍生碳化矽之多型體將包括：3C-SiC (β – SiC或β 3C-SiC)，其具有ABCABC...之疊積序列；2H-SiC，其具有ABAB...之疊積序列；4H-SiC，其具有ABCBABCB...之疊積序列；及6H-SiC(α碳化矽之一般形式，α 6H-SiC)，其具有ABCACBABCACB...之疊積序列。由α碳化矽形成之其他者的實例將包括8H、10H、16H、18H、19H、15R、21R、24H、33R、39R、27R、48H、及51R。Embodiments of the alpha species of polycrystalline silicon oxycarbide derived SiC typically contain hexagonal (H), rhombohedral (R), triangular (T) structures and may contain combinations of these. Beta species typically contain cubic (C) or sphalerite structures. Thus, for example, polytypes of polycrystalline silicon oxycarbide derived silicon carbide would include: 3C-SiC (β-SiC or β 3C-SiC), which has the stacking sequence ABCABC...; 2H-SiC, which has The stacking sequence of ABAB...; 4H-SiC, which has the stacking sequence of ABCBABCB...; and 6H-SiC (the general form of alpha silicon carbide, α6H-SiC), which has the stacking sequence of ABCACBABCACB... Product sequence. Examples of others formed from alpha silicon carbide would include 8H, 10H, 16H, 18H, 19H, 15R, 21R, 24H, 33R, 39R, 27R, 48H, and 51R.

多晶碳氧矽衍生SiC之實施例可為多晶或單一(單)結晶的。通常，在多晶材料中，在材料之兩個顆粒或微晶之間存在顆粒邊界作為界面。該些顆粒邊界可在具有不同定向的相同多型體之間、或在具有相同或不同定向之不同多型體之間、及該些者之組合及變化。單結晶結構由單一多型體製成且基本上不具有顆粒邊界。Embodiments of polycrystalline silicon oxycarbide derived SiC may be polycrystalline or single (single) crystalline. Typically, in polycrystalline materials, grain boundaries exist as interfaces between two grains or crystallites of the material. The grain boundaries can be between the same polytype with different orientations, or between different polytypes with the same or different orientations, and combinations and variations of these. A single crystalline structure is made of a single polytype and has essentially no grain boundaries.

本發明之方法的實施例產生SiC之胚晶，較佳單晶胚晶。該些胚晶可具有以下長度：約 ¹/ ₂吋至約5吋、約 ¹/ ₂吋至約3吋、約1吋至約2吋、大於約 ¹/ ₂吋、大於約1吋及大於約2吋。涵蓋較大及較小大小，以及該些大小範圍內之所有值。胚晶可具有以下橫截面，例如，直徑：約 ¹/ ₂吋至約9吋、約2吋至約8吋、約1吋至約6吋、大於約1吋、大於約2吋、大於約4吋、約4吋、約6吋及約8吋約、約12吋及約18吋。涵蓋其他大小，以及該些大小範圍內之所有值。 Embodiments of the method of the present invention produce SiC embryos, preferably single crystal embryos. The embryo crystals can have the following lengths: about ^1/2 _inch to about 5 inches, about ^1/2 inch to about 3 inches, about ₁ inch to about ₂ inches, greater than about ^1/2 inch, greater than about 1 inch, and greater than About 2 inches. Covers larger and smaller sizes, and all values within those size ranges. Embryocrystals can have the following cross-sections, e.g., diameters: about ^1/2 _inch to about 9 inches, about 2 inches to about 8 inches, about 1 inch to about 6 inches, greater than about 1 inch, greater than about 2 inches, greater than about 4 inches, about 4 inches, about 6 inches and about 8 inches, about 12 inches and about 18 inches. Other sizes are covered, and all values within those size ranges.

大體上，用於自SiC胚晶製造電子部件之製程涉及將SiC單結晶胚晶切割成薄晶圓。晶圓具有胚晶之直徑且典型地具有約100 μm至約500 μm之厚度。隨後將晶圓在一側或兩側上拋光。隨後將拋光晶圓用作用於所製造微電子半導體裝置之基板。因此，晶圓用作用於微電子裝置之基板，該等微電子裝置建構在晶圓中，建構在晶圓上或兩者兼有。該些微電子裝置之製造包括微製造處理步驟，諸如，各種材料之磊晶生長、摻雜或離子植入、蝕刻、沉積，及光刻圖案化，僅舉幾例。一旦自晶圓製造，該晶圓及因此個別微電路在稱為切割的製程中分離成個別半導體裝置。該些裝置隨後用於製造，例如，併入各種較大半導體及電子裝置中。In general, the process for fabricating electronic components from SiC embryos involves dicing SiC single crystal embryos into thin wafers. The wafer has the diameter of an embryonic crystal and typically has a thickness of about 100 μm to about 500 μm. The wafer is then polished on one or both sides. The polished wafers are then used as substrates for the fabricated microelectronic semiconductor devices. Thus, wafers are used as substrates for microelectronic devices built in the wafer, on the wafer, or both. The fabrication of these microelectronic devices includes microfabrication processing steps such as epitaxial growth of various materials, doping or ion implantation, etching, deposition, and photolithographic patterning, to name a few. Once fabricated from a wafer, the wafer and thus the individual microcircuits are separated into individual semiconductor devices in a process called dicing. These devices are subsequently used in fabrication, for example, for incorporation into various larger semiconductor and electronic devices.

本發明之方法及所得SiC晶圓之實施例包括尤其約2吋直徑晶圓及較小晶圓、約3吋直徑晶圓、約4吋直徑晶圓、約5吋直徑晶圓、約6吋直徑晶圓、約7吋直徑晶圓、約12吋直徑晶圓及潛在地較大晶圓，具有約2吋至約8吋之直徑的晶圓、具有約4吋至約6吋之直徑的晶圓，正方形成形、圓形成形、及其他形體，每一側約1平方吋、約4平方吋、約8平方吋、約10平方吋、約12平方吋、約30平方吋、約50平方吋、及較大及較小之表面面積，約100 μm之厚度、約200 μm之厚度、約300 μm之厚度、約500 μm之厚度、約700 μm之厚度、約50 μm至約800 μm之厚度、約100 μm至約 700 μm之厚度、約100 μm至約400 μm之厚度、約100 μm至約300 μm之厚度、約100 μm至約200 μm之厚度及較大及較小厚度，及該些者之組合及變化，以及該些尺寸範圍內之所有值。Embodiments of the method and resulting SiC wafers of the present invention include, inter alia, about 2 inch diameter wafers and smaller wafers, about 3 inch diameter wafers, about 4 inch diameter wafers, about 5 inch diameter wafers, about 6 inch diameter wafers, about 6 inch diameter wafers, diameter wafers, about 7 inch diameter wafers, about 12 inch diameter wafers and potentially larger wafers, wafers with diameters from about 2 inches to about 8 inches, wafers with diameters from about 4 inches to about 6 inches Wafers, square shaped, round shaped, and other shapes, about 1 square inch, about 4 square inches, about 8 square inches, about 10 square inches, about 12 square inches, about 30 square inches, about 50 square inches per side inches, and larger and smaller surface areas, thickness of about 100 μm, thickness of about 200 μm, thickness of about 300 μm, thickness of about 500 μm, thickness of about 700 μm, thickness of about 50 μm to about 800 μm Thickness, thickness of about 100 μm to about 700 μm, thickness of about 100 μm to about 400 μm, thickness of about 100 μm to about 300 μm, thickness of about 100 μm to about 200 μm and greater and lesser thicknesses, and Combinations and variations of these, and all values within these dimensional ranges.

本發明之方法及所得切割及拋光晶圓之實施例亦可包括用於起始胚晶之生長(亦即作為「晶種」)，自其所生長的胚晶之剩餘部分匹配結構。晶圓或晶種可尤其為約2吋直徑晶圓及較小晶圓、約3吋直徑晶圓、約4吋直徑晶圓、約5吋直徑晶圓、約6吋直徑晶圓、約7吋直徑晶圓、約12吋直徑晶圓及潛在地較大晶圓，具有約2吋至約8吋之直徑的晶圓、具有約4吋至約6吋之直徑的晶圓，正方形成形、圓形成形、及其他形體，每一側約4平方吋、約8平方吋、約12平方吋、約30平方吋、約50平方吋、及較大及較小之表面面積，約100 μm之厚度、約200 μm之厚度、約300 μm之厚度、約500 μm之厚度、約1500 μm之厚度、約2500 μm之厚度、約50 μm至約2000 μm之厚度、約500 μm至約1800 μm之厚度、約800 μm至約1500 μm之厚度、約500 μm至約1200 μm之厚度、約200 μm至約2000 μm之厚度、約50 μm至約2500 μm之厚度、及較大及較小厚度，及該些者之組合及變化，以及該些尺寸範圍內之所有值。Embodiments of the method of the present invention and resulting diced and polished wafers may also include growth (ie, as a "seed") for an initial embryo crystal from which the remainder of the embryo crystal grows to match the structure. Wafers or seeds can be about 2 inch diameter wafers and smaller wafers, about 3 inch diameter wafers, about 4 inch diameter wafers, about 5 inch diameter wafers, about 6 inch diameter wafers, about 7 inch diameter wafers, and smaller wafers, among others. inch diameter wafers, about 12 inch diameter wafers and potentially larger wafers, wafers with diameters from about 2 inches to about 8 inches, wafers with diameters from about 4 inches to about 6 inches, square shaped, Circular shapes, and other shapes, of about 4 square inches, about 8 square inches, about 12 square inches, about 30 square inches, about 50 square inches, and larger and smaller surface areas of about 100 μm per side Thickness, thickness of about 200 μm, thickness of about 300 μm, thickness of about 500 μm, thickness of about 1500 μm, thickness of about 2500 μm, thickness of about 50 μm to about 2000 μm, thickness of about 500 μm to about 1800 μm Thickness, thickness from about 800 μm to about 1500 μm, thickness from about 500 μm to about 1200 μm, thickness from about 200 μm to about 2000 μm, thickness from about 50 μm to about 2500 μm, and larger and smaller thicknesses, and combinations and variations thereof, and all values within these dimensional ranges.

本發明之SiC胚晶、SiC晶圓、及自彼等晶圓製造的微電子器件之實施例尤其在以下各方面找到應用及實用性：二極體、寬頻帶放大器、軍事通訊、雷達、電信、資料鏈路及戰術資料鏈路、衛星通訊及點對點無線電功率電子器件、LED、雷射器、照明及感測器。另外，該些實施例可在電晶體中找到應用及用途，諸如高電子遷移率電晶體(High-electron-mobility transisitor; HEMT)，包括基於HEMT之單片微波積體電路(monolithic microwave integrated circuit; MMIC)。該些電晶體可使用分佈式(行進波)放大器設計方法，且具有SiC之較大能帶隙，從而賦能在小覆蓋區中達成極寬帶寬。因此，本發明之實施例將包括由本發明之方法、氣相沉積技術、及聚合物衍生SiC、SiC胚晶、SiC晶圓及由該些晶圓製造的微電子器件製得或在其他情況下基於此等的該些裝置及製品。Embodiments of the SiC embryos, SiC wafers, and microelectronic devices fabricated from these wafers of the present invention find application and utility, inter alia, in: diodes, broadband amplifiers, military communications, radar, telecommunications , data links and tactical data links, satellite communications and point-to-point radio power electronics, LEDs, lasers, lighting and sensors. In addition, these embodiments can find applications and uses in transistors, such as high-electron-mobility transistors (High-electron-mobility transistors; HEMTs), including HEMT-based monolithic microwave integrated circuits (monolithic microwave integrated circuits; MMIC). These transistors can use a distributed (traveling wave) amplifier design approach and have the larger bandgap of SiC, enabling extremely wide bandwidths in a small footprint. Accordingly, embodiments of the invention will include those made by the methods, vapor deposition techniques, and polymer-derived SiC, SiC embryos, SiC wafers, and microelectronic devices fabricated from these wafers, or otherwise These devices and articles based on them.

多晶碳氧矽衍生SiC、尤其高純度SiC之實施例具有許多獨特的性質，尤其使得其在用於電子、太陽能、及電力輸送工業及應用中為有利的及合乎需要的。其可用作半導體材料，其極穩定且適於若干有需求之應用及用途，包括高功率、高頻率、高溫、及腐蝕環境。聚合物衍生SiC為具有424 GPa之楊氏模數的極硬材料。其基本上為化學惰性的，且在室溫下將不與任何材料反應。Embodiments of polycrystalline silicon oxycarbide derived SiC, especially high purity SiC, have a number of unique properties that make them advantageous and desirable for use in the electronics, solar, and power delivery industries and applications, among others. It can be used as a semiconductor material, which is extremely stable and suitable for several demanding applications and uses, including high power, high frequency, high temperature, and corrosive environments. Polymer derived SiC is an extremely hard material with a Young's modulus of 424 GPa. It is essentially chemically inert and will not react with any materials at room temperature.

本發明之實施例具有提供呈空間結構之高純度SiOC及SiC的能力且為呈空間結構之高純度SiOC及SiC，例如，圓片、壓塊、磚、塊體、小片、彈丸、板、圓盤、正方體、球、棒、隨機形體等等。該些空間形體具有廣範圍之大小，通常，大於或等於1/32 in ³(吋 ³)、大於或等於1/16 in ³、大於或等於1/8 in ³、大於或等於1/4 in ³、約1/16 in ³至約1 ft ³，儘管涵蓋較大及較小體積，以及該些尺寸範圍內之所有值。空間結構之實施例可為硬的、結構固體，或軟的及脆的。對於圓盤、板、彈丸、及其他更一般而言類似平面的空間結構而言，最大表面(亦即，寬度而非厚度)之面積可大於或等於約1/32 in ²、大於或等於約1/16 in ²、大於或等於約1/8 in ²、大於或等於約1/4 in ²、大於或等於約1/2 in ²、大於或等於約1 in ²、及大於或等於約2 in ²、及約1/4 in ²至約3 in ²、約1/2 in ²至約4 in ²及約1/8 in ²至約3/4 in ²。該些平面類型空間形體可具有小於1/64 in、小於1/32、小於1/2 in、約1/16 in至約3/4 in、約1/8吋至約1/2 in、及大於或等於1/8 in、大於或等於1/4 in之厚度，及該些者之組合及變化，以及該些尺寸範圍內之所有值。 Embodiments of the present invention have the ability to provide spatially structured high-purity SiOC and SiC and are spatially structured high-purity SiOC and SiC, for example, wafers, briquettes, bricks, blocks, chips, pellets, plates, circles Disks, cubes, balls, sticks, random shapes, etc. These spatial shapes have a wide range of sizes, generally, greater than or equal to 1/32 in ³ (inch ³ ), greater than or equal to 1/16 in ³ , greater than or equal to 1/8 in ³ , greater than or equal to 1/4 in ^3. From about 1/16 in ³ to about 1 ft ³ , although larger and smaller volumes are encompassed, and all values within these size ranges. Embodiments of spatial structures may be hard, structurally solid, or soft and brittle. For disks, plates, projectiles, and other more generally planar-like spatial structures, the area of the largest surface (ie, width but not thickness) may be greater than or equal to about 1/32 in ² , greater than or equal to about 1/16 in ² , greater than or equal to about 1/8 in ² , greater than or equal to about 1/4 in ² , greater than or equal to about 1/2 in ² , greater than or equal to about 1 in ² , and greater than or equal to about 2 in 2 in ² , and about 1/4 in ² to about 3 in ² , about 1/2 in ² to about 4 in ² , and about 1/8 in ² to about 3/4 in ² . These planar type space shapes can have less than 1/64 in, less than 1/32, less than 1/2 in, about 1/16 in to about 3/4 in, about 1/8 in to about 1/2 in, and Thicknesses greater than or equal to 1/8 inch, greater than or equal to 1/4 inch, combinations and variations thereof, and all values within these dimensional ranges.

在較佳實施例中，空間形體具有適於使用的強度，例如，操縱時保存及保持結構上完整之能力，以便其可裝運、打開包裝、及裝載至用於生長胚晶之氣相沉積設備中。取決於所使用的黏合劑或其他接合製程，該些空間形體亦可具有相當大的強度。In preferred embodiments, the spatial body has a strength suitable for use, e.g., the ability to preserve and maintain structural integrity when manipulated, so that it can be shipped, unpacked, and loaded into vapor deposition equipment for growing embryonic crystals middle. Depending on the adhesive or other bonding process used, these spatial features can also have considerable strength.

SiC空間結構之實施例可具有以下彈性模數：約100 kPa至約100 MPa、約500 kPa至約500 Mpa、約100 kPa至約1 GPa、約50 kPa至約300 GPa、及較大及較小值，及該些者之組合及變化，以及該些性質範圍內之所有值。Embodiments of SiC spacers may have the following elastic moduli: about 100 kPa to about 100 MPa, about 500 kPa to about 500 MPa, about 100 kPa to about 1 GPa, about 50 kPa to about 300 GPa, and larger and higher Small values, and combinations and variations of these, and all values within the range of these properties.

SiC空間結構之實施例可具有以下硬度：約10 Kg/mm ²至約2,500 Kg/mm ²、約10 Kg/mm ²至約1,500 Kg/mm ²、約100 Kg/mm ²至約2,000 Kg/mm ²、約150 Kg/mm ²至約1,000 Kg/mm ²、約300 Kg/mm ²至約1,750 Kg/mm ²、及較大及較小值，及該些者之組合及變化，以及該些性質範圍內之所有值。 Embodiments of SiC spacers may have the following hardnesses: about 10 Kg/mm ² to about 2,500 Kg/mm ² , about 10 Kg/mm ² to about 1,500 Kg/mm ² , about 100 Kg/mm ² to about 2,000 Kg/mm 2 mm ² , about 150 Kg/mm ² to about 1,000 Kg/mm ² , about 300 Kg/mm ² to about 1,750 Kg/mm ² , and larger and smaller values, and combinations and variations thereof, and the All values within the range of these properties.

SiC空間結構之實施例可具有以下剛度：約5 kPa至約15 MPa、約10 kPa至約10 MPa、約100 kPa至約1 MPa、及大於或等於約10 kPa、大於或等於約100 kPa、及大於或等於約1 MPa、及較大及較小值，及該些者之組合及變化，以及該些性質範圍內之所有值。Embodiments of SiC spacers may have stiffnesses of about 5 kPa to about 15 MPa, about 10 kPa to about 10 MPa, about 100 kPa to about 1 MPa, and greater than or equal to about 10 kPa, greater than or equal to about 100 kPa, and greater than or equal to about 1 MPa, and greater and lesser values, and combinations and variations thereof, and all values within the range of these properties.

SiC空間結構之實施例可具有以下壓縮強度：約1 MPa至約3.5 GPa、約10 MPa至約2.5 GPa、約50 MPa至約1 GPa、約50 MPa至約750 MPa、約100 MPa至約2 GPa、約200 MPa至約800 MPa、及較大及較小值，及該些者之組合及變化，以及該些性質範圍內之所有值。Embodiments of SiC spacers may have the following compressive strengths: about 1 MPa to about 3.5 GPa, about 10 MPa to about 2.5 GPa, about 50 MPa to about 1 GPa, about 50 MPa to about 750 MPa, about 100 MPa to about 2 GPa, about 200 MPa to about 800 MPa, and higher and lower values, and combinations and variations thereof, and all values within the range of these properties.

在可視為較高強度實施例的該些結構之實施例中，該些SiC空間結構可具有：彈性模數，其小於約200 MPa、小於約150 MPa、小於約75 MPa、及小於約10 MPa及較小值；硬度，其小於約1,400 Kg/mm ²、小於約800 Kg/mm ²、小於約400 Kg/mm ²、小於約100 Kg/mm ²及較小值；及，壓縮強度，其小於約1,850 MPa、小於約1,000 MPa、小於約750 MPa、小於約200 MPa、小於約50 MPa、及較小值，及該些者之組合及變化，以及該些性質範圍內之所有值。 In embodiments of the structures, which may be considered higher strength embodiments, the SiC spacers may have a modulus of elasticity less than about 200 MPa, less than about 150 MPa, less than about 75 MPa, and less than about 10 MPa and less; hardness, which is less than about 1,400 Kg/mm ² , less than about 800 Kg/mm ² , less than about 400 Kg/mm ² , less than about 100 Kg/mm ² and less; and, compressive strength, which Less than about 1,850 MPa, less than about 1,000 MPa, less than about 750 MPa, less than about 200 MPa, less than about 50 MPa, and smaller values, and combinations and variations thereof, and all values within these properties.

該些SiC空間結構可具有：彈性模數，其大於或等於約100 MPa、大於或等於約200 MPa、及大於或等於300 MPa；硬度，其大於或等於約700 Kg/mm ²、大於或等於約1,000 Kg/mm ²、及大於或等於約2,000 Kg/mm ²；及，壓縮強度，其大於或等於約50 MPa、大於或等於約200 MPa、及大於或等於約500 MPa，及該些者之組合及變化，以及該些性質範圍內之所有值。 The SiC spatial structures may have: a modulus of elasticity greater than or equal to about 100 MPa, greater than or equal to about 200 MPa, and greater than or equal to 300 MPa; a hardness of greater than or equal to about 700 Kg/mm ² , greater than or equal to About 1,000 Kg/mm ² , and greater than or equal to about 2,000 Kg/mm ² ; and, compressive strength, which is greater than or equal to about 50 MPa, greater than or equal to about 200 MPa, and greater than or equal to about 500 MPa, and these combinations and variations, and all values within the range of these properties.

在可視為具有較低強度的該些空間結構之實施例中，該些實施例可具有較低或較小剛度值。例如，剛度減至10 MPa或更小。在該些較低強度結構之實施例中，例如可使用烴蠟且顯著地提供比例如陶瓷黏合劑更少的剛度。In embodiments of the spatial structures that may be considered to have lower strength, the embodiments may have lower or smaller stiffness values. For example, the stiffness is reduced to 10 MPa or less. In embodiments of these lower strength structures, hydrocarbon waxes, for example, may be used and provide significantly less stiffness than, for example, vitrified adhesives.

大體上，在一些實施例中，該些SiC空間形體弱於其下伏SiC材料，該下伏SiC材料構成其結構，且具有以下報告值：約410 GPa之彈性模數、約2,800 Kg/mm ²之硬度及約3,900 MPa之壓縮強度，該些者之組合及變化，以及該些性質範圍內之所有值。藉由氦比重測定法量測的SiC之實際密度為約3.0至3.5 g/cc、或約3.1至3.4 g/cc、或約3.2至3.3 g/cc，及該些者之組合及變化，以及該些性質範圍內之所有值。例如團塊、彈丸等等的SiC之空間形體之實施例的表觀密度或比重可顯著更低。 In general, in some embodiments, the SiC spacers are weaker than the underlying SiC material that makes up their structure and have the following reported values: elastic modulus of about 410 GPa, about 2,800 Kg/mm ² and compressive strength of about 3,900 MPa, combinations and variations of these, and all values within the range of these properties. the actual density of SiC as measured by helium pycnometric method is about 3.0 to 3.5 g/cc, or about 3.1 to 3.4 g/cc, or about 3.2 to 3.3 g/cc, and combinations and variations thereof, and All values within the range of these properties. Embodiments of spatial features of SiC such as pellets, pellets, etc. may have significantly lower apparent densities or specific gravity.

在實施例中，SiC之空間形體之質量較佳地及典型地具有比其SiC實際密度低的表觀密度，例如，SiC顆粒之實際密度應為約3.1 g/cc至3.3 g/cc。空間形體(例如，圓片、團塊、立方體、球、珠粒、圓盤或板)之表觀密度可小於約3 g/cc、小於約2 g/cc、小於約1 g/cc及更低，且可為約0.5 g/cc至約1.8 g/cc、約0.4 g/cc至約2 g/cc。SiC之粒子的體密度可小於約3.0 g/cc、小於約2.0 g/cc、小於約1 g/cc、及約0.1 g/cc至約2 g/cc、0.5 g/cc至約1.5 g/cc。亦涵蓋較大及較低表現密度及體密度。此外，聚合物衍生SiC之空間形體的特定，亦即，預定及精確表現密度可提供來匹配，且較佳地增進且更佳地最佳化稍後的製造製程。例如，在PVT晶圓製造中，SiC顆粒之空間形體可具有經特定設計及特製來匹配特定PVT設備之表觀密度。以此方式，設施中的每一PVT設備可具有客製進料儲備，其藉由使用具有預定及精確特性的進料儲備(例如，SiC之空間形體)賦能每一設備之效能得以最佳化，該等特性諸如形狀、體積、重量、填積因子、體密度、敲緊密度、及表觀密度。In an embodiment, the quality of the SiC spatial features preferably and typically has an apparent density lower than the actual density of SiC, eg, the actual density of SiC particles should be about 3.1 g/cc to 3.3 g/cc. Apparent densities of spatial forms (e.g., discs, pellets, cubes, spheres, beads, discs, or plates) can be less than about 3 g/cc, less than about 2 g/cc, less than about 1 g/cc, and more Low, and can be from about 0.5 g/cc to about 1.8 g/cc, from about 0.4 g/cc to about 2 g/cc. Particles of SiC can have a bulk density of less than about 3.0 g/cc, less than about 2.0 g/cc, less than about 1 g/cc, and about 0.1 g/cc to about 2 g/cc, 0.5 g/cc to about 1.5 g/cc cc. Greater and lower apparent densities and volume densities are also covered. Furthermore, the specificity of the spatial morphology of polymer derived SiC, ie a predetermined and precise representation density can be provided to match and preferably enhance and better optimize the later manufacturing process. For example, in PVT wafer fabrication, the spatial profile of SiC particles can have a specifically designed and tailored apparent density to match a particular PVT device. In this way, each PVT device in a facility can have a custom feedstock that enables the performance of each device to be optimized by using a feedstock with predetermined and precise characteristics (e.g., SiC's spatial profile) Chemical properties such as shape, volume, weight, packing factor, bulk density, tapped density, and apparent density.

在實施例中，SiC之空間形體可具有建構在形體中的多孔性，其較佳地藉由黏合劑或連同黏合劑一起提供。此多孔性係較佳地為開孔、或實質上開孔多孔性。以此方式，空間形體典型地提供比粒狀SiC實質上大的可用表面面積，因為形體之結構包括將不會存在於SiC粒子之疏鬆堆中的孔隙表面，例如，顆粒彼此抵靠填積的情況。因此，例如，若SiC之圓盤係用於氣相沉積製程以製成SiC胚晶(用於後續轉化成SiC晶圓)，則相較可典型地自在此種製程中使用粒狀SiC所獲得者而言，該些SiC圓盤將提供實質上更大的表面面積以自其產生SiC蒸汽，及用於SiC蒸汽之移動的實質上更大路徑。理論上，增加的表面面積及增加的路徑提供增加SiC胚晶之生長速率、SiC胚晶(及因此後續晶圓)之品質及此二者的能力。SiC圓盤，例如，SiC之空間形體可比粒狀SiC材料更易於操縱、量測、及使用。In an embodiment, the spatial features of SiC may have porosity built into the features, preferably provided by or in conjunction with a binder. The porosity is preferably open-cell, or substantially open-cell porosity. In this way, spatial features typically provide substantially greater usable surface area than granular SiC because the structure of the features includes pore surfaces that would not exist in a loose pack of SiC particles, e.g., where the particles pack against each other. Condition. Thus, for example, if a disk of SiC is used in a vapor deposition process to make SiC embryos (for subsequent conversion into SiC wafers), then compared to that typically obtained from the use of granular SiC in such a process Alternatively, the SiC discs will provide a substantially larger surface area from which to generate SiC vapor, and a substantially larger path for movement of the SiC vapor. In theory, the increased surface area and increased pathways provide the ability to increase the growth rate of the SiC embryo, the quality of the SiC embryo (and thus the subsequent wafer), and both. SiC discs, for example, SiC spatial features can be easier to manipulate, measure, and use than granular SiC material.

在實施例中，空間形體可由SiC之顆粒製成，該等顆粒藉由將自熱解爐移除的SiC之易碎質塊***開來獲得。就此而言，可控制用於製造空間形體的顆粒大小。在一些實施例中，此舉亦提供對黏合劑添加及混合製程的較大控制。In an embodiment, the spatial body can be made of particles of SiC obtained by breaking apart a friable mass of SiC removed from a pyrolysis furnace. In this regard, the size of the particles used to create the spatial features can be controlled. In some embodiments, this also provides greater control over the binder addition and mixing process.

對實施例而言，SiC之易碎質塊較佳地及典型地具有比其實際密度顯著更低的表觀密度，例如，實際密度應為約3.2 g/cc。大體上，自壓碎易碎質塊獲得的粒狀SiC具有基本上相等的表現密度及實際密度，例如，約3.1至3.3 g/cc。For embodiments, the friable mass of SiC preferably and typically has an apparent density that is significantly lower than its actual density, eg, the actual density should be about 3.2 g/cc. In general, granular SiC obtained from crushing friable masses has substantially equal apparent and actual densities, eg, about 3.1 to 3.3 g/cc.

高純度多晶碳氧矽SiC之特徵提供在氣相沉積製程、系統及設備、以及用於生長或產生SiC質塊、結構、製品或空間形體的其他技術中例如作為Si及C來源或起始材料使用之若干優點及益處。該些特徵包括：具有高純度位準之能力、高純度位準、控制粒子大小分佈(形狀、大小及兩者)之能力；預定粒子大小分佈；具有空間形體之能力；預定空間形體(例如，圓片、彈丸、圓盤等等)；具有多孔性及控制多孔性之能力；預定多孔性；控制碳之量的能力；預定碳量(皆過量，亦即，大於化學計量，貧量，亦即，小於化學計量，及等於，亦即，化學計量)；及該些及其他性質之組合及變化。雖然可看到本發明之另外的優點，但當前來說及舉例而言，氣相沉積製程中之該些優點將包括縮短生長胚晶或其他結構的時間、在清潔之前的較長運作時間、最佳化設備之能力、生長較大直徑胚晶或其他結構的能力、增加品質之能力、減少來自胚晶或其他結構的問題區域、問題區或問題發生率(例如，管、阻塞、缺陷)之能力、降低成本、對製程的較大控制、該些者之組合及變化。Characterization of high-purity polycrystalline silicon oxycarbide SiC provides for example as a source or starting point for Si and C in vapor deposition processes, systems and equipment, and other techniques for growing or producing SiC masses, structures, articles or spatial features Some advantages and benefits of using the material. These characteristics include: ability to have high purity level, high purity level, ability to control particle size distribution (shape, size and both); predetermined particle size distribution; ability to have spatial shape; predetermined spatial shape (e.g., discs, pellets, disks, etc.); having porosity and the ability to control porosity; predetermined porosity; ability to control the amount of carbon; predetermined amount of carbon (both excess, i.e., greater than stoichiometric, lean, also ie, less than stoichiometric, and equal to, ie, stoichiometric); and combinations and variations of these and other properties. While additional advantages of the present invention may be seen, such advantages in vapor deposition processes, presently and by way of example, would include reduced time to grow embryos or other structures, longer run times before cleaning, Ability to optimize equipment, ability to grow larger diameter embryos or other structures, ability to increase quality, reduce problem areas, problem areas, or incidence of problems (e.g., tubes, clogs, defects) from embryos or other structures capabilities, cost reduction, greater control over the process, combinations and variations of these.

在實施例中，若需要將摻雜劑添加至材料，則其可藉助於前驅物添加且因此以用於生長成胚晶、或其他結構的受控方式及量存在。前驅物調配物之實施例可具有摻雜劑或複合物，該等複合物運載及結合摻雜劑至陶瓷中且隨後轉化SiC，以便在氣相沉積製程時摻雜劑為可利用的且呈可使用形式的。In an embodiment, if a dopant needs to be added to the material, it can be added by means of a precursor and thus present in a controlled manner and amount for growth into an embryonic crystal, or other structure. Embodiments of the precursor formulation may have dopants or complexes that carry and bind the dopants into the ceramic and subsequently convert SiC so that the dopants are available and present during the vapor deposition process. available form.

另外，摻雜劑或其他添加劑為由聚合物衍生SiC之實施例製得的晶圓、層及結構提供客製或預定的性質。在此等實施例中，此種增進性質的添加劑將不視為雜質，因為其意欲處於、必要時必須處於最終產品中。增進性質之添加劑可併入液體前驅物材料。取決於增進性質之添加劑的特性，其可為前驅物骨幹之一部分，其可為複合的、或複合物之部分，或將其併入液體前驅物中，或其可以其他形式存在，從而賦能其保存(例如，呈使其在最終材料中按所欲起作用的形式)。增進性質之添加劑亦可作為塗層添加至SiC或SiOC粉末材料，可在處理期間作為蒸汽或氣體添加，或可呈粉末形式且與聚合物衍生SiC或SiOC粒子混合，僅舉幾例。在實施例中，增進性質之添加劑包含用於空間形體之黏合劑或為黏合劑之一部分。在實施例中，增進性質之添加劑可為空間形體上之塗層。另外，增進性質之添加劑存在的形式及方式應較佳地使得其對最終產品之處理條件、處理時間、及品質具有最少不利效應及更佳地不具有不利效應。因此，具有大於5個九純度、大於6個九純度及大於7個九純度的多晶碳氧矽衍生SiC或SiC空間形體可具有大量存在的增進性質之添加劑。該些量可為約0.01%至約50%、約0.1%至約5%、約1%至約10%、小於25%、小於20%、小於10%及小於1%，以及較大及較小量，此取決於添加劑及其意欲賦予的預定性質。In addition, dopants or other additives provide customized or predetermined properties to wafers, layers, and structures made from embodiments of polymer-derived SiC. In these examples, such property-enhancing additives would not be considered impurities, as they are intended to be, and if necessary must be, in the final product. Property-enhancing additives may be incorporated into the liquid precursor material. Depending on the nature of the property-enhancing additive, it may be part of the backbone of the precursor, it may be complex, or part of a complex, or it may be incorporated into the liquid precursor, or it may exist in other forms to enable It is preserved (eg, in a form that enables it to function as intended in the final material). Property enhancing additives may also be added to SiC or SiOC powder materials as a coating, may be added as a vapor or gas during processing, or may be in powder form and mixed with polymer derived SiC or SiOC particles, just to name a few. In an embodiment, the property-enhancing additive comprises or is part of a binder for the spatial form. In an embodiment, the property-enhancing additive may be a coating on the spatial form. In addition, the property-enhancing additive should preferably be present in a form and in such a manner that it has the least and preferably no adverse effects on the processing conditions, processing time, and quality of the final product. Thus, polycrystalline silicon oxycarbide derived SiC or SiC steric bodies with greater than 5 nines, greater than 6 nines, and greater than 7 nines may have a substantial presence of property-enhancing additives. These amounts can be from about 0.01% to about 50%, from about 0.1% to about 5%, from about 1% to about 10%, less than 25%, less than 20%, less than 10%, and less than 1%, as well as greater and less Small amounts, depending on the additive and the intended properties it is intended to impart.

超純聚合物衍生SiC之使用、本發明SiC之空間形體之使用、及本發明之氣相沉積技術之使用個別地及共同地提供優越品質，且當相較於由其他SiC來源，亦即，基於非聚合物衍生陶瓷的SiC製得的胚晶及晶圓時，減少由該些超純聚合物衍生材料製得的胚晶、晶圓及半導體中之缺陷。雖然不受當前理論約束，但咸信用於自液體SiOC起始材料，例如，多晶碳氧矽前驅物獲得超純SiC的聚合物衍生陶瓷製程提供具有與其他SiC來源不同的特徵及形態學之起始原材料，該等差異允許聚合物衍生陶瓷材料在氣相沉積技術中比其他SiC來源顯著更好地預成型。進一步，咸信本發明之空間形體及氣相沉積技術提供進一步得益於超純聚合物衍生SiC之益處及協同地依賴該等益處的能力。此外，當聚合物衍生陶瓷SiC係用作晶種時，咸信可達成超過其他SiC晶種的胚晶及晶圓品質及製造效率之另外增進。The use of ultrapure polymer derived SiC, the use of the spatial morphology of the SiC of the present invention, and the use of the vapor deposition technique of the present invention individually and collectively provide superior quality when compared to SiC derived from other SiC sources, namely, Reduction of defects in embryos, wafers, and semiconductors made from these ultrapure polymer-derived materials when based on SiC-based embryos and wafers that are not polymer-derived ceramics. While not being bound by current theory, it is believed that the polymer-derived ceramic process for obtaining ultrapure SiC from liquid SiOC starting materials, e.g., polycrystalline silicon oxycarbide precursors, provides the ability to have characteristics and morphologies that are distinct from other SiC sources. Starting raw materials, these differences allow polymer derived ceramic materials to be preformed significantly better in vapor deposition techniques than other SiC sources. Further, it is believed that the spatial shape and vapor deposition techniques of the present invention provide the ability to further benefit from the benefits of ultrapure polymer derived SiC and to synergistically rely on these benefits. Furthermore, when the polymer-derived ceramic SiC system is used as the seed, it is believed that additional improvements in embryo and wafer quality and manufacturing efficiency over other SiC seeds can be achieved.

因此，咸信及在理論上，來自超純聚合物衍生SiC之使用、本發明SiC之空間形體之使用、及本發明之氣相沉積技術之使用的利益及改良特徵個別地及共同地包括以下性質及特徵中至少一者或更多者及較佳地全部的增進及改良，及以下有害性質或效應中至少一者或更多者及較佳地全部的減少(以達到其在使用習知SiC起始材料的氣相沉積製程中存在的程度)：Accordingly, it is believed and theorized that the benefits and improved features from the use of ultrapure polymer derived SiC, the use of the spatial morphology of SiC of the present invention, and the use of the vapor deposition technique of the present invention individually and collectively include the following The improvement and improvement of at least one or more and preferably all of the properties and characteristics, and the reduction of at least one or more and preferably all of the following harmful properties or effects (in order to achieve the Existence in the vapor phase deposition process of SiC starting material):

彎曲度—晶圓之中間面的凹入或凸起變形之量度，其獨立於可存在的任何厚度變化。彎曲度在晶圓之中心點處相對於參考平面測定，其係藉由在直徑比標稱晶圓直徑小6.35 mm的圓上等間隔的三個點來測定。彎曲度為晶圓之整體性質、而非暴露表面之性質。通常，彎曲度係利用處於自由、無夾持位置中的晶圓來測定。(不與翹曲度混淆。)Bowness—a measure of the concave or convex deformation of the midplane of the wafer, independent of any thickness variations that may exist. Bow is measured at the center point of the wafer relative to a reference plane by taking three points equally spaced on a circle with a diameter 6.35 mm less than the nominal wafer diameter. Bow is a bulk property of the wafer, not a property of exposed surfaces. Typically, bow is measured using the wafer in a free, unclamped position. (Not to be confused with warpage.)

直徑—跨於圓形矽晶圓之直線距離，其包括晶圓中心且排除任何平坦或其他周邊基準區域。Diameter—The linear distance across a circular silicon wafer that includes the center of the wafer and excludes any flat or other peripheral reference areas.

邊緣輪廓—藉由研磨或蝕刻成形的晶圓邊緣之橫截面外形。邊緣可為倒圓或傾斜的。Edge Profile - The cross-sectional shape of a wafer edge formed by grinding or etching. Edges may be rounded or beveled.

平坦度—對晶圓表面而言，當晶圓之背表面理想地為平坦時，如當藉由真空向下牽引至理想的清潔平坦卡盤上時，前表面相對於指定參考平面之偏差，其係表達為TIR或最大FPD。晶圓之平坦度可描述為：總體平坦度；位點平坦度之最大值，如在所有位點上所量測的；或具有等於或小於指定值之位點平坦度的位點之百分比。Flatness—For a wafer surface, the deviation of the front surface from a specified reference plane when the back surface of the wafer is ideally flat, such as when pulled down by vacuum onto an ideally clean flat chuck, It is expressed as TIR or maximal FPD. The flatness of a wafer can be described as: overall flatness; the maximum value of site flatness, as measured on all sites; or the percentage of sites with site flatness equal to or less than a specified value.

平坦度品質區域—指定平坦度值施加於其上的晶圓表面之部分。平坦度品質區域係最常用邊緣排除區域(edge exclusion area)來界定，該邊緣排除區域為通常3 mm寬之周邊環帶。Flatness Quality Area—Specifies the portion of the wafer surface to which the flatness value is applied. The flatness quality area is most commonly defined by the edge exclusion area, which is a peripheral ring usually 3 mm wide.

焦平面—垂直於成像系統之光軸的平面，其含有成像系統之焦點。focal plane—the plane perpendicular to the optical axis of the imaging system that contains the focal point of the imaging system.

焦平面偏差(focal plane deviation; FPD)—與光軸平行的自晶圓表面上之一點至焦平面的距離。總體平坦度—平坦度品質區域內相對於指定參考平面的TIR或最大FPD。focal plane deviation (FPD)—the distance parallel to the optical axis from a point on the wafer surface to the focal plane. Overall Flatness—The TIR or maximum FPD within the flatness quality area relative to a specified reference plane.

最大FPD-焦平面偏差之絕對值中最大者。Maximum FPD - the largest of the absolute values of the focal plane deviation.

主平坦面—相對於特定結晶學平面定向的最長長度之平坦面。亦稱為主要平坦面。Principal Planar Plane - the planar face of longest length oriented relative to a particular crystallographic plane. Also known as the major flat face.

參考平面—藉由以下一者指定的平面：在晶圓之前表面上的指定位置處的三個點；使用平坦度品質區域內的所有點對晶圓之前表面的最小平方擬合；使用一位點內的所有點對晶圓之前表面的最小平方擬合；或理想背表面(等效於接觸晶圓的理想平坦卡盤表面)。Reference Plane—a plane specified by either: three points at specified locations on the front surface of the wafer; a least squares fit to the front surface of the wafer using all points within the flatness quality region; using a bit A least squares fit of all points within a point to the front surface of the wafer; or the ideal back surface (equivalent to an ideal flat chuck surface touching the wafer).

次平坦面—具有短於主平坦面之長度的長度之一或多個平坦面，其角坐標相對於主平坦面而言識別晶圓之傳導性類型及定向。亦稱為次要平坦面。Secondary planar surface - one or more planar surfaces having a length shorter than that of the primary planar surface, the angular coordinates of which identify the conductivity type and orientation of the wafer relative to the primary planar surface. Also known as a secondary flat.

位點—晶圓之前表面上的矩形區域，其側面平行於及垂直於主平坦面且其中心落在平坦度品質區域內。Site—a rectangular area on the front surface of a wafer with sides parallel and perpendicular to the major planar plane and whose center falls within the flatness quality region.

位點平坦度—落在平坦度品質區域內的位點之部分的TIR或最大FPD。Site Flatness - TIR or maximum FPD for the portion of the site that falls within the flatness quality region.

厚度—在前表面及背表面上的相應點之間穿過晶圓的距離。Thickness - the distance across the wafer between corresponding points on the front and back surfaces.

總指示器讀值(total indicator reading; TIR)—在皆與參考平面平行的兩個平面之間的最小垂直距離，該等平面包圍晶圓之前表面上的指定平坦度品質區域或位點內的所有點。total indicator reading (TIR)—the minimum vertical distance between two planes, both parallel to the reference plane, that enclose a specified flatness quality area or site on the front surface of the wafer all points.

總厚度變化(total thickness variation; TTV)—在晶圓上的掃描模式或一系列點量測期間遇到的最大厚度值與最小厚度值之間的差異。total thickness variation (TTV)—the difference between the maximum and minimum thickness values encountered during a scan pattern or series of spot measurements on a wafer.

翹曲度—在掃描模式期間遇到的晶圓之中間面距離參考平面的最大距離與最小距離之間的差異。翹曲度為晶圓之整體性質、而非暴露表面之性質。中間面可含有具有向上或向下曲率或兩者的區域。通常，翹曲度係利用處於自由、無夾持位置中的晶圓來測定。(不與彎曲度混淆。)Warpage—The difference between the maximum and minimum distances of the inter-wafer midplanes from the reference plane encountered during scan mode. Warpage is a property of the bulk of the wafer, not of exposed surfaces. The midplane may contain regions with upward or downward curvature or both. Typically, warpage is measured using the wafer in a free, unclamped position. (Not to be confused with curvature.)

自摻雜—來自不同於有意添加至汽相的摻雜劑之來源的摻雜劑，其係在生長期間併入磊晶層中。Self-doping - dopants from sources other than those intentionally added to the vapor phase that are incorporated into the epitaxial layer during growth.

自摻雜阻障—在磊晶沉積期間阻止雜質原子自基板之背表面傳輸至磊晶層的膜或層。亦稱為倒密封層(backseal)。Self-doping barrier - a film or layer that prevents the transport of impurity atoms from the back surface of the substrate to the epitaxial layer during epitaxial deposition. Also known as backseal.

傳導性類型—定義在矽中大多數載流子之性質：其中電子為主體載流子的N型材料係在供體摻雜劑雜質添加至矽時形成；其中電洞為主體載流子的P型材料係在受體摻雜劑雜質添加至矽時形成。Conductivity Type—Defines the nature of the majority carriers in silicon: N-type materials, where electrons are the majority carriers, are formed when donor dopant impurities are added to the silicon; P-type material is formed when acceptor dopant impurities are added to silicon.

晶體定向—結晶軸，矽晶體係生長在該結晶軸上。Crystal Orientation - The crystallographic axis on which the silicon crystal system grows.

錯位—晶體中之線缺陷，其形成晶體之滑動及非滑動區域之間的邊界。Dislocation - a linear defect in a crystal that forms a boundary between slipping and non-slipping regions of the crystal.

錯位密度—在暴露晶圓表面上每單位面積的錯位蝕坑之數量。Dislocation Density—The number of dislocation etch pits per unit area on the exposed wafer surface.

錯位蝕坑—在受應力或缺陷晶格之最接近區域中的尖銳限定凹陷，其由優先蝕刻產生。Dislocation Etch Pit - A sharply defined depression in the immediate region of a stressed or defective crystal lattice, created by preferential etching.

摻雜劑—來自週期表之第三(諸如硼)或第五(諸如磷或銻)欄之化學元素，其係以痕量有意地併入矽晶體中以建立其傳導性類型及電阻率。P型硼，0,001-50 ohmcm；N型磷，0,1-40 ohmcm；銻0,005-0,025 ohmcm；砷＜ 0,005 ohmcm。Dopant - A chemical element from the third (such as boron) or fifth (such as phosphorus or antimony) column of the periodic table that is intentionally incorporated in trace amounts into a silicon crystal to establish its conductivity type and resistivity. P-type boron, 0,001-50 ohmcm; N-type phosphorus, 0,1-40 ohmcm; antimony 0,005-0,025 ohmcm; arsenic < 0,005 ohmcm.

異質吸除—藉由機械手段或藉由將多晶矽或其他膜沉積在矽晶圓之背表面上而有意引入的對晶體結構之受控破壞或應力。Hetero gettering - Controlled damage or stress to the crystal structure introduced intentionally by mechanical means or by depositing polysilicon or other films on the back surface of the silicon wafer.

平坦定向(主)—結晶學平面，其理想地與主平坦面之表面重合。主平坦面通常為＜110＞平面。Planar Orientation (Principal) - A crystallographic plane that ideally coincides with the surface of the principal planar plane. The main planar surface is usually a <110> plane.

米勒指數—分別具有x軸、y軸、及z軸的結晶學平面之截距的倒數。例如，垂直於x軸的立方體面為＜100＞平面。平面族係藉由波形括號表示；例如，所有立方體面為＜100＞平面。方向係藉由方括號中的米勒指數表示；例如，x軸為＜100＞方向，立方體對角線為＜111＞方向。方向族係藉由尖括號表示；例如，所有立方軸為＜100＞方向。負方向係藉由指數上之負號表示；例如，負x軸為＜ ^—100＞方向。 Miller Index—the reciprocal of the intercept of a crystallographic plane having an x-axis, y-axis, and z-axis, respectively. For example, a cube face perpendicular to the x-axis is a <100> plane. Plane families are indicated by curly brackets; for example, all cube faces are <100> planes. Directions are indicated by Miller indices in square brackets; for example, the x-axis is the <100> direction, and the cube diagonal is the <111> direction. Orientation families are indicated by angle brackets; for example, all cube axes are <100> orientation. Negative directions are indicated by a negative sign on the exponent; for example, a negative x-axis is < ^- 100> direction.

多晶矽(多矽、聚矽)—由隨機定向微晶構成且含有大角度顆粒邊界、雙晶界、或兩者的矽。Polycrystalline silicon (polysilicon, polysilicon)—silicon composed of randomly oriented crystallites and containing high-angle grain boundaries, twin grain boundaries, or both.

徑向氧變化—在對稱地位於矽晶圓上的一或多個點處的平均氧濃度與在晶圓之中心處的氧濃度之間的差異，其係表達為在中心處的濃度之百分比。除非另作說明，徑向氧變化係使用在離晶圓之邊緣10 mm的兩個點處的氧濃度之平均值來測定。徑向氧變化有時係使用在中心與晶圓之邊緣之間半程處的若干對稱點處的氧濃度之平均值來測定。亦稱為氧梯度。Radial Oxygen Variation—the difference between the average oxygen concentration at one or more points symmetrically located on the silicon wafer and the oxygen concentration at the center of the wafer, expressed as a percentage of the concentration at the center . Radial oxygen variation is determined using the average of the oxygen concentration at two points 10 mm from the edge of the wafer, unless otherwise stated. Radial oxygen variation is sometimes measured using the average of the oxygen concentrations at several symmetrical points halfway between the center and the edge of the wafer. Also known as oxygen gradient.

徑向電阻率變化—在對稱地位於矽晶圓上的一或多個點處的平均電阻率與在晶圓之中心處的電阻率之間的差異，其係表達為在中心處的電阻率之百分比。除非另作說明，否則徑向電阻率變化可使用在兩個垂直直徑上離晶圓之邊緣6 mm的四個點之平均電阻率來測定。徑向電阻率變化有時係使用在相同直徑上在中心與晶圓之邊緣之間半程處的四個點處的電阻率之平均值來測定。亦稱為電阻率梯度。Radial Resistivity Variation—the difference between the average resistivity at one or more points symmetrically located on the silicon wafer and the resistivity at the center of the wafer, expressed as the resistivity at the center percentage. Unless otherwise stated, radial resistivity variation can be determined using the average resistivity at four points 6 mm from the edge of the wafer on two perpendicular diameters. Radial resistivity variation is sometimes determined using the average of the resistivities at four points on the same diameter halfway between the center and the edge of the wafer. Also known as resistivity gradient.

電阻率(ohm cm)—與電流平行的電位梯度(電場)對電流密度之比率。在矽中，電阻率係藉由添加摻雜劑雜質來控制；較低電阻率係藉由添加更多摻雜劑來達成。Resistivity (ohm cm)—the ratio of the potential gradient (electric field) parallel to the current flow to the current density. In silicon, resistivity is controlled by adding dopant impurities; lower resistivity is achieved by adding more dopants.

滑動—一種塑性變形過程，其中晶體之一部分相對於另一部分以保存矽之結晶度的方式經歷剪切位移。在優先蝕刻之後，滑動係藉由每毫米10個或更多個錯位蝕坑之一或多個平行直線的圖案來表明，該等錯位蝕坑不必為彼此的。在＜111＞表面上，多組線係以彼此60°傾斜；在＜100＞表面上，其係以彼此90°傾斜。Slip—A plastic deformation process in which one part of a crystal undergoes a shear displacement relative to another in a manner that preserves the crystallinity of the silicon. After preferential etching, slippage is indicated by a pattern of one or more parallel lines of 10 or more dislocation etch pits per mm, which do not have to be relative to each other. On the <111> surface, the sets of lines are inclined at 60° to each other; on the <100> surface, they are inclined at 90° to each other.

疊積缺層—由與晶體中原子之正常疊積序列的偏差產生的二維缺陷。其可存在於主體晶體中，在磊晶沉積期間生長(通常係由受污染或結構上不完整的基板表面產生)；或在氧化期間生成。在＜111＞表面上，疊積缺層係藉由優先蝕刻顯露為閉合或者部分等邊三角形。在＜100＞表面上，疊積缺層係顯露為閉合或部分正方形。Stacking Defects - Two-dimensional defects resulting from deviations from the normal stacking sequence of atoms in a crystal. It can be present in host crystals, grown during epitaxial deposition (often resulting from contaminated or structurally incomplete substrate surfaces); or generated during oxidation. On the <111> surface, the build-up defects are revealed as closed or partially equilateral triangles by preferential etching. On the <100> surface, the laminated defect system appears as closed or partially square.

條紋—矽晶圓之表面上與雜質濃度之局部變化相關聯的螺旋特徵。此種變化係歸結於在晶體生長期間在旋轉固-液界面處發生的摻雜劑併入中的週期性差異。在優先蝕刻之後條紋係肉眼可見的且在100倍放大率下呈現為連續的。Streak - a helical feature on the surface of a silicon wafer associated with local variations in impurity concentration. This variation is attributed to periodic differences in dopant incorporation that occurs at the rotating solid-liquid interface during crystal growth. Streaks were visible to the naked eye after preferential etching and appeared continuous at 100X magnification.

表面下破壞—僅在拋光矽表面之優先蝕刻之後明顯的殘留結晶學不完整性。此種破壞通常係視為藉由晶圓之機械處理引起。Subsurface damage—residual crystallographic imperfections evident only after preferential etching of polished silicon surfaces. Such damage is generally considered to be caused by mechanical handling of the wafer.

雙晶—其中晶格由在定向上作為跨於稱為雙晶平面或雙晶邊界的相干平面界面之鏡像彼此有關的兩個部分組成的晶體。在矽中，此平面為＜111＞平面。亦稱為雙晶。Twin - a crystal in which the crystal lattice consists of two parts related to each other in orientation as mirror images across a coherent plane interface known as the twin plane or twin boundary. In silicon, this plane is the <111> plane. Also known as twin crystals.

晶圓定向—就米勒指數描述的結晶學平面，具有此結晶學平面的晶圓之表面係理想地重合的。一般地，晶圓之表面在幾度內與垂直於生長軸的低指數平面相應。在此等情況下，定向亦可就低指數結晶學平面與拋光晶圓表面之角度偏差描述。Wafer Orientation—A crystallographic plane described by the Miller indices with which the surfaces of wafers are ideally coincident. Typically, the surface of the wafer corresponds to a low-index plane perpendicular to the growth axis within a few degrees. In these cases, orientation can also be described in terms of the angular deviation of the low-index crystallographic plane from the polished wafer surface.

碎屑—其中材料已自晶圓之表面或邊緣移除的區域。碎屑之大小係由其最大徑向深度及周邊弦長界定，如在試樣輪廓線之正射陰影投影上所量測的。亦稱為蛤殼、貝殼狀斷口、邊緣碎屑、薄片、凹痕、周邊碎屑、周邊壓痕、及表面碎屑。Debris - An area where material has been removed from the surface or edge of a wafer. The size of the debris is defined by its maximum radial depth and peripheral chord length, as measured on the orthographic projection of the sample contour. Also known as clamshells, conchoids, edge chips, flakes, dimples, peripheral chips, peripheral indentations, and surface chips.

污染—在晶圓表面上肉眼可見的廣泛種類之外來物質。在大多數情況下，其可藉由氣體吹洩、清潔劑洗滌、或化學作用來移除。亦參見微粒污染、汙跡。Contamination - A broad variety of foreign matter visible to the naked eye on the wafer surface. In most cases, it can be removed by gas blowing, detergent washing, or chemical action. See also particulate contamination, smear.

裂紋—延伸至晶圓之表面的裂縫，其可或可不穿過晶圓之整體厚度。亦稱為裂隙；亦參見裂痕。Crack - a crack that extends to the surface of the wafer, which may or may not pass through the entire thickness of the wafer. Also called fissure; see also fissure.

凹蝕—具有光滑中心區域的不規則閉合脊部之表面紋理。鴉爪紋(crow's-foot)—相交裂紋，其呈類似於在＜111＞表面上之「鴉爪」(Y)及＜100＞表面上之十字的圖案。Etch - A surface texture of irregular closed ridges with a smooth central region. Crow's-foot—an intersecting crack in a pattern similar to the "crow's-foot" (Y) on the <111> surface and the cross on the <100> surface.

凹坑—在晶圓表面上之光滑表面凹陷，其直徑大於3 mm。Dimple—a smooth surface depression on a wafer surface, the diameter of which is greater than 3 mm.

裂痕—具有從一點輻射出的單一或多個線之裂紋。Fissure - A fissure having single or multiple lines radiating from a point.

凹槽—具有倒圓邊緣的淺劃痕，通常為在拋光期間未完全移除的劃痕之劃痕殘跡。Groove—A shallow scratch with rounded edges, usually the remnant of a scratch that was not completely removed during polishing.

霾—可歸結於因微觀表面不規則性之集中引起的光散射的混濁或模糊外觀，該等不規則性諸如小坑、小丘、小脊或劃痕、粒子等等。Haze - A cloudy or cloudy appearance attributable to light scattering due to concentrations of microscopic surface irregularities, such as pits, hillocks, ridges or scratches, particles, and the like.

嵌入式研磨粒—機械地推入矽晶圓之表面中的研磨粒子。此類型之污染可發生在切片、精磨、或拋光期間。Embedded abrasive particles—abrasive particles that are mechanically pushed into the surface of a silicon wafer. This type of contamination can occur during sectioning, lapping, or polishing.

壓痕—自矽晶圓之前表面延伸至背表面的邊緣缺陷。Indentation - An edge defect extending from the front surface to the back surface of a silicon wafer.

光點缺陷(light point defect; LPD)—在藉由垂直於晶圓表面保持的窄射束光源照明晶圓時看到的個別反射光細點。light point defect (LPD)—an individual fine point of reflected light seen when a wafer is illuminated by a narrow beam light source held perpendicular to the wafer surface.

小丘—具有一或多個小面的不規則形狀投影。小丘可為大塊材料或各種形式之污染或兩者之延伸部分。高密度之小丘亦可呈現為霾。Hillock—An irregularly shaped projection with one or more facets. A hillock may be an extension of bulk material or various forms of contamination or both. High-density hills can also appear as haze.

橙皮—在螢光燈下但通常不在窄射束照明下肉眼可見的類似於橙色皮膚的大型特徵化粗糙表面。Orange Peel—a large, characteristic rough surface resembling orange skin visible to the naked eye under fluorescent lighting but not usually under narrow-beam lighting.

微粒污染—一種污染形式，其包含置於晶圓之表面上且與表面明顯不同的粒子，諸如灰塵、棉絨、或其他材料。可通常利用清潔的乾氮自表面吹洩。Particulate Contamination - A form of contamination that includes particles, such as dust, lint, or other materials, that are placed on the surface of a wafer and are distinct from the surface. Blowing from surfaces can usually be done with clean dry nitrogen.

小坑—表面中之凹陷，其中凹陷之傾斜側面以可辨識方式觸碰晶圓表面(與凹坑之倒圓側面對比)。Dimple—a depression in a surface in which the sloped sides of the depression touch the wafer surface in a identifiable manner (as opposed to the rounded sides of the dimple).

鋸條缺陷—在具有鋸條行進之圖案特性的拋光之後可見的粗造化區域。其在化學拋光之前可為可辨別的。亦稱為鋸痕。Saw Blade Defect - A roughened area visible after polishing with a pattern characteristic of the blade travel. It may be discernible prior to chemical polishing. Also known as saw marks.

劃痕—在表面之確立平面下方的具有大於5:1的長度對寬度比率之淺凹槽或切口。宏觀劃痕係 =0.12 μm深度且在白熾(窄射束)及螢光照明下肉眼可見。微觀劃痕係＜0.12 μm深度且在螢光照明下肉眼不可見。Scratch - A shallow groove or cut below an established plane of a surface having a length to width ratio greater than 5:1. Macroscopic scratches are = 0.12 μm deep and are visible to the naked eye under incandescent (narrow beam) and fluorescent lighting. Microscopic scratches are <0.12 μm deep and invisible to the naked eye under fluorescent lighting.

尖釘—常常發生在磊晶層之表面中的凹部中心處的高的、薄樹枝狀結晶或結晶長絲。Spikes - Tall, thin dendrites or crystalline filaments that often occur in the center of depressions in the surface of an epitaxial layer.

汙跡—一種污染形式，其係諸如含有諸如有機物或鹽的外來化學化合物之條痕、汙斑、或斑點。Stain - a form of contamination such as streaks, stains, or spots containing foreign chemical compounds such as organics or salts.

螺紋邊緣錯位(Threading Edge Dislocation; TED)。Threading Edge Dislocation (TED).

螺紋螺旋位錯(Threading Screw Dislocation; TSD)。Threading Screw Dislocation (TSD).

基部平面錯位(Basal Plan Dislocation; BPD)。Basal Plan Dislocation (BPD).

微管。microtubules.

胚晶中之宏觀缺陷。Macroscopic defects in embryo crystals.

碳夾雜物。carbon inclusions.

矽微滴。Silicon droplets.

空隙。void.

具有以下特徵之晶圓可用聚合物衍生超純SiC材料製成。類型描述 2” 6H N型 6H-N 2"直徑，類型/摻雜劑：N/氮定向：＜0001＞+/-0.5度厚度：330 ± 25 μm D級，MPDa100 cm-2 D級，RT：0.02-0.2 Ω cm 利用CMP單面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 2” 6H N型 6H-N 2”直徑，類型/摻雜劑：N/氮定向：＜0001＞+/-0.5度厚度：330 ± 25 μm B級，MPDa30 cm-2 B級，RT 0.02 ~ 0.2 Ω cm 利用CMP單面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 2” 4H N型 4H-N 2”直徑，類型/摻雜劑：N/氮定向：＜0001＞+/-0.5度厚度：330 ± 25 μm D 級，MPDa100 cm-2 D 級，RT：0.01-0.1 Ω cm D級，彎曲度/翹曲度/TTV＜25um 利用CMP單面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 2” 4H N型 4H-N 2”直徑，類型/摻雜劑：N/氮定向：＜0001＞+/-0.5度厚度：330 ± 25 μm B級，MPDa30 cm-2 B 級，RT：0.01-0.1 Ω cm B 級，彎曲度/翹曲度/TTV＜25um 利用CMP單面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 3” 4H N型 4H-N 3”直徑，類型/摻雜劑：N/氮定向：4度+/-0.5度厚度：350 ± 25 μm D級，MPDa100 cm-2 D級，RT：0.01-0.1 Ω cm D級，彎曲度/翹曲度/TTV＜35um 利用CMP雙面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 3” 4H N型 4H-N 3"直徑，類型/摻雜劑：N/氮定向：4度+/-0.5度厚度：350 ± 25 μm B級，MPDa30 cm-2 B級，RT：0.01-0.1 Ω cm B級，彎曲度/翹曲度/TTV＜35um 利用CMP雙面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 3” 4H SI 4H-SI 3”直徑，類型/摻雜劑：半絕緣/V 定向：＜0001＞+/-0.5度厚度：350 ± 25 μm D 級，MPDa100 cm-2 D級，RT：70 % ≥1E5 Ω cm 利用CMP雙面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 3” 4H SI 4H-SI 3”直徑，類型/摻雜劑：半絕緣/V 定向：＜0001＞+/-0.5度厚度：350 ± 25 μm B級，MPDa30 cm-2 B級，RT：80 % ＞1E5 Ω cm 利用CMP雙面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 2” 6H SI 6H-SI 2”直徑，類型/摻雜劑：半絕緣/V 定向：＜0001＞+/-0.5度厚度：330 ± 25 μm D級，MPDa100 cm-2 D級，RT：70 % ＞1E5 Ω cm 利用CMP單面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 2” 6H SI 6H-SI 2”直徑，類型/摻雜劑：半絕緣/V 定向：＜0001＞+/-0.5度厚度：330 ± 25 μm B級，MPDa30 cm-2 B級，RT：85 % ＞1E5 Ω cm 利用CMP單面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm 4” 4H N型 4H-N 4”直徑.(100 mm±0.38 mm)，類型/摻雜劑：N/氮定向：4.0°±0.5° 厚度：350 μm±25 μm D級，MPDa100 cm-2 D級，0.01~0.1 Ω cm D級，TTV/彎曲度/翹曲度＜45um 利用CMP雙面拋光/Si面備用於磊晶，表面粗糙度：＜0.5 nm Wafers with the following characteristics can be fabricated from polymer-derived ultrapure SiC materials. type describe 2” 6H Type N 6H-N 2" Diameter, Type/Dopant: N/Nitrogen Orientation: <0001>+/-0.5 degrees Thickness: 330 ± 25 μm Class D, MPDa100 cm-2 Class D, RT: 0.02-0.2 Ω cm Utilized CMP single side polishing/Si side is prepared for epitaxy, surface roughness: <0.5 nm 2” 6H Type N 6H-N 2” Diameter, Type/Dopant: N/Nitrogen Orientation: <0001>+/-0.5 degrees Thickness: 330 ± 25 μm Class B, MPDa30 cm-2 Class B, RT 0.02 ~ 0.2 Ω cm Utilize CMP Single side polishing/Si side is prepared for epitaxy, surface roughness: <0.5 nm 2” 4H Type N 4H-N 2” Diameter, Type/Dopant: N/Nitrogen Orientation: <0001>+/-0.5 degrees Thickness: 330 ± 25 μm Class D, MPDa100 cm-2 Class D, RT: 0.01-0.1 Ω cm D Level, curvature/warpage/TTV<25um, use CMP single-side polishing/Si side is prepared for epitaxy, surface roughness:<0.5 nm 2” 4H Type N 4H-N 2” Diameter, Type/Dopant: N/Nitrogen Orientation: <0001>+/-0.5 degrees Thickness: 330 ± 25 μm Class B, MPDa30 cm-2 Class B, RT: 0.01-0.1 Ω cm B Level, curvature/warpage/TTV<25um, use CMP single-side polishing/Si side is prepared for epitaxy, surface roughness:<0.5 nm 3” 4H Type N 4H-N 3” Diameter, Type/Dopant: N/Nitrogen Orientation: 4 degrees +/- 0.5 degrees Thickness: 350 ± 25 μm Class D, MPDa100 cm-2 Class D, RT: 0.01-0.1 Ω cm Class D , curvature/warpage/TTV<35um, use CMP double-sided polishing/Si side for epitaxy, surface roughness:<0.5 nm 3” 4H Type N 4H-N 3" Diameter, Type/Dopant: N/Nitrogen Orientation: 4 degrees +/- 0.5 degrees Thickness: 350 ± 25 μm Class B, MPDa30 cm-2 Class B, RT: 0.01-0.1 Ω cm Class B , curvature/warpage/TTV<35um, use CMP double-sided polishing/Si side for epitaxy, surface roughness:<0.5 nm 3” 4H SI 4H-SI 3” Diameter, Type/Dopant: Semi-insulating/V Orientation: <0001>+/-0.5 degrees Thickness: 350 ± 25 μm Class D, MPDa100 cm-2 Class D, RT: 70 % ≥1E5 Ω cm Use CMP double-sided polishing/Si side for epitaxy, surface roughness: <0.5 nm 3” 4H SI 4H-SI 3” Diameter, Type/Dopant: Semi-insulating/V Orientation: <0001>+/-0.5 degrees Thickness: 350 ± 25 μm Class B, MPDa30 cm-2 Class B, RT: 80 % >1E5 Ω cm Use CMP double-sided polishing/Si side for epitaxy, surface roughness: <0.5 nm 2” 6H SI 6H-SI 2” Diameter, Type/Dopant: Semi-insulating/V Orientation: <0001>+/-0.5 degrees Thickness: 330 ± 25 μm Class D, MPDa100 cm-2 Class D, RT: 70 % >1E5 Ω cm Use CMP single side polishing/Si side for epitaxy, surface roughness: <0.5 nm 2” 6H SI 6H-SI 2” Diameter, Type/Dopant: Semi-insulating/V Orientation: <0001>+/-0.5 degrees Thickness: 330 ± 25 μm Class B, MPDa30 cm-2 Class B, RT: 85 % >1E5 Ω cm Use CMP single side polishing/Si side for epitaxy, surface roughness: <0.5 nm 4” 4H Type N 4H-N 4” Diameter. (100 mm±0.38 mm), Type/Dopant: N/Nitrogen Orientation: 4.0°±0.5° Thickness: 350 μm±25 μm Class D, MPDa100 cm-2 Class D, 0.01~ 0.1 Ω cm Grade D, TTV/curvature/warpage<45um, use CMP double-sided polishing/Si side for epitaxy, surface roughness:<0.5 nm

SSP =單側拋光、DSP =雙側拋光、E =經蝕刻、C =剛切割、L =精磨的、Und =未摻雜(本質)SSP = single side polished, DSP = double side polished, E = etched, C = just cut, L = lapped, Und = undoped (essential)

理論上，可存在用於使得SiC粉末成為空間形體之另外實施例：使用石墨部件或石墨泡沫作為生長腔室中之***物來迫使粉末成為特定幾何形狀(例如，間隔物)；使用水或其他高純度揮發性液體來製得「濕砂」且使用「砂堡」模來在生長腔室中製成形體—隨後在生長胚晶之前使揮發性液體輕柔地蒸發；由多孔碳或多孔SiC製得的可滲透犧牲模(例如，由相容性材料製得的K形杯)。實例 In theory, there could be additional embodiments for spatially shaping SiC powder: using graphite parts or graphite foam as inserts in the growth chamber to force the powder into specific geometries (e.g., spacers); using water or other High-purity volatile liquids to create "green sand" and use "sandcastle" molds to form shapes in growth chambers—then gently evaporate the volatile liquids before growing embryo crystals; made of porous carbon or porous SiC The resulting permeable sacrificial mold (eg, a K-cup made of a compatible material). example

提供以下實例來說明本發明之系統、製程、組合物、應用及材料之各種實施例。該些實例係用於說明性目的，可為預言性的，且不應視為本發明之範疇，且不另外限制本發明之範疇。除非另外明確地提供，否則用於實例中之百分比為總物質之重量百分比，該總物質例如調配物、混合物、產物、或結構。除非另外明確地提供，否則使用X/Y或XY指示調配物中X之%及Y之%。除非另外明確地提供，否則使用X/Y/Z或XYZ指示調配物中X之%、Y之%及Z之%。The following examples are provided to illustrate various embodiments of the systems, processes, compositions, applications and materials of the present invention. These examples are for illustrative purposes, may be prophetic, and should not be considered and do not otherwise limit the scope of the invention. Percentages used in the examples are by weight of the total substance, such as a formulation, mixture, product, or structure, unless expressly provided otherwise. X/Y or XY is used to indicate % of X and % of Y in the formulation unless expressly provided otherwise. X/Y/Z or XYZ are used to indicate % of X, % of Y and % of Z in the formulation unless expressly provided otherwise.

實例1Example 1

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將41% MHF及59% TV混合在一起來製成調配物。此前驅物調配物具有0.68莫耳之氫化物、0.68莫耳之乙烯基、及1.37莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.37 25% C 2.74 50% O 1.37 25% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. Formulations were made by mixing together 41% MHF and 59% TV at room temperature. This precursor formulation has 0.68 moles of hydride, 0.68 moles of vinyl, and 1.37 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.37 25% C 2.74 50% o 1.37 25%

如所計算的，來源於此調配物的SiOC將在已移除所有CO之後具有計算的1.37莫耳之C，且具有0%過量C。隨後將此材料熱解成陶瓷且進一步轉化成將為化學計量的SiC粒子，且形成為圓片。As calculated, the SiOC derived from this formulation would have a calculated 1.37 molar C with 0% excess C after all CO had been removed. This material is then pyrolyzed into a ceramic and further converted into what will be stoichiometric SiC particles and formed into discs.

實例2Example 2

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將90%甲基封端苯乙基聚矽氧烷(具有27% X)及10% TV混合在一起來製成調配物。此前驅物調配物具有1.05莫耳之氫化物、0.38莫耳之乙烯基、0.26莫耳之苯基、及1.17莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.17 20% C 3.47 60% O 1.17 20% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. Formulations were made by mixing together 90% methyl-terminated phenylethylpolysiloxane (with 27% X) and 10% TV at room temperature. This precursor formulation has 1.05 moles of hydride, 0.38 moles of vinyl, 0.26 moles of phenyl, and 1.17 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.17 20% C 3.47 60% o 1.17 20%

如所計算的，來源於此調配物的SiOC將在已移除所有CO之後具有計算的2.31莫耳之C，且具有98%過量C。隨後將此材料熱解成陶瓷且進一步轉化成將具有過量C之SiC粒子，且形成為圓片。As calculated, the SiOC derived from this formulation would have a calculated 2.31 molar C with 98% excess C after all CO had been removed. This material is then pyrolyzed into a ceramic and further converted into SiC particles that will have an excess of C and formed into discs.

起始材料之過量碳及起始空間形體可藉由若干實施例獲得。例如過量碳可自具有自PDC路線殘留的過量C之調配物獲得，諸如調配物(例如，DCPD型調配物)中之過量C應在完全熱解至＞1600℃之後產生作為平衡相之SiC及C。在另一實施例中，過量C可藉由在固化及熱解之前將C粉末或含C物質添加至液體PDC調配物來獲得。在另一實施例中，具有過量游離C之SiOC顏料可添加至空間形體。進一步，可使用在圓片形成中分解成C的黏合劑。此外，含C粉末與黏合劑組合以將更多C併入調配物中。The carbon excess and the starting steric shape of the starting material can be obtained by several embodiments. For example, excess carbon can be obtained from formulations with excess C remaining from the PDC route, such as excess C in formulations (e.g., DCPD-type formulations) should yield SiC and SiC as equilibrium phases after complete pyrolysis to >1600°C c. In another embodiment, excess C can be obtained by adding C powder or C-containing species to the liquid PDC formulation prior to curing and pyrolysis. In another embodiment, SiOC pigments with excess free C can be added to the spacers. Further, a binder that decomposes into C in wafer formation may be used. Additionally, C-containing powders are combined with binders to incorporate more C into the formulation.

實例3Example 3

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將70%甲基封端苯乙基聚矽氧烷(具有14% X)及30% TV混合在一起來製成調配物。此前驅物調配物具有0.93莫耳之氫化物、0.48莫耳之乙烯基、0.13莫耳之苯基、及1.28莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.28 23% C 3.05 54% O 1.28 23% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. Formulations were made by mixing together 70% methyl-terminated phenylethylpolysiloxane (with 14% X) and 30% TV at room temperature. This precursor formulation has 0.93 moles of hydride, 0.48 moles of vinyl, 0.13 moles of phenyl, and 1.28 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.28 twenty three% C 3.05 54% o 1.28 twenty three%

如所計算的，來源於此調配物的SiOC將在已移除所有CO之後具有計算的1.77莫耳之C，且具有38%過量C。隨後將此材料熱解成陶瓷且進一步轉化成將具有過量C之SiC粒子，且形成為圓片。在具有過量碳的該些非化學計量調配物(亦即，Si:C莫耳比率不為1:1)中之一些中，起始材料之實際密度將為＜ 3.21 g/cc。As calculated, the SiOC derived from this formulation would have a calculated 1.77 molar C with 38% excess C after all CO had been removed. This material is then pyrolyzed into a ceramic and further converted into SiC particles that will have an excess of C and formed into discs. In some of these non-stoichiometric formulations with excess carbon (ie, Si:C molar ratio other than 1:1), the actual density of the starting material will be <3.21 g/cc.

實例4Example 4

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將50%甲基封端苯乙基聚矽氧烷(具有20% X)及50% TV混合在一起來製成調配物。此前驅物調配物具有0.67莫耳之氫化物、0.68莫耳之乙烯基、0.10莫耳之苯基、及1.25莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.25 22% C 3.18 56% O 1.25 22% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. Formulations were made by mixing together 50% methyl-terminated phenylethylpolysiloxane (with 20% X) and 50% TV at room temperature. This precursor formulation has 0.67 moles of hydride, 0.68 moles of vinyl, 0.10 moles of phenyl, and 1.25 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.25 twenty two% C 3.18 56% o 1.25 twenty two%

如所計算的，來源於此調配物的SiOC將在已移除所有CO之後具有計算的1.93莫耳之C，且具有55%過量C。隨後將此材料熱解成陶瓷且進一步轉化成將具有過量C之SiC粒子，且形成為圓片。As calculated, the SiOC derived from this formulation would have a calculated 1.93 molar C with 55% excess C after all CO had been removed. This material is then pyrolyzed into a ceramic and further converted into SiC particles that will have an excess of C and formed into discs.

實例5Example 5

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將65%甲基封端苯乙基聚矽氧烷(具有40% X)及35% TV混合在一起來製成調配物。此前驅物調配物具有0.65莫耳之氫化物、0.66莫耳之乙烯基、0.25莫耳之苯基、及1.06莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.06 18% C 3.87 54% O 1.06 28% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. Formulations were made by mixing together 65% methyl-terminated phenylethylpolysiloxane (with 40% X) and 35% TV at room temperature. This precursor formulation has 0.65 moles of hydride, 0.66 moles of vinyl, 0.25 moles of phenyl, and 1.06 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.06 18% C 3.87 54% o 1.06 28%

如所計算的，來源於此調配物的SiOC將在已移除所有CO之後具有計算的2.81莫耳之C，且具有166%過量C。隨後將此材料熱解成陶瓷且進一步轉化成將具有過量C之SiC粒子，且形成為圓片。As calculated, the SiOC derived from this formulation would have a calculated 2.81 molar C with 166% excess C after all CO had been removed. This material is then pyrolyzed into a ceramic and further converted into SiC particles that will have an excess of C and formed into discs.

實例6Example 6

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將65% MHF及35%二環戊二烯(dicyclopentadiene; DCPD)混合在一起來製成調配物。此前驅物調配物具有1.08莫耳之氫化物、0.53莫耳之乙烯基、0.0莫耳之苯基、及1.08莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.08 18% C 3.73 64% O 1.08 18% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. The formulation was made by mixing together 65% MHF and 35% dicyclopentadiene (DCPD) at room temperature. This precursor formulation has 1.08 moles of hydride, 0.53 moles of vinyl, 0.0 moles of phenyl, and 1.08 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.08 18% C 3.73 64% o 1.08 18%

如所計算的，來源於此調配物的SiOC將在已移除所有CO之後具有計算的2.65莫耳之C，且具有144%過量C。隨後將此材料熱解成陶瓷且進一步轉化成將具有過量C之SiC粒子，且形成為圓片。As calculated, the SiOC derived from this formulation would have a calculated C of 2.65 moles after all CO had been removed, with a 144% excess C. This material is then pyrolyzed into a ceramic and further converted into SiC particles that will have an excess of C and formed into discs.

實例7Example 7

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將82% MHF及18%二環戊二烯(DCPD)混合在一起來製成調配物。此前驅物調配物具有1.37莫耳之氫化物、0.27莫耳之乙烯基、0.0莫耳之苯基、及1.37莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.37 25% C 2.73 50% O 1.37 25% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. Formulations were made by mixing together 82% MHF and 18% dicyclopentadiene (DCPD) at room temperature. This precursor formulation has 1.37 moles of hydride, 0.27 moles of vinyl, 0.0 moles of phenyl, and 1.37 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.37 25% C 2.73 50% o 1.37 25%

實例8Example 8

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將46% MHF、34% TV及20% VT混合在一起來製成調配物。此前驅物調配物具有0.77莫耳之氫化物、0.40莫耳之乙烯基、0.0莫耳之苯基、及1.43莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.43 30% C 1.95 40% O 1.43 30% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. Formulations were made by mixing together 46% MHF, 34% TV and 20% VT at room temperature. This precursor formulation has 0.77 moles of hydride, 0.40 moles of vinyl, 0.0 moles of phenyl, and 1.43 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.43 30% C 1.95 40% o 1.43 30%

如所計算的，來源於此調配物的SiOC將在已移除所有CO之後具有計算的0.53莫耳之C，且具有63% C不足，或為63%貧C的。隨後將此材料熱解成陶瓷且進一步轉化成將為貧C的SiC粒子，且形成為圓片。As calculated, the SiOC derived from this formulation would have a calculated C of 0.53 moles after all CO had been removed, and be 63% C deficient, or 63% C depleted. This material is then pyrolyzed into a ceramic and further converted into SiC particles which will be C-depleted, and formed into discs.

例如，藉由具有相對於存在的氧及存在的矽而言為貧C的起始材料或起始圓片(例如，來源於僅MHF作為其前驅物材料之SiOC陶瓷)可獲得富Si調配物。取決於在氣相沉積製程期間何者為限制性試劑，保持者為Si-C及C，且SiO ₂+C將反應以形成SiC + C；或SiO ₂+C將不完全地反應以形成Si-O(離開設備)及Si及SiC。在另一實施例中，起始材料或起始圓片係調配為SiC + Si粉末+黏合劑以製成形體。此將提供富Si起始材料。 For example, Si-rich formulations can be obtained by having a starting material or wafer that is C-depleted relative to the oxygen present and the silicon present (e.g., derived from a SiOC ceramic with only MHF as its precursor material) . Depending on which is the limiting reagent during the vapor deposition process, the holders are Si-C and C, and _SiO2 +C will react to form SiC+C; or _SiO2 +C will react incompletely to form Si- O (leaving the device) and Si and SiC. In another embodiment, the starting material or the starting wafer is formulated as SiC+Si powder+binder to form the body. This will provide a Si rich starting material.

實例9Example 9

使用混合型方法調配多晶碳氧矽調配物。藉由在室溫下將70% MHF、20% TV及10% VT混合在一起來製成調配物。此前驅物調配物具有1.17莫耳之氫化物、0.23莫耳之乙烯基、0.0莫耳之苯基、及1.53莫耳之甲基。前驅物調配物具有基於100 g之調配物的以下莫耳量之Si、C及O。莫耳 Si、C、O之莫耳比率(「莫耳」欄中之總莫耳數之%) Si 1.53 31% C 1.87 38% O 1.53 31% The polycrystalline silicon oxycarbide formulation is formulated using a hybrid approach. Formulations were made by mixing together 70% MHF, 20% TV and 10% VT at room temperature. This precursor formulation has 1.17 moles of hydride, 0.23 moles of vinyl, 0.0 moles of phenyl, and 1.53 moles of methyl. The precursor formulations had the following molar amounts of Si, C and O based on 100 g of the formulation. mole Mole ratio of Si, C, O (% of the total mole number in the "Mole" column) Si 1.53 31% C 1.87 38% o 1.53 31%

如所計算的，來源於此調配物的SiOC將在已移除所有CO之後具有計算的0.33莫耳之C，且具有78% C不足，或為78%貧C的。隨後將此材料熱解成陶瓷且進一步轉化成將為貧C的SiC粒子，且形成為圓片。As calculated, the SiOC derived from this formulation would have a calculated C of 0.33 moles after all CO had been removed, and be 78% C deficient, or 78% C depleted. This material is then pyrolyzed into a ceramic and further converted into SiC particles which will be C-depleted, and formed into discs.

實例10Example 10

製成約100公克之多晶碳氧矽調配物。將調配物在室溫下摻合15分鐘且隨後添加1%觸媒並將混合物攪拌另外10分鐘。觸媒在短鏈乙烯基封端聚矽氧烷中具有10 ppm Pt。Prepare about 100 grams of polycrystalline silicon oxycarbide compound. The formulation was blended at room temperature for 15 minutes and then 1% catalyst was added and the mixture was stirred for an additional 10 minutes. The catalyst has 10 ppm Pt in short chain vinyl terminated polysiloxane.

將調配物傾倒至鐵氟龍(PTFE，聚四氟乙烯)塗佈的鋁箔鍋且在90℃下在氬或空氣中固化2.5小時。The formulations were poured into Teflon (PTFE, polytetrafluoroethylene) coated aluminum foil pans and cured at 90°C in argon or air for 2.5 hours.

將固化聚合物機械地破碎成適配至陶瓷舟(例如，為3.5"長x 2.5"寬x 5/8"深的坩堝)中的大小；且將其置放於彼等陶瓷舟中。將含有固化聚合物之陶瓷舟在填充有以500 cc/min流動的氬氣的不銹鋼蒸餾罐中如下加熱： l 室溫至82.2℃，加熱速率為82.2℃/hr，在82.2℃下保持1小時； l 82.2℃至182℃，加熱速率為48.9℃/hr，在182℃下保持1小時； l 182℃至210℃，加熱速率為48.9℃/hr，在210℃下保持2小時； l 210℃至1,100℃，加熱速率為115.6℃/hr，在1,100℃下保持2小時；及， l 在打開之前將熔爐冷卻至204.4℃。 The solidified polymers were mechanically broken into sizes that fit into ceramic boats (e.g., crucibles that were 3.5" long x 2.5" wide x 5/8" deep); and placed in those ceramic boats. A ceramic boat containing solidified polymer was heated in a stainless steel retort filled with argon flowing at 500 cc/min as follows: l From room temperature to 82.2°C, heating rate is 82.2°C/hr, keep at 82.2°C for 1 hour; l 82.2°C to 182°C, heating rate is 48.9°C/hr, keep at 182°C for 1 hour; l 182°C to 210°C, heating rate is 48.9°C/hr, keep at 210°C for 2 hours; l 210°C to 1,100°C at a heating rate of 115.6°C/hr, holding at 1,100°C for 2 hours; and, l Cool the furnace to 204.4°C before opening it.

將熱解材料置放於石墨舟中，其中熱解材料係呈粉末形式或呈團塊形式。將石墨舟置放於具有兩個絕緣端塊及端蓋的氧化鋁管熔爐中以允許氣體流入及廢氣流出。氬氣以50 cc/min之速率流動穿過管式爐。隨後在10小時時期內將材料加熱至1,650℃(約3℃/min加熱速率)且在此溫度下保持另外10小時。隨後在5小時時期內將熔爐緩慢地冷卻至700℃，隨後將熔爐進一步冷卻，其中當溫度為至少低於300℃時移除端蓋。The pyrolyzed material is placed in a graphite boat, where the pyrolyzed material is either in powder form or in agglomerate form. The graphite boat was placed in an alumina tube furnace with two insulated end blocks and end caps to allow gas inflow and exhaust gas outflow. Argon was flowed through the tube furnace at a rate of 50 cc/min. The material was then heated to 1,650°C (approximately 3°C/min heating rate) over a period of 10 hours and held at this temperature for an additional 10 hours. The furnace was then cooled slowly to 700°C over a period of 5 hours, and then the furnace was cooled further, with the end caps removed when the temperature was at least below 300°C.

自熔爐移除所得多晶碳氧矽衍生SiC。The resulting polycrystalline silicon oxycarbide derived SiC was removed from the furnace.

隨後藉由在高於已熔融混合至SiC粉末中的蠟黏合劑之熔融溫度的溫度下將SiC粉末壓製在圓筒形模中將SiC形成為圓盤。模可經大小設定以使得經壓製及燒結粉末之單一獨石塊可滑動至坩堝中以供PVT生長。模亦可經大小設定來產生圓盤「晶片(chip)」以傾倒至坩堝中。The SiC is then formed into discs by pressing the SiC powder in a cylindrical mold at a temperature above the melting temperature of the wax binder that has been melt mixed into the SiC powder. The mold can be sized so that a single monolithic block of pressed and sintered powder can be slid into the crucible for PVT growth. The mold can also be sized to create a disc "chip" to pour into the crucible.

實例11Example 11

在清潔室環境中使用已經清潔以便基本上移除所有潛在雜質的玻璃器皿來製得多晶碳氧矽調配物，該等雜質尤其包括Al、Fe、及B。將調配物在室溫下摻合約10至20分鐘且隨後添加0.25%至2%觸媒溶液且將混合物攪拌另外10分鐘。觸媒溶液具有10 ppm Pt。最終催化調配物具有在10 ppb與50 ppb之間的Pt。The polycrystalline oxycarbide formulations were prepared in a clean room environment using glassware that had been cleaned to remove substantially all potential impurities, including Al, Fe, and B, among others. The formulation was blended at room temperature for about 10-20 minutes and then 0.25% to 2% catalyst solution was added and the mixture was stirred for an additional 10 minutes. The catalyst solution has 10 ppm Pt. The final catalytic formulation has between 10 ppb and 50 ppb Pt.

在清潔室環境中，將調配物置放於PFA (全氟烷氧基聚合物)瓶或罐中，用氬沖洗，且加蓋閉合。在75℃至160℃下將調配物固化1.5小時至4小時。In a clean room environment, the formulations are placed in PFA (perfluoroalkoxy polymer) bottles or jars, flushed with argon, and capped closed. The formulation was cured at 75°C to 160°C for 1.5 hours to 4 hours.

在清潔室環境中，將固化聚合物置放於陶瓷坩堝中。隨後將經填充的坩堝用陶瓷蓋覆蓋，且置放於用以500 cc/min流動的氬氣填充的陶瓷蒸餾器中。坩堝、熔爐及所有相關聯設備及儀器為清潔的且基本上無污染物；且尤其使得其不Al或B之來源。以約30℃至約180℃/hr之增加速率如下加熱坩堝： l 室溫至1,000℃，加熱速率為180℃/hr，在1,000℃下保持2小時；及， l 在打開之前將熔爐冷卻至204.4℃。 In a clean room environment, the cured polymer is placed in a ceramic crucible. The filled crucible was then covered with a ceramic lid and placed in a ceramic retort filled with argon flowing at 500 cc/min. Crucibles, furnaces, and all associated equipment and instruments were clean and substantially free of contamination; and especially so that they were not sources of Al or B. The crucible was heated at an increasing rate of about 30°C to about 180°C/hr as follows: l from room temperature to 1,000°C at a heating rate of 180°C/hr for 2 hours at 1,000°C; and, l Cool the furnace to 204.4°C before opening it.

將熱解材料置放於石墨舟中，其中熱解材料係呈粉末形式或呈團塊形式。將石墨舟置放於具有兩個絕緣端塊及端蓋的氧化鋁管熔爐中以允許氣體流入及廢氣流出。(可使用石墨箱式爐、RF熔爐、或其他類型的適合加熱設備)。坩堝、熔爐及所有相關聯設備及儀器為清潔的且基本上無污染物；且尤其使得其不Al、Fe、或B之來源。氬氣以50 cc/min之速率流動穿過管式爐。隨後在7至15小時時期內將材料加熱至1,400℃至1,650℃(約3℃/min加熱速率)且在此溫度下保持另外10小時。隨後在5小時時期內將熔爐緩慢地冷卻至700℃，隨後將熔爐進一步冷卻，其中當溫度為至少低於300℃時移除端蓋。The pyrolyzed material is placed in a graphite boat, where the pyrolyzed material is either in powder form or in agglomerate form. The graphite boat was placed in an alumina tube furnace with two insulated end blocks and end caps to allow gas inflow and exhaust gas outflow. (Graphite box furnace, RF furnace, or other type of suitable heating equipment may be used). Crucibles, furnaces, and all associated equipment and instruments are clean and substantially free of contamination; and especially so that they are not sources of Al, Fe, or B. Argon was flowed through the tube furnace at a rate of 50 cc/min. The material was then heated to 1,400°C to 1,650°C (approximately 3°C/min heating rate) over a period of 7 to 15 hours and held at this temperature for an additional 10 hours. The furnace was then cooled slowly to 700°C over a period of 5 hours, and then the furnace was cooled further, with the end caps removed when the temperature was at least below 300°C.

實例12aExample 12a

實例11之SiC隨後係藉由與10 wt%原始多晶碳氧矽前驅物混合且混合直至藉由樹脂均勻地潤濕來形成為實例13-28之空間形體。隨後將糊狀物使用冷壓機及模來壓製成形體。將形體自模移除且置放於石墨坩堝。將坩堝放入石墨熔爐中且加熱至1750℃歷時至少1小時。樣本為具有3.21 g/cc之比重的可操縱形體。The SiC of Example 11 was then formed into the spatial features of Examples 13-28 by mixing with 10 wt% of the original polycrystalline silicon oxycarbide precursor and mixing until uniformly wetted by the resin. The paste is then pressed into shaped bodies using a cold press and dies. The form was removed from the mold and placed in a graphite crucible. The crucible was placed in a graphite furnace and heated to 1750°C for at least 1 hour. Samples are steerable bodies with a specific gravity of 3.21 g/cc.

實例12bExample 12b

實例11之SiC隨後係藉由與14 wt%原始多晶碳氧矽前驅物混合且混合直至藉由樹脂均勻地潤濕來形成為實例13-28之空間形體。隨後將糊狀物使用冷壓機及模來壓製成形體。將形體自模移除且置放於石墨坩堝。將坩堝放入石墨熔爐中且加熱至1750℃歷時至少1小時。樣本為具有3.21 g/cc之比重的可操縱形體。The SiC of Example 11 was then formed into the spatial features of Examples 13-28 by mixing with 14 wt% virgin polysilicon oxycarbide precursor and mixing until uniformly wetted by the resin. The paste is then pressed into shaped bodies using a cold press and dies. The form was removed from the mold and placed in a graphite crucible. The crucible was placed in a graphite furnace and heated to 1750°C for at least 1 hour. Samples are steerable bodies with a specific gravity of 3.21 g/cc.

實例12cExample 12c

實例11之SiC隨後係藉由與20 wt%原始多晶碳氧矽前驅物混合且混合直至藉由樹脂均勻地潤濕來形成為實例13-28之空間形體。隨後將糊狀物使用冷壓機及模來壓製成形體。將形體自模移除且置放於石墨坩堝。將坩堝放入石墨熔爐中且加熱至1750℃歷時至少1小時。樣本為具有3.21 g/cc之比重的可操縱形體。The SiC of Example 11 was then formed into the spatial features of Examples 13-28 by mixing with 20 wt% of the original polycrystalline silicon oxycarbide precursor and mixing until uniformly wetted by the resin. The paste is then pressed into shaped bodies using a cold press and dies. The form was removed from the mold and placed in a graphite crucible. The crucible was placed in a graphite furnace and heated to 1750°C for at least 1 hour. Samples are steerable bodies with a specific gravity of 3.21 g/cc.

實例12dExample 12d

實例11之SiC隨後係藉由與30 wt%原始多晶碳氧矽前驅物混合且混合直至藉由樹脂均勻地潤濕來形成為實例13-28之空間形體。隨後將糊狀物使用冷壓機及模來壓製成形體。將形體自模移除且置放於石墨坩堝。將坩堝放入石墨熔爐中且加熱至1750℃歷時至少1小時。樣本為具有3.21 g/cc之比重的可操縱形體。The SiC of Example 11 was then formed into the spatial features of Examples 13-28 by mixing with 30 wt% of the original polycrystalline silicon oxycarbide precursor and mixing until uniformly wetted by the resin. The paste is then pressed into shaped bodies using a cold press and dies. The form was removed from the mold and placed in a graphite crucible. The crucible was placed in a graphite furnace and heated to 1750°C for at least 1 hour. Samples are steerable bodies with a specific gravity of 3.21 g/cc.

實例13Example 13

在第1A圖至第1D圖中，提供呈圓柱體1之形式的空間形體，其具有平坦頂部2、側面3、及平坦底部。在此實施例中，形體具有約4吋之高度及約6吋之直徑。涵蓋用於此形體的其他大小，包括例如約1至6吋之高度及約2至12吋之直徑；及約1/2至7吋之高度及約1/2至約17之直徑。In Figures 1A to 1D, a spatial body is provided in the form of a cylinder 1 with a flat top 2, sides 3, and a flat bottom. In this embodiment, the shapes have a height of about 4 inches and a diameter of about 6 inches. Other sizes for this form are contemplated, including, for example, a height of about 1 to 6 inches and a diameter of about 2 to 12 inches; and a height of about 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches.

實例14Example 14

在第2A圖至第2D圖中，提供呈圓柱體形式的空間形體200，其具有平坦底部203及在頂部201中的環形洞204。環形洞204具有底部且不會完全地延伸穿過空間形體200。空間形體200具有側面202。形體具有約3吋之高度及4吋之直徑。環形開口之直徑為約1 ¹/ ₂吋。轉向第2D圖，提供此類型形體之橫截面示意圖。應瞭解，示意圖將繞軸200旋轉以提供3-D形狀。涵蓋用於此形體的其他大小，包括例如約1至6吋之高度及約2至12吋之直徑；及約1/2至7吋之高度及約1/2至約17之直徑。 In FIGS. 2A to 2D , a spatial body 200 is provided in the form of a cylinder with a flat bottom 203 and an annular hole 204 in the top 201 . The annular hole 204 has a bottom and does not completely extend through the spatial body 200 . The spatial body 200 has a side surface 202 . The figures have a height of approximately 3 inches and a diameter of 4 inches. The diameter of the annular opening is about 1 ^1/2 _inches . Turning to Figure 2D, a schematic cross-sectional view of this type of shape is provided. It should be appreciated that the schematic will be rotated about axis 200 to provide a 3-D shape. Other sizes for this form are contemplated, including, for example, a height of about 1 to 6 inches and a diameter of about 2 to 12 inches; and a height of about 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches.

實例15Example 15

在第3A圖至第3F圖中，提供呈圓柱體形式的空間形體，其具有形成在頂部301中的球形開口303及形成在底部304中的球形開口305。形體具有側面302。形體具有約4吋之高度及約4 ³/ ₄吋之直徑。開口具有約3 ³/ ₄吋之直徑。轉向第3F圖，提供此類型形體之橫截面示意圖。應瞭解，示意圖將繞軸300旋轉以提供3-D形狀。涵蓋用於此形體的其他大小，包括例如約1至6吋之高度及約2至12吋之直徑；及約1/2至7吋之高度及約1/2至約17之直徑。 In FIGS. 3A to 3F , a spatial body in the form of a cylinder having a spherical opening 303 formed in the top 301 and a spherical opening 305 formed in the bottom 304 is provided. The body has sides 302 . The figures have a height of about 4 inches and a diameter of about 4 ^3/4 _inches . The opening has a diameter of about 3 ^3/4 _inches . Turning to Figure 3F, a schematic cross-sectional view of this type of shape is provided. It should be appreciated that the schematic will be rotated about axis 300 to provide a 3-D shape. Other sizes for this form are contemplated, including, for example, a height of about 1 to 6 inches and a diameter of about 2 to 12 inches; and a height of about 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches.

在此實施例(以及該實例之其他實施例)中，開口係與軸同軸的。應瞭解，在實施例中，開口可為離軸的，例如，不在與空間形體之軸相同的軸上。In this embodiment (and other embodiments of this example), the opening is coaxial with the shaft. It should be appreciated that in embodiments, the openings may be off-axis, eg, not on the same axis as the spatial body's axis.

實例16Example 16

在第4A圖至第4F圖中，提供空間形體，其為具有平坦頂部410及平坦底部413之圓錐體。頂部410具有形成在其中的成角度環形開口414、或通道。空間形體具有側面412。頂部之直徑為約4 ¹/ ₈吋且底部之直徑為約4 ³/ ₈吋。高度為約2 ¹/ ₂吋。環形通道具有約 ¹/ ₂吋之開口寬度且向下延伸至形體中約1吋。轉向第4F圖，提供此類型形體400之橫截面示意圖。應瞭解，示意圖將繞軸401旋轉以提供3-D形狀。成角度環形通道具有長度(藉由雙箭頭410展示)及藉由雙箭頭411展示的寬度。環形通道414之角度405係藉由在線402 (其為通道414之橫截面的中心線)與軸401之間形成的角度決定。第4F圖中的此角度405為60°，且在實施例中，範圍可在約89°至約0°且較佳地約80°至約40°，及該些者之組合及變化，以及該些角度範圍內之所有值。涵蓋用於此形體之其他大小，包括例如約1至6吋之高度及約2至12吋之直徑；及約1/2至7吋之高度及約1/2至約17之直徑，及該些者之組合及變化，以及該些尺寸範圍內之所有值。 In FIGS. 4A to 4F , a spatial shape is provided, which is a cone with a flat top 410 and a flat bottom 413 . The top 410 has an angled annular opening 414, or channel, formed therein. The spatial body has side surfaces 412 . The diameter of the top is about 4 ^1/8 _inches and the diameter of the bottom is about 4 ^3/8 _inches . Height is about 2 ^1/2 _inches . The annular channel has an opening width of about ^1/2 _inch and extends down into the form about 1 inch. Turning to Figure 4F, a schematic cross-sectional view of this type of feature 400 is provided. It should be appreciated that the schematic will be rotated about axis 401 to provide a 3-D shape. The angled annular channel has a length (shown by double arrow 410 ) and a width shown by double arrow 411 . Angle 405 of annular channel 414 is determined by the angle formed between line 402 (which is the centerline of the cross-section of channel 414 ) and axis 401 . This angle 405 in Figure 4F is 60°, and in embodiments, may range from about 89° to about 0° and preferably from about 80° to about 40°, and combinations and variations of these, and All values within these angular ranges. Other sizes for this shape are contemplated, including, for example, a height of about 1 to 6 inches and a diameter of about 2 to 12 inches; and a height of about 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, and the Combinations and variations of these, and all values within these dimensional ranges.

實例17Example 17

在第5A圖至第5F圖中，提供圓錐形體，其具有平坦頂部501及平坦底部503，且頂部501及底部503具有開口502、504。形體具有側面505，例如，側壁或側表面或外側表面。開口可為球形(如第5F圖所示)，具有平坦底部之圓錐形(如第5A圖至第5E圖)所示或圓錐形。頂部之直徑為約3 ¹/ ₂吋且在底部處為約5吋。側壁之長度為約2 7/8吋。轉向第5F圖，提供此類型形體之橫截面示意圖。應瞭解，示意圖將繞軸500旋轉以提供3-D形狀。涵蓋用於此形體的其他大小，包括例如約1至6吋之高度及約2至12吋之直徑；及約1/2至7吋之高度及約1/2至約17之直徑。 In FIGS. 5A to 5F , a conical body is provided having a flat top 501 and a flat bottom 503 with openings 502 , 504 . The body has a side 505, eg, a side wall or a side surface or an outer side surface. The opening can be spherical (as shown in Figure 5F), conical with a flat bottom (as shown in Figures 5A-5E ), or conical. The diameter at the top is about ³ _1/2 inches and at the bottom is about 5 inches. The length of the side walls is about 2 7/8 inches. Turning to Figure 5F, a schematic cross-sectional view of this type of shape is provided. It should be appreciated that the schematic will be rotated about axis 500 to provide a 3-D shape. Other sizes for this form are contemplated, including, for example, a height of about 1 to 6 inches and a diameter of about 2 to 12 inches; and a height of about 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches.

實例18Example 18

在第6A圖至第6D圖，提供圓錐形體，其具有平坦頂部601及平坦底部603，且底部603具有開口604。形體具有側面607。開口604具有圓錐形側壁604a (例如，內壁，側面607為外壁)及平坦底表面604b。在實施例中，開口可為其他形狀。底部之直徑為約5 ¹/ ₂吋且頂部為約3吋。開口之直徑為約2 ¹/ ₈吋。高度為約2 ³/ ₈吋。轉向第6D圖，提供此類型形體之橫截面示意圖。應瞭解，示意圖將繞軸600旋轉以提供3-D形狀。涵蓋用於此形體之其他大小，包括例如約1至6吋之高度及約2至12吋之直徑；及約1/2至7吋之高度及約1/2至約17之直徑，及該些者之組合及變化，以及該些大小範圍內之所有值。 In FIGS. 6A to 6D , a conical body with a flat top 601 and a flat bottom 603 is provided, and the bottom 603 has an opening 604 . The body has sides 607 . The opening 604 has conical sidewalls 604a (eg, inner walls, side 607 is the outer wall) and a flat bottom surface 604b. In embodiments, the openings can be other shapes. The diameter of the bottom is about 5 ^1/2 _inches and the top is about 3 inches. The diameter of the opening is about 2 ^1/8 _inches . Height is about 2 ^3/8 _inches . Turning to Figure 6D, a schematic cross-sectional view of this type of shape is provided. It should be appreciated that the schematic will be rotated about axis 600 to provide a 3-D shape. Other sizes for this shape are contemplated, including, for example, a height of about 1 to 6 inches and a diameter of about 2 to 12 inches; and a height of about 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, and the Combinations and variations of these, and all values within these size ranges.

實例19Example 19

在第20A圖至第20C圖，提供圓錐形體，其具有平坦頂部2001及平坦底部2003、及側壁2005。形體在頂部、底部或側面中不具有表面開口。頂部之直徑為約3 ³/ ₄吋且底部之直徑為約4 ¹/ ₄吋。高度為約2 ¹/ ₂吋。涵蓋用於此形體的其他大小，包括例如約1至6吋之高度及約2至12吋之直徑；及約1/2至7吋之高度及約1/2至約17之直徑。 In FIGS. 20A-20C , a conical body with a flat top 2001 and a flat bottom 2003 , and side walls 2005 is provided. The figure has no surface openings in the top, bottom or sides. The diameter of the top is about ³ _3/4 inches and the diameter of the bottom is about 4 ^1/4 _inches . Height is about 2 ^1/2 _inches . Other sizes for this form are contemplated, including, for example, a height of about 1 to 6 inches and a diameter of about 2 to 12 inches; and a height of about 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches.

實例20Example 20

轉向第7圖，提供圓柱形體之橫截面示意圖。形體具有頂部701、側面705及底部703。底部具有開口704。應瞭解，示意圖將繞軸700旋轉以提供3-D形狀。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小。Turning to Figure 7, a schematic cross-sectional view of a cylindrical body is provided. The shape has a top 701 , sides 705 and a bottom 703 . The bottom has an opening 704 . It should be appreciated that the schematic will be rotated about axis 700 to provide a 3-D shape. Sizes for such figures include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, with other sizes also contemplated.

實例21Example 21

轉向第8圖，提供具有頂部開口的圓錐形體之橫截面示意圖。形體具有平坦頂部801、平坦底部803及側面或外壁805。頂部801中存在開口802，其向下延伸至形體中達形體高度之至少40%、至少50%、至少60%及至少80%。開口802具有為圓柱形的側壁802a，及為圓形的底表面802b。應瞭解，示意圖將繞軸800旋轉以提供3-D形狀。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小。Turning to Figure 8, a schematic cross-sectional view of a conical body with an open top is provided. The figure has a flat top 801 , a flat bottom 803 and sides or outer walls 805 . There are openings 802 in the top 801 that extend down into the figure for at least 40%, at least 50%, at least 60%, and at least 80% of the figure's height. The opening 802 has a cylindrical sidewall 802a and a circular bottom surface 802b. It should be appreciated that the schematic will be rotated about axis 800 to provide a 3-D shape. Sizes for such figures include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, with other sizes also contemplated.

實例22Example 22

轉向第9圖，提供具有中心穿通開口902的圓柱形體之橫截面示意圖。因此，開口902自頂部延伸穿過形體之底部。以此方式，形體可視為環形。應瞭解，示意圖將繞軸900旋轉以提供3-D形狀。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小。Turning to FIG. 9 , a schematic cross-sectional view of a cylindrical body with a central through opening 902 is provided. Thus, the opening 902 extends from the top through the bottom of the shape. In this way, the shape can be viewed as a ring. It should be appreciated that the schematic will be rotated about axis 900 to provide a 3-D shape. Sizes for such figures include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, with other sizes also contemplated.

實例23Example 23

轉向第10圖，提供具有中心穿通開口的圓錐形體之橫截面示意圖。形體具有平坦頂表面1001、平坦底表面1003、及側壁1002。形體具有延伸穿過頂部1001及底部1003表面之中心開口1005。開口1005a具有側壁1005a。開口1005不具有底部。應瞭解，示意圖將繞軸1000旋轉以提供3-D形狀。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小。Turning to Figure 10, a schematic cross-sectional view of a conical body with a central through opening is provided. The shape has a flat top surface 1001 , a flat bottom surface 1003 , and sidewalls 1002 . The figure has a central opening 1005 extending through the top 1001 and bottom 1003 surfaces. The opening 1005a has a sidewall 1005a. Opening 1005 has no bottom. It should be appreciated that the schematic will be rotated about axis 1000 to provide a 3-D shape. Sizes for such figures include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, with other sizes also contemplated.

實例24Example 24

轉向第11圖，提供具有頂部及底部開口的圓柱形體之橫截面示意圖。形體具有頂部開口1102，其具有圓錐形側壁1102a及圓形底表面1102b。形體具有底部開口1103，其具有圓錐形側壁1103a及底表面1103b。應瞭解，示意圖將繞軸1100旋轉以提供3-D形狀。因此，底表面1103b、1102b為圓形。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小。Turning to Figure 11, a schematic cross-sectional view of a cylindrical body with top and bottom openings is provided. The body has a top opening 1102 with conical sidewalls 1102a and a circular bottom surface 1102b. The body has a bottom opening 1103 with conical sidewalls 1103a and a bottom surface 1103b. It should be appreciated that the schematic will be rotated about axis 1100 to provide a 3-D shape. Accordingly, the bottom surfaces 1103b, 1102b are circular. Sizes for such figures include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, with other sizes also contemplated.

實例25Example 25

轉向第12圖，提供具有頂部開口1202及底部開口1203之圓錐形體之橫截面示意圖。應瞭解，示意圖將繞軸1200旋轉以提供3-D形狀。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小。Turning to Figure 12, a schematic cross-sectional view of a conical body having a top opening 1202 and a bottom opening 1203 is provided. It should be appreciated that the schematic will be rotated about axis 1200 to provide a 3-D shape. Sizes for such figures include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, with other sizes also contemplated.

實例26Example 26

轉向第13圖，提供具有球形頂部開口1302的圓柱形體之橫截面示意圖。開口1302具有表面1302a形成開口之底部及側壁兩者。應瞭解，示意圖將繞軸1300旋轉以提供3-D形狀。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小。Turning to Fig. 13, a schematic cross-sectional view of a cylindrical body with a spherical top opening 1302 is provided. The opening 1302 has a surface 1302a forming both the bottom and the sidewalls of the opening. It should be appreciated that the schematic will be rotated about axis 1300 to provide a 3-D shape. Sizes for such figures include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, with other sizes also contemplated.

實例27Example 27

轉向第14圖，提供具有球形頂部開口1402的圓錐形體之橫截面示意圖。形體具有頂部1401、側面1405。球形頂部開口1402具有表面1402a，其形成開口1402之側壁及底部兩者。應瞭解，示意圖將繞軸1400旋轉以提供3-D形狀。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小。Turning to Figure 14, a schematic cross-sectional view of a conical body with a spherical top opening 1402 is provided. The shape has a top 1401 and sides 1405 . The spherical top opening 1402 has a surface 1402a that forms both the sidewalls and the bottom of the opening 1402 . It should be appreciated that the schematic will be rotated about axis 1400 to provide a 3-D shape. Sizes for such figures include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, with other sizes also contemplated.

實例28Example 28

轉向第15圖，提供具有頂部環形開口1505的圓柱形體之橫截面示意圖。形體具有側壁表面1515及頂部或頂表面1510。應瞭解，示意圖將繞軸1500旋轉以提供3-D形狀。環形通道1505之角度1502係藉由在線1501 (其為通道1505之橫截面的中心線)與軸1501之間形成的角度決定。第4F圖中之此角度在此圖式之實施例中為60°，且範圍可在約89°至約0°及較佳地約80°至約40°。用於此形體的大小，包括例如1/2至7吋之高度及約1/2至約17吋之直徑，亦涵蓋其他大小，以及該些大小範圍內之所有值。Turning to Figure 15, a schematic cross-sectional view of a cylindrical body with a top annular opening 1505 is provided. The body has sidewall surfaces 1515 and a top or top surface 1510 . It should be appreciated that the schematic will be rotated about axis 1500 to provide a 3-D shape. Angle 1502 of annular channel 1505 is determined by the angle formed between line 1501 (which is the centerline of the cross-section of channel 1505 ) and axis 1501 . This angle in Figure 4F is 60° in the embodiment of this Figure, and may range from about 89° to about 0° and preferably from about 80° to about 40°. Sizes for this feature include, for example, a height of 1/2 to 7 inches and a diameter of about 1/2 to about 17 inches, and other sizes are also encompassed, and all values within those size ranges.

實例29Example 29

將具有7個九純度及具有0.2 μm之初級粒子D ₅₀大小的粒狀聚合物衍生SiC如下製成空間形體。 Particulate polymer-derived SiC with a purity of 7 nines and a primary particle _D50 size of 0.2 μm was spaced as follows.

將多晶碳氧矽衍生SiC研磨至0.2 μm且在冷壓機中利用達成預固化強度的適合黏合劑壓實成形體(例如，自壓製至固化操作且包括固化操作來操縱形體的能力)。隨後將樣本置放於熱等靜壓機中且在氬氣氛中加熱至2100℃及30000 psi且在緩慢地冷卻降溫之前保持多至5小時。The polycrystalline silicon oxycarbide derived SiC is ground to 0.2 μm and the shaped body is compacted in a cold press with a suitable binder to achieve pre-cured strength (eg, the ability to manipulate the shape from compaction to and including curing operations). The samples were then placed in a hot isostatic press and heated to 2100°C and 30000 psi in an argon atmosphere and held for up to 5 hours before slowly cooling down.

形體可為實例13至28之形體中的任何形體。The shape can be any of the shapes of Examples 13-28.

實例30Example 30

將具有7個九純度及具有1.0 μm之初級粒子D ₅₀大小的粒狀聚合物衍生SiC製成實例13至28之形體中的任何形體。 Particulate polymer derived SiC with a purity of 7 nines and a primary particle _D50 size of 1.0 μm was made into any of the shapes of Examples 13-28.

實例31Example 31

將具有7個九純度及具有1.5 μm之初級粒子D50大小的粒狀聚合物衍生SiC製成實例13至28之形體中的任何形體。Particulate polymer derived SiC with a purity of 7 nines and a primary particle D50 size of 1.5 μm was formed into any of the shapes of Examples 13 to 28.

實例32Example 32

具有約0.4 μm之平均直徑的多晶碳氧矽衍生SiC粒子本質在其表面上不含氧化物層。SiC粒子係使用無氧黏合劑形成為實例13至28之形體中的任何形體。Polycrystalline silicon oxycarbide derived SiC particles with an average diameter of about 0.4 μm are essentially free of oxide layers on their surfaces. SiC particles were formed into any of the shapes of Examples 13-28 using an oxygen-free binder.

實例33Example 33

具有約0.6 μm之平均直徑的多晶碳氧矽衍生SiC粒子本質在其表面上不含氧化物層。SiC粒子係使用僅含有碳及氫之黏合劑形成為實例13至28之形體中的任何形體。Polycrystalline silicon oxycarbide derived SiC particles with an average diameter of about 0.6 μm are essentially free of oxide layers on their surfaces. SiC particles were formed into any of the shapes of Examples 13-28 using a binder containing only carbon and hydrogen.

實例34Example 34

具有約0.4至0.6 μm之平均直徑的多晶碳氧矽衍生SiC粒子本質在其表面上不含氧化物層。SiC粒子係使用含有氫及碳，但不含氧之黏合劑形成為實例13至28之形體中的任何形體。Polycrystalline silicon oxycarbide derived SiC particles having an average diameter of about 0.4 to 0.6 μm are essentially free of oxide layers on their surfaces. SiC particles were formed into any of the shapes of Examples 13-28 using a binder containing hydrogen and carbon, but no oxygen.

實例35Example 35

SiC粒子係使用多晶碳氧矽黏合劑形成為實例13至28之形體中的任何形體。小片具有2 MPa之模數與7.47 MPa之壓縮強度。SiC particles were formed into any of the shapes of Examples 13-28 using a polycrystalline silicon oxycarbide binder. The pellets have a modulus of 2 MPa and a compressive strength of 7.47 MPa.

若需要較大強度，則SiC空間形體可在使用之前經處理用於高溫燒結操作(諸如熱壓或熱等靜壓)。此種操作趨向於提供較低多孔性結構，例如，多孔性＜20%。If greater strength is required, the SiC spacers can be processed for high temperature sintering operations (such as hot pressing or hot isostatic pressing) before use. Such manipulations tend to provide lower porosity structures, eg, <20% porosity.

實例36Example 36

實例13至28之形體中的任何形體之空間形體係由85%至95%之多晶碳氧矽衍生SiC粉末及13%至5%之41/59 MH/TV多晶碳氧矽前驅物製成。The spatial shape system of any of the shapes of Examples 13 to 28 is made of 85% to 95% polycrystalline silicon oxycarbide derived SiC powder and 13% to 5% 41/59 MH/TV polycrystalline silicon oxycarbide precursor become.

實例37Example 37

99%至88%之多晶碳氧矽衍生SiC粉末係與1%至12%之超高純烴蠟(或聚乙烯或僅具有C及H原子之聚合物/油)混合。在壓製成彈丸之前，此混合物係熔融且與實例13至28之形體中的任何或其他空間形體混合在一起。99% to 88% polycrystalline silicon oxycarbide derived SiC powder is mixed with 1% to 12% ultra-high purity hydrocarbon wax (or polyethylene or polymer/oil with only C and H atoms). This mixture was melted and mixed with any of the shapes of Examples 13-28 or other spatial shapes before being pressed into pellets.

實例38Example 38

100%至95%多晶碳氧矽衍生SiC粉末係與0%至5%超高純烴黏合劑混合，且使用火花電漿燒結壓製，產生實例13至28之形體中的任何形體之SiC空間形體，其在部分燒結時具有約0-5%過量碳含量。100% to 95% polycrystalline silicon oxycarbide derived SiC powder is mixed with 0% to 5% ultra-high purity hydrocarbon binder and pressed using spark plasma sintering to produce SiC spaces in any of the shapes of Examples 13 to 28 A body having about 0-5% excess carbon content when partially sintered.

實例40Example 40

實例13-38之空間形體係用於氣相沉積設備以生長單晶SiC之胚晶。胚晶可為3吋、4吋、6吋、8吋及較大，以及該些大小範圍內之所有值。The steric systems of Examples 13-38 were used in vapor deposition equipment to grow embryonic crystals of single crystal SiC. Embryocrystals can be 3 inches, 4 inches, 6 inches, 8 inches and larger, and all values within these size ranges.

用於3吋胚晶之生長的氣相沉積製程概述如下： 1. 石墨部件之清潔及分離：在最少1000℃下真空歷時至少3 h。 2. 加熱：坩堝之頂部處2100-2250℃且壓力為500-700 Torr，氣體流量：100 sccm Ar 在10 h內加熱；達到例如2130-2145℃之溫度；降低溫度至2073℃ 3. 開始生長循環：減小壓力至所要生長壓力(0.1至50托)以起始昇華及生長，隨後減少壓力至15托 4. 生長循環：在2145℃下生長(在坩堝之頂部處的量測點) 5. 生長循環之結束用500-700托氬回填反應器腔室 6. 冷卻在40 h內冷卻降至約環境溫度 The vapor deposition process for the growth of 3-inch embryo crystals is summarized as follows: 1. Cleaning and separation of graphite parts: Vacuum at a minimum of 1000 °C for at least 3 h. 2. Heating: The top of the crucible is at 2100-2250°C and the pressure is 500-700 Torr, Gas Flow: 100 sccm Ar Heating within 10 h; reaching a temperature of e.g. 2130-2145°C; Lower the temperature to 2073°C 3. Start the growth cycle: Reduce pressure to desired growth pressure (0.1 to 50 Torr) to initiate sublimation and growth, then reduce pressure to 15 Torr 4. Growth cycle: Growth at 2145°C (measurement point at top of crucible) 5. The end of the growth cycle Backfill the reactor chamber with 500-700 Torr argon 6. Cooling Cool down to approx. ambient temperature within 40 h

生長循環時間為73小時，生長速率為平均360 μm/h，且胚晶之高度為26.8 mm。消耗約67%之源材料(自610 g起始材料剩下204 g)。The growth cycle time was 73 hours, the growth rate was an average of 360 μm/h, and the height of the embryo crystals was 26.8 mm. About 67% of the source material was consumed (204 g remaining from 610 g starting material).

實例40aExample 40a

實例40之胚晶係使用晶圓切割設備切割成晶圓，該晶圓切割設備諸如金鋼線鋸、多線金剛石鋸、漿料線鋸、具有較大切口損失之其他切割設備，諸如葉片式金剛石切斷鋸或摩切鋸，或具有較小切口損失之其他設備，諸如藉由Disco Tech (KABRA technique，參見，例如，www.discousa.com)報告的光學雷射切刀。晶圓亦可藉由Takatori之多線鋸切割，該等鋸以商標GTI TECHNOLOGIES在美國分銷。所切割晶圓可在需要時使用研磨機研磨。適合的研磨機例如藉由REVASUM提供。參見，例如，www.revasum.com。The embryonic crystals of Example 40 were cut into wafers using wafer cutting equipment such as diamond wire saws, multi-wire diamond saws, slurry wire saws, other cutting equipment with large kerf loss, such as blade type Diamond cut-off saws or friction saws, or other equipment with less kerf loss, such as optical laser cutters reported by Disco Tech (KABRA technique, see, eg, www.discousa.com). Wafers can also be diced by Takatori's multi-wire saws, which are distributed in the United States under the trademark GTI TECHNOLOGIES. The diced wafers can be ground using a grinder if required. Suitable grinders are offered, for example, by REVASUM. See, eg, www.revasum.com.

實例40bExample 40b

實例40a之晶圓在一側上拋光且較佳地在兩側上拋光。拋光儀器例如將包括化學機械拋光(chemical mechanical polishing; CMP)、精磨、研磨、漿料拋光、及乾式拋光。適合的拋光機例如藉由GigaMat Technologies提供。參見，例如，www.gigamat.com。The wafer of Example 40a was polished on one side and preferably on both sides. Polishing equipment includes, for example, chemical mechanical polishing (CMP), lapping, lapping, slurry polishing, and dry polishing. Suitable polishing machines are offered, for example, by GigaMat Technologies. See, eg, www.gigamat.com.

實例40cExample 40c

實例40b之晶圓具有印刷在其上的電路(例如，藉由磊晶術或半導體晶圓處理)以形成電子學部件，例如，電路、電路系統、積體電路。針對6吋晶圓，可形成約300-5000個個別部件。本發明之方法及所得晶圓提供比可由當前晶圓形成的多約3倍至4倍的可使用部件，亦即，可使用裝置之數量，該等當前晶圓係由當前起始材料及製程(亦即，本發明之前的晶圓及製程)製得。例如，約20%至60%、約20%至約50%、約20%或更多的由當前晶圓製得的裝置不可使用。由本發明之晶圓製得的本發明之裝置可使約80%至100%之該些裝置為可操作的，約80%或更多、約90%或更多、約95%或更多、約99%或更多的該些裝置為可操作的。The wafer of Example 40b has circuits printed thereon (eg, by epitaxy or semiconductor wafer processing) to form electronic components, eg, circuits, circuitry, integrated circuits. For a 6-inch wafer, about 300-5000 individual components can be formed. The method and resulting wafers of the present invention provide about 3 to 4 times more usable parts, i.e., the number of usable devices, than can be formed from current wafers from current starting materials and processes (ie, wafers and processes prior to the present invention) were produced. For example, about 20% to 60%, about 20% to about 50%, about 20% or more of devices made from current wafers are unusable. Devices of the present invention made from wafers of the present invention can have about 80% to 100% of the devices operational, about 80% or more, about 90% or more, about 95% or more, About 99% or more of these devices were operational.

實例40dExample 40d

實例40c之電子部件係組裝至電子模組中。模組可含有少數，例如，1-10個電子部件至約100個及約1000個電子部件。模組可為例如電力變壓器單元、金屬氧半導體場效應電晶體(metal oxide semiconductor field effect transistor; MOSFET)、接面場效電晶體(junction field effect transistor; JFET)、絕緣閘雙極電晶體(insulated gate bipolar transistor; IGBT)及雙極型接面電晶體(bipolar junction transistor; BJT)。The electronic components of Example 40c were assembled into an electronic module. Modules may contain a small number, eg, 1-10 electronic components to about 100 and about 1000 electronic components. The module can be, for example, a power transformer unit, a metal oxide semiconductor field effect transistor (MOSFET), a junction field effect transistor (junction field effect transistor; JFET), an insulated gate bipolar transistor (insulated gate bipolar transistor; IGBT) and bipolar junction transistor (bipolar junction transistor; BJT).

實例40eInstance 40e

實例40d之模組係組裝至電力區塊中。約1至約100個模組可用於電力區塊。The module of Example 40d was assembled into a power block. From about 1 to about 100 modules can be used in a power block.

實例40finstance 40f

40d之模組或實例40e之電力區塊係組裝至系統中，該系統例如可為太陽能變換器、風力轉換器、混合車、資料中心、醫學成像裝置，諸如MRI。The module of 40d or the power block of example 40e is assembled into a system such as a solar inverter, a wind inverter, a hybrid vehicle, a data center, a medical imaging device such as an MRI.

實例40gExample 40g

實例40之製程具有6個9純的起始材料，具有在空間形體中之直接通量通道且80%之起始材料在生長循環期間消耗。The process for Example 40 had 6 9 pure starting materials with direct flux channels in the spatial form and 80% of the starting material was consumed during the growth cycle.

實例40hinstance 40h

實例40之製程具有6個9純的起始材料，具有在空間形體中之直接通量通道且90%之起始材料在生長循環期間消耗。The process of Example 40 had 6 9 pure starting materials with direct flux channels in the spatial form and 90% of the starting material was consumed during the growth cycle.

實例40iInstance 40i

實例40之製程具有6個9純的起始材料，具有在空間形體中之直接通量通道且95%之起始材料在生長循環期間消耗。The process for Example 40 had 6 9 pure starting materials with direct flux channels in the spatial form and 95% of the starting material was consumed during the growth cycle.

實例41Example 41

實例40a之晶圓具有DOW CORNING PRIME ULTRA SiC晶圓之特徵。100 mm晶圓具有MPD (＜ 0.1 cm-2)、TSD (＜ 300 cm-2)及BPD (＜ 500 cm-2)。150 mm晶圓具有MPD (＜ 1 cm-2)、TSD (＜ 200 cm-2)及BPD (＜ 3,000 cm-2)。The wafer of Example 40a is characteristic of a DOW CORNING PRIME ULTRA SiC wafer. 100 mm wafers have MPD (< 0.1 cm-2), TSD (< 300 cm-2) and BPD (< 500 cm-2). 150 mm wafers have MPD (< 1 cm-2), TSD (< 200 cm-2) and BPD (< 3,000 cm-2).

實例42Example 42

實例40a之晶圓具有以下特徵，150 mm晶圓具有MPD (＜ 0.1 cm-2)、TSD (＜ 300 cm-2)及BPD (＜ 500 cm-2)。The wafer of Example 40a has the following characteristics, the 150 mm wafer has MPD (<0.1 cm-2), TSD (<300 cm-2) and BPD (<500 cm-2).

實例43Example 43

實例40a之晶圓具有在20℃下大於約10,000 ohm-cm之電阻率。The wafer of Example 40a had a resistivity greater than about 10,000 ohm-cm at 20°C.

對於前述實例，應瞭解，在較佳實施例中，開口在頂部、底部或兩者中；且該些開口與形體之軸同軸且開口各自具有相同一般類型，例如，在頂部及底部兩者上為球形。應理解，在實施例中，開口可在側壁中，其可為相同的或不同於頂部、底部或側壁。開口可相對於形體之軸為同軸或其為離軸的。 概述—多晶碳氧矽調配物、方法及材料 With regard to the preceding examples, it should be understood that in preferred embodiments the openings are in the top, bottom, or both; is spherical. It should be understood that in embodiments the opening may be in a side wall, which may be the same or different from the top, bottom or side wall. The opening can be on-axis relative to the axis of the feature or it can be off-axis. Overview - polycrystalline silicon oxycarbide formulations, methods and materials

用於各種多晶碳氧矽之調配物、製程、製造方法、及組合物係教示及揭示在以下美國專利號：9,499,677、9,481,781，及以下美國專利公開案號：2014/0274658、2014/0323364、2015/0175750、2016/0207782、2016/0280607、2017/0050337中，其每一者之全部揭示內容係以引用方式併入本文中。 用於獲得多晶碳氧矽前驅物之一般製程 Formulations, processes, manufacturing methods, and compositions for various polycrystalline silicon oxycarbides are taught and disclosed in the following U.S. Patent Nos.: 9,499,677; 9,481,781; 2015/0175750, 2016/0207782, 2016/0280607, 2017/0050337, the entire disclosure of each of which is incorporated herein by reference. General process for obtaining polycrystalline silicon oxycarbide precursors

典型地，聚合物衍生陶瓷前驅物調配物、及尤其多晶碳氧矽前驅物調配物可通常藉由三種類型之製程來製成，儘管可利用其他製程、及該些製程之變化及組合。該些製程通常涉及將前驅物組合來形成前驅物調配物。一種類型之製程通常涉及較佳地在無溶劑製程中將前驅物材料混合在一起而基本上無化學反應發生，例如，「混合製程」。其他類型之製程通常涉及化學反應，例如，「反應型製程」以形成特定，例如，客製的前驅物調配物，其可為單體、二聚體、三聚體及聚合物。第三類型之製程在無溶劑環境中具有兩種或兩種以上組分的化學反應，例如，「反應摻合型製程」。通常，在混合製程中，基本上所有及較佳地所有化學反應在後續處理期間發生，諸如在固化、熱解及兩者期間發生。Typically, polymer derived ceramic precursor formulations, and in particular polycrystalline silicon oxycarbide precursor formulations, can generally be made by three types of processes, although other processes, and variations and combinations of these processes can be utilized . These processes generally involve combining precursors to form a precursor formulation. One type of process generally involves mixing precursor materials together, preferably in a solvent-free process, with substantially no chemical reaction occurring, eg, a "hybrid process." Other types of processes generally involve chemical reactions, eg, "reactive processes" to form specific, eg, customized precursor formulations, which can be monomers, dimers, trimers, and polymers. The third type of process involves the chemical reaction of two or more components in a solvent-free environment, for example, "reactive blending process". Typically, in a hybrid process, substantially all and preferably all of the chemical reactions occur during subsequent processing, such as during curing, pyrolysis, and both.

應理解，該些術語—反應型製程、反應摻合型製程、及混合型製程—係出於方便起見且作為速記參考。該些術語，亦即，製程類型不為且不應視為限制。例如，反應型製程可用於產生前驅物材料，其隨後與另一前驅物材料用於混合型製程。It should be understood that these terms—reactive process, reactive blending process, and hybrid process—are used for convenience and as shorthand references. These terms, ie, process type are not and should not be considered limiting. For example, a reactive process can be used to generate a precursor material that is then used in a hybrid process with another precursor material.

該些製程類型係以其各別標題描述於本說明書中以及其他處。應理解，以一個標題對一個製程的教示及以其他標題對其他製程的教示可彼此適用，以及適用於本說明書中之其他部分、實施例及教示內容，且反之亦然。用於一種類型之製程的起始或前驅物材料可用於其他類型之製程。進一步，應理解，以該些標題描述的製程應在上下文中利用本說明書之整體來解讀，包括各種實例及實施例。These process types are described under their respective headings in this specification and elsewhere. It should be understood that teachings of one process under one heading and teachings of other processes under other headings are applicable to each other, as well as to other parts, examples, and teachings in this specification, and vice versa. Starting or precursor materials used in one type of process can be used in other types of process. Further, it should be understood that the processes described under these headings are to be read in context with this specification as a whole, including the various examples and embodiments.

應理解，該些製程之組合及變化可用於達成前驅物調配物，及達成中間物、終點產物、及最終產物。取決於特定製程及產品之所要特徵，用於一種製程類型的前驅物及起始材料可用於其他製程類型。來自混合型製程之調配物可在反應型製程或反應摻合型製程中用作前驅物、或組分。類似地，來自反應型製程之調配物可用於混合型製程及反應摻合製程。類似地，來自反應摻合型製程之調配物可用於混合型製程及反應型製程。因此且較佳地，來自其他製程之最佳效能及特徵可加以組合且用來提供成本有效及高效的製程及終點產物。該些製程提供大的靈活性來產生用於中間物、終點產物、及最終產物之客製特徵，且因此，該些製程之任何製程及其組合可提供特定預定產品。在選擇何種類型之製程為較佳時，可考慮諸如成本、可控制性、儲存壽命、按比例放大、製造簡易性等等之因素。It is understood that combinations and variations of these processes can be used to arrive at precursor formulations, and to arrive at intermediates, end products, and final products. Precursors and starting materials used in one process type may be used in other process types depending on the desired characteristics of the particular process and product. Formulations from hybrid processes can be used as precursors, or components, in reactive or reactive blending processes. Similarly, formulations from reactive processes can be used in hybrid and reactive blending processes. Similarly, formulations from reactive blending processes can be used in hybrid and reactive processes. Thus and preferably, the best properties and features from other processes can be combined and used to provide a cost-effective and efficient process and end product. These processes provide great flexibility to produce custom features for intermediates, end products, and final products, and thus, any of these processes and combinations thereof can provide a specific intended product. Factors such as cost, controllability, shelf life, scale-up, ease of manufacture, etc. may be considered in selecting which type of process is preferred.

前驅物調配物可用以形成「純淨」材料(「純淨」材料係意指所有及基本上所有結構係由前驅物材料或未填充調配物製得；及因此，例如，不存在填料或加強物)。前驅物調配物可用以形成經填充材料，其例如具有除前驅物之外的添加劑或其他材料。其可用以形成複合材料，例如，在其中具有諸如加強物的其他材料之結構或塗層。其可用以形成非加強材料，其為主要、基本上、及較佳地僅由前驅物材料製得的材料，該等前驅物材料例如填充最少的材料，其中填料不意欲增加或增進強度；及未填充材料。其可用於形成加強材料，例如具有纖維或其他材料來增加強度、耐磨性、耐久性、或其他特徵或性質之材料，該等性質通常在廣義上視為強度相關的。Precursor formulations can be used to form "pure" materials ("pure" material means that all and substantially all structures are made from precursor materials or unfilled formulations; and thus, for example, no fillers or reinforcements are present) . Precursor formulations may be used to form filled materials, for example, with additives or other materials other than the precursors. It can be used to form composite materials, for example, structures or coatings with other materials such as reinforcements therein. It can be used to form a non-reinforcing material, which is a material made primarily, substantially, and preferably only from precursor materials, such as minimally filled materials, where the filler is not intended to add or enhance strength; and Unfilled material. It can be used to form reinforced materials, such as materials having fibers or other materials to add strength, wear resistance, durability, or other characteristics or properties generally considered to be strength related in a broad sense.

通常，填料材料之類型包括例如：惰性填料，諸如在固化、熱解或使用期間不與SiOC基質反應的無機材料；反應性填料，諸如在固化、熱解、使用、或該些者之組合期間與SiOC基質反應的鋯、氫氧化鋁、及硼化合物；及，活性填料，諸如在終點產物之使用期間釋放以為彼產物提供特定特徵的材料，例如，潤滑劑。填料可歸入一種以上的該些類型。Typically, types of filler materials include, for example: inert fillers, such as inorganic materials that do not react with the SiOC matrix during curing, pyrolysis, or use; reactive fillers, such as during curing, pyrolysis, use, or combinations thereof Zirconium, aluminum hydroxide, and boron compounds reacted with the SiOC matrix; and, active fillers, such as materials released during the use of the end product to provide specific characteristics to that product, eg, lubricants. Fillers may fall into more than one of these types.

填料材料亦可由與已形成為固化或熱解固體之調配物相同的材料製得或來源於該材料，或其可由已形成為固化固體或半固體、或熱解固體的不同前驅物調配物材料。The filler material may also be made from or derived from the same material as the formulation that has been formed as a cured or pyrolyzed solid, or it may be derived from a different precursor formulation material that has been formed as a cured solid or semi-solid, or a pyrolyzed solid. .

多晶碳氧矽調配物及由彼調配物衍生或製得的產物可具有金屬及金屬錯合物。因此，作為氧化物、碳化物或矽化物之金屬可以受控方式引入前驅物調配物中，且因此引入二氧化矽基質中。例如，過渡金屬之有機金屬、金屬鹵化物(氯化物、溴化物、碘化物)、金屬烷氧化物及金屬醯胺化合物可在二氧化矽基質中經由併入前驅物調配物中來共聚。Polycrystalline silicon oxycarbide formulations and products derived or made from such formulations may have metals and metal complexes. Thus, metals as oxides, carbides or silicides can be introduced in a controlled manner into the precursor formulation, and thus into the silica matrix. For example, organometallics of transition metals, metal halides (chlorides, bromides, iodides), metal alkoxides, and metal amide compounds can be copolymerized in a silica matrix by incorporation into the precursor formulation.

填料材料可賦予、調節或增進例如以下各項之特徵及性質：電阻、磁能力、能帶隙特徵、p-n接面特徵、P型特徵、N型特徵、摻雜劑、導電率、半導體特徵、抗靜電性、光學性質(例如，反射率、折射係數及暈彩)、化學電阻率、耐腐蝕性、耐磨性、抗磨性、熱絕緣、UV穩定性、UV保護性、及可在終點產物或材料中可為合乎需要、必需、及二者兼有的其他特徵或性質。The filler material can impart, adjust or enhance the characteristics and properties of the following items such as: resistance, magnetic ability, energy bandgap characteristics, p-n junction characteristics, P-type characteristics, N-type characteristics, dopants, conductivity, semiconductor characteristics, Antistatic properties, optical properties (e.g., reflectivity, refractive index, and iridescence), chemical resistivity, corrosion resistance, abrasion resistance, abrasion resistance, thermal insulation, UV stability, UV protection, and end point Other features or properties in a product or material that may be desirable, necessary, and both.

因此，填料材料可包括銅鉛絲、熱導電填料、導電填料、鉛、光纖、陶瓷著色劑、顏料、氧化物、染料、粉末、陶瓷細料、聚合物衍生陶瓷粒子、孔隙成形劑、碳氧矽烷(carbosilane)、矽烷、矽氮烷、碳化矽、碳氧矽氮烷(carbosilazane)、矽氧烷、金屬粉末、陶瓷粉末、金屬、金屬錯合物、碳、纖維束、纖維、切斷纖維、含硼材料、研磨纖維、玻璃、玻璃纖維、纖維玻璃、及奈米結構(包括前述各項之奈米結構)，僅舉幾例。例如，可將壓碎的聚合物衍生陶瓷粒子，例如，細料或珠粒添加至多晶碳氧矽調配物且隨後固化以形成經填充的固化塑膠材料，其具有作為塗層或在裝置或裝置之部件中的顯著防火性質。Thus, filler materials may include copper lead wires, thermally conductive fillers, conductive fillers, lead, optical fibers, ceramic colorants, pigments, oxides, dyes, powders, ceramic fines, polymer derived ceramic particles, pore formers, carboxysilanes (carbosilane), silane, silazane, silicon carbide, carbosilazane, siloxane, metal powder, ceramic powder, metal, metal complex, carbon, fiber bundle, fiber, chopped fiber, Boron-containing materials, milled fibers, glass, glass fibers, fiberglass, and nanostructures (including nanostructures of the foregoing), to name a few. For example, crushed polymer-derived ceramic particles, e.g., fines or beads, can be added to the polycrystalline oxycarbide formulation and subsequently cured to form a filled cured plastic material that has Significant fire protection properties in the components.

多晶碳氧矽前驅物調配物可與加強材料一起使用來形成複合層或塗層。因此，例如，調配物可流動至、浸漬至、吸收於或以其他方式組合以薄的加強材料，諸如碳纖維、玻璃纖維、梭織物、非織物、圓錐形纖維、纖維、繩、編織結構、陶瓷粉末、玻璃粉末、碳粉末、石墨粉末、陶瓷纖維、金屬粉末、碳化物團塊或部件、切斷纖維、纖維束、上述各項之奈米結構、PDC、滿足製程及終點產物之溫度要求的任何其他材料、及該些材料之組合及變化。因此，例如，加強材料可為當前與現存塑膠及陶瓷複合材料一起使用或能夠與之一起使用的任何耐高溫加強材料。另外，因為多晶碳氧矽前驅物調配物可經調配用於較低溫度固化(例如，SATP)或例如約37.8℃(100°F)至約204.4℃(400°F)之固化溫度，所以加強材料可為聚合物、有機聚合物，諸如耐綸、聚丙烯、及聚乙烯，以及芳綸纖維，諸如NOMEX或KEVLAR。The polycrystalline silicon oxycarbide precursor formulations can be used with reinforcing materials to form composite layers or coatings. Thus, for example, the formulation can be flowed onto, impregnated into, absorbed into, or otherwise combined with thin reinforcing materials such as carbon fibers, fiberglass, wovens, non-wovens, conical fibers, fibers, ropes, braided structures, ceramics Powder, glass powder, carbon powder, graphite powder, ceramic fiber, metal powder, carbide agglomerates or parts, chopped fibers, fiber bundles, nanostructures of the above, PDC, to meet the temperature requirements of the process and end products Any other materials, and combinations and variations of these materials. Thus, for example, the reinforcement material may be any high temperature resistant reinforcement material currently used or capable of being used with existing plastic and ceramic composite materials. Additionally, because the polysilicon oxycarbide precursor formulations can be formulated for lower temperature cure (e.g., SATP) or cure temperatures such as about 37.8°C (100°F) to about 204.4°C (400°F), Reinforcing materials can be polymers, organic polymers such as nylon, polypropylene, and polyethylene, and aramid fibers such as NOMEX or KEVLAR.

加強材料亦可由與已形成為纖維、固化成固體、熱解成陶瓷的調配物相同的材料製成或來源於該材料，或其可由已形成為纖維、熱解成陶瓷的不同前驅物調配物材料製成，及該些者之組合及變化。除來源於可用作加強材料的前驅物調配物材料的陶瓷纖維之外，可使用來源於前驅物調配物材料之其他多孔、實質上多孔、及非多孔陶瓷結構。The reinforcing material may also be made of or derived from the same material as the formulation that has been formed into fibers, cured into a solid, pyrolyzed into a ceramic, or it may be formulated from a different precursor that has been formed into fibers, pyrolyzed into a ceramic materials, and combinations and variations of these. In addition to ceramic fibers derived from precursor formulation materials that can be used as reinforcement materials, other porous, substantially porous, and non-porous ceramic structures derived from precursor formulation materials can be used.

多晶碳氧矽材料(例如，前驅物批料、前驅物、調配物、主體液體等等)可具有存在的在預定條件下抑制、調節、或促進固化的各種抑制劑、觸媒及起始劑。因此，多晶碳氧矽塗層材料可具有存在的足夠抑制劑，或缺少觸媒，以提供用於儲存材料的所需儲存壽命。 混合型製程 Polycrystalline silicon oxycarbide materials (e.g., precursor batches, precursors, formulations, host liquids, etc.) can have various inhibitors, catalysts, and initiators present that inhibit, regulate, or promote curing under predetermined conditions. agent. Thus, the polycrystalline oxycarbide coating material may have sufficient inhibitor present, or lack of catalyst, to provide the desired shelf life for storing the material. hybrid process

前驅物材料可為甲基氫(甲基封端氫化物取代的聚矽氧烷)、甲基氫流體(甲基封端氫化物甲基取代聚矽氧烷，具有很少至不具有二甲基)及經取代及修飾的甲基氫、矽氧烷主鏈材料、矽氧烷主鏈添加劑、反應性單體、矽氧烷主鏈添加劑與矽烷改質劑或有機改質劑之反應產物、及其他類似類型之材料，諸如基於矽烷的材料、基於矽氮烷的材料、基於碳氧矽烷的材料、非基於矽的有機交聯劑、基於苯酚/甲醛的材料、該些者之組合及變化。前驅物在室溫下較佳地為液體，儘管其可為固體，其經熔融或在其他前驅物之一者中為可溶的。(然而，在此情形中，應理解，當一種前驅物溶解另一前驅物時，其決不被考慮為「溶劑」，因為彼術語係相對於使用非構成性溶劑，例如，不形成終點產物之一部分或組分、視為廢產物、及兩者兼有的溶劑的先前技術製程來使用。)Precursor materials can be methyl hydrogen (methyl-terminated hydride-substituted polysiloxanes), methyl-hydrogen fluids (methyl-terminated hydride methyl-substituted polysiloxanes, with little to no dimethyl base) and substituted and modified methyl hydrogen, siloxane backbone materials, siloxane backbone additives, reactive monomers, reaction products of siloxane backbone additives and silane modifiers or organic modifiers , and other similar types of materials, such as silane-based materials, silazane-based materials, carboxysilane-based materials, non-silicon-based organic crosslinkers, phenol/formaldehyde-based materials, combinations thereof, and Variety. The precursor is preferably liquid at room temperature, although it may be solid, melted or soluble in one of the other precursors. (In this case, however, it should be understood that one precursor is never considered a "solvent" when it dissolves another, as that term is relative to the use of non-constitutive solvents, e.g., no end product formation part or component, considered waste products, and solvents used in prior art processes for both.)

前驅物較佳地在室溫下在容器中混合在一起。較佳地，很少及更佳地無溶劑添加至前驅物材料之此混合物，該等溶劑例如水、有機溶劑、極性溶劑、非極性溶劑、己烷、THF、甲苯。較佳地，每一前驅物材料與其他材料為可混溶的，例如，其可以任何相對量、或以任何比例混合，且將不分離或沉澱。此處，「前驅物混合物」或「多晶碳氧矽前驅物調配物」為競爭性的(注意，若僅使用單一前驅物，則材料將簡單地為「多晶碳氧矽前驅物」或「多晶碳氧矽前驅物調配物」或「調配物」)。雖然相競爭，但可將填料及增強物添加至調配物。在調配物之較佳實施例中，在混合調配物時，或在調配物在固化之前正保持在容器中、預浸體上或歷經一時間段時基本上無及更佳地無化學反應，例如，交聯或聚合發生在該調配物內。The precursors are preferably mixed together in a vessel at room temperature. Preferably, little and preferably no solvent is added to this mixture of precursor materials, such as water, organic solvents, polar solvents, non-polar solvents, hexane, THF, toluene. Preferably, each precursor material is miscible with the other materials, eg, they can be mixed in any relative amount, or in any proportion, and will not separate or precipitate. Here, "precursor mixture" or "polysilicon precursor formulation" are competing (note that if only a single precursor is used, the material will simply be "polysilicon precursor" or "polycrystalline silicon oxycarbide precursor formulation" or "formulation"). Although competing, fillers and reinforcements can be added to the formulation. In preferred embodiments of the formulation, there is substantially no and more preferably no chemical reaction while the formulation is being mixed, or while the formulation is being held in a container, on a prepreg, or over a period of time prior to curing, For example, crosslinking or polymerization occurs within the formulation.

前驅物可在眾多類型之氣氛及條件下混合，例如，空氣、惰性氣體、N ₂、氬、流動氣體、靜態氣體、減壓、高壓、環境壓力、及該些者之組合及變化。 Precursors can be mixed under many types of atmospheres and conditions, such as air, inert gas, _N2 , argon, flowing gas, static gas, reduced pressure, high pressure, ambient pressure, and combinations and variations of these.

另外，可將諸如環己烷、1-乙炔基-1-環己醇(可自ALDRICH獲得)、八甲基化環四矽氧烷(可視為稀釋劑)、及四甲基四乙烯基環四矽氧烷之抑制劑添加至多晶碳氧矽前驅物調配物，例如，以形成抑制的多晶碳氧矽前驅物調配物。應注意，四甲基四乙烯基環四矽氧烷可充當反應物及反應阻滯劑(例如，抑制劑)，此取決於所存在的量及溫度，例如，在室溫下，其為阻滯劑且在高溫下，其為反應物。亦可將其他材料添加至多晶碳氧矽前驅物調配物，例如，在此處在處理中為填充的多晶碳氧矽前驅物調配物，包括填料，諸如SiC粉末、炭黑、砂、聚合物衍生陶瓷粒子、顏料、粒子、奈米管、鬚晶、或本說明書中論述或此項技術中另外已知的其他材料。進一步，具有抑制劑及填料兩者的調配物將考慮為經抑制、填充的多晶碳氧矽前驅物調配物。Additionally, compounds such as cyclohexane, 1-ethynyl-1-cyclohexanol (available from ALDRICH), octamethylcyclotetrasiloxane (which may be considered a diluent), and tetramethyltetravinylcyclo An inhibitor of tetrasiloxane is added to a polycrystalline silicon oxycarbide precursor formulation, for example, to form an inhibited polycrystalline silicon oxycarbide precursor formulation. It should be noted that tetramethyltetravinylcyclotetrasiloxane can act as a reactant as well as a reaction retarder (e.g., inhibitor) depending on the amount and temperature present, e.g., at room temperature, it is a retarding retarder and at high temperatures, it is a reactant. Other materials may also be added to the polycrystalline silicon oxycarbide precursor formulation, for example, here in the process a filled polycrystalline silicon oxycarbide precursor formulation, including fillers such as SiC powder, carbon black, sand, polymeric Derived ceramic particles, pigments, particles, nanotubes, whiskers, or other materials discussed in this specification or otherwise known in the art. Further, formulations with both suppressors and fillers would be considered suppressed, filled polycrystalline silicon oxycarbide precursor formulations.

可使用觸媒或起始劑，且可在固化之前，在將前驅物調配物形成或製成為結構之時、在此之前、在此前不久、或在此前較早時間添加。催化輔助、推進、且促進前驅物調配物之固化以形成固化材料或結構。A catalyst or initiator may be used and may be added prior to curing, at, before, shortly before, or at an earlier time before the precursor formulation is formed or fabricated into a structure. Catalysis assists, propels, and facilitates the curing of the precursor formulation to form a cured material or structure.

觸媒可為任何基於鉑(Pt)之觸媒，其可例如稀釋至以下範圍：約0.01百萬分率(parts per million; ppm) Pt至約250 ppm Pt、約0.03 ppm Pt、約0.1 ppm Pt、約0.2 ppm Pt、約0.5 ppm Pt、約0.02至0.5 ppm Pt、約1 ppm至200 ppm Pt及較佳地對一些應用及實施例而言，約5 ppm至50 ppm Pt。觸媒可為基於過氧化物之觸媒，其例如具有在高於90℃時10小時之半衰期，濃度在0.1%至3%過氧化物之間，及在約0.5%及2%過氧化物之間。其可為基於有機物之過氧化物。其可為能夠與Si-H鍵、Si-OH鍵、或不飽和碳鍵反應的任何有機金屬觸媒，該些觸媒可包括：二月桂酸二丁錫、辛酸鋅、例如鈦、鋯、銠、銥、鈀、鈷或鎳之過氧化物、有機金屬化合物。觸媒亦可為任何其他的銠、錸、銥、鈀、鎳、及釕類型或基於其之觸媒。可使用該些及其他觸媒之組合及變化。觸媒可自ARKEMA以商標名LUPEROX獲得，例如，LUPEROX 231；及自Johnson Matthey以商標名：Karstedt氏觸媒、Ashby氏觸媒、Speier氏觸媒獲得。亦可使用過渡金屬催化，諸如Fe催化、Ni催化、及Co催化，其例如用於生長有序及高度有序的碳結構，諸如碳奈米管。The catalyst can be any platinum (Pt) based catalyst, which can be diluted, for example, to the following ranges: about 0.01 parts per million (ppm) Pt to about 250 ppm Pt, about 0.03 ppm Pt, about 0.1 ppm Pt, about 0.2 ppm Pt, about 0.5 ppm Pt, about 0.02 to 0.5 ppm Pt, about 1 ppm to 200 ppm Pt, and preferably for some applications and embodiments, about 5 ppm to 50 ppm Pt. The catalyst may be a peroxide-based catalyst, for example with a half-life of 10 hours above 90°C, at a concentration between 0.1% and 3% peroxide, and between about 0.5% and 2% peroxide between. It may be an organic based peroxide. It can be any organometallic catalyst capable of reacting with Si-H bonds, Si-OH bonds, or unsaturated carbon bonds, and these catalysts can include: dibutyltin dilaurate, zinc octoate, such as titanium, zirconium, Peroxides and organometallic compounds of rhodium, iridium, palladium, cobalt or nickel. The catalyst may also be any other rhodium, rhenium, iridium, palladium, nickel, and ruthenium types or catalysts based thereon. Combinations and variations of these and other catalysts can be used. Catalysts are available from ARKEMA under the trade names LUPEROX, eg, LUPEROX 231; and from Johnson Matthey under the trade names: Karstedt's catalyst, Ashby's catalyst, Speier's catalyst. Transition metal catalysis, such as Fe catalysis, Ni catalysis, and Co catalysis, for example for growing ordered and highly ordered carbon structures such as carbon nanotubes, can also be used.

進一步，可使用該些及其他觸媒之客製及特定組合，以使得其匹配於特定調配物，且以此方式，選擇性地及特定地催化特定成分之反應。此外，使用該些類型之匹配觸媒-調配物系統，以及製程條件可用以提供預定產品特徵，諸如例如，孔隙結構、多孔性、密度、密度分佈、高純度、超高純度、及固化結構或材料及在一些情況下由固化結構或材料形成的陶瓷之其他形態學或特徵。Further, custom and specific combinations of these and other catalysts can be used such that they are matched to a specific formulation and in this way selectively and specifically catalyze the reaction of specific ingredients. Furthermore, using these types of matched catalyst-formulation systems, and process conditions can be used to provide predetermined product characteristics such as, for example, pore structure, porosity, density, density distribution, high purity, ultrahigh purity, and solidified structure or Other morphology or characteristics of materials and, in some cases, ceramics formed from cured structures or materials.

在用於製造前驅物調配物之此混合型製程中，較佳地化學反應或分子重排僅在製造原始起始材料期間、在固化製程期間、及在熱解製程中發生。較佳地，在該些混合型之調配物及製程之實施例中，聚合、交聯或其他化學反應主要、較佳地基本上、及更佳地僅僅在固化製程期間發生。In this hybrid process for making precursor formulations, preferably chemical reactions or molecular rearrangements occur only during the manufacture of the pristine starting material, during the curing process, and during the pyrolysis process. Preferably, in these hybrid formulation and process embodiments, polymerization, crosslinking or other chemical reactions occur primarily, preferably substantially, and more preferably only during the curing process.

前驅物可為甲基封端氫化物取代的聚矽氧烷，其可在本文稱為甲基氫(MH)，其具有下文展示的式。

The precursor may be a methyl-terminated hydride-substituted polysiloxane, which may be referred to herein as methyl hydrogen (MH), having the formula shown below.

MH例如可具有約400 mw至約10,000 mw、約600 mw至約3,000 mw之分子量(molecular weight;「mw」，其可作為amu中重量平均分子量之或作為g/mol量測)，且可具有較佳地約20 cps至約60 cps之黏度。甲基矽氧烷單元之百分比「X」可為1%至100%。二甲基矽氧烷單元之百分比「Y」可為0%至99%。此前驅物可用以為固化預成型件及陶瓷材料提供交聯結構之主鏈，以及其他特徵及特性。此前驅物亦可尤其藉由與不飽和碳化合物反應來改質以生產新的或另外的前驅物。典型地，甲基氫流體(methyl hydrogen fluid; MHF)具有最少量之「Y」，且更佳地「Y」對所有目的而言皆為零。MH, for example, can have a molecular weight (molecular weight; "mw", which can be measured as the weight average molecular weight in amu or as g/mol) of about 400 mw to about 10,000 mw, about 600 mw to about 3,000 mw, and can have A viscosity of about 20 cps to about 60 cps is preferred. The percentage "X" of methylsiloxane units can range from 1% to 100%. The percentage "Y" of dimethylsiloxane units can range from 0% to 99%. This precursor can be used to provide the backbone of the cross-linked structure, among other features and properties, for curing preforms and ceramic materials. This precursor can also be modified to produce new or additional precursors, inter alia by reacting with unsaturated carbon compounds. Typically, methyl hydrogen fluid (MHF) has the least amount of "Y", and more preferably "Y" is zero for all purposes.

前驅物可為任何以下直鏈矽氧烷主鏈材料。The precursor can be any of the following linear siloxane backbone materials.

前驅物可為乙烯基取代的聚二甲基矽氧烷，其式在下文展示。

The precursor may be a vinyl substituted polydimethylsiloxane, the formula of which is shown below.

此前驅物例如可具有約400 mw至約10,000 mw之分子量(mw)，且可具有較佳地約50 cps至約2,000 cps之黏度。甲基乙烯基矽氧烷單元之百分比「X」可為1%至100%。二甲基矽氧烷單元之百分比「Y」可為0%至99%。較佳地，Ｘ為約100%。此前驅物可用以為固化預成型件及陶瓷材料增加交聯密度並改良韌性，以及其他特徵及特性。The precursor, for example, may have a molecular weight (mw) of about 400 mw to about 10,000 mw, and may preferably have a viscosity of about 50 cps to about 2,000 cps. The percentage "X" of methylvinylsiloxane units may range from 1% to 100%. The percentage "Y" of dimethylsiloxane units can range from 0% to 99%. Preferably, X is about 100%. This precursor can be used to increase crosslink density and improve toughness, among other features and properties, for cured preforms and ceramic materials.

前驅物可為乙烯基取代及乙烯基封端的聚二甲基矽氧烷，其式在下文展示。

The precursors can be vinyl-substituted and vinyl-terminated polydimethylsiloxanes, the formulas of which are shown below.

此前驅物例如可具有約500 mw至約15,000 mw之分子量(mw)，且可較佳地具有約500 mw至1,000 mw之分子量，且可具有較佳地約10 cps至約200 cps之黏度。甲基乙烯基矽氧烷單元之百分比「X」可為1%至100%。二甲基矽氧烷單元之百分比「Y」可為0%至99%。此前驅物可用以為固化預成型件及陶瓷材料提供分支並減少固化溫度，以及其他特徵及特性。The precursor, for example, may have a molecular weight (mw) of about 500 mw to about 15,000 mw, and may preferably have a molecular weight of about 500 mw to 1,000 mw, and may have a viscosity of preferably about 10 cps to about 200 cps. The percentage "X" of methylvinylsiloxane units may range from 1% to 100%. The percentage "Y" of dimethylsiloxane units can range from 0% to 99%. This precursor can be used to provide branching and reduce curing temperature for curing preforms and ceramic materials, among other features and properties.

前驅物可為乙烯基取代及氫封端的聚二甲基矽氧烷，其式在下文展示。

The precursor may be a vinyl-substituted and hydrogen-terminated polydimethylsiloxane, the formula of which is shown below.

此前驅物可具有約300 mw至約10,000 mw之分子量(mw)，且可較佳地具有約400 mw至800 mw之分子量，且可具有較佳地約20 cps至約300 cps之黏度。甲基乙烯基矽氧烷單元之百分比「X」可為1%至100%。二甲基矽氧烷單元之百分比「Y」可為0%至99%。此前驅物可用以為固化預成型件及陶瓷材料提供分支並減少固化溫度，以及其他特徵及特性。This precursor may have a molecular weight (mw) of about 300 mw to about 10,000 mw, and may preferably have a molecular weight of about 400 mw to 800 mw, and may have a viscosity of preferably about 20 cps to about 300 cps. The percentage "X" of methylvinylsiloxane units may range from 1% to 100%. The percentage "Y" of dimethylsiloxane units can range from 0% to 99%. This precursor can be used to provide branching and reduce curing temperature for curing preforms and ceramic materials, among other features and properties.

前驅物可為烯丙基封端的聚二甲基矽氧烷，其式在下文展示。

The precursor may be an allyl terminated polydimethylsiloxane, the formula of which is shown below.

此前驅物可具有約400 mw至約10,000 mw之分子量(mw)，且可具有較佳地約40 cps至約400 cps之黏度。重複單元為相同的。此前驅物可用以為固化預成型件及陶瓷材料提供UV可固化性並延伸聚合鏈，以及其他特徵及特性。This precursor may have a molecular weight (mw) of about 400 mw to about 10,000 mw, and may preferably have a viscosity of about 40 cps to about 400 cps. Repeating units are identical. This precursor can be used to provide UV curability and extend polymeric chains, among other features and properties, for curing preforms and ceramic materials.

前驅物可為乙烯基封端的聚二甲基矽氧烷(VT)，其式在下文展示。

The precursor may be vinyl terminated polydimethylsiloxane (VT), the formula of which is shown below.

此前驅物可具有約200 mw至約5,000 mw之分子量(mw)，且可較佳地具有約400 mw至1,500 mw之分子量，且可具有較佳地約10 cps至約400 cps之黏度。重複單元為相同的。此前驅物可用以為固化預成型件及陶瓷材料提供聚合鏈延伸劑，改良韌性並提供較低固化溫度至例如室溫固化，以及其他特徵及特性。This precursor may have a molecular weight (mw) of about 200 mw to about 5,000 mw, and may preferably have a molecular weight of about 400 mw to 1,500 mw, and may have a viscosity of preferably about 10 cps to about 400 cps. Repeating units are identical. This precursor can be used to provide polymeric chain extenders for curing preforms and ceramic materials, improve toughness and provide lower curing temperatures to, for example, room temperature curing, among other features and properties.

前驅物可為矽醇(羥基)封端的聚二甲基矽氧烷，其式在下文展示。

The precursor may be a silanol (hydroxyl) terminated polydimethylsiloxane, the formula of which is shown below.

此前驅物可具有約400 mw至約10,000 mw之分子量(mw)，且可較佳地具有約600 mw至1,000 mw之分子量，且可具有較佳地約30 cps至約400 cps之黏度。重複單元為相同的。此前驅物可用以為固化預成型件及陶瓷材料提供聚合鏈延伸劑，韌化機制，可產生奈米及微米尺度多孔性，且允許在室溫下固化，以及其他特徵及特性。This precursor may have a molecular weight (mw) of about 400 mw to about 10,000 mw, and may preferably have a molecular weight of about 600 mw to 1,000 mw, and may have a viscosity of preferably about 30 cps to about 400 cps. Repeating units are identical. This precursor can provide a polymeric chain extender for curing preforms and ceramic materials, a toughening mechanism, can generate nano- and micro-scale porosity, and allow curing at room temperature, among other features and properties.

前驅物可為矽醇(羥基)封端的乙烯基取代的二甲基矽氧烷，其式在下文展示。

The precursor may be a silanol (hydroxyl) terminated vinyl substituted dimethylsiloxane, the formula of which is shown below.

此前驅物可具有約400 mw至約10,000 mw之分子量(mw)，且可較佳地具有約600 mw至1,000 mw之分子量，且可具有較佳地約30 cps至約400 cps之黏度。甲基乙烯基矽氧烷單元之百分比「X」可為1%至100%。二甲基矽氧烷單元之百分比「Y」可為0%至99%。此前驅物可尤其用於雙固化系統；以此方式，雙固化可允許在單一調配物中使用多種固化機制。例如，可使用縮合型固化及加成型固化兩者。此繼而提供具有複合固化分佈之能力，其例如可經由一種類型之固化提供初始固化且經由單獨類型之固化提供最終固化。This precursor may have a molecular weight (mw) of about 400 mw to about 10,000 mw, and may preferably have a molecular weight of about 600 mw to 1,000 mw, and may have a viscosity of preferably about 30 cps to about 400 cps. The percentage "X" of methylvinylsiloxane units may range from 1% to 100%. The percentage "Y" of dimethylsiloxane units can range from 0% to 99%. This precursor is especially useful in dual-cure systems; in this way, dual-cure can allow the use of multiple cure mechanisms in a single formulation. For example, both condensation-type curing and addition-type curing can be used. This in turn provides the ability to have a composite cure profile which, for example, can provide an initial cure via one type of cure and a final cure via a separate type of cure.

前驅物可為氫(氫化物)封端的聚二甲基矽氧烷，其式在下文展示。

The precursor may be a hydrogen (hydride) terminated polydimethylsiloxane, the formula of which is shown below.

此前驅物可具有約200 mw至約10,000 mw之分子量(mw)，且可較佳地具有約500 mw至1,500 mw之分子量，且可具有較佳地約20 cps至約400 cps之黏度。重複單元為相同的。此前驅物可用以為固化預成型件及陶瓷材料提供聚合鏈延伸劑，作為增韌劑，且其允許較低溫度固化，例如，室溫，以及其他特徵及特性。This precursor may have a molecular weight (mw) from about 200 mw to about 10,000 mw, and may preferably have a molecular weight from about 500 mw to 1,500 mw, and may have a viscosity, preferably from about 20 cps to about 400 cps. Repeating units are identical. This precursor can provide polymeric chain extenders for curing preforms and ceramic materials, act as a toughening agent, and it allows lower temperature curing, eg, room temperature, among other features and properties.

前驅物可為二苯基封端的矽氧烷(其亦可稱為苯基封端的)，其式在下文展示。

The precursor may be a diphenyl-terminated siloxane (which may also be referred to as phenyl-terminated), the formula of which is shown below.

其中此處的R為反應性基團，諸如乙烯基、羥基、或氫化物。此前驅物可具有約500 mw至約2,000 mw之分子量(mw)，且可具有較佳地約80 cps至約300 cps之黏度。甲基-R-矽氧烷單元「X」之百分比可為1%至100%。二甲基矽氧烷單元之百分比「Y」可為0%至99%。此前驅物可用以為固化預成型件及陶瓷材料提供增韌劑，並調整聚合物之折射率以匹配各種類型玻璃之折射率，提供示例性透明纖維玻璃，以及其他特徵及特性。Wherein R here is a reactive group, such as vinyl, hydroxyl, or hydride. This precursor may have a molecular weight (mw) of about 500 mw to about 2,000 mw, and may preferably have a viscosity of about 80 cps to about 300 cps. The percentage of methyl-R-siloxane units "X" can range from 1% to 100%. The percentage "Y" of dimethylsiloxane units can range from 0% to 99%. This precursor can provide a toughening agent for curing preforms and ceramic materials, and adjust the refractive index of the polymer to match that of various types of glass, provide exemplary transparent fiberglass, among other features and properties.

前驅物可為單苯基封端的矽氧烷(其亦可稱為三甲基封端、苯基封端的矽氧烷)，其式在下文展示。

The precursor may be a monophenyl-terminated siloxane (which may also be referred to as trimethyl-terminated, phenyl-terminated siloxane), the formula of which is shown below.

其中R為反應性基團，諸如乙烯基、羥基、或氫化物。此前驅物可具有約500 mw至約2,000 mw之分子量(mw)，且可具有較佳地約80 cps至約300 cps之黏度。甲基-R-矽氧烷單元「X」之百分比可為1%至100%。二甲基矽氧烷單元之百分比「Y」可為0%至99%。此前驅物可用以為固化預成型件及陶瓷材料提供增韌劑並調整聚合物之折射率以匹配各種類型玻璃之折射率，提供示例性透明纖維玻璃，以及其他特徵及特性。wherein R is a reactive group such as vinyl, hydroxyl, or hydride. This precursor may have a molecular weight (mw) of about 500 mw to about 2,000 mw, and may preferably have a viscosity of about 80 cps to about 300 cps. The percentage of methyl-R-siloxane units "X" can range from 1% to 100%. The percentage "Y" of dimethylsiloxane units can range from 0% to 99%. This precursor can be used to provide a toughening agent for curing preforms and ceramic materials and adjust the refractive index of the polymer to match that of various types of glass, provide exemplary transparent fiberglass, and other features and properties.

前驅物可為聯苯二甲基聚矽氧烷，其式在下文展示。

The precursor may be biphenyldimethylpolysiloxane, the formula of which is shown below.

此前驅物可具有約500 mw至約20,000 mw之分子量(mw)，且可具有約800至約4,000之分子量，且可具有較佳地約100 cps至約800 cps之黏度。二甲基矽氧烷單元之百分比「X」可為25%至95%。聯苯矽氧烷單元之百分比「Y」可為5%至75%。此前驅物可用以為固化預成型件及陶瓷材料提供與單苯基封端的矽氧烷類似的特性，以及其他特徵及特性。The precursor may have a molecular weight (mw) of about 500 mw to about 20,000 mw, and may have a molecular weight of about 800 to about 4,000, and may have a viscosity of preferably about 100 cps to about 800 cps. The percentage "X" of dimethylsiloxane units may range from 25% to 95%. The percentage "Y" of biphenylsiloxane units may range from 5% to 75%. This precursor can be used to provide properties similar to monophenyl terminated siloxanes, as well as other features and properties, for cured preforms and ceramic materials.

前驅物可為乙烯基封端的聯苯二甲基聚矽氧烷，其式在下文展示。

The precursor may be a vinyl terminated biphenyl dimethicone, the formula of which is shown below.

此前驅物可具有約400 mw至約20,000 mw之分子量(mw)，且可具有約800至約2,000之分子量，且可具有較佳地約80 cps至約600 cps之黏度。二甲基矽氧烷單元之百分比「X」可為25%至95%。聯苯矽氧烷單元之百分比「Y」可為5%至75%。此前驅物可用以為固化預成型件及陶瓷材料提供鏈延伸、增韌劑、改變或變更的折射率、及對固化材料之高溫熱穩定性的改良，以及其他特徵及特性。The precursor may have a molecular weight (mw) of about 400 mw to about 20,000 mw, and may have a molecular weight of about 800 to about 2,000, and may have a viscosity of preferably about 80 cps to about 600 cps. The percentage "X" of dimethylsiloxane units may range from 25% to 95%. The percentage "Y" of biphenylsiloxane units may range from 5% to 75%. This precursor can be used to provide chain extensions, tougheners, altered or altered refractive indices, and improvements to high temperature thermal stability of cured materials, among other features and properties, for cured preforms and ceramic materials.

前驅物可為羥基封端的聯苯二甲基聚矽氧烷，其式在下文展示。

The precursor may be a hydroxyl-terminated biphenyldimethylpolysiloxane, the formula of which is shown below.

此前驅物可具有約400 mw至約20,000 mw之分子量(mw)，且可具有約800至約2,000之分子量，且可具有較佳地約80 cps至約400 cps之黏度。二甲基矽氧烷單元之百分比「X」可為25%至95%。聯苯矽氧烷單元之百分比「Y」可為5%至75%。此前驅物可用以為固化預成型件及陶瓷材料提供鏈延伸、增韌劑、改變或變更的折射率、及對固化材料之高溫熱穩定性的改良，可產生奈米及微米尺度多孔性，以及其他特徵及特性。This precursor may have a molecular weight (mw) of about 400 mw to about 20,000 mw, and may have a molecular weight of about 800 to about 2,000, and may have a viscosity of preferably about 80 cps to about 400 cps. The percentage "X" of dimethylsiloxane units may range from 25% to 95%. The percentage "Y" of biphenylsiloxane units may range from 5% to 75%. This precursor can be used to provide chain extension, toughening agent, modified or modified refractive index, and improvement of high temperature thermal stability of cured materials for curing preforms and ceramic materials, which can produce nano- and micro-scale porosity, and other features and characteristics.

此前驅物可為甲基封端的苯乙基聚矽氧烷(其亦可稱為苯乙烯乙烯基苯二甲基聚矽氧烷)，其式在下文展示。

This precursor may be methyl-terminated phenylethylpolysiloxane (which may also be referred to as styrenevinylxyldimethylpolysiloxane), the formula of which is shown below.

此前驅物可具有約800 mw至至少約10,000 mw至至少約20,000 mw之分子量(mw)，且可具有較佳地約50 cps至約350 cps之黏度。苯乙烯乙烯基苯矽氧烷單元之百分比「X」可為1%至60%。二甲基矽氧烷單元之百分比「Y」可為40%至99%。此前驅物可用以為固化預成型件及陶瓷材料提供改良韌性，降低反應固化放熱量，可改變或變更折射率，調整聚合物之折射率以匹配各種類型玻璃之折射率，提供示例性透明纖維玻璃，以及其他特徵及特性。This precursor may have a molecular weight (mw) from about 800 mw to at least about 10,000 mw to at least about 20,000 mw, and may have a viscosity preferably from about 50 cps to about 350 cps. The percentage "X" of styrene vinylphenyl siloxane units may range from 1% to 60%. The percentage "Y" of dimethylsiloxane units may range from 40% to 99%. This precursor can be used to provide improved toughness for curing preforms and ceramic materials, reduce the reaction curing exotherm, can change or change the refractive index, adjust the refractive index of the polymer to match the refractive index of various types of glass, and provide exemplary transparent fiberglass , and other features and properties.

前述直鏈矽氧烷主鏈材料係舉例而言，且應瞭解其他類似的直鏈矽氧烷主鏈材料亦可用作前驅物。更多複雜直鏈及支鏈的矽氧烷主鏈材料可用作前驅物，但不為較佳的。The foregoing linear siloxane backbone materials are examples, and it should be understood that other similar linear siloxane backbone materials may also be used as precursors. More complex linear and branched siloxane backbone materials can be used as precursors, but are not preferred.

各種環矽氧烷可用作調配物中之前驅物，且為反應性分子。其可藉由以下命名系統或式來描述：DxD*y，其中「D」表示二甲基矽氧基單元且「D*」表示取代的甲基矽氧基單元，其中「*」基團可為乙烯基、烯丙基、氫化物、羥基、苯基、苯乙烯基、烷基、環戊二烯基、或其他有機基團，x為0-8，y為＞ = 1，且x+y為3-8。進一步，在此命名系統中，-D表示-SiO ₂基團，典型地Me ₂SiO ₂，Q表示SiO ₄，T表示-SiO ₃基團，典型地MeSiO ₃且M表示-SiO基團，典型地Me ₃SiO。 Various cyclosiloxanes can be used as precursors in formulations and are reactive molecules. It can be described by the following nomenclature system or formula: DxD*y, where "D" denotes a dimethylsiloxy unit and "D*" denotes a substituted methylsiloxy unit, where the "*" group can be is vinyl, allyl, hydride, hydroxyl, phenyl, styryl, alkyl, cyclopentadienyl, or other organic groups, x is 0-8, y is >= 1, and x+ y is 3-8. Further, in this nomenclature system, -D represents a -SiO ₂ group, typically Me ₂ SiO ₂ , Q represents SiO ₄ , T represents a -SiO ₃ group, typically MeSiO ₃ and M represents a -SiO group, typically to Me ₃ SiO.

前驅物批料亦可：(i)含有非基於矽的前驅物，諸如非基於矽的交聯劑；(ii)為非基於矽的交聯劑及基於矽的前驅物之反應產物；及，(iii)該些者之組合及變化。非基於矽的交聯劑意欲且提供在固化期間交聯的能力。例如，非基於矽的交聯劑包括：環戊二烯(cyclopentadiene; CP)、甲基環戊二烯(methylcyclopentadiene; MeCP)、二環戊二烯(dicyclopentadiene; DCPD)、甲基二環戊二烯(methyldicyclopentadiene; MeDCPD)、三環戊二烯(tricyclopentadiene; TCPD)、1,3-戊二烯、二乙烯基苯、異戊二烯、降莰二烯、乙烯基降莰烯、丙烯基降莰烯、異丙烯基降莰烯、甲基乙烯基降莰烯、二環壬二烯、甲基二環壬二烯、丙二烯、4-乙烯基環己烯、1,3-庚二烯、環庚二烯、1,3-丁二烯、環辛二烯及其異構物。通常，含有兩個(或更多個)可與前驅物中的Si-H或其他矽鍵反應的不飽和C = C鍵的任何烴可用作交聯劑。含有氧、氮、及硫的一些有機材料亦可充當交聯劑。The precursor batch can also: (i) contain a non-silicon-based precursor, such as a non-silicon-based crosslinker; (ii) be the reaction product of a non-silicon-based crosslinker and a silicon-based precursor; and, (iii) combinations and variations of these. Non-silicon based crosslinkers are intended and provide the ability to crosslink during curing. For example, non-silicon-based cross-linking agents include: cyclopentadiene (CP), methylcyclopentadiene (MeCP), dicyclopentadiene (DCPD), methyldicyclopentadiene Methyldicyclopentadiene (MeDCPD), tricyclopentadiene (TCPD), 1,3-pentadiene, divinylbenzene, isoprene, norcamdiene, vinyl norcamphene, propenyl norcamphene Camphene, Isopropenylnorcamphene, Methylvinylnorcamphene, Bicyclononadiene, Methylbicyclononadiene, Propylene, 4-Vinylcyclohexene, 1,3-Heptanediene ene, cycloheptadiene, 1,3-butadiene, cyclooctadiene and their isomers. In general, any hydrocarbon containing two (or more) unsaturated C=C bonds that can react with Si-H or other silicon bonds in the precursor can be used as a crosslinker. Some organic materials containing oxygen, nitrogen, and sulfur can also act as crosslinkers.

非基於矽的交聯劑對基於矽的前驅物之量可為約10%至90%非基於矽的交聯劑至10%至90%基於矽的前驅物(較佳地，矽主鏈，例如，-Si-O-主鏈材料)。因此，量之範圍可為例如：DCPD/MHF為10/90至90/10、約40/60至60/40、約50/50、及該些比率之組合及變化，以及其他比率。亦可使用第三及第四前驅物材料。因此，非矽交聯劑/矽主鏈前驅物/第三前驅物之比率可為：約10%至約80%非基於矽的交聯劑；約10%至80%基於矽的前驅物：及約0.1%至40%第三前驅物。範圍及量可例如：DCPD/MHF/第三前驅物為約10/20/70至70/20/10、約10/20/70至10/70/20、約45/55/10至約55/45/10、約40/55/5至約55/40/5及該些比率之組合及變化以及其他比率。The amount of non-silicon-based crosslinker to silicon-based precursor can be about 10% to 90% non-silicon-based crosslinker to 10% to 90% silicon-based precursor (preferably, the silicon backbone, For example, -Si-O- backbone material). Thus, ranges of amounts can be, for example: DCPD/MHF of 10/90 to 90/10, about 40/60 to 60/40, about 50/50, and combinations and variations of these ratios, among other ratios. Third and fourth precursor materials may also be used. Thus, the ratio of non-silicon crosslinker/silicon backbone precursor/third precursor can be: about 10% to about 80% non-silicon-based crosslinker; about 10% to 80% silicon-based precursor: and about 0.1% to 40% of the third precursor. The range and amount can be for example: DCPD/MHF/the third precursor is about 10/20/70 to 70/20/10, about 10/20/70 to 10/70/20, about 45/55/10 to about 55 /45/10, about 40/55/5 to about 55/40/5 and combinations and variations of these ratios and other ratios.

前驅物可為反應性單體。該些前驅物將包括分子，諸如四甲基四乙烯基環四矽氧烷(TV)，其式在下文展示。

Precursors can be reactive monomers. These precursors would include molecules such as tetramethyltetravinylcyclotetrasiloxane (TV), the formula of which is shown below.

此前驅物可用以為固化預成型件及陶瓷材料提供支化劑、三維交聯劑，以及其他特徵及特性。(亦應注意，在某些調配物，例如，高於2%，及某些溫度，例如，約室溫至約60℃中，此前驅物可充當交聯之抑制劑，例如，可抑制氫化物及乙烯基之交聯。)This precursor can be used to provide branching agents, three-dimensional crosslinking agents, and other features and properties for curing preforms and ceramic materials. (It should also be noted that in certain formulations, e.g., above 2%, and at certain temperatures, e.g., about room temperature to about 60° C., this precursor may act as an inhibitor of crosslinking, e.g., may inhibit hydrogenation Cross-linking of materials and vinyl.)

前驅物可為反應性單體，例如，諸如三乙烯基環四矽氧烷，

The precursor may be a reactive monomer such as, for example, trivinylcyclotetrasiloxane,

二乙烯基環四矽氧烷，

Divinylcyclotetrasiloxane,

三乙烯基單氫化物環四矽氧烷，

Trivinyl monohydride cyclotetrasiloxane,

二乙烯基二氫化物環四矽氧烷，

Divinyl dihydride cyclotetrasiloxane,

及六甲基環四矽氧烷，諸如，

and hexamethylcyclotetrasiloxane, such as,

前驅物可為矽烷改質劑，諸如乙烯基苯基甲基矽烷、聯苯矽烷、聯苯甲基矽烷、及苯基甲基矽烷(其中一些可用作封端劑或封端基團)。該些矽烷改質劑可提供鏈延伸劑及支化劑。其亦改良韌性，變更折射率，且改良固化材料之高溫固化穩定性，以及改良固化材料之強度，以及其他。諸如聯苯甲基矽烷之前驅物可充當封端劑，其亦可改良韌性，變更折射率，且改良固化材料之高溫固化穩定性，以及，改良固化材料之強度，以及其他。The precursor can be a silane modifier such as vinylphenylmethylsilane, biphenylsilane, biphenylmethylsilane, and phenylmethylsilane (some of which can be used as capping agents or capping groups). These silane modifiers can provide chain extenders and branching agents. It also improves toughness, changes the refractive index, and improves the high temperature cure stability of the cured material, and improves the strength of the cured material, among others. Precursors such as biphenylmethylsilane can act as capping agents, which can also improve toughness, change the refractive index, and improve the high temperature curing stability of the cured material, and improve the strength of the cured material, among others.

前驅物可為矽烷改質劑與乙烯基封端的矽氧烷主鏈添加劑之反應產物。前驅物可為矽烷改質劑與羥基封端的矽氧烷主鏈添加劑之反應產物。前驅物可為矽烷改質劑與氫化物封端的矽氧烷主鏈添加劑之反應產物。前驅物可為矽烷改質劑與TV之反應產物。前驅物可為矽烷之反應產物。前驅物可為矽烷改質劑與環矽氧烷之反應產物，考慮到立體阻礙。前驅物可為部分水解的正矽酸四乙酯，諸如TES 40或Silbond 40。前驅物亦可為甲基倍半矽氧烷，諸如可自Momentive (先前來自General Electric Company, Wilton, Conn)的SR-350。前驅物亦可為苯基甲基矽氧烷，諸如來自Wacker Chemie AG之604。前驅物亦可為甲基苯基乙烯基矽氧烷，諸如來自Wacker Chemie AG之H62 C。The precursor can be a reaction product of a silane modifier and a vinyl-terminated siloxane backbone additive. The precursor can be a reaction product of a silane modifier and a hydroxyl-terminated siloxane backbone additive. The precursor may be a reaction product of a silane modifier and a hydride-terminated siloxane backbone additive. The precursor can be the reaction product of silane modifier and TV. The precursors can be reaction products of silanes. The precursor can be the reaction product of silane modifying agent and cyclosiloxane, considering steric hindrance. The precursor may be partially hydrolyzed tetraethylorthosilicate, such as TES 40 or Silbond 40. The precursor may also be a methylsilsesquioxane such as SR-350 available from Momentive (formerly from General Electric Company, Wilton, Conn). The precursor may also be a phenylmethylsiloxane such as 604 from Wacker Chemie AG. The precursor may also be a methylphenylvinylsiloxane, such as H62C from Wacker Chemie AG.

前驅物亦可係選自以下各項：SiSiB® HF2020，三甲基矽基封端的甲基氫聚矽氧流體63148-57-2；SiSiB® HF2050三甲基矽基封端的甲基氫矽氧烷二甲基矽氧烷共聚物68037-59-2；SiSiB® HF2060氫化物封端的甲基氫矽氧烷二甲基矽氧烷共聚物69013-23-6；SiSiB® HF2038氫封端的聚聯苯矽氧烷；SiSiB® HF2068氫化物封端的甲基氫矽氧烷二甲基矽氧烷共聚物11548749-5；SiSiB® HF2078氫化物封端的聚(苯基二甲基矽氧基)矽氧烷苯基矽倍半氧烷，氫封端的68952-30-7；SiSiB® VF6060乙烯基二甲基封端的乙烯基甲基二甲基聚矽氧烷共聚物68083-18-1；SiSiB® VF6862乙烯基二甲基封端的二甲基聯苯聚矽氧烷共聚物68951-96-2；SiSiB® VF6872乙烯基二甲基封端的二甲基-甲基乙烯基-聯苯聚矽氧烷共聚物；SiSiB® PC9401 1,1,3,3-四甲基-1,3-二乙烯基二矽氧烷2627-95-4；SiSiB® PF1070矽醇封端的聚二甲基矽氧烷(OF1070) 70131-67-8；SiSiB® OF1070矽醇封端的聚二甲基矽氧烷70131-67-8；OH-封端的聚二甲基矽氧烷，羥基封端的聚二甲基矽氧烷73138-87-1；SiSiB® VF6030乙烯基封端的聚二甲基矽氧烷68083-19-2；及，SiSiB® HF2030氫封端的聚二甲基矽氧烷流體70900-21-9。The precursor can also be selected from the following: SiSiB® HF2020, trimethylsilyl-terminated methylhydrogen polysiloxane fluid 63148-57-2; SiSiB® HF2050 trimethylsilyl-terminated methylhydrogensiloxane Alkane Dimethicone Copolymer 68037-59-2; SiSiB® HF2060 Hydrogen Terminated Methyl Hydrogen Siloxane Dimethicone Copolymer 69013-23-6; SiSiB® HF2038 Hydrogen Terminated Polymer Phenylsiloxane; SiSiB® HF2068 Hydride-Terminated Methylhydrosiloxane Dimethicone Copolymer 11548749-5; SiSiB® HF2078 Hydride-Terminated Poly(phenyldimethylsiloxy)silicon Oxyphenylsilsesquioxane, Hydrogen-terminated 68952-30-7; SiSiB® VF6060 Vinyldimethyl-terminated vinylmethyldimethylpolysiloxane copolymer 68083-18-1; SiSiB® VF6862 Vinyldimethyl-terminated Dimethylbiphenylpolysiloxane Copolymer 68951-96-2; SiSiB® VF6872 Vinyldimethylterminated Dimethyl-Methylvinyl-Biphenylpolysiloxane Copolymer; SiSiB® PC9401 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane 2627-95-4; SiSiB® PF1070 Silanol Terminated Polydimethylsiloxane ( OF1070) 70131-67-8; SiSiB® OF1070 Silanol Terminated Dimethicone 70131-67-8; OH-terminated Dimethicone, Hydroxyl Terminated Dimethicone 73138-87-1; SiSiB® VF6030 Vinyl Terminated Dimethicone 68083-19-2; and, SiSiB® HF2030 Hydrogen Terminated Dimethicone Fluid 70900-21-9.

因此，除前述類型之前驅物外，涵蓋前驅物可為以下通式之化合物。

Therefore, in addition to the aforementioned types of precursors, contemplated precursors may be compounds of the following general formula.

其中封端劑E1及E2係選自諸如以下各項之基團：三甲基矽基(三甲基矽) (-Si(CH ₃) ₃)、二甲基矽基羥基(二甲基矽羥基) (-Si(CH ₃) ₂OH)、二甲基氫合矽基(二甲基矽氫化物) (-Si(CH ₃) ₂H)、二甲基乙烯基矽基(二甲基乙烯基矽) (-Si(CH ₃) ₂(CH=CH ₂))、二甲基苯基矽基(-Si(CH ₃) ₂(C ₆H ₅))及二甲基烷氧基矽基(二甲基烷氧基矽) (-Si(CH ₃) ₂(OR)。R基團R ₁、R ₂、R ₃、及R ₄可全部為不同的，或一或多個可為相同的。因此，例如，R ₂與R ₃相同，R ₃與R ₄相同，R ₁及R ₂為不同的並且R ₃及R ₄為相同，等等。R基團係選自諸如以下各項之基團：氫化物(-H)、甲基(Me)(-C)、乙基(-C-C)、乙烯基(-C=C)、烷基(-R)(C _nH ₂ _n+ ₁)、烯丙基(-C-C=C)、芳基('R)、苯基(Ph)(-C ₆H ₅)、甲氧基(-O-C)、乙氧基(-O-C-C)、矽氧基(-O-Si-R ₃)、烷氧基(-O-R)、羥基(-O-H)、苯乙基(-C-C-C ₆H ₅)及甲基,苯基-乙基(-C-C(-C)(-C ₆H ₅)。 Wherein the capping agents E1 and E2 are selected from groups such as the following: trimethylsilyl (trimethylsilyl) (-Si(CH ₃ ) ₃ ), dimethylsilyl hydroxyl (dimethylsilyl hydroxy) (-Si(CH ₃ ) ₂ OH), dimethylhydridosilyl (dimethylsilyl hydride) (-Si(CH ₃ ) ₂ H), dimethylvinylsilyl (dimethyl Vinyl silicon) (-Si(CH ₃ ) ₂ (CH=CH ₂ )), dimethylphenylsilyl (-Si(CH ₃ ) ₂ (C ₆ H ₅ )) and dimethylalkoxy silicon group (dimethylalkoxysilicon) (-Si(CH ₃ ) ₂ (OR). The R groups R ₁ , R ₂ , R ₃ , and R ₄ may all be different, or one or more may be The same. Thus, for example, _R2 is the same as _R3 , _R3 is the same as _R4 , _R1 and _R2 are different and _R3 and _R4 are the same, etc. R groups are selected from groups such as The group of items: hydride (-H), methyl (Me) (-C), ethyl (-CC), vinyl (-C=C), alkyl (-R) (C _n H ₂ _n+ ₁ ), allyl (-CC=C), aryl ('R), phenyl (Ph) (-C ₆ H ₅ ), methoxy (-OC), ethoxy (-OCC), silicon Oxygen (-O-Si-R ₃ ), alkoxyl (-OR), hydroxyl (-OH), phenethyl (-CCC ₆ H ₅ ) and methyl, phenyl-ethyl (-CC(- C) (-C ₆ H ₅ ).

通常，用於多晶碳氧矽調配物的調配物之實施例可例如具有約0%至50% MHF、約20%至約99% MHF、約0%至約30%矽氧烷主鏈材料、約20%至約99%矽氧烷主鏈材料、約0%至約70%反應性單體、約0%至約95% TV、約0%至約70%非基於矽的交聯劑、及約0%至約90%的矽氧烷主鏈添加劑與矽烷改質劑或有機改質劑反應產物之反應產物。In general, embodiments of formulations for polycrystalline oxycarbide formulations can have, for example, about 0% to 50% MHF, about 20% to about 99% MHF, about 0% to about 30% siloxane backbone materials , about 20% to about 99% silicone backbone material, about 0% to about 70% reactive monomer, about 0% to about 95% TV, about 0% to about 70% non-silicon-based crosslinker , and the reaction product of about 0% to about 90% of the siloxane backbone additive and the reaction product of a silane modifier or an organic modifier.

在混合調配物中，足夠的時間應用於允許前驅物變得有效混合及分散。通常，約15分鐘至一小時之混合為足夠的。典型地，前驅物調配物為相對的，且基本上為剪切不敏感的，且因此泵或混合之類型不為關鍵的。進一步應注意，在較高黏度調配物中，可需要另外的混合時間。在混合期間，調配物之溫度應較佳地保持低於約45℃、及較佳地約10℃。(應注意，該些混合條件係用於預催化調配物。) 反應型製程 In mixed formulations, sufficient time is used to allow the precursors to become effectively mixed and dispersed. Usually, about 15 minutes to one hour of mixing is sufficient. Typically, the precursor formulations are relatively and essentially shear insensitive, and thus the type of pumping or mixing is not critical. It should further be noted that in higher viscosity formulations, additional mixing time may be required. During mixing, the temperature of the formulation should preferably be kept below about 45°C, and preferably about 10°C. (It should be noted that these mixing conditions are for precatalyzed formulations.) reactive process

在反應型製程中，通常，化學反應係用於典型地在溶劑存在下將一種、兩種或兩種以上前驅物組合以形成前驅物調配物，其基本上由可隨後催化、固化及熱解的單一聚合物構成。此製程提供建構客製前驅物調配物之能力，該等調配物在固化時可提供具有獨特及合乎需要特徵之塑膠。固化材料亦可經熱解以形成具有獨特特徵的陶瓷。反應型製程允許藉由選擇用於併入構成前驅物調配物之聚合物中之官能基達成在終點產物中不同類型之功能性的預定平衡，該等官能基例如苯基，其典型地不用於陶瓷但具有用於為塑膠提供高溫能力之益處；及苯乙烯，其典型地不為塑膠提供高溫特徵但為陶瓷提供益處。In a reactive process, generally, a chemical reaction is used to combine one, two or more precursors, typically in the presence of a solvent, to form a precursor formulation that essentially consists of of a single polymer. This process provides the ability to build custom precursor formulations that, when cured, provide plastics with unique and desirable characteristics. Cured materials can also be pyrolyzed to form ceramics with unique characteristics. Reactive processes allow for a predetermined balance of different types of functionality in the end product by selecting functional groups for incorporation into the polymers making up the precursor formulation, such as phenyl groups, which are typically not used in Ceramic but has the benefit of being used to provide high temperature capabilities to plastics; and Styrene which typically does not provide high temperature characteristics to plastics but provides the benefits of ceramics.

通常，用作前驅物調配物之客製聚合物係藉由在縮合反應中反應前驅物以形成聚合物前驅物調配物來製成。此前驅物調配物隨後經由水解反應固化成預成型件，亦即，塑膠、固化固體或半固體材料。縮合反應形成下文展示類型之聚合物。

Typically, custom polymers used as precursor formulations are made by reacting precursors in a condensation reaction to form a polymer precursor formulation. This precursor formulation is then cured via a hydrolysis reaction into a preform, ie, a plastic, cured solid or semi-solid material. The condensation reaction forms polymers of the type shown below.

其中聚合物單元中之R ₁及R ₂可為氫化物(-H)、甲基(Me)(-C)、乙基(-C-C)、乙烯基(-C=C)、烷基(-R)(C _nH ₂ _n+ ₁)、不飽和烷基(-C _nH ₂ _n- ₁)、環狀烷基(-C _nH ₂ _n- ₁)、烯丙基(-C-C=C)、丁烯基(-C ₄H ₇)、戊烯基(-C ₅H ₉)、環戊烯基(-C ₅H ₇)、甲基環戊烯基(-C ₅H ₆(CH ₃))、降莰烯基(-C _xH _y，其中X = 7-15 且Y = 9-18)、芳基('R)、苯基(Ph)(-C ₆H ₅)、環庚烯基(-C ₇H ₁₁)、環辛烯基(-C ₈H ₁₃)、乙氧基(-O-C-C)、矽氧基(-O-Si-R ₃)、甲氧基(-O-C)、烷氧基、(-O-R)、羥基、(-O-H)、苯乙基(-C-C-C ₆H ₅)甲基,苯基-乙基(-C-C(-C)(-C ₆H ₅))及乙烯基苯基-乙基(-C-C(C ₆H ₄(-C=C)))。R ₁及R ₂可為相同的或不同的。客製前驅物聚合物可具有若干不同的聚合物單元，例如，A ₁、A ₂、A _n，且可包括多達10個、20個或更多個單元，或其可僅含有單一單元，例如，藉由反應過程製成的MHF可僅具有單一單元。 Wherein the R ₁ and R ₂ in the polymer unit can be hydride (-H), methyl (Me) (-C), ethyl (-CC), vinyl (-C=C), alkyl (- R)(C _n H ₂ _n+ ₁ ), unsaturated alkyl (-C _n H ₂ _n- ₁ ), cyclic alkyl (-C _n H ₂ _n- ₁ ), allyl (-CC=C) , Butenyl (-C ₄ H ₇ ), Pentenyl (-C ₅ H ₉ ), Cyclopentenyl (-C ₅ H ₇ ), Methylcyclopentenyl (-C ₅ H ₆ (CH ₃ )), norbornenyl (-C _x H _y , where X = 7-15 and Y = 9-18), aryl ('R), phenyl (Ph) (-C ₆ H ₅ ), cycloheptyl Alkenyl (-C ₇ H ₁₁ ), Cyclooctenyl (-C ₈ H ₁₃ ), Ethoxy (-OCC), Siloxy (-O-Si-R ₃ ), Methoxy (-OC) , alkoxy, (-OR), hydroxyl, (-OH), phenethyl (-CCC ₆ H ₅ ) methyl, phenyl-ethyl (-CC (-C) (-C ₆ H ₅ )) and vinylphenyl-ethyl ( _-CC ( _C6H4 (-C=C))). R ₁ and R ₂ may be the same or different. A custom precursor polymer may have several different polymer units, e.g., _A1 , _A2 , _An , and may include as many as 10, 20 or more units, or it may contain only a single unit, For example, MHF made by the reaction process may have only a single unit.

實施例可包括前驅物，其尤其包括三乙氧基甲基矽烷、二乙氧基甲基苯基矽烷、二乙氧基甲烷氫化矽烷、二乙氧基甲基乙烯基矽烷、二甲基乙氧基乙烯基矽烷、二乙氧基二甲基矽烷、乙氧基二甲基苯基矽烷、二乙氧基二氫化矽烷、三乙氧基苯基矽烷、二乙氧基氫化三甲基矽氧烷、二乙氧基甲基三甲基矽氧烷、三甲基乙氧基矽烷、聯苯二乙氧基矽烷、二甲基乙氧基氫化矽氧烷、及該些及其他前驅物之組合及變化，包括本說明書中闡述的其他前驅物。Embodiments may include precursors including, among others, triethoxymethylsilane, diethoxymethylphenylsilane, diethoxymethanehydrosilane, diethoxymethylvinylsilane, dimethylethylsilane, Oxyvinylsilane, Diethoxydimethylsilane, Ethoxydimethylphenylsilane, Diethoxydihydrosilane, Triethoxyphenylsilane, Diethoxyhydrotrimethylsilane oxane, diethoxymethyltrimethicone, trimethylethoxysilane, biphenyldiethoxysilane, dimethylethoxyhydridosiloxane, and these and other precursors Combinations and variations thereof, including other precursors described in this specification.

端部單元Si端1及Si端2可來自二甲基乙氧基乙烯基矽烷、乙氧基二甲基苯基矽烷、及三甲基乙氧基矽烷之前驅物。另外，若聚合製程受適當控制，則羥基封端物可自用於提供聚合物之重複單元的前驅物獲得。The end units Si-terminal 1 and Si-terminal 2 can be derived from dimethylethoxyvinylsilane, ethoxydimethylphenylsilane, and trimethylethoxysilane precursors. In addition, if the polymerization process is properly controlled, hydroxyl-terminated species can be obtained from the precursors used to provide the repeating units of the polymer.

通常，將前驅物添加至具有乙醇(或其他材料以吸收熱，例如，提供熱質量)、過量水、及鹽酸(或其他質子源)之容器。此混合物係加熱直至其達到其活化能，在此之後反應典型地為放熱的。通常，在此反應中，水與前驅物單體之矽烷之乙氧基反應，從而形成羥基(其中乙醇作為副產物)。一旦形成，此羥基變成經受與另一前驅物單體之矽上的乙氧基之反應，從而產生聚合反應。此聚合反應繼續直至建構所要鏈長。Typically, the precursors are added to a vessel with ethanol (or other material to absorb heat, eg, provide thermal mass), excess water, and hydrochloric acid (or other source of protons). This mixture is heated until it reaches its activation energy, after which time the reaction is typically exothermic. Typically, in this reaction, water reacts with the ethoxy groups of the silane of the precursor monomer to form hydroxyl groups (with ethanol as a by-product). Once formed, this hydroxyl group becomes subject to a reaction with an ethoxy group on the silicon of another precursor monomer, resulting in polymerization. This polymerization reaction continues until the desired chain length is built.

用於決定鏈長之控制因素尤其為：所選單體(通常，單體越小，在其開始自身纏繞及鍵結之前可添加的更多)；反應中引入封端劑的量及點；及水量與添加速率，以及其他。因此，鏈長可為約180 mw (黏度約5 cps)至約65,000 mw (約10,000 cps之黏度)、大於約1000 mw、大於約10,000 mw、大於約50,000 mw及更大。進一步，聚合的前驅物調配物可且典型地確實具有不同分子量之聚合物，其可預定來提供調配物、固化及陶瓷產品效能特徵。The controlling factors used to determine the chain length are, inter alia: the monomer chosen (generally, the smaller the monomer, the more can be added before it starts to wrap itself and bond); the amount and point of introduction of the capping agent in the reaction; and Amount of water vs. rate of addition, among others. Thus, the chain length can be from about 180 mw (viscosity of about 5 cps) to about 65,000 mw (viscosity of about 10,000 cps), greater than about 1000 mw, greater than about 10,000 mw, greater than about 50,000 mw, and greater. Further, polymeric precursor formulations can, and typically do, have polymers of varying molecular weights, which can be predetermined to provide formulation, curing, and ceramic product performance characteristics.

在完成聚合反應之後，將材料轉移至分離設備中，例如，分離漏斗，其具有例如為材料質量的約1.2倍至約1.5倍的去離子水量。將此混合物有力地攪拌約小於1分鐘且較佳地約5至30秒。一旦攪拌，使材料沉降且分離，此可耗費約1至2小時。聚合物為較高密度材料且自容器移除。此移除的聚合物隨後藉由在淺托盤中於90℃下升溫約兩小時；或，較佳地，使其通過擦淨的薄膜蒸餾設備以移除任何殘餘水及乙醇來乾燥。替代地，添加足以緩衝水層至約4至約7之pH的碳酸氫鈉。應進一步理解，可使用自材料混合、反應及分離聚合物之其他及商業方式。After the polymerization reaction is complete, the material is transferred to a separation device, eg, a separation funnel, with an amount of deionized water, eg, about 1.2 to about 1.5 times the mass of the material. This mixture is stirred vigorously for about less than 1 minute and preferably for about 5 to 30 seconds. Once stirred, the material is allowed to settle and separate, which can take about 1 to 2 hours. Polymers are higher density materials and are removed from the container. This removed polymer is then dried by warming at 90°C in shallow trays for about two hours; or, preferably, by passing it through a wiped thin film distillation apparatus to remove any residual water and ethanol. Alternatively, enough sodium bicarbonate is added to buffer the aqueous layer to a pH of about 4 to about 7. It is further understood that other and commercial means of mixing, reacting and isolating polymers from materials may be used.

較佳地，觸媒係用於來自反應型製程的聚合物前驅物調配物之固化製程。可使用如用於固化來自混合型製程的前驅物調配物的相同聚合物。應注意，通常與混合型調配物不同，不必要求觸媒固化反應型聚合物。亦可使用抑制劑。然而，若不使用觸媒，則反應時間及速率將較慢。來自反應製程的固化材料之固化及熱解基本上與來自混合製程及反應摻合製程的固化材料之固化及熱解相同。Preferably, the catalyst is used in the curing process of the polymer precursor formulation from a reactive process. The same polymers as used to cure the precursor formulation from a hybrid process can be used. It should be noted that catalytic curing of reactive polymers is not generally required, unlike hybrid formulations. Inhibitors may also be used. However, if no catalyst is used, the reaction time and rate will be slower. The curing and pyrolysis of cured materials from reactive processes are substantially the same as the curing and pyrolysis of cured materials from hybrid and reactive blending processes.

反應型製程可在眾多類型之氣氛及條件下進行，例如，空氣、惰性氣體、N ₂、氬、流動氣體、靜態氣體、減壓、環境壓力、高壓、及該些者之組合及變化。 反應摻合型製程 Reactive processes can be performed under many types of atmospheres and conditions, such as air, inert gas, _N2 , argon, flowing gas, static gas, reduced pressure, ambient pressure, high pressure, and combinations and variations of these. reactive blending process

在反應摻合型製程中，前驅物係在不存在溶劑下反應來形成前驅物調配物。例如，反應摻合型製程之實施例具有自MHF及二環戊二烯(Dicyclopentadiene; DCPD)製備的前驅物調配物。使用反應性摻合製程，產生MHF/DCPD聚合物且此聚合物係用作前驅物調配物。其可單獨使用以形成固化或熱解產物，或在混合或反應製程中用作前驅物。In reactive blending processes, precursors are reacted in the absence of a solvent to form a precursor formulation. For example, an embodiment of a reactive blending process has a precursor formulation prepared from MHF and Dicyclopentadiene (DCPD). Using a reactive incorporation process, MHF/DCPD polymers are produced and used as precursor formulations. They can be used alone to form cured or pyrolyzed products, or as precursors in mixing or reaction processes.

因此，例如，可使用具有已知分子量及氫化物當量質量的約40至90% MHF；約0.20 wt% P01觸媒；及具有≥ 83%純度的約10至60% DCPD。Thus, for example, about 40 to 90% MHF of known molecular weight and hydride equivalent mass; about 0.20 wt% PO1 catalyst; and about 10 to 60% DCPD with > 83% purity can be used.

P01為在四乙烯基環四矽氧烷中的2% Pt(0)四乙烯基環四矽氧烷錯合物，其利用四乙烯基環四矽氧烷稀釋20倍至0.1 %之Pt(0)錯合物。以此方式，每1%負荷之主體觸媒提供10 ppm Pt。P01 is a 2% Pt(0) tetravinylcyclotetrasiloxane complex in tetravinylcyclotetrasiloxane diluted 20-fold with tetravinylcyclotetrasiloxane to 0.1% Pt( 0) Complexes. In this way, 10 ppm Pt was provided per 1% loading of the host catalyst.

在製程之實施例中，具有混合器之可密封反應容器可用於反應。反應係在密封容器中，在空氣中進行；儘管可使用其他類型之氣氛。較佳地，反應係在大氣壓力下進行，但可使用較高及較低壓力。另外，反應摻合型製程可在眾多類型之氣氛及條件下進行，例如，空氣、惰性氣體、N ₂、氬、流動氣體、靜態氣體、減壓、環境壓力、高壓、及該些者之組合及變化。 In an embodiment of the process, a sealable reaction vessel with a mixer can be used for the reaction. Reactions were performed in air in sealed containers; although other types of atmospheres could be used. Preferably, the reaction is carried out at atmospheric pressure, although higher and lower pressures can be used. In addition, reactive blending processes can be performed under numerous types of atmospheres and conditions, such as air, inert gas, _N2 , argon, flowing gas, static gas, reduced pressure, ambient pressure, high pressure, and combinations of these and changes.

在實施例中，將850公克之MHF (總聚合物混合物之85%)添加至反應容器且加熱至約50℃。一旦達到此溫度，即將加熱器關閉，且將0.20% (以MHF之重量計)之P01鉑觸媒添加至反應容器中之MHF。典型地，在添加觸媒之後，氣泡將形成且溫度將最初上升大致2-20℃。In an example, 850 grams of MHF (85% of the total polymer mixture) was added to the reaction vessel and heated to about 50°C. Once this temperature was reached, the heater was turned off and 0.20% (by weight of MHF) of P01 platinum catalyst was added to the MHF in the reaction vessel. Typically, after catalyst addition, gas bubbles will form and the temperature will initially rise by approximately 2-20°C.

當溫度開始下降時，將約150 g之DCPD (總聚合物混合物之15 wt%)添加至反應容器。溫度可下降另一量，例如，約5-7℃。When the temperature started to drop, about 150 g of DCPD (15 wt% of the total polymer mixture) was added to the reaction vessel. The temperature may drop another amount, for example, about 5-7°C.

在此點，在反應製程中，反應容器之溫度經控制以隨時間維持預定溫度分佈，且管理可伴隨放熱的溫度增加。較佳地，反應容器之溫度在製程全程經調節、監視及控制。In this regard, during the reaction process, the temperature of the reaction vessel is controlled to maintain a predetermined temperature profile over time, and to manage a temperature increase that may be accompanied by an exotherm. Preferably, the temperature of the reaction vessel is adjusted, monitored and controlled throughout the process.

在反應製程之MHF/DCPD實施例之實施例中，溫度分佈可如下：使溫度達到約80℃(可耗費約15-40 min，其取決於所存在的材料量)；溫度隨後將增加且在約104℃處為峰值，一旦溫度開始下降，將加熱器設定溫度增加至100℃且反應混合物之溫度經監視以確保聚合物溫度保持高於80℃歷時最少總共約2小時及最大總共約4小時。在高於80℃2-4小時之後，將加熱器關閉，且將聚合物冷卻至環境溫度。應瞭解，在較大及較小分批、連續、半連續、及其他類型製程中，溫度及時間分佈可為不同的。In an embodiment of the MHF/DCPD embodiment of the reaction process, the temperature profile may be as follows: bring the temperature to about 80°C (it may take about 15-40 min, depending on the amount of material present); the temperature will then increase and at There is a peak at about 104°C, once the temperature begins to drop, the heater set point is increased to 100°C and the temperature of the reaction mixture is monitored to ensure that the polymer temperature remains above 80°C for a minimum of about 2 hours total and a maximum of about 4 hours total . After 2-4 hours above 80°C, the heater was turned off and the polymer was cooled to ambient temperature. It should be appreciated that temperature and time profiles may be different in larger and smaller batch, continuous, semi-continuous, and other types of processes.

在較大規模及商業操作中，可使用分批、連續、及該些者之組合。工業工廠自動化及控制系統可用於控制反應、在反應期間的溫度分佈及其他過程。In larger scale and commercial operations, batch, continuous, and combinations of these can be used. Industrial plant automation and control systems can be used to control reactions, temperature distribution during reactions, and other processes.

表A列出前驅物材料之各種實施例。Table A lists various examples of precursor materials.

表A 材料名稱聚合度當量 Si/mol 當量 O/mol 當量 H/mol 當量 Vi/mol 當量甲基/mol 當量 C/mol MW 乙烯基之公克/莫耳四甲基環四矽氧烷(D4) 4 4 4 4 0 4 4 240.51 MHF 33 35 34 33 0 39 39 2145.345 VMF 5 7 6 0 5 11 21 592.959 118.59 TV 4 4 4 0 4 4 12 344.52 86.13 VT 0200 125 127 126 0 2 254 258 9451.206 4725.60 VT 0020 24 26 25 0 2 52 56 1965.187 982.59 VT 0080 79 81 80 0 2 162 166 6041.732 3020.87 苯乙烯 2 104.15 52.08 二環戊二烯 2 132.2 66.10 1,4-二乙烯基苯 2 130.19 65.10 異戊二烯 2 62.12 31.06 1,3丁二烯 2 54.09 27.05 觸媒10 ppm Pt 觸媒LP 231 Table A material name Polymerization Equivalent Si/mol Equivalent O/mol Equivalent H/mol Equivalent Vi/mol Equivalent methyl group/mol Equivalent C/mol MW Gram/Mole of Vinyl Tetramethylcyclotetrasiloxane (D4) 4 4 4 4 0 4 4 240.51 MHF 33 35 34 33 0 39 39 2145.345 VMF 5 7 6 0 5 11 twenty one 592.959 118.59 TV 4 4 4 0 4 4 12 344.52 86.13 VT 0200 125 127 126 0 2 254 258 9451.206 4725.60 VT 0020 twenty four 26 25 0 2 52 56 1965.187 982.59 VT 0080 79 81 80 0 2 162 166 6041.732 3020.87 Styrene 2 104.15 52.08 Dicyclopentadiene 2 132.2 66.10 1,4-divinylbenzene 2 130.19 65.10 Isoprene 2 62.12 31.06 1,3 butadiene 2 54.09 27.05 Catalyst 10 ppm Pt Catalyst LP 231

在上表中，「聚合度」為附接在一起以形成聚合物的單體單元或重複單元之數量。「當量_/mol」係指莫耳當量。「乙烯基之公克/莫耳」係指提供1莫耳當量之乙烯基官能性所需的給定聚合物之量。「VMH」係指甲基乙烯基流體、來自乙氧基製程之直鏈乙烯基材料，其可替代TV。VT之數字「0200」等為對彼特定VT而言以厘泊計的黏度(例如，0200 = 200 cps)。固化及熱解 In the table above, "degree of polymerization" is the number of monomeric or repeating units that are attached together to form a polymer. "Equivalent_/mol" means molar equivalent. "Gram/mole of vinyl" refers to the amount of a given polymer required to provide 1 mole equivalent of vinyl functionality. "VMH" refers to Methyl Vinyl Fluid, a linear vinyl material from an ethoxy process, which is an alternative to TV. The number "0200" etc. for a VT is the viscosity in centipoise for that particular VT (eg, 0200 = 200 cps). Curing and Pyrolysis

包括來自上文類型之製程以及其他製程的多晶碳氧矽前驅物調配物的前驅物調配物可固化以形成固體、半固體、或塑膠類材料。典型地，將前驅物調配物展布、成形、或以其他方式形成為預成型件，其將包括任何空間結構或形體，包括薄膜及厚膜。在固化中，多晶碳氧矽前驅物調配物可經由初始固化處理，以提供部分固化材料，其亦可例如稱為預成型件，生料、或生固化物(不暗示有關材料顏色之任何內容)。生料可隨後經進一步固化。因此，可使用一或多個固化步驟。材料可經「終點固化」，亦即，固化至材料具有用於其所欲目的的必要實體強度及其他性質的點。固化之量可達最終固化(或「硬固化」)，亦即，所有或基本上所有化學反應已停止的點(如例如藉由在材料中不存在反應性基團所量測的，亦即，所有反應已停止，或反應性基團隨時間減少趨於平衡，亦即，基本上所有反應已停止)。因此，材料可固化至變化程度，此取決於其所欲用途及目的。例如，在一些情形中，終點固化及硬固化可為相同的。諸如氣氛及溫度之固化條件可實現固化材料之組成。Precursor formulations including polycrystalline silicon oxycarbide precursor formulations from processes of the above type, as well as others, can be cured to form solid, semi-solid, or plastic-like materials. Typically, the precursor formulation is spread, shaped, or otherwise formed into a preform, which will include any spatial structure or shape, including thin and thick films. In curing, the polycrystalline silicon oxycarbide precursor formulation may be subjected to an initial cure process to provide a partially cured material, which may also be referred to, for example, as a preform, green, or green cure (without implying any reference to the color of the material). content). The green mass can then be further cured. Thus, one or more curing steps may be used. The material may be "end-cured," that is, cured to the point where the material has the necessary physical strength and other properties for its intended purpose. The amount of cure is up to final cure (or "hard cure"), that is, the point at which all or substantially all chemical reactions have ceased (as measured, for example, by the absence of reactive groups in the material, i.e. , all reactions have ceased, or the reactive groups decrease over time towards equilibrium, ie substantially all reactions have ceased). Thus, the material can be cured to varying degrees, depending on its intended use and purpose. For example, in some cases the endpoint cure and hard cure may be the same. Curing conditions such as atmosphere and temperature can achieve the composition of the cured material.

在多層或複合結構及形體中，多晶碳氧矽材料之層可固化至變化程度，例如，在多層實施例中，層可經生固化以促進層黏著，隨後最終固化至硬固化物。在多層結構中之每一層可固化至相同固化程度，至不同固化程度，經受一個、兩個、三個或更多個固化步驟，及該些者之組合及變化。In multilayer or composite structures and shapes, layers of polycrystalline silicon oxycarbide material may be cured to varying degrees, for example, in multilayer embodiments, the layers may be green cured to promote layer adhesion followed by final cure to a hard set. Each layer in a multilayer structure can be cured to the same degree of cure, to a different degree of cure, subjected to one, two, three or more curing steps, and combinations and variations of these.

固化可在標準環境溫度及壓力下(「SATP」，1個大氣壓，25℃)、在高於或低於彼溫度的溫度下、在高於或低於彼壓力的壓力下、及歷經變化的時間段進行。固化可經由各種加熱、加熱速率、及溫度分佈(例如，保持時間及溫度、連續溫度變化、循環溫度變化，例如，加熱繼之以維持、冷卻、再加熱等等)來進行。用於固化之時間可為幾秒(例如，小於約1秒、小於5秒)，至小於一分鐘，至數分鐘，至數小時，至數天(或可能更長)。固化亦可在任何類型之周圍環境中進行，包括例如，氣體、液體、空氣、水、含表面活性劑之液體、惰性氣氛、N ₂、氬、流動氣體(例如，掃掠氣)、靜態氣體、減壓O ₂(例如，低於大氣壓的O ₂量，諸如小於20% O ₂、小於15% O ₂、小於10% O ₂、小於5% O ₂)、減壓(例如，小於大氣壓)、高壓(例如，大於大氣壓)、富集的O ₂(例如，大於大氣壓的O ₂量)、環境壓力、受控分壓及該些及其他處理條件之組合及變化。 Curing can be at standard ambient temperature and pressure ("SATP", 1 atmosphere, 25°C), at temperatures above or below that temperature, at pressures above or below that pressure, and over varying time period. Curing can be performed via various heating, heating rates, and temperature profiles (eg, hold times and temperatures, continuous temperature changes, cyclic temperature changes, eg, heating followed by holding, cooling, reheating, etc.). The time for curing can range from seconds (eg, less than about 1 second, less than 5 seconds), to less than a minute, to minutes, to hours, to days (or possibly longer). Curing can also be performed in any type of ambient environment including, for example, gas, liquid, air, water, surfactant-containing liquid, inert atmosphere, _N2 , argon, flowing gas (e.g., sweep gas), static gas , reduced _O2 (e.g., an amount of _O2 below atmospheric pressure, such as less than 20% _O2 , less than 15% _O2 , less than 10% _O2 , less than 5% _O2 ), reduced pressure (e.g., less than atmospheric pressure) , high pressure (eg, greater than atmospheric pressure), enriched _O2 (eg, greater than atmospheric _O2 amount), ambient pressure, controlled partial pressure, and combinations and variations of these and other processing conditions.

在實施例中，固化環境，例如，熔爐、氣氛、容器及該些者之組合及變化可具有貢獻於或實現例如預成型件、固化材料、陶瓷及最終應用或產品中之組成、催化、化學計量、特徵、效能及該些者之組合及變化的材料。In embodiments, the curing environment, e.g., furnace, atmosphere, vessel, and combinations and variations of these can have a contribution to or enable, for example, compositional, catalytic, chemical Materials of measurement, characteristics, performance and combinations and variations of these.

對於高純度材料，熔爐、容器、操縱儀器、氣氛、及固化設備及製程之其他部件為清潔的，基本上不含且不貢獻將認為是固化材料之雜質或污染物的任何元素或材料。For high purity materials, furnaces, vessels, manipulators, atmospheres, and other components of curing equipment and processes are clean, substantially free of and do not contribute to any element or material that would be considered an impurity or contamination of the curing material.

較佳地，在固化製程之實施例中，固化係發生在以下範圍內之溫度下：約5℃或更大、約20℃至約250℃、約20℃至約150℃、約75℃至約125℃、及約80℃至90℃。然而可使用較高及較低溫度及各種加熱分佈(例如，隨時間的溫度變化率(「勻變速率」，例如，∆度/時間)、保持時間、及溫度)。Preferably, in embodiments of the curing process, curing occurs at a temperature in the range of about 5°C or greater, about 20°C to about 250°C, about 20°C to about 150°C, about 75°C to About 125°C, and about 80°C to 90°C. However, higher and lower temperatures and various heating profiles (eg, rate of temperature change over time ("ramp rate", eg, Δ°/time), hold time, and temperature) can be used.

例如溫度、時間、勻變速率之固化條件可取決於且在一些實施例中可整體或部分地藉由調配物預定以匹配例如預成型件之大小、預成型件之形體、或保持預成型件以防止應力開裂、廢氣、或與固化製程相關聯其他現象的模。進一步，固化條件可使得較佳地以受控方式利用先前可能已察覺為與固化製程相關聯的問題的事物。因此，例如，廢氣可用以產生具有開口或閉合結構之泡沫材料。類似地，固化條件可用於產生或控制材料之微結構及奈米結構。通常，固化條件可用於影響、控制或改質製程之動力學及熱力學，從而可影響形態學、效能、特徵及功能，以及其他。Cure conditions such as temperature, time, ramp rate may depend on and in some embodiments may be predetermined in whole or in part by the formulation to match, for example, the size of the preform, the shape of the preform, or hold the preform Molds to prevent stress cracking, outgassing, or other phenomena associated with the curing process. Further, the curing conditions may be such that what may have previously been perceived as problems associated with the curing process can be exploited in a preferably controlled manner. Thus, for example, exhaust gases can be used to generate foams with open or closed structures. Similarly, curing conditions can be used to create or control the microstructure and nanostructure of the material. In general, curing conditions can be used to influence, control or modify the kinetics and thermodynamics of the process, which can affect morphology, performance, characteristics and function, among others.

在固化多晶碳氧矽前驅物調配物之後，發生交聯反應，其在一些實施例中提供尤其具有例如-R ₁-Si-C-C-Si-O-Si-C-C-Si-R ₂-之交聯結構，其中R ₁及R ₂取決於及基於用於調配物中之前驅物變化。在固化材料之實施例中，其可具有交聯結構，具有與另一矽原子之3配位矽中心，其藉由在矽原子之間少於5個原子分離。然而涵蓋固化材料之另外的其他結構及類型。因此，例如，Luperox 231之使用可自相同單體產生結構，其為-Si-C-C-C-Si-。當使用其他交聯劑時，例如，DCPD及二乙烯基苯，矽原子之間的碳原子數量將大於5個原子。交聯，例如，固化材料之一些實施例的通式將為-Si-R ₃-Si-，其中R ₃將為乙基(例如來自乙烯基前驅物)、丙基(例如來自烯丙基前驅物)、二環戊烷(例如來自DCPD前驅物)、降莰烷(例如來自降莰二烯前驅物)、二乙基苯(例如來自二乙烯基苯前驅物)、及其他。 After curing the polycrystalline silicon oxycarbide precursor formulation, a crosslinking reaction occurs, which in some embodiments provides a compound having, for example, -R ₁ -Si-CC-Si-O-Si-CC-Si-R ₂ - among others. Cross-linked structures where _R1 and _R2 depend on and vary based on the precursors used in the formulation. In an embodiment of the cured material, it may have a cross-linked structure with a 3-coordinated silicon center to another silicon atom separated by less than 5 atoms between the silicon atoms. Still other structures and types of cured materials are contemplated, however. Thus, for example, the use of Luperox 231 can result in a structure from the same monomer, which is -Si-CCC-Si-. When using other crosslinkers, such as DCPD and divinylbenzene, the number of carbon atoms between silicon atoms will be greater than 5 atoms. Crosslinking, for example, the general formula of some embodiments of the cured material will be -Si- _R3 -Si-, where _R3 will be ethyl (eg from a vinyl precursor), propyl (eg from an allyl precursor species), dicyclopentane (eg, from DCPD precursors), norbornane (eg, from norbornadiene precursors), diethylbenzene (eg, from divinylbenzene precursors), and others.

在固化製程期間，一些調配物可展現放熱，亦即，自加熱反應，其可產生少量熱來輔助或驅動固化反應，或可產生大量熱，其可需要加以管理並移除以便避免諸如應力破裂之問題。在固化期間，典型地發生排廢氣且產生材料損失，此損失係通常藉由剩餘材料之量，例如，固化產率來定義。本發明之實施例的調配物、固化條件、及多晶碳氧矽前驅物調配物之實施例可具有至少約90%、約92%、約100%之固化產率。事實上，利用空氣固化時，材料可具有高於100%，例如，約101-105%之固化產率，其係由於自空氣吸收的氧。另外，在固化期間，材料典型地收縮，此收縮可取決於預成型形體之調配物、固化條件、及性質，及預成型件是否為加強、填充、純或未加強的，收縮約20%、小於20%、小於約15%、小於約5%、小於約1%、小於約0.5%、小於約0.25%及更小。During the curing process, some formulations may exhibit an exothermic, i.e., self-heating reaction, which may generate a small amount of heat to aid or drive the curing reaction, or a large amount of heat, which may need to be managed and removed to avoid conditions such as stress cracking question. During curing, outgassing typically occurs and a loss of material occurs, which is usually defined by the amount of remaining material, eg, the curing yield. Embodiments of formulations, curing conditions, and polycrystalline silicon oxycarbide precursor formulations of embodiments of the present invention may have cure yields of at least about 90%, about 92%, about 100%. In fact, when curing with air, the material may have a cure yield higher than 100%, eg, about 101-105%, due to the oxygen absorbed from the air. Additionally, during curing, the material typically shrinks, this shrinkage can be about 20%, depending on the formulation, curing conditions, and nature of the preform, and whether the preform is reinforced, filled, pure, or unreinforced. Less than 20%, less than about 15%, less than about 5%, less than about 1%, less than about 0.5%, less than about 0.25%, and less.

固化可藉由具有必要的溫度及環境控製程度的任何類型之加熱設備、或機制、技術、或形態學來完成。固化可經由例如以下方式來完成：加熱水浴、電爐、微波、煤氣爐、熔爐、強制熱空氣、塔、噴霧乾燥、降膜式反應器、流體化床反應器、間接加熱元件、直接加熱(例如，加熱表面、圓筒、及板)、紅外加熱、UV照射(燈)、RF熔爐、經由高剪切混合之現場持續乳化、經由超音波處理之現場持續乳化、廣譜白光、IR光、相干電磁輻射(例如，雷射，包括可見光、UV及IR)、及對流加熱，僅舉幾例。Curing can be accomplished by any type of heating equipment, or mechanism, technique, or morphology with the necessary degree of temperature and environmental control. Curing can be accomplished via, for example, heated water baths, electric ovens, microwaves, gas ovens, furnaces, forced hot air, towers, spray drying, falling film reactors, fluidized bed reactors, indirect heating elements, direct heating (e.g. , heated surfaces, cylinders, and plates), infrared heating, UV irradiation (lamps), RF furnaces, continuous in-situ emulsification via high-shear mixing, continuous in-situ emulsification via ultrasonic treatment, broad-spectrum white light, IR light, coherent Electromagnetic radiation (eg, laser, including visible light, UV, and IR), and convective heating, to name a few.

在實施例中，對具有足夠量之觸媒的實施例，固化亦可在環境條件下發生。In embodiments, curing may also occur under ambient conditions for embodiments with a sufficient amount of catalyst.

若對一實施例進行熱解，則固化材料可例如加熱至約600℃至約2,300℃；約650℃至約1,200℃、約800℃至約1300℃、約900℃至約1,200℃及約950℃至1,150℃。在該些溫度下，典型地所有有機結構經移除或與無機成分組合以形成陶瓷。典型地，在約650℃至1,200℃範圍中的溫度下，所得材料為非晶形玻璃狀陶瓷。當經加熱高於約1,200℃時，材料典型地可形成奈米結晶結構，或微米結晶結構，諸如SiC、Si ₃N ₄、SiCN、β SiC，且在高於1,900℃，可形成α SiC結構，且在高於2,200℃，典型地形成α SiC。例如，經熱解的陶瓷材料可為單晶、多晶、非晶形、及該些及其他類型之形態學之組合、變化及子群。 If pyrolysis is performed on an embodiment, the cured material can be heated, for example, to a temperature of about 600°C to about 2,300°C; about 650°C to about 1,200°C; about 800°C to about 1300°C; about 900°C to about 1,200°C; °C to 1,150 °C. At these temperatures, typically all organic structures are removed or combined with inorganic components to form a ceramic. Typically, at temperatures in the range of about 650°C to 1,200°C, the resulting material is an amorphous glass-like ceramic. Materials typically form nanocrystalline structures, or microcrystalline structures, such as SiC, _Si3N4 _, SiCN, βSiC, and above 1,900°C, alpha SiC structures when heated above about 1,200°C , and above 2,200 °C, α SiC is typically formed. For example, pyrolyzed ceramic materials can be single crystal, polycrystalline, amorphous, and combinations, variations, and subgroups of these and other types of morphologies.

熱解可在不同加熱及環境條件下進行，從而較佳地包括熱控制、動力學控制及該些者之組合及變化，以及其他。例如，熱解可具有各種加熱勻變速率、加熱循環及環境條件。在一些實施例中，溫度可升高，且保持預定溫度以幫助已知轉變(例如，產氣、揮發、分子重排等等)且隨後提高至相應於下一已知轉變的下一保持溫度。熱解可發生在以下各項中：還原氣氛、氧化氣氛、低O ₂、富集氣體(例如，火焰內或直接相鄰於火焰)、惰性氣體、N ₂、氬、空中、減壓、環境壓力、高壓、流動氣體(例如，掃掠氣，具有例如約15.0 GHSV (氣體時空速度)至約0.1 GHSV、約6.3 GHSV至約3.1 GHSV、及約3.9 GHSV之流動速率)、靜態氣體、及該些者之組合及變化。 Pyrolysis can be performed under different heating and environmental conditions, thereby preferably including thermal control, kinetic control and combinations and variations of these, among others. For example, pyrolysis can have various heating ramp rates, heating cycles, and ambient conditions. In some embodiments, the temperature may be raised and held at a predetermined temperature to aid a known transition (e.g., gassing, volatilization, molecular rearrangement, etc.) and then raised to the next held temperature corresponding to the next known transition . Pyrolysis can occur in the following: reducing atmosphere, oxidizing atmosphere, low _O2 , enriched gas (e.g., within a flame or directly adjacent to a flame), inert gas, _N2 , argon, air, reduced pressure, ambient Pressure, high pressure, flowing gas (e.g., sweep gas, having flow rates such as about 15.0 GHSV (gas hourly space velocity) to about 0.1 GHSV, about 6.3 GHSV to about 3.1 GHSV, and about 3.9 GHSV), static gas, and the Combinations and variations of these.

在一些實施例中，在熱解之後，石墨烯、石墨、非晶形碳結構及該些者之組合及變化係存在於Si-O-C陶瓷。由SiOxCy結構組成的產生SiO ₄、SiO ₃C、SiO ₂C ₂、SiOC ₃、及SiC ₄之矽物質之分佈係以變化比率形成，該等變化比率係產生自前驅物選擇及其處理歷史。碳通常結合在相鄰碳之間及/或結合至矽原子。通常，在陶瓷狀態中，碳大部分不與氧原子配位，因此氧大部分與矽配位。 In some embodiments, graphene, graphite, amorphous carbon structures, and combinations and variations of these are present in Si-OC ceramics after pyrolysis. The distribution of silicon species consisting of SiOxCy structures yielding _SiO4 , _SiO3C _, _SiO2C2 , _SiOC3 , and _SiC4 is formed at varying rates resulting from the choice of precursors and their processing history. Carbon is usually bonded between adjacent carbons and/or to silicon atoms. In general, in a ceramic state, most of carbon is not coordinated to oxygen atoms, and thus most of oxygen is coordinated to silicon.

熱解可在維持要求溫度及環境控制之任何加熱設備中進行。因此，例如，熱解可利用以下各項來進行：高壓爐、箱式爐、管式爐、晶體生長熔爐、石墨箱式爐、電弧熔化熔爐、感應爐、窯爐、MoSi ₂加熱元件熔爐、碳熔爐、真空爐、氣體燃爐、電爐、直接加熱、間接加熱、流體化床、RF熔爐、窯爐、隧道式窯爐、箱式窯爐、梭動窯爐、焦炭型設備、雷射器、微波、其他電磁輻射、及可獲得用於熱解之要求溫度的該些及其他加熱設備及系統之組合及變化。 Pyrolysis can be performed in any heating apparatus that maintains the required temperature and environmental controls. Thus, for example, pyrolysis can be performed using: high pressure furnaces, chamber furnaces, tube furnaces, crystal growth furnaces, graphite chamber furnaces, arc melting furnaces, induction furnaces, kilns, _MoSi2 heating element furnaces, Carbon Furnace, Vacuum Furnace, Gas Furnace, Electric Furnace, Direct Heating, Indirect Heating, Fluidized Bed, RF Furnace, Kiln, Tunnel Furnace, Box Furnace, Shuttle Furnace, Coke Type Equipment, Laser , microwaves, other electromagnetic radiation, and combinations and variations of these and other heating equipment and systems that can obtain the desired temperature for pyrolysis.

在多晶碳氧矽衍生陶瓷材料之實施例中，其具有表B中列出的達成材料總量的任何量之Si、O、C。In an embodiment of the polycrystalline silicon oxycarbide derived ceramic material, it has Si, O, C in any of the amounts listed in Table B to achieve the total amount of material.

表B Si O C Lo Hi Lo Hi Lo Hi Wt% 35.00% 50.00% 10.00% 35.00% 5.00% 30.00% 莫耳比率 1.000 1.429 0.502 1.755 0.334 2.004 莫耳% 15.358% 63.095% 8.821% 56.819% 6.339% 57.170% Form B Si o C Lo hi Lo hi Lo hi Wt% 35.00% 50.00% 10.00% 35.00% 5.00% 30.00% molar ratio 1.000 1.429 0.502 1.755 0.334 2.004 Mole % 15.358% 63.095% 8.821% 56.819% 6.339% 57.170%

大體而言，熱解陶瓷多晶碳氧矽材料之實施例可具有約20%至約65%重量百分比的Si，可具有約5%至約50%重量百分比的O，且可具有約3%至約55%重量百分比的碳。亦涵蓋較大及較小的量。In general, embodiments of the pyrolytic ceramic polycrystalline silicon oxycarbide material can have about 20% to about 65% by weight Si, can have about 5% to about 50% by weight O, and can have about 3% to about 55% by weight carbon. Larger and smaller quantities are also covered.

大體而言，熱解陶瓷多晶碳氧矽材料之實施例可具有對Si而言約0.5至約2.5之莫耳比率(基於總Si、O、及C)，可具有對O而言約0.2至約2.5之莫耳比率，且可具有對C而言約0.1至約4.5之莫耳比率。亦涵蓋較大及較小的量。In general, embodiments of the pyrolytic ceramic polycrystalline silicon oxycarbide material may have a molar ratio (based on total Si, O, and C) to Si of about 0.5 to about 2.5, may have a molar ratio of about 0.2 to O to a molar ratio of about 2.5, and may have a molar ratio to C of about 0.1 to about 4.5. Larger and smaller quantities are also covered.

大體而言，熱解陶瓷多晶碳氧矽材料之實施例可具有對Si而言約13%至約68%之莫耳%(總Si、O、及C之百分比)，可具有對O而言約6%至約60%之莫耳%，且可具有對C而言約4%至約75%之莫耳%。亦涵蓋較大及較小的量。In general, embodiments of the pyrolytic ceramic polycrystalline silicon oxycarbide material may have a molar % to Si (percentage of total Si, O, and C) of about 13% to about 68%, may have a molar % for O and The mole % for C is about 6% to about 60%, and may have a mole % for C of about 4% to about 75%. Larger and smaller quantities are also covered.

存在於多晶碳氧矽衍生陶瓷顏料之實施例中的碳之類型可為游離碳(例如，碳之無序重疊、非晶形、石墨烯、石墨形式)及結合至矽的碳。具有游離碳及矽結合之碳(Si-C)的陶瓷多晶碳氧矽材料之實施例在表C中列出。亦涵蓋較大及較小量及不同百分比的游離碳及矽結合之碳。The type of carbon present in embodiments of polycrystalline silicon oxycarbide derived ceramic pigments can be free carbon (eg, random stacks of carbon, amorphous, graphene, graphite forms) and carbon bound to silicon. Examples of ceramic polycrystalline oxycarbide materials with free carbon and silicon-bonded carbon (Si-C) are listed in Table C. Larger and smaller amounts and different percentages of free carbon and silicon-bound carbon are also contemplated.

表surface CC 實施例 Example 游離碳% Free carbon % Si-C類型% Si-C type% 1 1 64.86 64.86 35.14 35.14 2 2 63.16 63.16 36.85 36.85 3 3 67.02 67.02 32.98 32.98 4 4 58.59 58.59 41.41 41.41 5 5 68.34 68.34 31.66 31.66 6 6 69.18 69.18 30.82 30.82 7 7 65.66 65.66 34.44 34.44 8 8 72.74 72.74 27.26 27.26 9 9 72.46 72.46 27.54 27.54 10 10 78.56 78.56 21.44 21.44

通常，多晶碳氧矽衍生陶瓷材料之實施例可具有約30%游離碳至約70%游離碳、約20%游離碳至約80%游離碳、及約10%游離碳至約90%游離碳，及約30% Si-C鍵結之碳至約70% Si-C鍵結之碳、約20% Si-C鍵結之碳至約80% Si-C鍵結之碳、及約10% Si-C鍵結之碳至約90% Si-C鍵結之碳。亦涵蓋較大及較小的量。 金屬及金屬配合物 Typically, embodiments of polycrystalline oxycarbide derived ceramic materials can have from about 30% free carbon to about 70% free carbon, from about 20% free carbon to about 80% free carbon, and from about 10% free carbon to about 90% free carbon. Carbon, and about 30% Si-C bonded carbon to about 70% Si-C bonded carbon, about 20% Si-C bonded carbon to about 80% Si-C bonded carbon, and about 10 % Si-C bonded carbon to about 90% Si-C bonded carbon. Larger and smaller quantities are also covered. Metals and metal complexes

例如，可用作填充材料之金屬及金屬錯合物將包括可使用的過渡金屬之環戊二烯基化合物。過渡金屬之環戊二烯基化合物可有機化成兩種類型：雙環戊二烯基錯合物；及單環戊二烯基錯合物。環戊二烯基錯合物可包括C ₅H ₅、C ₅Me ₅、C ₅H ₄Me、CH ₅R ₅(其中R = Me、Et、丙基、異丙基、丁基、異丁基、第二丁基)。在該些情況之任一者中，Si可直接鍵結至環戊二烯基配位體或Si中心可附接至烷基鏈，繼而附接至環戊二烯基配位體。 For example, metals and metal complexes that may be used as filler materials would include cyclopentadienyl compounds of transition metals that may be used. Cyclopentadienyl compounds of transition metals can be organized into two types: dicyclopentadienyl complexes; and monocyclopentadienyl complexes. Cyclopentadienyl complexes _may include _C5H5 , _C5Me5 , _C5H4Me , _CH5R5 ₍ where R = Me, _Et , _propyl , isopropyl, butyl, isobutyl base, second butyl). In either of these cases, the Si can be directly bonded to the cyclopentadienyl ligand or the Si center can be attached to an alkyl chain, which in turn is attached to the cyclopentadienyl ligand.

可與前驅物調配物一起使用且用於產品中的環戊二烯基錯合物可包括以下各項之雙環戊二烯基金屬錯合物：第一列過渡金屬(鈦、釩、鉻、鐵、鈷、鎳)；第二列過渡金屬(鋯、鉬、釕、銠、鈀)；第三列過渡金屬(鉿、鉭、鎢、銥、鋨、鉑)；鑭系(La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho)；及錒系(Ac、Th、Pa、U、Np)。Cyclopentadienyl complexes that may be used with the precursor formulation and in the product may include dicyclopentadienyl metal complexes of the following: first row transition metals (titanium, vanadium, chromium, iron, cobalt, nickel); second column transition metals (zirconium, molybdenum, ruthenium, rhodium, palladium); third column transition metals (hafnium, tantalum, tungsten, iridium, osmium, platinum); lanthanides (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho); and actinides (Ac, Th, Pa, U, Np).

單環戊二烯基錯合物亦可用於向前驅物調配物提供金屬官能性，且當較佳地利用適當配位體(例如氯化物或羰基)穩定時，將包括以下各項之單環戊二烯基錯合物：第一列過渡金屬(鈦、釩、鉻、鐵、鈷、鎳)；第二列過渡金屬(鋯、鉬、釕、銠、鈀)；第三列過渡金屬(鉿、鉭、鎢、銥、鋨、鉑)。Monocyclopentadienyl complexes may also be used to provide metal functionality to the precursor formulation and, when preferably stabilized with appropriate ligands such as chloride or carbonyl, would include monocyclic Pentadienyl complexes: transition metals in the first column (titanium, vanadium, chromium, iron, cobalt, nickel); transition metals in the second column (zirconium, molybdenum, ruthenium, rhodium, palladium); transition metals in the third column ( hafnium, tantalum, tungsten, iridium, osmium, platinum).

金屬之烷基錯合物亦可用於向前驅物調配物及產品提供金屬官能性。在該些烷基錯合物中，Si中心具有烷基(乙基、丙基、丁基、乙烯基、丙烯基、丁烯基)，其可直接經由σ鍵鍵結至過渡金屬。進一步地，此在利用後期過渡金屬諸如Pd、Rh、Pt、Ir的情況下將更為普遍。Alkyl complexes of metals can also be used to provide metal functionality to precursor formulations and products. In these alkyl complexes, the Si center has an alkyl group (ethyl, propyl, butyl, vinyl, propenyl, butenyl), which can be directly bonded to the transition metal via a σ bond. Further, this will be more prevalent with late transition metals such as Pd, Rh, Pt, Ir.

金屬之配位錯合物亦可用於向前驅物調配物及產品提供金屬官能性。在該些配位錯合物中，Si中心具有不飽和烷基(乙烯基、丙烯基、丁烯基、伸乙醯基、丁二烯基)，其可鍵結至Cr、Mo、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni羰基錯合物或烯錯合物。Si中心亦可附接至苯基、經取代的苯基或其他芳基化合物(吡啶、嘧啶)且苯基或芳基可位移金屬中心上之羰基。Coordination complexes of metals can also be used to provide metal functionality to precursor formulations and products. In these coordination complexes, the Si center has an unsaturated alkyl group (vinyl, propenyl, butenyl, acetyl, butadienyl), which can be bonded to Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni carbonyl complexes or alkene complexes. The Si center can also be attached to a phenyl, substituted phenyl, or other aryl compound (pyridine, pyrimidine) and the phenyl or aryl can displace the carbonyl on the metal center.

金屬烷氧化物亦可用於向前驅物調配物及產品提供金屬官能性。金屬烷氧化物化合物可與矽前驅物化合物混合且隨後用氫氧化物處理以與聚合物、共聚物同時形成氧化物。此亦可用金屬鹵化物及金屬醯胺來進行。較佳地，此係使用前期過渡金屬連同鋁、鎵及銦，後期過渡金屬：Fe、Mn、Cu，及鹼土金屬：Ca、Sr、Ba、Mg來進行。Metal alkoxides can also be used to provide metal functionality to precursor formulations and products. Metal alkoxide compounds can be mixed with silicon precursor compounds and then treated with hydroxide to form oxides simultaneously with polymers, copolymers. This can also be done with metal halides and metal amides. Preferably, this is done using early transition metals together with aluminum, gallium and indium, late transition metals: Fe, Mn, Cu, and alkaline earth metals: Ca, Sr, Ba, Mg.

其中Si直接鍵結至藉由鹵化物或有機基團穩定的金屬中心的化合物亦可用於向前驅物調配物及產品提供金屬官能性。Compounds in which Si is directly bonded to a metal center stabilized by a halide or organic group can also be used to provide metal functionality to precursor formulations and products.

另外，應理解，金屬及金屬錯合物可在熱解或後續熱處理之後為連續相。調配物可特定地設計來與所選金屬反應以現場形成金屬碳化物、氧化物及其他金屬化合物，通常稱為陶瓷金屬(例如，陶瓷金屬化合物)。調配物可與所選金屬反應以現場形成化合物，諸如富鋁紅柱石、鋁矽酸鹽、及其他。調配物或終點產物中相對於二氧化矽之量的金屬之量可為約0.1莫耳%至99.9莫耳%、約1莫耳%或更大、約10莫耳%或更大、及約20莫耳百分比或更大。金屬與本發明之前驅物式之前述使用可用於控制並提供預定化學計量。標題及實施例 Additionally, it should be understood that metals and metal complexes may be the continuous phase after pyrolysis or subsequent heat treatment. Formulations can be specifically designed to react with selected metals to form metal carbides, oxides, and other metal compounds in situ, commonly referred to as cermets (eg, cermets). Formulations can react with selected metals to form compounds in situ, such as mullite, aluminosilicates, and others. The amount of metal relative to the amount of silica in the formulation or end product can be from about 0.1 mol % to 99.9 mol %, about 1 mol % or greater, about 10 mol % or greater, and about 20 mole percent or greater. The aforementioned use of metals with precursors of the present invention can be used to control and provide a predetermined stoichiometry. Title and Example

應理解，本說明書中標題之使用係處於清晰性目的，且不以任何方式為限制性。因此，在標題下所描述的製程及揭示內容應在上下文利用本說明書之整體來解讀，包括各種實例。本說明書中標題之使用不應限制本發明提供的保護範疇。It should be understood that the use of headings in this specification is for the purpose of clarity and is not limiting in any way. Accordingly, the processes and disclosures described under the headings should be read in context with this specification as a whole, including the various examples. The use of headings in this specification shall not limit the scope of protection afforded by the invention.

應注意，不要求提供或說明為本發明之實施例之標的或與本發明之實施例相關聯的新穎及開創性製程、材料、效能或其他有益特徵及性質所隱含的理論。然而，本說明書中提供各種理論來進一步推進此領域中的技藝。本說明書中提出該些理論，且除非另外明確地陳述，否則絕不限制、約束或縮窄所主張發明所提供的保護範疇。可不需要或實踐該些理論來利用本發明。應進一步理解，本發明可引出新的及迄今未知的理論來解釋本發明之方法、製品、材料、裝置及系統之實施例的功能特徵；且此等稍後發展的理論不應限制本發明提供的保護範疇。It should be noted that there is no requirement to present or explain the theory underlying the novel and inventive processes, materials, performance or other beneficial features and properties which are the subject of or associated with the embodiments of the present invention. However, various theories are provided in this specification to further advance the art in this field. These theories are set forth in this specification and, unless expressly stated otherwise, in no way limit, restrict, or narrow the scope of protection afforded by the claimed invention. These theories may not be required or practiced to utilize the present invention. It is further to be understood that the present invention may introduce new and heretofore unknown theories to explain the functional features of embodiments of the methods, articles, materials, devices and systems of the present invention; and that such later developed theories shall not limit the scope of the present invention provided scope of protection.

本說明書中闡述的調配物、組合物、製品、塑膠、陶瓷、材料、部件、晶圓、胚晶、空間結構、用途、應用、儀器、方法、活動、及操作之各種實施例可用於各種其他領域及用於各種其他活動、用途及實施例。另外，該些實施例例如可與以下各項一起使用：現有系統、製品、組合物、材料、操作或活動；可與將來可發展的系統、製品、組合物、材料操作或活動一起使用；及與可部分地基於本說明書之教示修改的此種系統、製品、組合物、材料、操作或活動一起使用。進一步，本說明書中闡述的各種實施例及實例可彼此一起整體地或部分地及以不同及各種組合使用。因此，例如，提供於本說明書之各種實施例及實例中的配置可彼此一起使用；且本發明提供的保護範疇不應受限於在特定實施例、實例、或在特定圖式中的實施例中闡述的特定實施例、實例、配置或佈置。Various embodiments of formulations, compositions, articles, plastics, ceramics, materials, components, wafers, embryos, spatial structures, uses, applications, apparatus, methods, activities, and operations described in this specification can be used in various other field and for various other activities, uses and embodiments. In addition, the embodiments may be used, for example, with existing systems, articles, compositions, materials, operations, or activities; with systems, articles, compositions, materials, operations, or activities that may be developed in the future; and For use with such systems, articles of manufacture, compositions, materials, operations or activities that may be modified in part based on the teachings of this specification. Further, various embodiments and examples set forth in this specification may be used together with each other in whole or in part and in different and various combinations. Thus, for example, the configurations provided in the various embodiments and examples of this specification can be used with each other; and the scope of protection provided by the present invention should not be limited to the specific embodiments, examples, or embodiments in the specific drawings. A particular embodiment, example, configuration or arrangement set forth in .

本發明可以非本文特定揭示之彼等形式的其他形式來體現而不脫離其精神或本質特性。所描述的實施例將在所有方面僅考慮為說明性的且非限制性的。The present invention may be embodied in other forms than those specifically disclosed herein without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive.

1:圓柱體 2:平坦頂部 3:側面 150a:儲存槽 150b:儲存槽 151a:蒸餾設備 151b:蒸餾設備 152:混合容器 153:容器 154:熔爐 155a:熱解爐 155b:熱解爐 155c:熱解爐 157a:清潔室環境 158a:掃掠氣進口管線 158b:掃掠氣進口管線 158c:掃掠氣進口管線 159a:廢氣去除管線 159b:廢氣去除管線 159c:廢氣去除管線 160a:廢氣去除管線 160b:廢氣去除管線 160c:廢氣去除管線 161:掃掠氣進口 162:廢氣去除管線 163:廢氣處理總成 164:進口管線 190:空間形體形成區域 170:黏合劑槽 171:管線 172:混合容器 173:混合裝置 175:成形設備 177:烘箱 180:包裝裝置 190:區域 190a:區域 190b:區域 190c:區域 200:空間形體 201:頂部 202:側面 203:平坦底部 204:環形洞 205:軸 300:軸 301:頂部 302:側面 303:球形開口 304:底部 305:球形開口 400:形體 410:平坦頂部 401:軸 402:線 405:角度 410:平坦頂部/雙箭頭 411:雙箭頭 412:側面 413:平坦底部 414:環形開口/環形通道 500:軸 501:平坦頂部 502:開口 503:平坦底部 504:開口 505:側面 600:軸 601:平坦頂部 603:平坦底部 604:開口 604a:圓錐形側壁 604b:平坦底表面 607:側面 2001:平坦頂部 2003:平坦底部 2005:側壁 700:軸 701:頂部 703:底部 704:開口 705:側面 800:軸 801:平坦頂部 802:開口 802a:側壁 802b:底表面 803:平坦底部 805:外壁 900:軸 902:中心穿通開口 1000:軸 1001:平坦頂表面 1002:側壁 1003:平坦底表面 1005:中心開口 1005a:側壁 1100:軸 1102:頂部開口 1102a:圓錐形側壁 1102b:圓形底表面 1103:底部開口 1103a:圓錐形側壁 1103b:底表面 1200:軸 1202:頂部開口 1203:底部開口 1300:軸 1302:球形頂部開口 1302a:表面 1400:軸 1401:頂部 1402:球形頂部開口 1402a:表面 1405:側面 1500:軸 1501:線 1502:角度 1505:頂部環形開口/環形通道 1510:頂表面 1515:側壁表面 1800:氣相沉積裝置 1801:圓片 1802:晶種 1802a:表面 1803:可移動平臺 1804:加熱元件 1805:埠 1806:埠 1807:埠 1808:側壁/壁 1809:底部/底部壁/壁 1810:頂部/頂部壁/壁 1820:橫截面/直徑 1822:橫截面/直徑 1823:頂表面/高度 1824:底表面 1850:區域 2100:胚晶 2101:面 2101a:彎曲表面 2102:箭頭 2103:箭頭 2104:半徑 1: Cylinder 2: flat top 3: side 150a: storage tank 150b: storage tank 151a: Distillation equipment 151b: Distillation equipment 152: mixing container 153: container 154: Furnace 155a: pyrolysis furnace 155b: Pyrolysis furnace 155c: pyrolysis furnace 157a: Clean room environment 158a: Sweep gas inlet pipeline 158b: Sweep gas inlet pipeline 158c: Sweep gas inlet pipeline 159a: Exhaust gas removal line 159b: Exhaust gas removal line 159c: Exhaust gas removal pipeline 160a: Exhaust gas removal pipeline 160b: Exhaust gas removal pipeline 160c: Exhaust gas removal pipeline 161: Sweep gas inlet 162: Exhaust gas removal pipeline 163: Exhaust gas treatment assembly 164: Inlet pipeline 190: Spatial shape formation area 170: Adhesive Slot 171: pipeline 172: mixing container 173: mixing device 175: Forming equipment 177: Oven 180: Packaging device 190: area 190a: Area 190b: Area 190c: Area 200: Spatial Shape 201: top 202: side 203: flat bottom 204: Ring Hole 205: shaft 300: axis 301: top 302: side 303: spherical opening 304: bottom 305: spherical opening 400: shape 410: flat top 401: axis 402: line 405: Angle 410: Flat Top/Double Arrow 411: double arrow 412: side 413: flat bottom 414: Ring opening/Ring channel 500: axis 501: flat top 502: opening 503: flat bottom 504: opening 505: side 600: axis 601: flat top 603: flat bottom 604: opening 604a: Conical sidewall 604b: flat bottom surface 607: side 2001: Flat top 2003: Flat bottom 2005: Sidewall 700: axis 701: top 703: bottom 704: opening 705: side 800: axis 801: flat top 802: opening 802a: side wall 802b: bottom surface 803: flat bottom 805: outer wall 900: axis 902: Center through opening 1000: axis 1001: flat top surface 1002: side wall 1003: flat bottom surface 1005: center opening 1005a: side wall 1100: axis 1102: top opening 1102a: conical sidewall 1102b: circular bottom surface 1103: bottom opening 1103a: conical sidewall 1103b: bottom surface 1200: axis 1202: top opening 1203: bottom opening 1300: axis 1302: spherical top opening 1302a: surface 1400: axis 1401: top 1402: spherical top opening 1402a: surface 1405: side 1500: axis 1501: line 1502: angle 1505: top ring opening/ring channel 1510: top surface 1515: side wall surface 1800: Vapor deposition device 1801: Wafer 1802: Seed 1802a: surface 1803: Movable platform 1804: Heating element 1805: port 1806: port 1807: port 1808: side wall/wall 1809: Bottom/bottom wall/wall 1810: top/top wall/wall 1820: Cross Section/Diameter 1822: Cross Section/Diameter 1823: Top Surface/Height 1824: bottom surface 1850: area 2100: Embryo 2101: surface 2101a: curved surface 2102: Arrow 2103: Arrow 2104: Radius

第1A圖為根據本發明之空間形體之實施例的透視圖(6吋直徑，平坦頂部及底部)。Figure 1A is a perspective view of an embodiment of a spatial shape (6 inch diameter, flat top and bottom) in accordance with the present invention.

第1B圖為第1A圖之實施例之頂部透視圖。Figure 1B is a top perspective view of the embodiment of Figure 1A.

第1C圖為第1A圖之實施例之側視圖。Figure 1C is a side view of the embodiment of Figure 1A.

第1D圖為第1A圖之實施例之頂視圖。Figure 1D is a top view of the embodiment of Figure 1A.

第2A圖為根據本發明之空間形體之實施例的頂部透視圖(4 ¹/ ₂吋直徑，部分中心圓筒形開口頂部)。 Figure 2A is a top perspective view of an embodiment of a spatial form (4 ^1/2 _inch diameter, partially central cylindrical open top) in accordance with the present invention.

第2B圖為第2A圖之實施例之側面透視圖。Figure 2B is a side perspective view of the embodiment of Figure 2A.

第2C圖為第2A圖之實施例之頂視圖。Figure 2C is a top view of the embodiment of Figure 2A.

第2D圖為第2A圖至第2C圖中展示的實施例之一般類型之示意橫截面視圖。Figure 2D is a schematic cross-sectional view of the general type of embodiment shown in Figures 2A-2C.

第3A圖為根據本發明之空間形體之實施例的透視圖。Fig. 3A is a perspective view of an embodiment of a spatial body according to the present invention.

第3B圖為第3A圖之實施例之側面透視圖。Figure 3B is a side perspective view of the embodiment of Figure 3A.

第3C圖為第3A圖之實施例之頂視圖。Figure 3C is a top view of the embodiment of Figure 3A.

第3D圖為第3A圖之實施例之橫截面的透視圖。Figure 3D is a perspective view of a cross-section of the embodiment of Figure 3A.

第3E圖為第3D圖之橫截面之側視圖。Figure 3E is a side view of the cross-section of Figure 3D.

第3F圖為第3A圖至第3E圖中展示的實施例之一般類型之示意橫截面視圖。Figure 3F is a schematic cross-sectional view of the general type of embodiment shown in Figures 3A-3E.

第4A圖為根據本發明之空間形體之實施例的透視圖(具有頂部成角環形通道之錐形圓柱體)。Fig. 4A is a perspective view of an embodiment of a spatial body according to the present invention (conical cylinder with an angled top annular channel).

第4B圖為第4A圖之實施例之側面透視圖。Figure 4B is a side perspective view of the embodiment of Figure 4A.

第4C圖為第4A圖之實施例之側面透視圖。Figure 4C is a side perspective view of the embodiment of Figure 4A.

第4D圖為第4A圖之實施例之頂視圖。Figure 4D is a top view of the embodiment of Figure 4A.

第4E圖為第4A圖之實施例之橫截面的側面透視圖。Figure 4E is a side perspective view in cross section of the embodiment of Figure 4A.

第4F圖為第4A圖至第4E圖中展示的實施例之一般類型之示意橫截面視圖。Figure 4F is a schematic cross-sectional view of the general type of embodiment shown in Figures 4A-4E.

第5A圖為根據本發明之空間形體之實施例的頂視圖(具有頂部及底部切口之錐形圓柱體)。Fig. 5A is a top view of an embodiment of a spatial body (tapered cylinder with top and bottom cutouts) according to the present invention.

第5B圖為第5A圖之實施例之底視圖。Figure 5B is a bottom view of the embodiment of Figure 5A.

第5C圖為第5A圖之實施例之橫截面的透視圖。Figure 5C is a perspective view of a cross-section of the embodiment of Figure 5A.

第5D圖為第5A圖之實施例之橫截面的側視圖。Figure 5D is a side view in cross section of the embodiment of Figure 5A.

第5E圖為第5A圖之實施例之橫截面的側視圖。Figure 5E is a side view in cross section of the embodiment of Figure 5A.

第5F圖為第5A圖至第5E圖中展示的實施例之一般類型之示意橫截面視圖。Figure 5F is a schematic cross-sectional view of the general type of embodiment shown in Figures 5A-5E.

第6A圖為根據本發明之空間形體之實施例的底部透視圖(具有底部切口之錐形圓柱體)。Figure 6A is a bottom perspective view of an embodiment of a spatial body according to the present invention (tapered cylinder with bottom cutout).

第6B圖為第6A圖之實施例之底視圖。Figure 6B is a bottom view of the embodiment of Figure 6A.

第6C圖為第6A圖之實施例之側面透視圖。Figure 6C is a side perspective view of the embodiment of Figure 6A.

第6D圖為第6A圖至第6C圖中展示的實施例之一般類型之示意橫截面視圖。Figure 6D is a schematic cross-sectional view of the general type of embodiment shown in Figures 6A-6C.

第7圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 7 is a schematic cross-sectional view of an embodiment of a spatial shape according to the present invention.

第8圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 8 is a schematic cross-sectional view of an embodiment of a spatial shape according to the present invention.

第9圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 9 is a schematic cross-sectional view of an embodiment of a spatial body according to the present invention.

第10圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 10 is a schematic cross-sectional view of an embodiment of a spatial body according to the present invention.

第11圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 11 is a schematic cross-sectional view of an embodiment of a spatial body according to the present invention.

第12圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 12 is a schematic cross-sectional view of an embodiment of a spatial body according to the present invention.

第13圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 13 is a schematic cross-sectional view of an embodiment of a spatial body according to the present invention.

第14圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 14 is a schematic cross-sectional view of an embodiment of a spatial body according to the present invention.

第15圖為根據本發明之空間形體之實施例的示意橫截面視圖。Fig. 15 is a schematic cross-sectional view of an embodiment of a spatial body according to the present invention.

第16圖為根據本發明之系統及方法之實施例的製程流程圖。Figure 16 is a process flow diagram of an embodiment of the system and method according to the present invention.

第17圖為SiC、Si ₂C、及SiC ₂之分壓曲線。 Fig. 17 is the partial pressure curves of SiC, Si ₂ C, and SiC ₂ .

第18圖為根據本發明之氣相沉積設備及製程之示意橫截面。Figure 18 is a schematic cross-section of a vapor deposition apparatus and process according to the present invention.

第19圖為展示根據本發明之胚晶生長速率之實施例的圖表。Fig. 19 is a graph showing an example of the growth rate of an embryonic crystal according to the present invention.

第20A圖為根據本發明之空間形體之頂部透視圖(錐形圓柱體，無切口，平坦底部及頂部)。Fig. 20A is a top perspective view of a spatial body according to the present invention (tapered cylinder, no cutout, flat bottom and top).

第20B圖為第20A圖之空間形體之頂部透視圖。Figure 20B is a top perspective view of the spatial form of Figure 20A.

第20C圖為第20A圖之空間形體之側面透視圖。Fig. 20C is a side perspective view of the space shape in Fig. 20A.

第21圖為胚晶之實施例之示意圖，其說明胚晶面之曲率半徑的測定。Figure 21 is a schematic diagram of an embodiment of an embryo crystal, which illustrates the measurement of the radius of curvature of the embryo crystal surface.

為達到在圖式中展示的尺度，將為彼圖之實施例及彼實施例之特徵提供比例尺。該比例尺用於說明目的且不限制或約束實施例至其他大小、形狀及比例。In order to achieve the dimensions shown in the figures, scale bars are provided for the embodiments of that figure and the features of that embodiment. The scale is for illustrative purposes and does not limit or constrain the embodiments to other sizes, shapes and proportions.

國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無 Domestic deposit information (please note in order of depositor, date, and number) none

國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記) 無 Overseas storage information (please note in order of storage country, organization, date, and number) none

410:平坦頂部/雙箭頭 410: Flat Top/Double Arrow

412:側面 412: side

414:環形開口/環形通道 414: Ring opening/Ring channel

Claims

一種用作為在氣相沉積設備中生長SiC晶胚的源材料之結構，該結構界定材料之空間形體；該結構包含藉由一黏合劑結合在一起之SiC顆粒，其中該結構具有一結構完整性；該結構具有一內部多孔性；且該結構具有一頂部、一底部及一側面；該結構具有一空隙，該空隙係形成於該頂部、該底部及該側面之一或更多者；其中該空隙界定一開口，該開口具有至少0.5吋（12.7 mm）之橫截面。A structure used as a source material for growing SiC embryos in a vapor deposition apparatus, the structure defining the spatial shape of the material; the structure comprising SiC particles bound together by a binder, wherein the structure has a structural integrity ; the structure has an internal porosity; and the structure has a top, a bottom, and a side; the structure has a void formed in one or more of the top, the bottom, and the side; wherein the The void defines an opening having a cross-section of at least 0.5 inches (12.7 mm).

如請求項1所述之結構，其中該開口包含下列一或更多者：一環形開口、一球形開口及一通道。The structure according to claim 1, wherein the opening comprises one or more of the following: an annular opening, a spherical opening and a channel.

如請求項1所述之結構，包含形成於該頂部之該空隙、形成於該底部之該空隙、或同時形成於該頂部及該底部之該空隙。The structure according to claim 1 includes the void formed on the top, the void formed on the bottom, or the void formed on both the top and the bottom.

如請求項1所述之結構，其中該底部具有較該頂部更大之一直徑。The structure of claim 1, wherein the bottom has a larger diameter than the top.

如請求項2所述之結構，其中該頂部具有較該底部更大之一直徑。The structure of claim 2, wherein the top has a larger diameter than the bottom.

如請求項1所述之結構，其中該黏合劑為一陶瓷黏合劑。The structure according to claim 1, wherein the adhesive is a ceramic adhesive.

如請求項2所述之結構，其中該黏合劑為一陶瓷黏合劑。The structure according to claim 2, wherein the adhesive is a ceramic adhesive.

如請求項1～7任一項所述之結構，其中該頂部具有2吋（50.8 mm）至12吋（304.8 mm）之一直徑，該底部具有2吋（50.8 mm）至12吋（304.8 mm）之一直徑，且該側面具有0.5吋（12.7 mm）至7吋（177.8 mm）之一高度。The structure of any one of claims 1-7, wherein the top has a diameter of 2 inches (50.8 mm) to 12 inches (304.8 mm) and the bottom has a diameter of 2 inches (50.8 mm) to 12 inches (304.8 mm) ) and the side has a height of 0.5 inches (12.7 mm) to 7 inches (177.8 mm).

如請求項1～7任一項所述之結構，其中該結構為富碳的。The structure according to any one of claims 1 to 7, wherein the structure is carbon-rich.

如請求項1～7任一項所述之結構，其中該結構為貧碳的。The structure according to any one of claims 1-7, wherein the structure is carbon-depleted.

如請求項1～7任一項所述之結構，其中該內部多孔性為38%。The structure as claimed in any one of claims 1 to 7, wherein the internal porosity is 38%.

如請求項1～7任一項所述之結構，其中該內部多孔性包含一開孔多孔性。The structure of any one of claims 1-7, wherein the internal porosity comprises an open porosity.

如請求項1～7任一項所述之結構，其中該結構完整性之特徵在於約100 kPa至約100 MPa之一彈性模數。9. The structure of any one of claims 1-7, wherein the structural integrity is characterized by a modulus of elasticity of from about 100 kPa to about 100 MPa.

如請求項1～7任一項所述之結構，其中該結構完整性之特徵在於約100 Kg/mm ²至約2,000 Kg/mm ²之一硬度。 7. The structure of any one of claims 1-7, wherein the structural integrity is characterized by a hardness of about 100 Kg/mm ² to about 2,000 Kg/mm ² .

如請求項1～7任一項所述之結構，其中該結構具有約50 kPa至約300 GPa之一彈性模數；且其中該結構完整性之特徵在於約100 Kg/mm ²至約2,000 Kg/mm ²之一硬度。 The structure of any one of claims 1-7, wherein the structure has a modulus of elasticity of from about 50 kPa to about 300 GPa; and wherein the structural integrity is characterized by from about 100 Kg/mm ^to about 2,000 Kg /mm ² one hardness.

如請求項1～7任一項所述之結構，其中該結構完整性之特徵在於約100 kPa至約1 GPa之一彈性模數、以及約10 Kg/mm ²至約2,500 Kg/mm ²之一硬度。 The structure of any one of claims 1 to 7, wherein the structural integrity is characterized by a modulus of elasticity of from about 100 kPa to about 1 GPa, and a modulus of from about 10 Kg/mm ² to about 2,500 Kg/mm ² One hardness.

如請求項1～7任一項所述之結構，其中該頂部具有2吋（50.8 mm）至12吋（304.8 mm）之一直徑，該底部具有2吋（50.8 mm）至12吋（304.8 mm）之一直徑，且該側面具有0.5吋（12.7 mm）至7吋（177.8 mm）之一高度；且其中該結構完整性之特徵在於大於500 kPa之一彈性模數、以及大於10 Kg/mm ²之一硬度。 The structure of any one of claims 1-7, wherein the top has a diameter of 2 inches (50.8 mm) to 12 inches (304.8 mm) and the bottom has a diameter of 2 inches (50.8 mm) to 12 inches (304.8 mm) ), and the side has a height of 0.5 inches (12.7 mm) to 7 inches (177.8 mm); and wherein the structural integrity is characterized by a modulus of elasticity greater than 500 kPa, and greater than 10 Kg/mm One of ² hardness.

如請求項1～7任一項所述之結構，其中該頂部具有2吋（50.8 mm）至12吋（304.8 mm）之一直徑，該底部具有2吋（50.8 mm）至12吋（304.8 mm）之一直徑，且該側面具有0.5吋（12.7 mm）至7吋（177.8 mm）之一高度；且其中該結構完整性之特徵在於大於100 kPa之一彈性模數、以及大於100 Kg/mm ²之一硬度。 The structure of any one of claims 1-7, wherein the top has a diameter of 2 inches (50.8 mm) to 12 inches (304.8 mm) and the bottom has a diameter of 2 inches (50.8 mm) to 12 inches (304.8 mm) ), and the side has a height of 0.5 inches (12.7 mm) to 7 inches (177.8 mm); and wherein the structural integrity is characterized by a modulus of elasticity greater than 100 kPa, and greater than 100 Kg/mm One of ² hardness.

一種製造用於在氣相沉積設備中生長SiC晶胚的源材料之方法，該方法包含： a). 將SiC顆粒與一黏合劑混合以形成一漿料；b). 將該漿料壓製成一空間形體預成形件；以及c). 加熱該空間形體預成形件，以提供用於在氣相沉積設備中生長 SiC 晶胚的源材料；且d). 其中該源材料具有一內部多孔性。 A method of manufacturing a source material for growing SiC embryos in a vapor deposition apparatus, the method comprising: a). mixing SiC particles with a binder to form a slurry; b). pressing the slurry into a space-shaped preform; and c). heating the space-shaped preform to provide A source material for growing SiC embryos in the phase deposition apparatus; and d). wherein the source material has an internal porosity.

如請求項19所述之方法，進一步包含將SiC之易碎質塊打散，以提供該SiC顆粒。The method according to claim 19, further comprising breaking up the friable masses of SiC to provide the SiC particles.

如請求項19所述之方法，包含使用約100 g至約12,000 g之SiC顆粒，其具有約0.1 μm至約100 μm之一粒子大小。The method of claim 19 comprising using about 100 g to about 12,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm.

如請求項20所述之方法，包含使用約100 g至約12,000 g之SiC顆粒，其具有約0.1 μm至約100 μm之一粒子大小。The method of claim 20 comprising using about 100 g to about 12,000 g of SiC particles having a particle size of about 0.1 μm to about 100 μm.

如請求項19所述之方法，其中該源材料包含一頂部、一底部及一側面；該源材料具有一空隙，該空隙係形成於該頂部、該底部及該側面之一或更多者；其中該空隙界定一開口。The method of claim 19, wherein the source material includes a top, a bottom, and a side; the source material has a void formed in one or more of the top, the bottom, and the side; Wherein the gap defines an opening.

如請求項19所述之方法，其中該源材料具有約100 kPa至約100 MPa之一彈性模數。The method of claim 19, wherein the source material has a modulus of elasticity of about 100 kPa to about 100 MPa.

如請求項19所述之方法，其中該源材料具有約100 Kg/mm ²至約2,000 Kg/mm ²之一硬度。 The method of claim 19, wherein the source material has a hardness of about 100 Kg/mm ² to about 2,000 Kg/mm ² .

如請求項19所述之方法，其中該源材料具有大於500 kPa之一彈性模數、以及大於10 Kg/mm ²之一硬度。 The method of claim 19, wherein the source material has a modulus of elasticity greater than 500 kPa, and a hardness greater than 10 Kg/mm ² .

如請求項19所述之方法，其中該源材料具有大於100 kPa之一彈性模數、以及大於100 Kg/mm ²之一硬度。 The method of claim 19, wherein the source material has a modulus of elasticity greater than 100 kPa, and a hardness greater than 100 Kg/mm ² .

如請求項19～27任一項所述之方法，其中步驟c)之加熱包含：一固化步驟、一熱解步驟、或一固化步驟及一熱解步驟。The method according to any one of claims 19-27, wherein the heating in step c) includes: a curing step, a pyrolysis step, or a curing step and a pyrolysis step.

如請求項19～27任一項所述之方法，其中步驟c)之加熱包含一固化步驟；且其中該固化步驟包含將該預成形件加熱至約75℃至約125℃之一溫度。The method of any one of claims 19-27, wherein the heating of step c) comprises a curing step; and wherein the curing step comprises heating the preform to a temperature of about 75°C to about 125°C.

如請求項19～27任一項所述之方法，其中步驟c)之加熱包含一熱解步驟；且其中該熱解步驟包含將該預成形件加熱至約900℃至約1,200℃之一溫度。The method of any one of claims 19 to 27, wherein the heating of step c) comprises a pyrolysis step; and wherein the pyrolysis step comprises heating the preform to a temperature of about 900°C to about 1,200°C .

如請求項19～27任一項所述之方法，其中步驟c)之加熱包含一熱解步驟；且其中該熱解步驟包含將該預成形件加熱至約1,200℃至約2,550℃之一溫度。The method of any one of claims 19 to 27, wherein the heating of step c) comprises a pyrolysis step; and wherein the pyrolysis step comprises heating the preform to a temperature of about 1,200°C to about 2,550°C .

如請求項19～27任一項所述之方法，其中步驟c)之加熱包含：將該預成形件加熱至2,100℃之一溫度、處於30,000 psi之一壓力下、或上述兩者。The method of any one of claims 19-27, wherein the heating of step c) comprises: heating the preform to a temperature of 2,100° C., to a pressure of 30,000 psi, or both.

如請求項19～27任一項所述之方法，其中該漿料以重量計包含約0.1%至約65%之黏合劑。The method according to any one of claims 19-27, wherein the slurry comprises about 0.1% to about 65% of binder by weight.

如請求項19～27任一項所述之方法，其中該漿料以重量計包含約20%至約40%之黏合劑。The method according to any one of claims 19-27, wherein the slurry comprises about 20% to about 40% of binder by weight.

如請求項19～27任一項所述之方法，其中該源材料包含一種能夠在用於一氣相沉積設備中生長 SiC 晶胚時，提供一均勻通量的手段。The method of any one of claims 19-27, wherein the source material comprises a means capable of providing a uniform flux when used in a vapor deposition apparatus to grow SiC embryos.

如請求項19～27任一項所述之方法，其中該源材料包含一種能夠在用於一氣相沉積設備中生長 SiC 晶胚時，提供一方向性通量的手段。The method of any one of claims 19-27, wherein the source material comprises a means capable of providing a directional flux when used in a vapor deposition apparatus to grow SiC embryos.

如請求項19～27任一項所述之方法，其中該源材料包含一種能夠在用於一氣相沉積設備中生長 SiC 晶胚時，提供一致速率之通量形成的手段。The method of any one of claims 19-27, wherein the source material comprises a means capable of providing a consistent rate of flux formation when used in a vapor deposition apparatus to grow SiC embryos.

如請求項19～27任一項所述之方法，其中該源材料包含一種能夠在用於一氣相沉積設備中生長 SiC 晶胚時，提供均勻且一致速率之通量形成的手段。The method of any one of claims 19-27, wherein the source material comprises a means capable of providing a uniform and consistent rate of flux formation when used in a vapor deposition apparatus to grow SiC embryos.

如請求項19～27任一項所述之方法，其中該空間形體預成形件具有一頂部、一底部及一側面；且其中該空間形體預成形件具有一空隙，該空隙係形成於該頂部、該底部及該側面之一或更多者；其中該空隙界定一開口，該開口具有至少0.5吋（12.7 mm）之橫截面。The method according to any one of claims 19 to 27, wherein the spatial shape preform has a top, a bottom and a side; and wherein the spatial shape preform has a void formed in the top , one or more of the bottom and the side; wherein the void defines an opening having a cross-section of at least 0.5 inches (12.7 mm).

如請求項19～27任一項所述之方法，其中該空間形體預成形件具有一頂部、一底部及一側面；且其中該空間形體預成形件具有一空隙，該空隙係形成於該頂部、該底部及該側面之一或更多者；其中該空隙界定一開口；且其中該開口包含下列一或更多者：一環形開口、一球形開口及一通道。The method according to any one of claims 19 to 27, wherein the spatial shape preform has a top, a bottom and a side; and wherein the spatial shape preform has a void formed in the top , one or more of the bottom and the side; wherein the void defines an opening; and wherein the opening comprises one or more of: an annular opening, a spherical opening, and a channel.

如請求項19～27任一項所述之方法，其中該源材料為富碳的。The method of any one of claims 19-27, wherein the source material is carbon-rich.

如請求項19～27任一項所述之方法，其中該源材料為貧碳的。The method of any one of claims 19-27, wherein the source material is carbon-depleted.

一種生長SiC晶胚之方法，該方法包含： a). 將一源材料結構置於一氣相沉積設備中，該源材料結構界定材料之空間形體；該源材料結構包含藉由一黏合劑結合在一起之SiC顆粒，其中該結構具有一結構完整性；該結構具有一內部多孔性；b). 使該源材料結構昇華以形成一通量；c). 使該通量沉積於一生長面，藉此生長 SiC晶胚；d). 其中在昇華期間，該源材料結構未展現出鈍化。 A method of growing SiC embryos, the method comprising: a). A source material structure is placed in a vapor deposition apparatus, the source material structure defines the spatial shape of the material; the source material structure comprises SiC particles bound together by a binder, wherein the structure has a structural integrity The structure has an internal porosity; b). The source material structure is sublimated to form a flux; c). The flux is deposited on a growth surface, thereby growing SiC embryos; d). Wherein During sublimation, the source material structure exhibits no passivation.

一種生長SiC晶胚之方法，該方法包含： a). 將一源材料結構置於一氣相沉積設備中，該源材料結構界定材料之空間形體；該源材料結構包含藉由一黏合劑結合在一起之SiC顆粒，其中該結構具有一結構完整性；該結構具有一內部多孔性；b). 使該源材料結構昇華以形成一通量；c). 使該通量沉積於一生長面，藉此生長SiC晶胚；d). 其中在昇華期間，該源材料結構展現出分餾。 A method of growing SiC embryos, the method comprising: a). A source material structure is placed in a vapor deposition apparatus, the source material structure defines the spatial shape of the material; the source material structure comprises SiC particles bound together by a binder, wherein the structure has a structural integrity The structure has an internal porosity; b). The source material structure is sublimated to form a flux; c). The flux is deposited on a growth surface, thereby growing SiC embryos; d). Wherein During sublimation, the source material structure exhibits fractionation.

一種生長SiC晶胚之方法，該方法包含： a). 將一源材料結構置於一氣相沉積設備中，該源材料結構界定材料之空間形體；該源材料結構包含藉由一黏合劑結合在一起之SiC顆粒，其中該結構具有一結構完整性；該結構具有一內部多孔性；b). 於該氣相沉積設備中在昇華條件下，使該源材料結構昇華以形成一通量；c). 使該通量沉積於一生長面，藉此生長SiC晶胚；d). 其中在昇華期間，相較於具有與該源材料結構相同重量且處於昇華條件下之SiC粉末源材料堆，該源材料結構減少了鈍化的程度。 A method of growing SiC embryos, the method comprising: a). A source material structure is placed in a vapor deposition apparatus, the source material structure defines the spatial shape of the material; the source material structure comprises SiC particles bound together by a binder, wherein the structure has a structural integrity The structure has an internal porosity; b). In the vapor deposition apparatus under sublimation conditions, the source material structure is sublimated to form a flux; c). The flux is deposited on a growth surface, Thereby growing a SiC embryo; d). wherein during sublimation the source material structure has a reduced degree of passivation compared to a stack of SiC powder source material having the same weight as the source material structure and under sublimation conditions.

如請求項43～45任一項所述之方法，其中該源材料結構具有一頂部、一底部及一側面；且該源材料結構具有一空隙，該空隙係形成於該頂部、該底部及該側面之一或更多者；其中該空隙界定一開口。The method according to any one of claims 43 to 45, wherein the source material structure has a top, a bottom, and a side; and the source material structure has a void formed at the top, the bottom, and the one or more of the sides; wherein the void defines an opening.

如請求項43～45任一項所述之方法，其中該源材料結構具有一頂部、一底部及一側面；且該源材料結構具有一空隙，該空隙係形成於該頂部、該底部及該側面之一或更多者；其中該空隙界定一開口；且其中該開口包含下列一或更多者：一環形開口、一球形開口及一通道。The method according to any one of claims 43 to 45, wherein the source material structure has a top, a bottom, and a side; and the source material structure has a void formed at the top, the bottom, and the one or more of the sides; wherein the void defines an opening; and wherein the opening comprises one or more of: an annular opening, a spherical opening, and a channel.

如請求項43～45任一項所述之方法，其中該源材料結構具有一頂部、一底部及一側面；且該源材料結構具有一空隙，該空隙係形成於該頂部、該底部及該側面之一或更多者；且其中該頂部具有2吋（50.8 mm）至12吋（304.8 mm）之一直徑，該底部具有2吋（50.8 mm）至12吋（304.8 mm）之一直徑，且該側面具有0.5吋（12.7 mm）至7吋（177.8 mm）之一高度。The method according to any one of claims 43 to 45, wherein the source material structure has a top, a bottom, and a side; and the source material structure has a void formed at the top, the bottom, and the one or more of the sides; and wherein the top has a diameter of 2 inches (50.8 mm) to 12 inches (304.8 mm) and the bottom has a diameter of 2 inches (50.8 mm) to 12 inches (304.8 mm), And the sides have a height ranging from 0.5 inches (12.7 mm) to 7 inches (177.8 mm).

如請求項43～45任一項所述之方法，其中該源材料結構為富碳的。The method of any one of claims 43-45, wherein the source material structure is carbon-rich.

如請求項43～45任一項所述之方法，其中該源材料結構具有約100 kPa至約100 MPa之一彈性模數。43. The method of any one of claims 43-45, wherein the source material structure has an elastic modulus of about 100 kPa to about 100 MPa.

如請求項43～45任一項所述之方法，其中該源材料結構具有約100 Kg/mm ²至約2,000 Kg/mm ²之一硬度。 The method of any one of claims 43-45, wherein the source material structure has a hardness of about 100 Kg/mm ² to about 2,000 Kg/mm ² .

如請求項43～45任一項所述之方法，其中該源材料結構具有大於500 kPa之一彈性模數、以及大於10 Kg/mm ²之一硬度。 The method of any one of claims 43-45, wherein the source material structure has an elastic modulus greater than 500 kPa, and a hardness greater than 10 Kg/mm ² .