TW201404950A - Lining for refractory surfaces for purification of silicon - Google Patents

Abstract

A crucible for molten silicon comprises at least one refractory material having an inner surface and a lining deposited onto the inner surface, the lining comprising silicon carbide particles bound together by a colloidal silica. A method for silicon purification comprises melting a first silicon in an interior of a melting crucible to provide a first molten silicon, the melting crucible comprising a first refractory material having at least one first inner surface defining the melting crucible interior, directionally solidifying the first molten silicon in a directional solidification mold to provide a second silicon, the directional solidification mold comprising a second refractory material having at least one second inner surface defining a mold interior, and coating at least a portion of at least one of the first inner surface and the second inner surface with a lining comprising silicon carbide particles bound together by a colloidal silica.

Description

用於純化矽之耐火表面之襯裡Lining used to purify the refractory surface of tantalum

本發明是有關於一種 用於純化矽之耐火材料 ，特別是有關於一種 用於純化矽之耐火材料表面之襯裡。This invention relates to a refractory material for the purification of tantalum, and more particularly to a lining for the surface of a refractory material for the purification of tantalum.

太陽能電池藉由利用其將陽光轉換為電能的能力，而可為一種能量來源 。矽是太陽能電池的製造中使用的半導體材料，然而，使用矽的限制涉及純化至太陽能級(SG)的成本。Solar cells can be an energy source by exploiting their ability to convert sunlight into electrical energy. Niobium is a semiconductor material used in the manufacture of solar cells, however, the limitation of using niobium involves the cost of purification to solar grade (SG).

有一些已知的用來純化用於太陽能電池的矽的技術。大部分這些技術的操作依據原理為，當矽正從熔融液中凝固時，不想要的雜質可傾向於殘留在熔融液中。舉例來說，浮區法(float zone technique)可用於製造單晶錠，而使用在固體材料中之液體移動區，將雜質移至材料的邊緣。在另一個例示中，丘克拉斯基法(Czochralski technique)可用於製造單晶錠，且使用晶種，係慢慢地由溶液拉出，使形成了矽的單晶柱，而將雜質留在溶液中。在又一例示中，布里治曼法(Bridgeman)或熱交換器技術可用來製造多晶錠，而使用的溫度梯度會引起定向凝固。There are some known techniques for purifying germanium for solar cells. Most of these techniques operate on the principle that when the crucible is solidifying from the melt, unwanted impurities may tend to remain in the melt. For example, a float zone technique can be used to make a single crystal ingot while using a liquid moving zone in a solid material to move the impurities to the edge of the material. In another illustration, the Czochralski technique can be used to make a single crystal ingot, and the seed crystal is slowly pulled out of solution to form a single crystal column of germanium, leaving impurities in the In solution. In yet another illustration, Bridgeman or heat exchanger technology can be used to make polycrystalline ingots, and the temperature gradients used can cause directional solidification.

鑒於目前的能源需求及供應的限制，本發明人已經認知到，需要以更具成本效益的方式來純化冶金級(MG)的矽氧烷(silicone)(或任何其它具有比太陽能級矽更大量雜質的矽)成為太陽能級矽。本揭露描述一種容器，像是由耐火材料製得的坩堝、像是可用於純化矽的氧化鋁、像是經由定向凝固。矽可在坩堝中熔化，或熔融矽可在坩堝內定向地凝固，以提供用於純化矽。襯裡可設置在坩堝的耐火材料的內表面上，以防止或減少耐火材料對於坩堝內的熔融矽的汙染，如從硼、磷或鋁的污染物。襯裡可包含屏障襯裡(barrier lining)，包含以膠體氧化矽結合在一起的碳化矽顆粒，或襯裡可包含活性純化襯裡(active purification lining)，包含膠體氧化矽，及選擇性地，一種或多種助熔劑材料。襯裡可提供每次定向凝固循環的更純的最終矽，特別是相對於硼、磷、及鋁的污染物而言。In view of current energy requirements and supply constraints, the inventors have recognized that there is a need to purify metallurgical grade (MG) silicones in a more cost effective manner (or any other having a greater mass than solar grades) The impurity 矽) becomes a solar grade 矽. The present disclosure describes a container, such as a crucible made of a refractory material, such as alumina that can be used to purify the crucible, such as via directional solidification. The crucible may be melted in the crucible or the crucible may be solidified in the crucible to provide for purification of the crucible. The lining may be disposed on the inner surface of the ruthenium refractory material to prevent or reduce contamination of the refractory material with molten ruthenium in the crucible, such as from boron, phosphorus or aluminum. The liner may comprise barrier lining comprising cerium carbide particles bonded together by colloidal cerium oxide, or the lining may comprise active purification lining, comprising colloidal cerium oxide, and optionally one or more Flux material. The lining provides a more pure final flaw for each directional solidification cycle, particularly with respect to boron, phosphorus, and aluminum contaminants.

本揭露描述一種用於容納熔融矽的坩堝，坩堝包含至少一耐火材料，其具有至少一內表面，以界定用於接收熔融矽的內側、以及設置於內表面上的襯裡，包含藉由膠體氧化矽而黏結在一起的碳化矽顆粒。The present disclosure describes a crucible for containing a molten crucible comprising at least one refractory material having at least one inner surface defining an inner side for receiving molten crucible and a liner disposed on the inner surface, including by colloidal oxidation Carbide particles that are bonded together.

本揭露亦描述一種用於純化矽的方法，該方法包含熔化在熔化坩堝的內側的第一矽，以提供第一熔融矽，熔化坩堝包含第一耐火材料，其具有至少一第一內表面，以界定熔化坩堝的內側；定向地凝固在定向凝固模具的第一熔融矽，以提供第二矽，定向凝固模具包含第二耐火材料，其具有至少一第二內表面，以界定模具的內側；以及將包含藉由膠體氧化矽而黏結在一起的碳化矽顆粒的襯裡，塗佈到第一內表面及第二內表面之至少其中之一的至少一部分。The present disclosure also describes a method for purifying a crucible comprising melting a first crucible on the inside of the crucible to provide a first melting crucible comprising a first refractory material having at least a first inner surface, To define an inner side of the melting crucible; to directionally solidify the first melting crucible in the directional solidification mold to provide a second crucible, the directional solidification mold comprising a second refractory material having at least a second inner surface to define an inner side of the mold; And coating a liner comprising cerium carbide particles bonded together by colloidal cerium oxide to at least a portion of at least one of the first inner surface and the second inner surface.

此概要係意欲提供本揭露的申請標的概述。而非意欲提供本發明的排他的或詳盡的解釋。詳細的描述包含在關於本公開提供的進一步的資訊中。This summary is intended to provide an overview of the subject matter of the disclosure. Rather than intending to provide an exclusive or exhaustive explanation of the invention. The detailed description is included in the further information provided in connection with the present disclosure.

2、4、6．．．熔融矽2, 4, 6. . . Melting enthalpy

10．．．坩堝10. . . crucible

12．．．耐火材料12. . . Refractory

14．．．底部14. . . bottom

16．．．側面16. . . side

18．．．內側18. . . Inside

20．．．內表面20. . . The inner surface

22．．．上表面twenty two. . . Upper surface

24．．．內表面twenty four. . . The inner surface

30．．．襯裡30. . . lining

32．．．碳化矽顆粒32. . . Tantalum carbide particles

34．．．黏著劑34. . . Adhesive

36．．．氧化矽顆粒36. . . Cerium oxide particles

38．．．液相38. . . Liquid phase

40．．．坩堝40. . . crucible

42．．．耐火材料42. . . Refractory

44．．．底部44. . . bottom

46．．．側面46. . . side

48．．．內側48. . . Inside

50．．．內表面50. . . The inner surface

52．．．上表面52. . . Upper surface

54．．．內表面54. . . The inner surface

60．．．襯裡60. . . lining

62．．．氧化鋁顆粒62. . . Alumina particles

64．．．液相64. . . Liquid phase

70．．．襯裡70. . . lining

72．．．助熔劑顆粒72. . . Flux particles

74．．．膠體氧化矽黏著劑74. . . Colloidal cerium oxide adhesive

76．．．氧化矽顆粒76. . . Cerium oxide particles

78．．．液相78. . . Liquid phase

80．．．坩堝80. . . crucible

82．．．耐火材料82. . . Refractory

84．．．內表面84. . . The inner surface

86．．．襯裡86. . . lining

88．．．第一層88. . . level one

90．．．第二層90. . . Second floor

92．．．顆粒92. . . Granule

94．．．黏著劑94. . . Adhesive

100．．．頂部加熱器100. . . Top heater

102．．．加熱構件102. . . Heating member

104．．．絕緣材料104. . . Insulation Materials

106．．．頂部加熱器外罩106. . . Top heater cover

120．．．定向凝固的裝置120. . . Directional solidification device

122．．．頂部加熱器122. . . Top heater

124．．．坩堝124. . . crucible

126．．．鏈條126. . . Chain

128．．．孔128. . . hole

130．．．垂直結構構件130. . . Vertical structural member

132．．．水平結構構件132. . . Horizontal structural member

134．．．唇部134. . . Lip

136．．．篩選箱136. . . Filter box

138．．．絕緣體138. . . Insulator

140．．．垂直結構構件140. . . Vertical structural member

142．．．水平結構構件142. . . Horizontal structural member

144．．．底部結構構件144. . . Bottom structural member

200．．．流程圖200. . . flow chart

202、204、206、208、210、212、214、216．．．步驟202, 204, 206, 208, 210, 212, 214, 216. . . step

300．．．隔距300. . . Gauge

2-2、4-4、7-7．．．坩堝內表面之襯裡的一部分2-2, 4-4, 7-7. . . Part of the lining of the inner surface

在圖式中，相似的 參考符號可用於描述在幾個視圖中相似的元件。具有不同的字母字尾的相似的參考符號可用於代表相似元件的不同視圖。藉由舉例的方式但不以限制的方式，圖式普遍地闡明在本文中所敘述的各種例示。In the drawings, like reference characters may be used to the Similar reference symbols with different letter suffixes can be used to represent different views of similar elements. The illustrations generally exemplify the various examples described herein by way of example and not limitation.

第1圖係為 可使用於純化矽的坩堝之例示之橫剖面圖。Figure 1 is an illustration of a cross-sectional view of an example of a crucible that can be used to purify a crucible.

第2圖係為 塗佈在第1圖之例示坩堝之內表面的襯裡的一例示之特寫橫剖面圖。Fig. 2 is a close-up cross-sectional view showing an example of a lining applied to the inner surface of the enamel of Fig. 1 .

第3圖係為 可使用於純化矽的坩堝之例示之橫剖面圖。Figure 3 is an illustration of a cross-sectional view of an example of a crucible that can be used to purify a crucible.

第4圖係為 塗佈在第3圖之例示坩堝之內表面的襯裡的一例示之特寫橫剖面圖。Fig. 4 is a close-up cross-sectional view showing an example of a lining applied to the inner surface of the enamel of Fig. 3;

第5圖係為 塗佈在第3圖之另一例示坩堝之內表面的襯裡的一例示之特寫橫剖面圖。Fig. 5 is a close-up cross-sectional view showing an example of a lining coated on the inner surface of another exemplary cymbal of Fig. 3.

第6圖係為 可使用於純化矽的坩堝之例示之橫剖面圖。Figure 6 is an illustration of a cross-sectional view of an example of a crucible that can be used to purify a crucible.

第7圖係為 塗佈在第6圖之例示坩堝之內表面的襯裡的一例示之特寫橫剖面圖。Fig. 7 is a schematic close-up cross-sectional view showing an example of a lining coated on the inner surface of the enthalpy of Fig. 6;

第8圖係為 可使用於矽的定向凝固之加熱器之例示之橫剖面圖。Fig. 8 is a cross-sectional view showing an example of a heater which can be used for directional solidification of crucibles.

第9圖 係為用於矽的定向凝固之裝置且包含一例示之加熱器設置於例示之定向凝固模具頂部之例示之三維投影圖。Figure 9 is a diagram of a directional solidification apparatus for crucibles and includes an exemplary three-dimensional projection of the heater disposed on top of the illustrated directional solidification mold.

第10圖 係為純化矽之例示方法之流程圖。Figure 10 is a flow chart of an exemplary method for purifying hydrazine.

第11圖 係為顯示比較由不具有例示的襯裡之融化坩堝以及由例示的襯裡塗佈之融化坩堝純化的矽中的硼之純度變化示意圖。Figure 11 is a graph showing the change in purity of boron in a crucible purified from a enthalpy without an exemplary liner and from a lining coated with a lining.

本揭露描述使用定向凝固以純化矽的一種裝置及方法。裝置及方法可包含使用容納熔融矽的容器內的襯裡，其中襯裡可防止或減少從容器的耐火材料的熔融矽而來的汙染物。本發明的裝置及方法可用來製造使用於太陽能電池的矽晶體。The present disclosure describes an apparatus and method for using directional solidification to purify hydrazine. The apparatus and method can include the use of a liner within a container containing the molten crucible, wherein the liner prevents or reduces contaminants from the melting of the refractory material of the container. The apparatus and method of the present invention can be used to fabricate tantalum crystals for use in solar cells.

定義definition

單數形式的「一(a)」、「一(an)」及「該(the)」可包含複數個對象，除非上下文中另有明確地規定。The singular forms "a", "an", "the" and "the" may include a plurality of <RTIgt;

如本文所用，在一些例示中，用語如「第一(first)」、「第二(second)」、「第三(third)」等，在適用於其他用語如「母液(mother liquor)」、「晶體(crystals)」、「熔融混合物(molten mixture)」、「混合物(mixture)」、「清洗溶液(rinse solution)」、「熔融矽(molten silicon)」等，僅僅使用作為區分步驟之間的通用用語，本身並不指示步驟的優先性或步驟順序，除非另有明確地指示。舉例來說，在一些實施例中，當沒有第一或第二母液可為實施例的元件時，「第三母液」可以是一個元件。在其他實施例中，第一、第二、及第三母液可皆為範例元件。As used herein, in some examples, terms such as "first", "second", "third", etc., apply to other terms such as "mother liquor", "crystals", "molten mixture", "mixture", "rinse solution", "molten silicon", etc., are used only as a step between the discrimination steps. The generic terms are not themselves indicative of the order of the steps or the order of the steps unless otherwise explicitly indicated. For example, in some embodiments, the "third mother liquor" can be one component when no first or second mother liquor can be an element of the embodiment. In other embodiments, the first, second, and third mother liquors can all be exemplary components.

如本文所用，「導管(conduit)」可指穿透材料的管狀孔，其中材料不一定是管狀。舉例來說，貫穿一塊材料的孔可以是一個導管。孔的長度可大於直徑。導管可藉由套一管(包含管道)在材料中而形成。As used herein, "conduit" may refer to a tubular aperture that penetrates a material, wherein the material is not necessarily tubular. For example, the hole through a piece of material can be a conduit. The length of the hole can be larger than the diameter. The catheter can be formed in the material by a tube (including a tube).

如本文所用，「接觸 (contacting) 」 可指觸摸、接觸、或導致物質成緊靠的行為。As used herein, "contacting" may refer to the act of touching, contacting, or causing a substance to abut.

如本文所用，「坩堝(crucible)」可指一個容器，其可容納熔融材料，如可容納熔化會變成熔融狀的材料之容器、可接受熔融材料，並保持材料在其熔融狀態之容器、以及可容納熔融材料固化或結晶或其組合之容器。As used herein, "crucible" may refer to a container that can hold a molten material, such as a container that can hold a material that melts into a melt, a molten material that is acceptable, and that holds the material in its molten state, and A container that can hold the molten material solidified or crystallized or a combination thereof.

如本文所用，「定向凝固(directional solidification)」或「定向地凝固(dir ectionally solidify)」等可指材料大致上在一個位置開始結晶，以大致線性的方向進行(例如垂直地、水平地或垂直於表面)，且大致上在另一個位置結束。如在本定義中，一個位置可以是一個點、一個平面、或一個彎曲面，包括一個環形或碗狀。As used herein, "directional solidification" or "diritionally solidify" or the like may mean that the material begins to crystallize substantially at one location, in a substantially linear direction (eg, vertically, horizontally, or vertically). On the surface) and generally ends at another location. As in this definition, a position can be a point, a plane, or a curved surface, including a ring or bowl.

如本文所用 ，「浮渣(dross)」可指大量漂浮在熔融金屬浴上的固體雜質。通常出現在低熔點金屬或合金的熔化，如錫、鉛、鋅或鋁，或藉由金屬的氧化。它可被移除，例如，藉由把它的表面撇取(skimming)。至於錫與鉛，浮渣亦可藉由加入氫氧化鈉顆粒，其溶解氧化物並形成一個熔渣而去除。至於其他金屬，可添加鹽類助熔劑以分離浮渣。浮渣與熔渣(slag)係有所區別，熔渣是一種黏性液體，藉由成為固體而漂浮在合金上。As used herein, "dross" can refer to a large amount of solid impurities that float on a molten metal bath. It usually occurs in the melting of low melting point metals or alloys, such as tin, lead, zinc or aluminum, or by oxidation of metals. It can be removed, for example, by skimming its surface. As for tin and lead, the scum can also be removed by adding sodium hydroxide particles which dissolve the oxide and form a slag. As for other metals, a salt flux may be added to separate the dross. The scum differs from the slag system in that it is a viscous liquid that floats on the alloy by becoming a solid.

如本文所用 ，「送風機(fan)」可指任何可推動空氣的設備或裝置。As used herein, "fan" can refer to any device or device that can propel air.

如本文所用，「助熔劑(flux)」可指一種化合物，其添加至熔融金屬浴以幫助除去如浮渣內的雜質。助熔劑材料可加至熔融金屬浴，使助熔劑材料可與一種或多種材料或熔融金屬浴中的化合物反應，以形成可被除去的爐渣。As used herein, "flux" may refer to a compound that is added to a molten metal bath to aid in the removal of impurities such as scum. A flux material can be added to the molten metal bath to allow the flux material to react with one or more materials or compounds in the molten metal bath to form a slag that can be removed.

如本文所用，「熔爐(furnace)」可指一種機器、設備、裝置、或其他結構，其具有用於加熱材料的隔室。As used herein, "furnace" may refer to a machine, apparatus, device, or other structure having a compartment for heating a material.

如本文所用，「加熱元件(heating element)」可指一片能產生熱的材料。在一些例示中，當電被允許流過該材料，加熱元件可產生熱量。As used herein, "heating element" may refer to a piece of material that is capable of generating heat. In some illustrations, the heating element can generate heat when electricity is allowed to flow through the material.

如本文所用，「感應加熱器(induction heater)」可指在材料上經由感應電流(inducement of electrical current)而添加熱至材料之加熱器。電流可藉由使交流電(alternating current)行經靠近被加熱的材料的金屬線圈行進而產生。As used herein, "induction heater" may refer to a heater that adds heat to a material via an inducement of electrical current. Current can be generated by causing an alternating current to travel through a metal coil proximate to the material being heated.

如本文所用，「錠(ingot)」可指鑄造材料的塊體。在一些實施例中，材料的形狀允許為錠而相對容易地運輸。舉例來說，金屬加熱超過其熔點且模塑成條狀或塊狀，可以稱之為錠。As used herein, "ingot" may refer to a block of cast material. In some embodiments, the shape of the material allows for relatively easy transport of the ingot. For example, metal heating beyond its melting point and molding into strips or blocks can be referred to as ingots.

如本文所用，「襯裡(lining)」可指塗佈於至少一部分的坩堝表面的材料層。襯裡可作為坩堝的內表面及容納在坩堝的內表面的熔融材料之間的屏障。As used herein, "lining" may refer to a layer of material applied to at least a portion of the surface of the crucible. The lining acts as a barrier between the inner surface of the crucible and the molten material contained within the inner surface of the crucible.

如本文所用，「熔化(melt)」或「熔化的(melting)」可指一物質接觸到足夠的熱量時，從固體變成液體。用語「熔化」亦可指一材料已經歷此相轉變，成為熔融液體。As used herein, "melt" or "melting" may refer to the transition from a solid to a liquid when a substance is exposed to sufficient heat. The term "melting" can also mean that a material has undergone this phase transition to become a molten liquid.

如本文所用，「熔融(molten)」可指一種熔化的物質，其中熔化是加熱固體物質到一個溫度(稱為熔點)，在此熔點該物質變成液體的過程。As used herein, "molten" may refer to a molten material in which melting is the process of heating a solid material to a temperature (referred to as the melting point) at which the material becomes a liquid.

如本文所用，「單晶矽(monocrystalline silicon)」可指具有一個單一 及連續的晶格結構，且幾乎沒有任何缺陷或雜質的矽。As used herein, "monocrystalline silicon" may mean a crucible having a single and continuous lattice structure with little or no defects or impurities.

如本文所用，「多晶矽(polycrystalline silicon)」或「複矽(poly-Si)」或「多晶矽(multicrystalline silicon)」可指一個包含多個單晶矽晶體的材料。As used herein, "polycrystalline silicon" or "poly-Si" or "multicrystalline silicon" may refer to a material comprising a plurality of single crystal germanium crystals.

如本文所用，「純化」可指將目標化學物質從外界或污染物質物理性或化學性分離。As used herein, "purified" may refer to the physical or chemical separation of a target chemical from the outside or a contaminant.

如本文所用，「耐火材料(refractory material)」可指一個在高溫時化學上及物理上穩定的材料，特別是有關於熔化及定向凝固矽之高溫下。耐火材料的例示包含但不限於氧化鋁、氧化矽、氧化鎂、氧化鈣、氧化鋯、氧化鉻、碳化矽、石墨、或其組合。As used herein, "refractory material" may refer to a material that is chemically and physically stable at elevated temperatures, particularly at elevated temperatures associated with melting and directional solidification. Examples of refractory materials include, but are not limited to, alumina, cerium oxide, magnesium oxide, calcium oxide, zirconium oxide, chromium oxide, tantalum carbide, graphite, or combinations thereof.

如本文所用，「側面(side)」或「側面(sides)」可指一個或多個側面，且除另有說明外，可指側面或側面或與一個與一個或多個物體的頂部或底部對比的物體。As used herein, "side" or "sides" may mean one or more sides and, unless otherwise indicated, may refer to the sides or sides or to the top or bottom of one or more objects. Contrast objects.

如本文所用，「矽(silicon)」可指具有化學符號Si的元素，且可指在任何純度等級的矽，但一般指至少為50%重量純度、較佳地為75%重量純度、更佳地為85%純度、更佳地為90%重量純度、及更佳地為95%重量純度，並且甚至更佳地為99%重量純度的矽。As used herein, "silicon" may mean an element having the chemical symbol Si and may refer to cerium at any purity level, but generally means at least 50% by weight purity, preferably 75% by weight purity, more preferably The ground is 85% pure, more preferably 90% by weight pure, and more preferably 95% by weight pure, and even more preferably 99% by weight pure hydrazine.

如本文所用，「分離(separating)」可指從另一種物質移除一種物質之過程(例如，從混合物中移除固體或液體)。過程可採用所屬技術領域中具有通常知識者已知的任何合適的技術，例如，傾析(decanting)混合物、從混合物中撇去(skimming)一種或多種液體、離心分離(centrifuging)混合物、從混合物中過濾(filtering)出固體、或其組合。As used herein, "separating" may refer to the process of removing a substance from another substance (eg, removing solids or liquids from the mixture). The process may employ any suitable technique known to those of ordinary skill in the art, for example, decanting the mixture, skimming one or more liquids from the mixture, centrifuging the mixture, from the mixture. Medium filtering, or a combination thereof.

如本文所用，「熔渣(slag)」可指冶煉礦石以純化金屬的副產物。其可被視為金屬氧化物的混合物，然而，其可以元素的形式包含金屬硫化物及金屬原子。熔渣通常用作金屬冶煉中的廢棄物移除機制。在自然界中，金屬礦石如鐵、銅、鉛、鋁、及其他金屬在不純的狀態被發現，往往與其他金屬的矽酸鹽氧化並混合。在冶煉過程中，當礦石暴露於高溫時，這些雜質會從熔融金屬分離出來，因此可移除。收集被去除的化合物是熔渣。熔渣亦可為各種氧化物及藉由設計而創造出來的其他材料的摻合物，以提升金屬的純化。As used herein, "slag" may refer to the smelting of ore to purify by-products of metals. It can be regarded as a mixture of metal oxides, however, it can contain metal sulfides and metal atoms in the form of elements. Slag is commonly used as a waste removal mechanism in metal smelting. In nature, metal ores such as iron, copper, lead, aluminum, and other metals are found in impure states and are often oxidized and mixed with the silicates of other metals. During the smelting process, when the ore is exposed to high temperatures, these impurities are separated from the molten metal and thus can be removed. The compound to be removed is slag. The slag can also be a blend of various oxides and other materials created by design to enhance the purification of the metal.

如本文所用，「管(tube)」可指一種中空管形材料(hollow pipe-shaped material)。管可具有一個內部的形狀，約與其外形匹配。管的內部形狀可為任何合適的形狀，包含圓形、方形、或具有任意數量的邊的形狀，包含非對稱的形狀。As used herein, "tube" can refer to a hollow pipe-shaped material. The tube can have an internal shape that matches its shape. The inner shape of the tube can be any suitable shape, including a circular, square, or shape having any number of sides, including an asymmetrical shape.

用於定向凝固的坩堝坩埚 for directional solidification

第1圖顯示根據本公開的坩堝10之例示。坩堝10可用於矽的定向凝固。舉例來說，坩堝10可用來作為在熔爐中熔化矽的坩堝。坩堝10亦可用作進行定向凝固的容器，也稱為定向凝固模具(directional solidification mold)。坩堝10可由至少一種耐火材料12而形成，其被配置以提供用於矽的熔化或熔融矽的定向凝固，或兩者兼有之。FIG. 1 shows an illustration of a crucible 10 in accordance with the present disclosure.坩埚10 can be used for directional solidification of 矽. For example, helium 10 can be used as a crucible for melting crucibles in a furnace. The crucible 10 can also be used as a container for directional solidification, also known as a directional solidification mold. The crucible 10 may be formed from at least one refractory material 12 that is configured to provide directional solidification for melting or melting of the crucible, or both.

坩堝10可具有底部14及從底部14向上延伸的一個或多個側面16。坩堝10可形似於厚壁大碗(thick-walled large bowl)，其可具有圓形或大致圓形的橫截面。坩堝10可具有其他橫截面形狀，包含但不限於，方形、或六角形、八角形、五邊形、或具有 任何適當數量的邊的任何適當的形狀。The crucible 10 can have a bottom portion 14 and one or more side surfaces 16 extending upwardly from the bottom portion 14. The crucible 10 can be shaped like a thick-walled large bowl, which can have a circular or substantially circular cross section. The crucible 10 can have other cross-sectional shapes including, but not limited to, square, or hexagonal, octagonal, pentagonal, or any suitable shape having any suitable number of sides.

底部14及側面16定義坩堝10的內側，可承受熔融材料，像是熔融矽2。內側亦可承受固體材料，像是可熔化以形成熔融材料的固體矽(未顯示)。耐火材料12可包含面向內側18的內表面20。在一個例示中，內表面20包含底部14的上表面22及一個或多個側面16的內表面24。The bottom 14 and side 16 define the inside of the crucible 10 and can withstand molten material, such as molten crucible 2. The inner side can also withstand solid materials, such as solid helium (not shown) that can be melted to form a molten material. The refractory material 12 can include an inner surface 20 that faces the inner side 18. In one illustration, inner surface 20 includes an upper surface 22 of bottom portion 14 and an inner surface 24 of one or more side surfaces 16.

耐火材料12可為任何適當的耐火材料，特別是適用於矽的熔化或定向凝固的坩堝之耐火材料。可用作耐火材料12的例示材料包含但不限於氧化鋁(Al2O3，亦稱為礬土(alumina))、氧化矽(SiO2，亦稱為矽土(silica))、氧化鎂(MgO，亦稱為氧化鎂(magnesia))、氧化鈣(CaO)、氧化鋯(ZrO2，亦稱為氧化鋯(zirconia))、氧化鉻(III)(Cr2O3，亦稱為氧化鉻(chromia))、碳化矽(SiC)、石墨、或其組合。坩堝10可包含一種耐火材料，或一種以上的耐火材料。坩堝10中所包含的耐火材料或多種材料可混合，或其可位於坩堝10中個別的部分，或其組合。一種或多種耐火材料12可配置在層中。坩堝10可包含一層以上的一種或多種耐火材料12。坩堝10可包含一層的一種或多種耐火材料12。坩堝10的側面16可由與底部14不同的耐火材料而形成。與坩堝10的底部14相較，側面16可為不同的厚度，包含不同的材料組合物，包含不同數量的材料，或其組合。在一例示中，側面16可包含熱面(hot face)耐火材料，如氧化鋁。坩堝10的底部14可包含導熱(heat-conductive)材料，像是舉例來說，碳化矽、石墨、鋼、不銹鋼、鑄鐵、銅、或其組合。在一例示中，側面16包含氧化鋁(礬土)耐火材料，而底部14包含具有磷的黏著劑之碳化矽耐火材料。The refractory material 12 can be any suitable refractory material, particularly a refractory material suitable for the melting or directionally solidification of tantalum. Exemplary materials that can be used as the refractory material 12 include, but are not limited to, alumina (Al 2 O 3 , also known as alumina), cerium oxide (SiO 2 , also known as silica), magnesium oxide (MgO, also known as It is magnesia, calcium oxide (CaO), zirconium oxide (ZrO2, also known as zirconia), chromium (III) oxide (Cr2O3, also known as chromia), niobium carbide ( SiC), graphite, or a combination thereof. The crucible 10 may comprise a refractory material, or more than one refractory material. The refractory material or materials included in the crucible 10 may be mixed, or they may be located in individual portions of the crucible 10, or a combination thereof. One or more refractory materials 12 can be disposed in the layer. The crucible 10 may comprise more than one layer of one or more refractory materials 12. The crucible 10 can comprise one or more layers of refractory material 12. The side 16 of the crucible 10 can be formed from a different refractory material than the bottom portion 14. The side faces 16 can be of different thicknesses, including different material compositions, including different amounts of material, or a combination thereof, as compared to the bottom 14 of the crucible 10. In one example, side 16 may comprise a hot face refractory material such as alumina. The bottom 14 of the crucible 10 can comprise a heat-conductive material such as, for example, tantalum carbide, graphite, steel, stainless steel, cast iron, copper, or combinations thereof. In one example, the side 16 comprises an alumina (alumina) refractory and the bottom 14 comprises a tantalum carbide refractory with an adhesive of phosphorus.

雜質可從耐火材料12通至熔融矽2，如此一些雜質的不純度水準可高於用於光伏打設備中使用的矽的可接受度。在純化矽的定向凝固階段期間，這可能特別有問題，因為定向凝固可以是用於矽的最終純化步驟其中之一的步驟，因此用於定向凝固的在如坩堝10之類的坩堝中的矽是整個過程中一些最純的矽。例如，硼或磷的雜質可存在於耐火材料12中。即使是非常小量的硼或磷水準，藉由因為存在於熔融矽2的耐火材料12所經歷的高溫下，硼或磷可被驅動以擴散出耐火材料12到熔融矽2中。此外，如果耐火材料12是由氧化鋁(Al2O3)製成，或是包含氧化鋁，氧化鋁可以在熔融矽2的存在下而經歷還原反應，以形成可能會污染熔融矽2的金屬鋁(Al)。Impurities may pass from the refractory material 12 to the melting enthalpy 2, and such impurities may have a level of impurity that is higher than the acceptability of hydrazine used in photovoltaic devices. This may be particularly problematic during the directional solidification stage of purifying the crucible since directional solidification may be a step in one of the final purification steps for the crucible, thus the crucible in crucibles such as crucible 10 for directional solidification. It is some of the purest flaws in the whole process. For example, impurities such as boron or phosphorus may be present in the refractory material 12. Even at very small amounts of boron or phosphorus levels, boron or phosphorus can be driven to diffuse out of the refractory material 12 into the molten crucible 2 due to the high temperatures experienced by the refractory material 12 present in the molten crucible 2. Further, if the refractory material 12 is made of alumina (Al 2 O 3 ) or contains alumina, the alumina may undergo a reduction reaction in the presence of molten ruthenium 2 to form a metal aluminum (Al which may contaminate the fused ruthenium 2 ).

襯裡30可設置在耐火材料12的內表面20，像是在上表面22及內表面或複數個內表面24。襯裡30可配置成防止或減少熔融矽2的污染物，如經由雜質的傳輸，如從坩堝10的耐火材料12中的硼(B)、磷(P)及鋁(Al)進到熔融矽2中，或經由反應，雜質或汙染物從耐火材料12進到熔融矽2中。襯裡30可提供針對可存在於耐火材料12中的汙染物或雜質的屏蔽。The liner 30 can be disposed on the inner surface 20 of the refractory material 12, such as on the upper surface 22 and the inner surface or a plurality of inner surfaces 24. The liner 30 can be configured to prevent or reduce contaminants from melting the crucible 2, such as via impurities, such as boron (B), phosphorus (P), and aluminum (Al) from the refractory 12 of the crucible 10 into the melting crucible 2 In or through the reaction, impurities or contaminants enter the molten crucible 2 from the refractory material 12. The liner 30 can provide shielding against contaminants or impurities that may be present in the refractory material 12.

第2圖顯示顯示設置在耐火材料12的內表面20的襯裡30的特寫橫剖面圖。如第2圖所示，襯裡30可包含由黏著劑材料34結合在一起的複數個顆粒32。在一個例示中，顆粒32可包含碳化矽(SiC)而黏著劑材料34可包含膠體氧化矽(SiO2)。碳化矽顆粒32可各自包含一個或多個碳化矽晶體。碳化矽顆粒32可作為一個對汙染物或雜質的屏障，如硼、磷及鋁。顆粒32可以是奈米顆粒，例如，顆粒32具有小於5公釐的尺寸或顆粒直徑，例如小於3.5公釐。2 shows a close-up cross-sectional view showing the liner 30 disposed on the inner surface 20 of the refractory material 12. As shown in FIG. 2, the liner 30 can comprise a plurality of particles 32 bonded together by an adhesive material 34. In one illustration, the particles 32 may comprise tantalum carbide (SiC) and the adhesive material 34 may comprise colloidal tantalum oxide (SiO2). The tantalum carbide particles 32 may each comprise one or more tantalum carbide crystals. The cerium carbide particles 32 act as a barrier to contaminants or impurities such as boron, phosphorus and aluminum. The particles 32 may be nanoparticles, for example, the particles 32 have a size or particle diameter of less than 5 mm, such as less than 3.5 mm.

碳化矽顆粒32可由商業供應商提供。在一例示中，碳化矽顆粒32包含具有低水準的汙染物或雜質的高純度碳化矽，可導致光伏打設備的性能較差或性能不如預期，如硼、磷、鋁及鐵。在一例示中，碳化矽顆粒32可由具有小於3百萬分之一重(ppmw)硼含量的商用碳化矽而形成，像是小於2.5百萬分之一重(ppmw)，例如小於2.11百萬分之一重(ppmw)。商用碳化矽可具有小於55百萬分之一重(ppmw)的磷含量，像是小於51.5百萬分之一重(ppmw)，例如小於50百萬分之一重(ppmw)。碳化矽可具有小於約1700百萬分之一重(ppmw)的鋁含量，像是小於1675百萬分之一重(ppmw)，例如小於1665百萬分之一重(ppmw)。碳化矽可具有小於約4100百萬分之一重(ppmw)的鐵含量。碳化矽可具有小於約1145百萬分之一重(ppmw)的鈦含量。在一實施例中，碳化矽顆粒32是不含或大體上不含硼及磷。在一例示中，碳化矽顆粒32可包含其他材料，只要這些材料不造成具有無法接受的含量的不想要的雜質(像是硼、磷、或鋁)浸出(leach)到熔融矽2中。在一例示中，碳化矽顆粒32可包含氧化矽(SiO2)、元素碳(C)、鐵(III)氧化物(Fe2O3)、及氧化鎂(MgO)。在一例示中，碳化矽顆粒32具有以下的組合物(以乾燥的計算)：87.4重量%的SiC、10.9重量%的SiO2、0.9重量%的碳、0.5重量%的Fe2O3、及0.1重量%的MgO。在一例示中，碳化矽顆粒32包含由聯合礦產公司(Allied Mineral Products, Inc.)，哥倫布市，俄亥俄州，美國，商品名奈米科技碳化矽(NANOTEK SiC)所出售的碳化矽。奈米科技碳化矽相對於硼、磷、及鋁，具有高純度，例如，具有約2.11百萬分之一重(ppmw)或更小量的硼，而約51.4百萬分之一重(ppmw)或更小量的磷。Tantalum carbide particles 32 are available from commercial suppliers. In one example, the tantalum carbide particles 32 comprise high purity tantalum carbide having low levels of contaminants or impurities that can result in poor performance or performance of photovoltaic equipment such as boron, phosphorus, aluminum and iron. In an illustration, the tantalum carbide particles 32 may be formed from commercial tantalum carbide having a boron content of less than 3 parts per million (ppmw), such as less than 2.5 parts per million (ppmw), such as less than 2.11 million. One part by weight (ppmw). Commercial tantalum carbide can have a phosphorus content of less than 55 parts per million (ppmw), such as less than 51.5 parts per million (ppmw), such as less than 50 parts per million (ppmw). The tantalum carbide may have an aluminum content of less than about 1700 parts per million (ppmw), such as less than 1675 parts per million (ppmw), such as less than 1665 parts per million (ppmw). Tantalum carbide can have an iron content of less than about 4100 parts per million (ppmw). Tantalum carbide can have a titanium content of less than about 1145 parts per million (ppmw). In one embodiment, the tantalum carbide particles 32 are free or substantially free of boron and phosphorus. In an illustration, the tantalum carbide particles 32 may comprise other materials as long as they do not cause undesired amounts of undesirable impurities (such as boron, phosphorus, or aluminum) to leach into the molten crucible 2. In an example, the cerium carbide particles 32 may include cerium oxide (SiO 2 ), elemental carbon (C), iron (III) oxide (Fe 2 O 3 ), and magnesium oxide (MgO). In an example, the tantalum carbide particles 32 have the following composition (calculated as dry): 87.4% by weight of SiC, 10.9% by weight of SiO2, 0.9% by weight of carbon, 0.5% by weight of Fe2O3, and 0.1% by weight MgO. In one example, tantalum carbide particles 32 comprise tantalum carbide sold by Allied Mineral Products, Inc., Columbus, Ohio, USA, under the trade name NANOTEK SiC. Nanotechnology cerium carbide has high purity relative to boron, phosphorus, and aluminum, for example, having a boron content of about 2.11 parts per million (ppmw) or less, and about 51.4 parts per million by weight (ppmw). ) or a smaller amount of phosphorus.

黏著劑34可從氧化矽(SiO2)的膠體懸浮物形成，本文稱為膠體氧化矽。膠體氧化矽可包含少量的懸浮在液相38中的非晶質氧化矽顆粒36之懸浮物。碳化矽顆粒32可混入膠體氧化矽黏著劑34中，然後混合物可沉積於耐火材料12的內表面20，像是藉由漆塗(painting)、鋪展(spreading)、或其他常見的液體沉積技術。膠體氧化矽黏著劑34可作用以接合及穩定碳化矽顆粒32，即使在與熔融矽2之存在相關之高溫下。Adhesive 34 can be formed from a colloidal suspension of cerium oxide (SiO2), referred to herein as colloidal cerium oxide. The colloidal cerium oxide may contain a small amount of a suspension of amorphous cerium oxide particles 36 suspended in the liquid phase 38. The cerium carbide particles 32 can be incorporated into the colloidal cerium oxide binder 34, and the mixture can then be deposited on the inner surface 20 of the refractory material 12, such as by painting, spreading, or other common liquid deposition techniques. The colloidal cerium oxide binder 34 acts to bond and stabilize the cerium carbide particles 32 even at the elevated temperatures associated with the presence of the molten cerium 2 .

黏著劑34的膠體氧化矽可經由氧化矽核(silica nuclei)的形成而形成，隨後生長出在液相38內的氧化矽顆粒36。在一例示中，鹼金屬矽酸鹽(silicate)溶液，如矽酸鈉溶液，係部分地中和，如藉由從矽酸鈉中選擇的除去至少一部分的鈉。鹼金屬矽酸鹽的中和可導致氧化矽核的形成及氧化矽的聚合化以形成非晶質氧化矽顆粒。氧化矽核可具有包含介於1奈米(nm)及5奈米之間的尺寸。氧化矽顆粒36可具有一個尺寸，例如包含介於1奈米(nm)及100奈米之間的直徑。在一個例示中，氧化矽顆粒36具有包含介於10nm及30nm之間的尺寸，如約20nm。在一個例示中，膠體氧化矽形成的黏著劑34具有氧化矽顆粒36之重量百分比，其包含介於25重量%及60重量%的氧化矽，如包含介於30重量%及50重量%的氧化矽，例如40重量%的氧化矽。The colloidal cerium oxide of the adhesive 34 can be formed via the formation of a silica nuclei, followed by growth of the cerium oxide particles 36 in the liquid phase 38. In one example, an alkali metal silicate solution, such as a sodium citrate solution, is partially neutralized, such as by removing at least a portion of the sodium selected from sodium citrate. Neutralization of the alkali metal ruthenate may result in the formation of a ruthenium oxide core and polymerization of ruthenium oxide to form amorphous ruthenium oxide particles. The cerium oxide core may have a size comprised between 1 nanometer (nm) and 5 nanometers. The cerium oxide particles 36 can have a size, for example, comprising a diameter between 1 nanometer (nm) and 100 nanometers. In one illustration, the cerium oxide particles 36 have a size comprised between 10 nm and 30 nm, such as about 20 nm. In one illustration, the adhesive 34 formed by the colloidal cerium oxide has a weight percentage of cerium oxide particles 36 comprising between 25% and 60% by weight of cerium oxide, such as containing 30% by weight and 50% by weight of oxidation. For example, 40% by weight of cerium oxide.

在一例示中，用於製造黏著劑34的膠體氧化矽是市售的膠體氧化矽，如威仕邦(WesBond)公司，威明頓(Wilmington)，德拉瓦州，美國，商品名BINDZIL 2040所出售的膠體氧化矽。In one example, the colloidal cerium oxide used to make the adhesive 34 is a commercially available colloidal cerium oxide, such as WesBond, Wilmington, Delaware, USA, under the trade name BINDZIL 2040. The colloidal cerium oxide sold.

碳化矽顆粒32及黏著劑34可混合在一起以形成前驅混合物(precursor mixture)，可設置在內表面20上以形成襯裡30。碳化矽顆粒32及黏著劑34可以重量比而混合在一起，可提供前驅混合物的塗佈性(coatability)或鋪展性(spreadability)、良好的滑塌(slumping)特性(例如，在鋪展後缺乏滑塌或最小化的滑塌)、可接受的乾燥時間(例如，足夠長的時間，因此混合物可在乾燥前充分地應用至內表面20，但足夠短的時間，以提供一個合理的製造過程中的乾燥時間)、可接受的結合至耐火材料12的接合強度(binding strength)、及可接受的雜質或污染物從耐火材料12到熔融矽2的傳輸(resistance to transmission)之抗性。在一例示中，襯裡30包含重量組合物包含介於30重量%的碳化矽顆粒32及80重量%的碳化矽顆粒(例如，包含介於20重量%的膠體氧化矽黏著劑34及70重量%的膠體氧化矽黏著劑34)，像是包含介於50重量%的碳化矽顆粒32及70重量%的碳化矽顆粒32(例如，包含介於30重量%的膠體氧化矽黏著劑34及50重量%的膠體氧化矽黏著劑34)，舉例來說，約40重量%的碳化矽顆粒32及約60重量%的膠體氧化矽黏著劑34。在乾燥後(例如，從膠體氧化矽黏著劑34中除去水及其它液體之後)，得到的襯裡30可包含從35重量%的碳化矽至95重量%的碳化矽(例如，包含從5重量%的氧化矽至65重量%的氧化矽)，像是包含從60重量%的碳化矽至90重量%的碳化矽(例如，包含從10重量%的氧化矽至40重量%的氧化矽)，舉例來說，包含從70重量%的碳化矽至85重量%的碳化矽(例如，包含從15重量%的氧化矽至30重量%的氧化矽)，像是約80重量%的碳化矽及約20重量%。The tantalum carbide particles 32 and the adhesive 34 may be mixed together to form a precursor mixture that may be disposed on the inner surface 20 to form the liner 30. The cerium carbide particles 32 and the binder 34 may be mixed together in a weight ratio to provide coatability or spreadability of the precursor mixture, and good slumping characteristics (for example, lack of slip after spreading) Collapse or minimized slippage), acceptable drying time (eg, long enough, so the mixture can be applied to the inner surface 20 sufficiently before drying, but short enough to provide a reasonable manufacturing process Drying time), acceptable binding strength to the refractory 12, and resistance to acceptable impurities or contaminants from the refractory 12 to the resistance to transmission. In one example, the liner 30 comprises a weight composition comprising between 30% by weight of cerium carbide particles 32 and 80% by weight of cerium carbide particles (eg, comprising between 20% by weight of colloidal cerium oxide binder 34 and 70% by weight) Colloidal cerium oxide adhesive 34), like comprising 50% by weight of cerium carbide particles 32 and 70% by weight of cerium carbide particles 32 (for example, containing 30% by weight of colloidal cerium oxide adhesive 34 and 50 weight % of the colloidal cerium oxide binder 34), for example, about 40% by weight of cerium carbide particles 32 and about 60% by weight of colloidal cerium oxide binder 34. After drying (eg, after removing water and other liquids from the colloidal cerium oxide binder 34), the resulting liner 30 can comprise from 35% by weight of cerium carbide to 95% by weight of cerium carbide (eg, from 5% by weight) The cerium oxide to 65% by weight of cerium oxide), such as from 60% by weight of cerium carbide to 90% by weight of cerium carbide (for example, containing from 10% by weight of cerium oxide to 40% by weight of cerium oxide), for example Including, from 70% by weight of cerium carbide to 85% by weight of cerium carbide (for example, containing 15% by weight of cerium oxide to 30% by weight of cerium oxide), such as about 80% by weight of cerium carbide and about 20% weight%.

襯裡30可相對不含污染物，如硼、磷、及鋁。在一例示中，襯裡30中的硼含量小於約5百萬分之一重(ppmw)，如小於約3百萬分之一重(ppmw)，例如小於約2百萬分之一重(ppmw)。襯裡30中的磷含量可小於約70百萬分之一重(ppmw)，如小於約60百萬分之一重(ppmw)，例如小於約50ppm百萬分之一重(ppmw)。在一個示例中，襯裡30中的磷水準可低至11.25百萬分之一重(ppmw)。在一個例示中，襯裡30中的鋁含量可小於約0.75重量%，如小於約0.6重量%，例如小於約0.5重量%。Liner 30 can be relatively free of contaminants such as boron, phosphorus, and aluminum. In one exemplary embodiment, the boron content in the liner 30 is less than about 5 parts per million (ppmw), such as less than about 3 parts per million (ppmw), such as less than about 2 parts per million (ppmw). ). The phosphorus content in the liner 30 can be less than about 70 parts per million (ppmw), such as less than about 60 parts per million (ppmw), such as less than about 50 ppm parts per million (ppmw). In one example, the level of phosphorus in the liner 30 can be as low as 11.25 parts per million (ppmw). In one illustration, the aluminum content in the liner 30 can be less than about 0.75% by weight, such as less than about 0.6% by weight, such as less than about 0.5% by weight.

襯裡30的厚度可依據坩堝10的內部和周圍條件以及正在坩堝10內進行的製程階段。舉例來說，如果坩堝10用來作為熔化坩堝(melting crucible)，為了熔化固體矽以形成熔融矽2，則可需要相對厚的襯裡30，由於整個坩堝10都為高溫因坩堝10置於熔爐中。相似地，如果坩堝10被用作定向凝固的模具，則可需要相對薄的襯裡30，由於熔融矽2內較低揮發性的環境及相對較低的溫度。在一例示中，襯裡30具有厚度包含介於約1公釐(mm)至約25公釐(mm)，像是包含介於約2mm至約15mm，舉例來說，從約3mm至約10mm，舉例來說，包含介於約4mm至約5mm，像是約4、約4.1mm、約4.2mm、約4.3mm、約4.4mm、4.5mm、約4.6mm、約4.7mm、約4.8mm、約4.9mm、約5mm、約5.1mm、約5.2mm、約5.3mm、約5.4mm、約5.5mm、5.6mm、約5.7mm、約5.8mm、約5.9mm、以及約6mm。The thickness of the liner 30 can depend on the internal and ambient conditions of the crucible 10 as well as the process stages being performed within the crucible 10. For example, if the crucible 10 is used as a melting crucible, in order to melt the solid crucible to form a molten crucible 2, a relatively thick liner 30 may be required, since the entire crucible 10 is at a high temperature because the crucible 10 is placed in the furnace. . Similarly, if the crucible 10 is used as a mold for directional solidification, a relatively thin liner 30 may be required due to the relatively low volatility environment within the crucible 2 and the relatively low temperature. In one illustration, the liner 30 has a thickness comprised between about 1 mm (mm) and about 25 mm (mm), such as from about 2 mm to about 15 mm, for example, from about 3 mm to about 10 mm. By way of example, it comprises between about 4 mm and about 5 mm, such as about 4, about 4.1 mm, about 4.2 mm, about 4.3 mm, about 4.4 mm, 4.5 mm, about 4.6 mm, about 4.7 mm, about 4.8 mm, about 4.9 mm, about 5 mm, about 5.1 mm, about 5.2 mm, about 5.3 mm, about 5.4 mm, about 5.5 mm, 5.6 mm, about 5.7 mm, about 5.8 mm, about 5.9 mm, and about 6 mm.

在一例示中，碳化矽顆粒32及膠體氧化矽黏著劑34的混合物可為一種液體或液體懸浮物，可藉由已知的液體塗佈方法而塗佈到內表面20。在一例示中，混合物可經由漆塗(painting)、噴塗(spraying)、鋪展(spreading)、刀塗佈(blade coating)、滴塗佈(drop coating)或浸漬塗佈(dip coating)至少其中之一而塗佈到內表面20。碳化矽顆粒32及膠體氧化矽黏著劑34的混合物可以應用在內表面20上，使具有一個均勻或大體上均勻的厚度。塗佈的混合物接著可乾燥，而可使氧化矽顆粒36成長，當液相38乾燥時，從而碳化矽顆粒32被一個大體上為固體的氧化矽黏著劑34束縛住，以形成襯裡30。In one example, the mixture of tantalum carbide particles 32 and colloidal cerium oxide binder 34 can be a liquid or liquid suspension that can be applied to inner surface 20 by known liquid coating methods. In one example, the mixture may be at least one of painting, spraying, spreading, blade coating, drop coating, or dip coating. It is applied to the inner surface 20 as soon as it is applied. A mixture of tantalum carbide particles 32 and colloidal cerium oxide binder 34 can be applied to inner surface 20 to have a uniform or substantially uniform thickness. The coated mixture can then be dried to allow the cerium oxide particles 36 to grow as the liquid phase 38 dries, whereby the cerium carbide particles 32 are bound by a substantially solid cerium oxide binder 34 to form the liner 30.

在一例示中，碳化矽顆粒32及膠體氧化矽黏著劑34的混合物可用以作為耐火材料12的內表面20上的複數個塗層。混合物的每個塗層可經如由漆塗(painting)、噴塗(spraying)或任何其它塗佈方法而使用，且在施加下一道塗層之前，允許在指定時間的期間內乾燥。在一例示中，從2到10個或更多的塗層可應用至內表面20上，如2個、3個、4個、5個、6個、7個、8個、9個、或10個塗層。在一例示中，各塗層之間的襯裡可被允許乾燥從包含約15分鐘至約6小時，如從包含約30分鐘至約2小時。在所有塗層已被應用以後，襯裡30可被允許乾燥從包含約1小時至約10小時，如從包含約2小時至約8小時，如從包含約4小時至約6個小時，如約4小時、約4.5小時、約5小時、約5.5小時，及約6小時。In one example, a mixture of tantalum carbide particles 32 and colloidal cerium oxide binder 34 can be used as a plurality of coatings on inner surface 20 of refractory material 12. Each coating of the mixture can be used, for example, by painting, spraying, or any other coating method, and allowed to dry for a specified period of time prior to application of the next coating. In an illustration, from 2 to 10 or more coatings may be applied to the inner surface 20, such as 2, 3, 4, 5, 6, 7, 8, 9, or 10 coatings. In one example, the liner between the coatings can be allowed to dry from about 15 minutes to about 6 hours, such as from about 30 minutes to about 2 hours. After all of the coating has been applied, the liner 30 can be allowed to dry from about 1 hour to about 10 hours, such as from about 2 hours to about 8 hours, such as from about 4 hours to about 6 hours, such as from about 4 hours, about 4.5 hours, about 5 hours, about 5.5 hours, and about 6 hours.

第3圖顯示根據本揭露的坩堝40的另一個例示。參照上述關於第1圖及第2圖中的坩堝10，坩堝40可用於矽的定向凝固。舉例來說，坩堝40可當作在熔爐或定相凝固模具裡面熔化矽的坩堝。坩堝40可由至少一種配置以提供用於矽的熔化或熔融矽的定向凝固，或兼有的耐火材料42而形成。耐火材料42可為如上述關於坩堝10的耐火材料12其中之一個或多個耐火材料。Figure 3 shows another illustration of a crucible 40 in accordance with the present disclosure. Referring to the above-described 坩埚10 in Figs. 1 and 2, 坩埚40 can be used for directional solidification of 矽. For example, the crucible 40 can be used as a crucible for melting crucibles in a furnace or a phasing solidification mold. The crucible 40 may be formed from at least one configuration to provide directional solidification of the molten or molten crucible for the crucible, or a combination of the refractory material 42. The refractory material 42 can be one or more refractory materials of the refractory material 12 as described above with respect to the crucible 10.

坩堝40可具有底部44及從底部44向上延伸的一個或多個側面46。坩堝40可形似於厚壁大碗(thick-walled large bowl)，其可具有一個圓形或大致圓形的橫截面。坩堝40可具有其他橫截面形狀，包含但不限於，方形、或六角形、八角形、五邊形、或具有任何適當數量的邊的任何適當的形狀。The crucible 40 can have a bottom portion 44 and one or more side surfaces 46 that extend upwardly from the bottom portion 44. The crucible 40 can be shaped like a thick-walled large bowl, which can have a circular or substantially circular cross section. The crucible 40 can have other cross-sectional shapes including, but not limited to, square, or hexagonal, octagonal, pentagonal, or any suitable shape having any suitable number of sides.

底部44及側面46可以定義坩堝40的內側48，其可接收熔融材料，像是熔融矽4。內側48可接收固體材料，像是固體矽(未顯示)，其可熔化以形成熔融材料。耐火材料42可包含面向內側48的內表面50。在一個例示中，內表面50包含底部44的上表面52及一個或多個側面46的內表面54。The bottom portion 44 and the side surface 46 may define an inner side 48 of the crucible 40 that receives molten material, such as a molten crucible 4. The inner side 48 can receive a solid material, such as a solid crucible (not shown), which can be melted to form a molten material. The refractory material 42 can include an inner surface 50 that faces the inner side 48. In one illustration, inner surface 50 includes an upper surface 52 of bottom portion 44 and an inner surface 54 of one or more side surfaces 46.

襯裡60可設置在坩堝40的內表面50，像是在上表面52及內表面或複數個內表面54。參照上述關於第1圖及第2圖中的襯裡30，襯裡60可配置成防止或減少熔融矽4的污染，像是藉由提供一個對可存在於耐火材料42中的汙染物或雜質的屏障。襯裡60亦可設置以提供用於熔融矽4的活性純化。如本文所用，熔融矽的「活性純化(active purification)」可指一種或多種，介於襯裡60之間一種或多種成分的化學反應，且熔融矽4的一種或多種成分可形成熔融矽4裡的浮渣(dross)或熔渣(slag)，其可被移除。The liner 60 can be disposed on the inner surface 50 of the crucible 40, such as on the upper surface 52 and the inner surface or a plurality of inner surfaces 54. Referring to the liner 30 described above with respect to Figures 1 and 2, the liner 60 can be configured to prevent or reduce contamination of the molten crucible 4, such as by providing a barrier to contaminants or impurities that may be present in the refractory material 42. . Liner 60 may also be provided to provide active purification for melting the crucible 4. As used herein, "active purification" of molten helium may refer to one or more chemical reactions of one or more components between the liners 60, and one or more components of the molten crucible 4 may form a molten crucible 4 Dross or slag, which can be removed.

襯裡60可藉由包含至少一種材料，其可作為助熔劑以用於熔融矽4內的熔渣或浮渣的形成，而提供熔融矽4的活性純化。在一例示中，襯裡60可包含氧化矽(SiO2)。氧化矽通常加入熔融矽中作為助熔劑，像是鬆散氧化矽的顆粒，從熔融矽中除去鋁或其他不需要的雜質。提供主要包含氧化矽的襯裡60可顯著地增加熔融矽4的暴露於氧化矽的表面積。熔融矽4的高溫可修正襯裡60內的氧化矽，如此襯裡60可化學性地以熔融矽4的助熔劑本質上相同的方式與熔融矽4反應。這可使污染物或雜質從熔融矽4質量傳輸(mass transfer)至襯裡60，像是經由吸收或與襯裡60的組成成分反應，或兩者兼有之，以除去從熔融矽4中的污染物或雜質。The liner 60 can provide active purification of the molten crucible 4 by including at least one material that acts as a flux for melting the slag or scum within the crucible 4. In one example, the liner 60 can comprise yttrium oxide (SiO2). Cerium oxide is usually added to the molten crucible as a flux, such as loose cerium oxide particles, to remove aluminum or other unwanted impurities from the molten crucible. Providing a liner 60 comprising primarily cerium oxide can significantly increase the surface area of the molten cerium 4 exposed to cerium oxide. The high temperature of the molten crucible 4 corrects the cerium oxide in the liner 60 such that the liner 60 can chemically react with the molten crucible 4 in a substantially identical manner to the flux of the molten crucible 4. This allows mass transfer of contaminants or impurities from the molten crucible 4 to the liner 60, such as by absorption or reaction with the constituents of the liner 60, or both, to remove contamination from the molten crucible 4. Object or impurity.

在一例示中，襯裡60可由本文敘述為膠體氧化矽的氧化矽的膠體懸浮物而形成，相似於形成如上所述的襯裡30的黏著劑34的膠體氧化矽。然而，襯裡60不包含碳化矽顆粒32。當碳化矽顆粒不存在時，襯裡60的氧化矽任意地與熔融矽4的組成成分反應，以形成爐渣。因此，襯裡60可作為助熔劑塗層，提供熔融矽4的進一步的活性純化。In one example, the liner 60 can be formed from a colloidal suspension of cerium oxide, described herein as colloidal cerium oxide, similar to the colloidal cerium oxide of the adhesive 34 forming the liner 30 as described above. However, the liner 60 does not contain the cerium carbide particles 32. When the cerium carbide particles are not present, the cerium oxide of the lining 60 is optionally reacted with the constituents of the molten cerium 4 to form slag. Thus, the liner 60 can act as a flux coating to provide further active purification of the molten crucible 4.

第4圖顯示設置在耐火材料52的內表面50上的襯裡60的特寫橫剖面圖。膠體氧化矽可形成襯裡60可包含小、無定形的懸浮在液相64中的氧化矽顆粒62之懸浮物。膠體氧化矽可經由氧化矽核的形成，隨後在液相64中的氧化矽顆粒62的生長而形成。在一例示中，鹼金屬矽酸鹽(silicate)溶液，如矽酸鈉溶液，係部分地中和，如藉由從矽酸鈉中選擇的除去至少一部分的鈉。鹼金屬矽酸鹽的中和可導致氧化矽核的形成及氧化矽的聚合化以形成無定形的氧化矽顆粒。氧化矽核可具有一個包含介於1奈米(nm)及5奈米之間的尺寸。氧化鋁顆粒62可具有一個尺寸，例如包含介於1奈米(nm)及100奈米之間的直徑。在一例示中，氧化鋁顆粒62具有一個包含介於10nm及30nm之間的尺寸，如約20nm。在一個例示中，膠體氧化矽形成的襯裡60具有氧化矽顆粒62之重量百分比，其包含介於25重量%及60重量%的氧化矽，如包含介於30重量%及50重量%的氧化矽，例如40重量%的氧化矽。FIG. 4 shows a close-up cross-sectional view of the liner 60 disposed on the inner surface 50 of the refractory material 52. The colloidal cerium oxide forming liner 60 can comprise a small, amorphous suspension of cerium oxide particles 62 suspended in the liquid phase 64. The colloidal cerium oxide can be formed via the formation of a cerium oxide core followed by the growth of cerium oxide particles 62 in the liquid phase 64. In one example, an alkali metal silicate solution, such as a sodium citrate solution, is partially neutralized, such as by removing at least a portion of the sodium selected from sodium citrate. Neutralization of the alkali metal ruthenate can result in the formation of a ruthenium oxide core and the polymerization of ruthenium oxide to form amorphous ruthenium oxide particles. The cerium oxide core may have a size comprised between 1 nanometer (nm) and 5 nanometers. The alumina particles 62 can have a size, for example comprising a diameter between 1 nanometer (nm) and 100 nanometers. In one example, the alumina particles 62 have a size comprised between 10 nm and 30 nm, such as about 20 nm. In one illustration, the lining 60 formed by the colloidal cerium oxide has a weight percentage of cerium oxide particles 62 comprising between 25% and 60% by weight of cerium oxide, such as between 30% and 50% by weight of cerium oxide. For example, 40% by weight of cerium oxide.

在一例示中，用於形成襯裡60的膠體氧化矽是市售的膠體氧化矽，如威仕邦(WesBond)公司，威明頓(Wilmington)，德拉瓦州，美國，商品名BINDZIL 2040所出售的膠體氧化矽。In one example, the colloidal cerium oxide used to form the liner 60 is a commercially available colloidal cerium oxide, such as WesBond, Wilmington, Delaware, USA, under the trade name BINDZIL 2040. Colloidal cerium oxide.

在一例示中，襯裡60主要由氧化矽組成，例如，由膠體氧化矽而形成，如上所述，這樣的材料將實質上改變襯裡60活性地純化不存在於襯裡60中的熔融矽4的能力。在一例示中，襯裡60由氧化矽組成，例如，由上述的膠體氧化矽形成。In one illustration, the liner 60 is comprised primarily of ruthenium oxide, for example, formed by colloidal ruthenium oxide, which, as described above, will substantially alter the ability of the liner 60 to actively purify the fused enthalpy 4 that is not present in the liner 60. . In one example, the liner 60 is composed of ruthenium oxide, for example, formed of the above-described colloidal ruthenium oxide.

襯裡60的厚度可依據坩堝40的內部和周圍條件以及正在坩堝40內進行的製程階段。舉例來說，如果坩堝40用來作為熔化坩堝(melting crucible)，為了熔化固體矽以形成熔融矽4，則可需要相對厚的襯裡60，由於整個坩堝40都為高溫因坩堝40置於熔爐中。相似地，如果坩堝40被用作定向凝固的模具，則可需要相對薄的襯裡60，由於熔融矽2內較低揮發性的環境及相對較低的溫度。在一例示中，襯裡60具有厚度包含介於約1公釐(mm)至約25公釐(mm)，像是包含介於約2mm至約15mm，舉例來說，從約3mm至約10mm，舉例來說，包含介於約4mm至約5mm，像是約4、約4.1mm、約4.2mm、約4.3mm、約4.4mm、4.5mm、約4.6mm、約4.7mm、約4.8mm、約4.9mm、長約5mm、約5.1mm、約5.2mm、約5.3mm、約5.4mm、約5.5mm、5.6mm、約5.7mm、約5.8mm、約5.9mm、以及約6mm。The thickness of the liner 60 may depend on the internal and ambient conditions of the crucible 40 and the process stages being performed within the crucible 40. For example, if the crucible 40 is used as a melting crucible, in order to melt the solid crucible to form a molten crucible 4, a relatively thick liner 60 may be required, since the entire crucible 40 is at a high temperature because the crucible 40 is placed in the furnace. . Similarly, if the crucible 40 is used as a mold for directional solidification, a relatively thin liner 60 may be required due to the relatively low volatility environment within the crucible 2 and the relatively low temperature. In one illustration, the liner 60 has a thickness comprised between about 1 mm (mm) and about 25 mm (mm), such as from about 2 mm to about 15 mm, for example, from about 3 mm to about 10 mm. By way of example, it comprises between about 4 mm and about 5 mm, such as about 4, about 4.1 mm, about 4.2 mm, about 4.3 mm, about 4.4 mm, 4.5 mm, about 4.6 mm, about 4.7 mm, about 4.8 mm, about 4.9 mm, about 5 mm long, about 5.1 mm, about 5.2 mm, about 5.3 mm, about 5.4 mm, about 5.5 mm, 5.6 mm, about 5.7 mm, about 5.8 mm, about 5.9 mm, and about 6 mm.

在一例示中，膠體氧化矽可為液體或液體懸浮液，可藉由已知的液體塗佈法將其塗佈至內表面50，以形成襯裡60。在一例示中，膠體氧化矽可經由漆塗(painting)、鋪展(spreading)、刀塗佈(blade coating)、滴塗佈(drop coating)或浸漬塗佈(dip coating)至少其中之一而塗佈到內表面50。膠體氧化矽可應用至內表面50，使具有一個均勻的或大致均勻的厚度。塗佈的膠體氧化矽接著可乾燥，而可使氧化矽顆粒62生長，當液相64乾燥時，從而碳化矽顆粒62形成一個大致上為固體的氧化矽襯裡60。像是上述的襯裡30，襯裡60可應用於作為複數個塗層，每道塗層可被允許在塗層之間的第一次乾燥時間與最後一次乾燥時間之間乾燥，如包含從約2小時至約10小時，舉例來說，在塗佈最後一道塗層後約6小時。In one example, the colloidal cerium oxide can be a liquid or liquid suspension that can be applied to the inner surface 50 by known liquid coating methods to form the liner 60. In an illustration, the colloidal cerium oxide may be applied by at least one of painting, spreading, blade coating, drop coating, or dip coating. Cloth to the inner surface 50. Colloidal cerium oxide can be applied to the inner surface 50 to have a uniform or substantially uniform thickness. The coated colloidal cerium oxide can then be dried to allow the cerium oxide particles 62 to grow as the liquid phase 64 dries, whereby the cerium carbide particles 62 form a substantially solid cerium oxide lining 60. Like the lining 30 described above, the lining 60 can be applied as a plurality of coatings, each coating being allowed to dry between the first drying time and the last drying time between coatings, such as from about 2 Hours to about 10 hours, for example, about 6 hours after the last coating is applied.

在一例示中，襯裡60可包含其他材料，可提供熔融矽4的進一步活性純化。舉例來說，襯層60可包含其它助熔劑材料，可提供從熔融矽4內的成分的熔渣的形成。可以被包含在襯裡60的熔融劑材料例示包含，但不限於，碳酸鈉(Na2CO3)、氧化鈣(CaO)、及氟化鈣(CaF2)。在一例示中，襯裡60可具有一組合物，其包含介於約30重量%的SiO2及約55重量%的SiO2、包含介於約40重量%的Na2CO3及約65重量%的Na2CO3、包含介於約0重量%及約15重量%的CaO、包含介於約0重量%的CaF2及約25重量%的CaF2。在一例示中，襯裡60的組合物可包含約42.7重量%的SiO2、約50.6重量%的Na2CO3、約1.7重量%的CaO、及約5重量%的CaF2。助熔劑組合物的進一步描述可發現於蒂雷納等人(Turenne et al)的美國臨時申請案，標題為「適用在用於純化矽之定向凝固之助熔劑組合物」，代理人卷號2552.036PRV，與本申請案同日申請，其係於此併入以作為參考。In one example, the liner 60 can comprise other materials that provide further active purification of the molten crucible 4. For example, the liner 60 can comprise other fluxing materials that provide for the formation of slag from the components within the melting crucible 4. The flux material that may be included in the liner 60 is exemplified by, but not limited to, sodium carbonate (Na2CO3), calcium oxide (CaO), and calcium fluoride (CaF2). In one example, the liner 60 can have a composition comprising between about 30% by weight SiO2 and about 55% by weight SiO2, comprising between about 40% by weight Na2CO3 and about 65% by weight Na2CO3, including About 0% by weight and about 15% by weight of CaO, including about 0% by weight of CaF2 and about 25% by weight of CaF2. In one example, the composition of the liner 60 can comprise about 42.7 wt% SiO2, about 50.6 wt% Na2CO3, about 1.7% wt% CaO, and about 5% wt% CaF2. A further description of the flux composition can be found in the U.S. Provisional Application of Turenne et al., entitled "Flux Composition for Directional Solidification for Purifying Crucibles", attorney No. 2552.036 The PRV, filed on the same day as the present application, is incorporated herein by reference.

在一個例示中，如第5圖所示，襯裡70可包含額外的助熔劑材料，以膠體氧化矽黏著劑74結合在一起的助熔劑顆粒72的形式添加進襯裡70中，相似於碳化矽顆粒32如何與膠體氧化矽黏著劑34結合在一起，以形成襯裡30，如上所述。像是膠體氧化矽黏著劑34及襯裡60中的膠體氧化矽，如上所述，膠體氧化矽黏著劑74可包含少量、懸浮在液相78中的非晶體氧化矽顆粒76之懸浮物。氧化矽顆粒76可具有一個尺寸，例如，包含介於1奈米(nm)及100奈米之間的直徑。在一例示中，氧化矽顆粒76具有一個包含介於10 nm及30 nm之間的尺寸，如約20 nm。在一例示中，膠體氧化矽形成的黏著劑74具有氧化矽顆粒76之重量百分比，其包含介於25重量%及60重量%的氧化矽，如包含介於30重量%及50重量%的氧化矽，例如40重量%的氧化矽。In one illustration, as shown in FIG. 5, the liner 70 may comprise additional fluxing material added to the liner 70 in the form of flux particles 72 in which the colloidal cerium oxide binder 74 is bonded, similar to the tantalum carbide particles. 32 how it is combined with the colloidal cerium oxide binder 34 to form the liner 30, as described above. Like the colloidal cerium oxide binder 34 and the colloidal cerium oxide in the lining 60, as described above, the colloidal cerium oxide binder 74 may comprise a small amount of a suspension of amorphous cerium oxide particles 76 suspended in the liquid phase 78. The cerium oxide particles 76 can have a size, for example, comprising a diameter between 1 nanometer (nm) and 100 nanometers. In one example, the cerium oxide particles 76 have a size comprised between 10 nm and 30 nm, such as about 20 nm. In an exemplary embodiment, the adhesive 74 formed by the colloidal cerium oxide has a weight percentage of cerium oxide particles 76 comprising between 25% and 60% by weight of cerium oxide, such as containing 30% by weight and 50% by weight of oxidation. For example, 40% by weight of cerium oxide.

助熔劑顆粒72及黏著劑74可混合在一起以形成前驅混合物(precursor mixture)，可設置在內表面50上以形成襯裡70。助熔劑顆粒72及黏著劑74可以重量比混合在一起，其可提供前驅混合物良好的塗佈性(coatability)或鋪展性(spreadability)，亦提供良好的對耐火材料52之接合強度(binding strength)。助熔劑顆粒72及黏著劑74的重量比亦可選擇，使膠體氧化矽黏著劑74的氧化矽及助熔劑顆粒72將為可利用的與熔融矽4的一種或多種組成份的反應，而可形成爐渣。因此，助熔劑顆粒72與黏著劑74的重量比可實質上低於如上述關於襯裡30裡(第1圖及第2圖)的碳化矽顆粒32與黏著劑34的重量比，因此，有較大的膠體氧化矽黏著劑74的表面積將暴露於熔融矽4中。一例示中，襯裡70包含重量組合物包含介於5重量%的助熔劑顆粒72及50重量%的助熔劑顆粒72 (例如，包含介於50重量%的膠體氧化矽黏著劑74及95重量%的膠體氧化矽黏著劑74)，像是包含介於10重量%的助熔劑顆粒72及35重量%的助熔劑顆粒72 (例如，包含介於65重量%的膠體氧化矽黏著劑74及90重量%的膠體氧化矽黏著劑74)，舉例來說，包含介於15重量%的助熔劑顆粒72及25重量%的助熔劑顆粒72(例如，包含介於75重量%的膠體氧化矽黏著劑72及85重量%的膠體氧化矽黏著劑74)，像是約20重量%的助熔劑顆粒72及約80重量%的膠體氧化矽黏著劑74。Flux particles 72 and adhesive 74 may be mixed together to form a precursor mixture that may be disposed on inner surface 50 to form liner 70. The flux particles 72 and the adhesive 74 can be mixed together in a weight ratio which provides good coatability or spreadability of the precursor mixture and also provides good bond strength to the refractory material 52. . The weight ratio of flux particles 72 and binder 74 may also be selected such that the cerium oxide and flux particles 72 of the colloidal cerium oxide binder 74 will be reactable with one or more constituents of the molten cerium 4, but may be Forming slag. Therefore, the weight ratio of the flux particles 72 to the adhesive 74 can be substantially lower than the weight ratio of the tantalum carbide particles 32 to the adhesive 34 as described above with respect to the liner 30 (Figs. 1 and 2). The surface area of the large colloidal cerium oxide binder 74 will be exposed to the molten crucible 4. In one example, the liner 70 comprises a weight composition comprising between 5% by weight of flux particles 72 and 50% by weight of flux particles 72 (eg, comprising between 50% by weight of colloidal cerium oxide binder 74 and 95% by weight) The colloidal cerium oxide binder 74) comprises, for example, 10% by weight of flux particles 72 and 35% by weight of flux particles 72 (for example, comprising 65% by weight of colloidal cerium oxide binder 74 and 90 weight) The % colloidal cerium oxide binder 74), for example, comprises between 15% by weight of flux particles 72 and 25% by weight of flux particles 72 (eg, comprising between 75% by weight of colloidal cerium oxide binder 72) And 85% by weight of colloidal cerium oxide binder 74), such as about 20% by weight of flux particles 72 and about 80% by weight of colloidal cerium oxide binder 74.

在一例示中，襯裡70基本上由氧化矽組成，例如，由膠體氧化矽黏著劑74形成，且至少一種助熔劑材料，像是碳酸鈉(Na2CO3)、氧化鈣(CaO)及氟化鈣(CaF2)至少其中之一這類的材料將實質上改變襯裡70活性地純化不存在於襯裡70中的熔融矽4的能力。在一例示中，襯裡70由氧化矽組成，例如，由膠體氧化矽黏著劑74形成，及其中至少一種的熔融劑材料，像是像是碳酸鈉(Na2CO3)、氧化鈣(CaO)及氟化鈣(CaF2)至少其中之一。In one illustration, the liner 70 consists essentially of ruthenium oxide, for example, formed of a colloidal ruthenium oxide binder 74, and at least one flux material such as sodium carbonate (Na2CO3), calcium oxide (CaO), and calcium fluoride ( The material of at least one of CaF2) will substantially alter the ability of the liner 70 to actively purify the molten crucible 4 that is not present in the liner 70. In one example, the liner 70 is composed of ruthenium oxide, for example, formed of a colloidal ruthenium oxide binder 74, and a flux material of at least one of them, such as sodium carbonate (Na2CO3), calcium oxide (CaO), and fluorinated. At least one of calcium (CaF2).

第6圖顯示根據本揭露的坩堝80的另一個例示。坩堝80可包含具有內表面84的耐火材料82，其中襯裡86可設置於耐火材料82。襯裡86可包含第一層88，其與耐火材料82的內表面84接觸、以及第二層90，當熔融矽存在於坩堝80裡，第二層90係與熔融矽6接觸。耐火材料82可為如上所述關於坩堝10的耐火材料12的一種或多種耐火材料。Figure 6 shows another illustration of a crucible 80 in accordance with the present disclosure. The crucible 80 can include a refractory material 82 having an inner surface 84, wherein the liner 86 can be disposed on the refractory material 82. The liner 86 can include a first layer 88 that is in contact with the inner surface 84 of the refractory material 82, and a second layer 90 that is in contact with the molten crucible 6 when the molten crucible is present in the crucible 80. The refractory material 82 can be one or more refractory materials for the refractory material 12 of the crucible 10 as described above.

第7圖顯示設置在耐火材料82的內表面84的襯裡86的特寫橫剖面圖。在一例示中，第一層88可包含以黏著劑94材料結合在一起的複數個顆粒92。第一層88實質上可與如上述第1圖及第2圖的襯裡30相同。舉例來說，顆粒92可包含碳化矽(SiC)，而黏著劑94可包含膠體氧化矽(SiO2)。第二層90可包含活性純化層，其實質上可與如上述第3圖及第4圖的襯裡60相同(例如，膠體氧化矽襯裡)，或與如上述第5圖及第6圖的襯裡70相同(例如，以膠體氧化矽黏著劑結合在一起的熔融劑材料顆粒的襯裡)。第一層88可提供一種被動的屏障層，防止或減少污染物或雜質從耐火材料82至熔融矽6的通過，且第二層90可提供熔融矽6的活性純化，作為含助熔劑之層。FIG. 7 shows a close-up cross-sectional view of the liner 86 disposed on the inner surface 84 of the refractory material 82. In one example, the first layer 88 can comprise a plurality of particles 92 bonded together with an adhesive 94 material. The first layer 88 can be substantially identical to the liner 30 of Figures 1 and 2 above. For example, the particles 92 may comprise tantalum carbide (SiC) and the adhesive 94 may comprise colloidal tantalum oxide (SiO2). The second layer 90 can comprise an active purification layer which can be substantially identical to the liner 60 of Figures 3 and 4 above (e.g., a colloidal ruthenium oxide lining), or a lining as in Figures 5 and 6 above. 70 is the same (for example, a lining of particles of a flux material bonded together by a colloidal cerium oxide binder). The first layer 88 can provide a passive barrier layer that prevents or reduces the passage of contaminants or impurities from the refractory material 82 to the molten crucible 6, and the second layer 90 provides active purification of the molten crucible 6 as a flux-containing layer. .

在一例示中，坩堝如上述坩堝10、40、或80，可容納約1公噸(metric tonne)或更多的熔融矽。在一例示中，坩堝可容納約1.4公噸或更多的熔融矽。在一例示中，坩堝可容納約2.1公噸或更多的熔融矽。在一例示中，坩堝可容納至少約1、1.2、1.4、1.6、1.8、2.0、2.1、2.5、3、3.5、4、4.5、或5公噸或更多的矽熔融。In one example, a crucible 10, 40, or 80 as described above can accommodate about 1 metric ton or more of molten enthalpy. In one example, the crucible can hold about 1.4 metric tons or more of molten germanium. In one example, the crucible can hold about 2.1 metric tons or more of molten germanium. In one example, the crucible can accommodate at least about 1, 1.2, 1.4, 1.6, 1.8, 2.0, 2.1, 2.5, 3, 3.5, 4, 4.5, or 5 metric tons or more of helium melt.

坩堝如上述坩堝10、40、或80 ，可包含其他功能，舉例來說，可提供在坩堝內更有效的矽的熔化定向凝固。可以被包含在坩堝中的結構或特徵之例示包含，但不限於，一個或多個絕緣層或其他結構、一個或多個熱傳導層或其他結構、一個或多個外 罩(jackets)、及一個或多個用於保持層聚集在一起或防止或減少鬆動的錨(anchors)。可以被包含在坩堝中的結構之例示描述於尼科爾等人(Nichol et al) 的美國專利申請案第 12/947,936號，標題為「用於矽的定向凝固之裝置及方法」，於2010年11月17日申請，指定的本申請案的受讓人，其係於此併入以作為參考。For example, 坩埚10, 40, or 80 above may include other functions, for example, providing more efficient melt directional solidification of the crucible in the crucible. Illustrative structures or features that may be included in the crucible include, but are not limited to, one or more insulating layers or other structures, one or more thermally conductive layers or other structures, one or more jackets, and one or A plurality of anchors for holding the layers together or preventing or reducing looseness. An example of a structure that can be included in a crucible is described in U.S. Patent Application Serial No. 12/947,936, to Nichol et al., entitled "A. The application of the assignee of the present application is hereby incorporated by reference.

頂部加熱器(Top Heater)Top Heater

若根據本揭露，像是如上述的坩堝10、40、或80，係用於定向凝固，頂部加熱器亦可被包含及設置在坩堝的頂部，以應用於加熱坩堝及在坩堝內的熔融矽。頂部加熱器可具有一個橫截面形狀，與坩堝的橫截面形狀大致匹配。藉由頂部加熱器，坩堝的熱量的應用可允許控制在坩堝中的熔融矽的溫度。頂部加熱器亦可不加熱而設置在坩鍋頂端的頂端，所以頂部加熱器可作為控制熱量從坩堝的釋放之絕緣體。藉由控制溫度或坩堝中的熱量釋放，可提供所希望的溫度梯度，其可更高度控制的定向凝固。最終，在溫度梯度的控制可允許一個更有效的定向凝固，其得到的矽之純度最大化。According to the present disclosure, such as 坩埚10, 40, or 80 as described above, for directional solidification, the top heater may also be included and disposed on the top of the crucible for application to the crucible and the melting crucible in the crucible. . The top heater can have a cross-sectional shape that substantially matches the cross-sectional shape of the crucible. With the top heater, the application of heat from the crucible allows for control of the temperature of the molten crucible in the crucible. The top heater can also be placed at the top end of the top of the crucible without heating, so the top heater acts as an insulator that controls the release of heat from the crucible. By controlling the temperature or heat release in the crucible, a desired temperature gradient can be provided which allows for more highly controlled directional solidification. Ultimately, control of the temperature gradient allows for a more efficient directional solidification, which maximizes the purity of the resulting ruthenium.

第8圖顯示頂部加熱器100之例示。頂部加熱器100可包含一個或多個加熱構件102。一個或多個加熱構件102中的每個可獨立地包含任何合適的材料。舉例來說，一個或多個加熱構件102中的每個可獨立地包含一個加熱元件，其中加熱元件可包含碳化矽(silicon carbide)、二矽化鉬(molybdenum disilicide)、石墨、或其組合，並且，一個或多個加熱構件102中的每個可選擇性地獨立地包含一個感應加熱器。在一個例示中，一個或多個加熱構件設置在大致相同的高度。在另一例示中，一個或多個加熱構件設置在不 同的高度。Figure 8 shows an illustration of the top heater 100. The top heater 100 can include one or more heating members 102. Each of the one or more heating members 102 can independently comprise any suitable material. For example, each of the one or more heating members 102 can independently comprise a heating element, wherein the heating element can comprise silicon carbide, molybdenum disilicide, graphite, or a combination thereof, and Each of the one or more heating members 102 can selectively include an induction heater independently. In one illustration, one or more of the heating members are disposed at substantially the same height. In another illustration, one or more of the heating members are disposed at different heights.

在一例示中，加熱構件102可包含碳化矽，可具有一定的優勢。舉例來說，碳化矽加熱構件102，較不可能在氧存在的高溫下的腐蝕。包含腐蝕的材料的加熱元件藉由使用一真空室而可減少氧腐蝕，但碳化矽加熱構件102可不須真空室而避免腐蝕。此外，碳化矽加熱構件102可不使用水冷式引線(water-cooled leads)。在一例示中，加熱構件被用於真空室中，以水冷式引線，或兩者兼有之。在一個例示中，加熱構件102不使用真空室，無水冷式引線，或兩者皆無。In one example, the heating member 102 can comprise tantalum carbide, which can have certain advantages. For example, the tantalum carbide heating member 102 is less likely to corrode at high temperatures in the presence of oxygen. The heating element containing the corroded material can reduce oxygen corrosion by using a vacuum chamber, but the tantalum carbide heating member 102 can avoid corrosion without requiring a vacuum chamber. Further, the tantalum carbide heating member 102 may not use water-cooled leads. In one example, the heating member is used in a vacuum chamber, with a water-cooled lead, or both. In one illustration, the heating member 102 does not use a vacuum chamber, a waterless cold lead, or both.

在一例示中，一個或多個加熱構件102為感應加熱器。感應加熱器102可嵌入進一個或多個耐火材料中。然後包含感應加熱線圈或多個線圈的耐火材料可放置在底模(bottom mold)上。耐火材料可為任何合適的材料，包含但不限於氧化鋁(aluminum oxide)、氧化矽(silicon oxide)、氧化鎂(magnesium oxide)、氧化鈣(calcium oxide)、氧化鋯(zirconium oxide)、氧化鉻(chromium oxide)、碳化矽(silicon carbide)、石墨(graphite)、或其組合。在另一例示中，感應加熱器102不嵌入進一個或多個耐火材料中。In one example, one or more of the heating members 102 are induction heaters. The induction heater 102 can be embedded in one or more refractory materials. The refractory material comprising the induction heating coil or coils can then be placed on a bottom mold. The refractory material may be any suitable material including, but not limited to, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, chromium oxide. (chromium oxide), silicon carbide, graphite, or a combination thereof. In another illustration, the induction heater 102 is not embedded in one or more refractory materials.

一個或多個加熱構件102可具有電力系統，因此若至少一個加熱構件102出現故障時，任何剩下的功能加熱構件102可繼續接收電力，以產生熱量。在一例示中，每個加熱構件102具有自己的電路。The one or more heating members 102 can have an electrical system such that if at least one of the heating members 102 fails, any remaining functional heating members 102 can continue to receive power to generate heat. In an illustration, each heating member 102 has its own circuitry.

頂部加熱器100可包含絕緣體104。絕緣體104可包含任何合適的絕緣材料，包含但不限於絕緣磚(insulating brick)、耐火材料、耐火材料的混合物、絕緣板(insulating board)、陶瓷紙(ceramic paper)、高溫羊毛(high temperature wool)、或其混合物。絕緣板可包含高溫陶瓷板。絕緣材料104及一個或多個加熱構件102的底部邊緣可大致等高，或加熱構件102可放置在絕緣材料104的底部邊緣的高度之上，或絕緣材料104的底部邊緣可放置在加熱構件102的高度之上。一個或多個加熱構件102及絕緣材料104的其他配置可被使用，像是一種或多種加熱構件102作為感應加熱器，絕緣材料104包含耐火材料，其中一個或多個加熱構件102包裹在耐火材料104中。在這樣的一個例示中，額外的絕緣材料亦可任選地被包含於內，其中額外的絕緣材料可為耐火材料，或額外的絕緣材料可為另一種合適的絕緣材料。The top heater 100 can include an insulator 104. The insulator 104 may comprise any suitable insulating material including, but not limited to, insulating bricks, refractory materials, mixtures of refractory materials, insulating boards, ceramic paper, high temperature wool. , or a mixture thereof. The insulating plate may comprise a high temperature ceramic plate. The bottom edge of the insulating material 104 and the one or more heating members 102 may be substantially equal, or the heating member 102 may be placed above the height of the bottom edge of the insulating material 104, or the bottom edge of the insulating material 104 may be placed over the heating member 102 Above the height. Other configurations of one or more heating members 102 and insulating material 104 may be utilized, such as one or more heating members 102 as induction heaters, and insulating material 104 comprising refractory material, wherein one or more heating members 102 are wrapped in refractory material 104. In such an illustration, additional insulating material may also optionally be included, wherein the additional insulating material may be a refractory material, or the additional insulating material may be another suitable insulating material.

頂部加熱器100可包含外罩106。外罩106可包含任何合適的材料，包含但不限於鋼、不銹鋼、銅、鑄鐵(cast iron)、耐火材料、耐火材料的混合物、或其組合。絕緣材料104可至少部分地設置在介於一個或多個加熱構件102及外罩106之間。外罩106的底部邊緣可大致地與絕緣材料104的底部邊緣以及與一個或多個加熱構件102一致，或外罩106的底部邊緣可從絕緣材料104的底部邊緣或與一個或多個加熱構件102，或兩者兼有之，而抵消。在一例示中，部分外罩106其覆蓋絕緣材料104的邊緣可包含相對低的導電性的材料，如合適的耐火材料，如氧化鋁、氧化矽、氧化鎂、氧化鈣、氧化鋯、氧化鉻、碳化矽、石墨、或其組合。The top heater 100 can include a housing 106. The outer cover 106 can comprise any suitable material including, but not limited to, steel, stainless steel, copper, cast iron, refractory materials, mixtures of refractory materials, or combinations thereof. The insulating material 104 can be at least partially disposed between the one or more heating members 102 and the outer cover 106. The bottom edge of the outer cover 106 can generally coincide with the bottom edge of the insulating material 104 and with the one or more heating members 102, or the bottom edge of the outer cover 106 can be from the bottom edge of the insulating material 104 or with one or more heating members 102, Or both, offset. In one example, a portion of the outer cover 106 covering the edge of the insulating material 104 may comprise a relatively low conductivity material such as a suitable refractory material such as alumina, yttria, magnesia, calcium oxide, zirconia, chromia, Tantalum carbide, graphite, or a combination thereof.

頂部加熱器外罩106可包含結構構件，如可增加頂部加熱器100的強度或剛性的構件。結構構件可包含鋼、不銹鋼、銅、鑄鐵、耐火材料、耐火材料的混合物、或其組合。在一例示中，頂部加熱器外罩106可包含一個或多個結構構件，其從頂部加熱器外罩106的外部延伸，方向係遠離頂部加熱器100的中心，以及圍繞頂部加熱器100的圓周或周圍水平延伸。一個或多個水平結構構件可設置在，例如，頂部加熱器外罩106的外部之較低的邊緣、在頂部加熱器外罩106的外部邊緣之頂端、或在頂部加熱器外罩106的外部邊緣介於底端與頂端之間的任何位置。在一例示中，頂部加熱器100包含三個水平結構構件，一個設置在頂部加熱器外罩106的底端邊緣，一個設置在頂部加熱器外罩106的頂端邊緣，以及一個設置在頂部加熱器外罩106的較低級較高邊緣之間的位置。The top heater shroud 106 can include structural members such as members that can increase the strength or rigidity of the top heater 100. The structural members may comprise steel, stainless steel, copper, cast iron, refractory materials, mixtures of refractory materials, or combinations thereof. In one illustration, the top heater shroud 106 can include one or more structural members that extend from the exterior of the top heater shroud 106, away from the center of the top heater 100, and around or around the circumference of the top heater 100. Extend horizontally. One or more horizontal structural members may be disposed, for example, at a lower edge of the exterior of the top heater shroud 106, at the top end of the outer edge of the top heater shroud 106, or at the outer edge of the top heater shroud 106 Any position between the bottom and the top. In one illustration, the top heater 100 includes three horizontal structural members, one disposed at a bottom end edge of the top heater housing 106, one disposed at a top edge of the top heater housing 106, and one disposed at the top heater housing 106. The position between the lower edge of the lower level.

頂部加熱器外罩106可包含在頂部加熱器外罩106外側的一個或多個結構構件，其沿頂部加熱器外罩106的外部延伸，方向係遠離頂部加熱器100的中心，垂直地 從 頂部加熱器外罩106的外側底端至頂部加熱器外罩106的外側頂端。在一例示中，頂部加熱器外罩106可包含8個垂直結構構件。垂直結構構件可在圍繞頂部加熱器100的圓周或周圍均勻地隔開。在一例示中，頂部加熱器外罩106可包含垂直及水平結構構件兩者。頂部加熱器外罩106可包含延伸橫跨頂部加熱器外罩106的頂端的結構構件。在頂端的結構構件可從頂部加熱器外罩106的頂端的一個外側邊緣，延伸到另一個頂部加熱器外罩106頂端的邊緣。在頂端的結構構件亦可部分地延伸橫跨外罩106的頂端。結構構件可以是條(strips)、桿(bars)、管(tubes)、或任何合適的結構，以用於給頂部加熱器添加結構支撐。結構構件可經由焊接(welding)、硬焊(brazing)、或其它合適的方法連接到頂部加熱器外罩106。結構構件可適用以方便裝置的運輸及物理操縱。舉例來說，在頂部加熱器外罩106的的外側頂端之結構構件可為管件，其有足夠的尺寸(size)、強度(strength)、定向(orientation)、間距(spacing)、或其組合，使得一個特定的堆高機(fork-lift)或其他升降機(lifting machine)可以抬起或移動或以其他方式操縱頂部加熱器。在另一個例示中，上述的作為設置在頂部加熱器外罩106的外側的結構構件可替代地或另外地設置於頂部加熱器外罩106的內側。在另一個例示中，頂部加熱器100可使用起重機(crane)或其它起重設備(lifting device)來移動，使用鏈條連接到頂部加熱器100，包含連接到頂部加熱器的結構構件、或連接到頂部加熱器100的非結構構件鏈條。舉例來說，鏈條可連接到頂部加熱器外罩106的上邊緣，以形成一個用於起重機之抬升以及其他方式移動頂部加熱器100之韁繩(bridle)。The top heater shroud 106 can include one or more structural members external to the top heater shroud 106 that extend along the exterior of the top heater shroud 106 in a direction away from the center of the top heater 100, vertically from the top heater shroud The outer bottom end of 106 is to the outer top end of the top heater housing 106. In one example, the top heater housing 106 can include eight vertical structural members. The vertical structural members may be evenly spaced around the circumference or circumference of the top heater 100. In one example, the top heater shroud 106 can include both vertical and horizontal structural members. The top heater shroud 106 can include structural members that extend across the top end of the top heater shroud 106. The structural members at the top end may extend from one outer edge of the top end of the top heater shroud 106 to the edge of the top end of the other top heater shroud 106. The structural member at the top portion may also extend partially across the top end of the outer cover 106. The structural members can be strips, bars, tubes, or any suitable structure for adding structural support to the top heater. The structural member can be coupled to the top heater shroud 106 via welding, brazing, or other suitable method. Structural members can be adapted to facilitate transportation and physical manipulation of the device. For example, the structural member at the outer top end of the top heater shroud 106 can be a tubular member having sufficient size, strength, orientation, spacing, or a combination thereof such that A particular fork-lift or other lifting machine can lift or move or otherwise manipulate the top heater. In another illustration, the structural member described above as being disposed outside of the top heater shroud 106 may alternatively or additionally be disposed inside the top heater shroud 106. In another illustration, the top heater 100 can be moved using a crane or other lifting device, connected to the top heater 100 using a chain, including structural members connected to the top heater, or connected to A non-structural member chain of the top heater 100. For example, a chain can be attached to the upper edge of the top heater shroud 106 to form a bridle for lifting the crane and otherwise moving the top heater 100.

冷卻cool down

如上所討論，藉由控制在坩堝中的溫度梯度，可完成高度控制的定向凝固。在溫度梯度及相應的定向結晶度的高度控制，可允許一個更有效的定向凝固，提供高純度的矽。在一例示中，定向凝固可大致上從坩堝的底部到頂部，使得溫度梯度在底部具有一較低的溫度，以及在頂部具有一較高的溫度。在頂部加熱器100的例示中，頂部加熱器100可以是控制熱量從坩堝進入或損失的一個方法。導電的耐火材料亦可用於坩堝以誘導熱量從坩堝底部散失。坩堝還可包含在坩堝的側面上的絕緣材料，以防止熱量從其散失，促進一個垂直熱梯度的形成，並阻擋水平熱梯度的形成。在一例示中，可使用一個或多個風扇吹出冷卻空氣遍及坩堝底部，例如遍及坩堝外罩的底部，以控制從坩堝底部的熱量損失。在一例示中，周圍空氣的循環不使用風扇可用於冷卻坩堝，包含坩堝的底部。As discussed above, highly controlled directional solidification can be accomplished by controlling the temperature gradient in the crucible. The high degree of control over the temperature gradient and corresponding directional crystallinity allows for a more efficient directional solidification, providing high purity bismuth. In one example, the directional solidification can be substantially from the bottom to the top of the crucible such that the temperature gradient has a lower temperature at the bottom and a higher temperature at the top. In the illustration of the top heater 100, the top heater 100 can be a method of controlling the entry or loss of heat from the crucible. Conductive refractory materials can also be used to induce heat loss from the bottom of the crucible. The crucible may also include an insulating material on the sides of the crucible to prevent heat from being dissipated therefrom, promoting the formation of a vertical thermal gradient and blocking the formation of a horizontal thermal gradient. In one example, one or more fans may be used to blow cooling air throughout the bottom of the crucible, such as throughout the bottom of the crucible housing, to control heat loss from the crucible bottom. In one example, the circulation of ambient air does not use a fan that can be used to cool the crucible, including the bottom of the crucible.

在一例示中，一個或多個傳熱片可附著在坩堝外罩的底部，以便於空氣冷卻。一個或多個風扇可藉由吹氣遍及外罩的底部以提高冷卻散熱片的冷卻效果。可使用任何合適數量的散熱片。一個或多個散熱片可從裝置的底部吸收熱量，並使熱量藉由散熱片的表面積促進空氣冷卻而移除。舉例來說，散熱片可以銅、鑄鐵、鋼、或不銹鋼製成。In one example, one or more heat transfer fins may be attached to the bottom of the crucible housing to facilitate air cooling. One or more fans may increase the cooling effect of the cooling fins by blowing air throughout the bottom of the housing. Any suitable number of heat sinks can be used. One or more fins can absorb heat from the bottom of the device and allow heat to be removed by the surface area of the fins promoting air cooling. For example, the heat sink can be made of copper, cast iron, steel, or stainless steel.

在一例示中，至少可包含一個液體導管在內，其中至少一個液體導管配置為允許冷卻液通過導管，從而從坩堝將熱量傳輸走。冷卻液可以是任何合適的冷卻液。冷卻液可以是一種液體或一個以上的液體的混合物。冷卻液的例示可用於包含但不限於，水、乙二醇(ethylene glycol)、二乙二醇(diethylene glycol)、丙二醇(propylene glycol)、油、及油的混合物中至少其一。In one example, at least one liquid conduit can be included, wherein at least one of the liquid conduits is configured to allow coolant to pass through the conduit to transfer heat away from the crucible. The coolant can be any suitable coolant. The coolant can be a liquid or a mixture of more than one liquid. An illustration of the cooling liquid can be used to include, but is not limited to, at least one of water, ethylene glycol, diethylene glycol, propylene glycol, oil, and a mixture of oils.

在一例示中，至少一個液體導管可包含一個管件。管件可包含用於熱傳遞的任何合適的材料，如銅、鑄鐵、鋼、不銹鋼、耐火材料、耐火材料的混合物、或其組合。該至少一個液體導管可包含通過材料的導管。該導管可通過任何合適的材料，如通過包含銅、碳化矽、石墨、鑄鐵、鋼、不銹鋼、耐火材料、耐火材料的混合物、或其組合的材料。該至少一個液體導管可為管件及通過材料的導管之組合。在一例示中，該至少一個液體導管可設置於鄰近裝置的底部、在裝置的底部之內、或鄰近裝置的底部以及在裝置的底部之內的組合。In one example, at least one liquid conduit can comprise a tubular member. The tubular member may comprise any suitable material for heat transfer, such as copper, cast iron, steel, stainless steel, refractory materials, mixtures of refractory materials, or combinations thereof. The at least one liquid conduit can comprise a conduit through the material. The conduit can be passed through any suitable material, such as a material comprising copper, tantalum carbide, graphite, cast iron, steel, stainless steel, refractory materials, mixtures of refractory materials, or combinations thereof. The at least one liquid conduit can be a combination of a tubular member and a conduit through the material. In one example, the at least one liquid conduit can be disposed adjacent to the bottom of the device, within the bottom of the device, or a combination adjacent the bottom of the device and within the bottom of the device.

液體導管可包含多種配置，以使冷卻液從定向凝固模具傳遞出熱量。一個泵(pump)可用於移動冷卻液。冷卻系統可用於從冷卻液帶走熱量。舉例來說，可使用一個或多個管件(tubes)，包括管材(pipes)。一個或多個管件可以是任何合適的形狀，包含圓形、方形、或平面。一個或多個管件可盤繞。一個或多個管件可鄰近外罩的外側。在一例示中，一個或多個管件可鄰近外罩的外側的底部。一個或多個管件可與外罩接觸，使得有充足的表面積接觸，可發生允許有效的從該裝置之熱傳遞至冷卻液中。一個或多個管件可以任何合適的方式與外罩接觸，包含沿著管件的邊緣。一個或多個管件可焊接(welded)、釬焊(brazed)、軟焊(soldered)、或藉由任何合適的方法附著在外罩的外側。一個或多個管件可被壓平至外罩的外側，以提高熱傳遞的效率。The liquid conduit can comprise a variety of configurations to transfer coolant from the directional solidification mold. A pump can be used to move the coolant. A cooling system can be used to remove heat from the coolant. For example, one or more tubes, including pipes, can be used. The one or more tubular members can be of any suitable shape, including circular, square, or planar. One or more tubes can be coiled. One or more tubular members may be adjacent the outer side of the outer cover. In one example, one or more of the tubular members may be adjacent the bottom of the outer side of the outer shroud. One or more of the tubular members may be in contact with the outer casing such that there is sufficient surface area contact that may occur to allow efficient heat transfer from the device to the cooling fluid. One or more of the tubular members may be in contact with the outer casing in any suitable manner, including along the edges of the tubular members. One or more of the tubular members may be welded, brazed, Soldered, or attached to the outside of the outer casing by any suitable means. One or more tubular members can be flattened to the outside of the outer casing to increase the efficiency of heat transfer.

在一例示中，該至少一個液體導管可以是貫穿坩堝底部的一個或多個導管。貫穿坩堝底部的導管可以是一個管件，包含在坩堝內的耐火材料。管件可進入外罩的一部分，貫穿在坩堝底部的耐火材料或導電材料或其組合，且由外罩的另一部分出去。封裝在坩堝的底部耐火材料或底部導電材料的管件可盤繞，或佈置成任何合適的形狀，包含在退出坩堝的底部以前來回移動一次或多次。In one example, the at least one liquid conduit can be one or more conduits that extend through the bottom of the crucible. The conduit through the bottom of the crucible can be a tubular member containing refractory material within the crucible. The tubular member can enter a portion of the outer casing, a refractory or electrically conductive material or a combination thereof that extends through the bottom of the crucible and exits the other portion of the outer casing. The tubular member of the bottom refractory or bottom conductive material encapsulated in the crucible may be coiled or arranged in any suitable shape, including one or more movements back and forth before exiting the bottom of the crucible.

在一例示中，該至少一個液體導管包含一管件，係包裹在一種耐火材料、導熱材料、或其組合中，其中材料係大宗材料，足夠大以使坩堝能放置其上。導管可以任何合適的材料通過。舉例來說，可通過導管的材料包含銅、碳化矽、石墨、鑄鐵、鋼、不銹鋼、耐火材料、耐火材料的混合物、或其組合。冷卻液可從坩堝座落於其上的耐火材料而移除熱量，從而從坩堝的底部移除熱量。In one example, the at least one liquid conduit comprises a tubular member encased in a refractory material, a thermally conductive material, or a combination thereof, wherein the material is a bulk material that is large enough to allow the crucible to be placed thereon. The catheter can be passed through any suitable material. For example, the material that can pass through the conduit comprises copper, tantalum carbide, graphite, cast iron, steel, stainless steel, refractory materials, mixtures of refractory materials, or combinations thereof. The coolant removes heat from the refractory material on which the crucible is seated, thereby removing heat from the bottom of the crucible.

概論Introduction

第9圖說明用於矽的定向凝固的裝置120之例示，包含設置在坩堝124的頂端之頂部加熱器122。鏈條126可經由在垂直結構構件130的孔128而連接至頂部加熱器122。鏈條126可形成一韁繩(bridle)，可使頂部加熱器122藉由起重機的使用而移動。裝置亦可移動，例如，藉由放置坩堝124在剪式升降機(scissor lift)上，而將頂部加熱器122移離坩堝124。Figure 9 illustrates an illustration of a device 120 for directional solidification of a crucible that includes a top heater 122 disposed at the top end of the crucible 124. The chain 126 can be coupled to the top heater 122 via a bore 128 in the vertical structural member 130. The chain 126 can form a bridle that allows the top heater 122 to be moved by the use of a crane. The device can also be moved, for example, by placing the crucible 124 on a scissor lift to move the top heater 122 away from the crucible 124.

垂直結構構件130可從頂部加熱器122的外罩的底部邊緣垂直地延伸至頂部加熱器122的外罩的頂部邊緣。垂直結構構件130可位於頂部加熱器外罩的外側上，且從外罩延伸，方向係平行於遠離頂部加熱器122的中心。頂部加熱器122亦可包含一個或多個水平結構構件132，其可位於頂部加熱器外罩的外側上，且可從外罩延伸，方向係平行於遠離頂部加熱器122的中心。頂部加熱器122亦可包含一個唇部134，其可為頂部加熱器122的外罩的一部分。唇部134可從頂部加熱器122的外罩而突出。唇部134可向內延伸至頂部加熱器122的中心軸線，使得其以任何合適的程度覆蓋頂部加熱器122的絕緣部分。或者，唇部134可向內延伸，僅到足以覆蓋頂部加熱器122的外罩的底部邊緣。一個或多個篩選箱(screen box)136可包圍加熱構件的尾端，從頂部加熱器122的外罩突出，保護使用者免遭受熱及電，而可出現在這些構件的尾端附近。The vertical structural member 130 can extend perpendicularly from the bottom edge of the outer shroud of the top heater 122 to the top edge of the outer shroud of the top heater 122. The vertical structural member 130 can be located on the outside of the top heater shroud and extends from the shroud in a direction parallel to the center away from the top heater 122. The top heater 122 can also include one or more horizontal structural members 132 that can be located on the outside of the top heater shroud and that can extend from the shroud in a direction parallel to the center away from the top heater 122. The top heater 122 can also include a lip 134 that can be part of the outer shroud of the top heater 122. The lip 134 can protrude from the outer cover of the top heater 122. The lip 134 can extend inwardly to the central axis of the top heater 122 such that it covers the insulating portion of the top heater 122 to any suitable extent. Alternatively, the lip 134 can extend inwardly only to the bottom edge of the outer cover sufficient to cover the top heater 122. One or more screen boxes 136 may surround the trailing end of the heating member, projecting from the outer cover of the top heater 122, protecting the user from heat and electricity, and may occur adjacent the trailing ends of the members.

絕緣體138可位於頂部加熱器122及坩堝124之間。至少一部分的一個或多個坩堝124的絕緣層可在坩堝124的外罩的高度上方延伸。坩堝124可包含一個或多個垂直結構構件140。垂直結構構件140可位於坩堝124的外罩的外表面上，從外罩延伸出去，方向係平行於遠離坩堝124的中心。垂直結構構件140可從外罩的底部邊緣垂直地延伸至外罩的頂部邊緣。坩堝124亦可包含一個或多個水平結構構件142。水平結構構件142可位於坩堝124的外罩的外表面上，從外罩延伸出去，方向係遠離坩堝124的中心。水平結構構件142可沿坩堝124的圓周水平方向地延伸。坩堝124還可包含底部結構構件144及146。底部結構構件144及146可從外罩延伸出去，方向係平行於遠離坩堝124的中心。底部結構構件144及146可以延伸穿過坩堝124的底部。一些底部結構構件146可被形塑，使得它們允許堆高機或其它機器抬起或以其他方式物理地操作其裝置。Insulator 138 can be located between top heater 122 and crucible 124. An insulating layer of at least a portion of the one or more turns 124 may extend above the height of the cover of the crucible 124. The crucible 124 can include one or more vertical structural members 140. The vertical structural member 140 can be located on the outer surface of the outer shroud of the weir 124, extending from the outer shroud in a direction parallel to the center away from the weir 124. The vertical structural member 140 can extend perpendicularly from the bottom edge of the outer cover to the top edge of the outer cover. The crucible 124 can also include one or more horizontal structural members 142. The horizontal structural member 142 can be located on the outer surface of the outer shroud of the weir 124, extending away from the outer shroud, away from the center of the weir 124. The horizontal structural member 142 can extend horizontally along the circumference of the crucible 124. The crucible 124 can also include bottom structural members 144 and 146. The bottom structural members 144 and 146 can extend from the outer casing in a direction parallel to the center away from the weir 124. The bottom structural members 144 and 146 can extend through the bottom of the crucible 124. Some of the bottom structural members 146 can be shaped such that they allow the stacker or other machine to lift or otherwise physically operate their device.

純化矽的方法Method for purifying hydrazine

第10圖係為純化矽之例示方法200之流程圖。方法200可包含，在202而言，以襯裡塗佈在熔化坩堝的內表面的至少一部分。在一例示中，熔化坩堝的內表面上塗佈的襯裡包含一個屏障層，其包含以膠體氧化矽黏著劑結合在一起的碳化矽顆粒，如上述第1圖及第2圖。在另一個例示中，熔化坩堝的內表面上塗佈的襯裡包含一活性純化層，其包含助熔劑組合物，該組合物含有膠體氧化矽，如上述關於第3圖及第4圖的例示的襯裡。助熔劑組合物亦可包含一個或多個助熔劑材料，包含但不限於，碳酸鈉(Na2CO3)、氧化鈣(CaO)、及氟化鈣(CaF2)至少其中之一，這樣的例示襯裡描述於上面第5圖。熔化坩堝的內表面上塗佈的襯裡，可包含含有以膠體氧化矽黏著劑結合在一起的碳化矽顆粒的屏障層、含有膠體氧化矽的活性純化層、以及選擇地一個或多個助熔劑材料，如上述關於第6圖及第7圖所述的襯裡。Figure 10 is a flow diagram of an exemplary method 200 for purifying hydrazine. The method 200 can include, at 202, coating at least a portion of the inner surface of the melting crucible with a liner. In one example, the liner coated on the inner surface of the fused crucible comprises a barrier layer comprising cerium carbide particles bonded together by a colloidal cerium oxide binder, as in Figures 1 and 2 above. In another illustration, the liner coated on the inner surface of the fused crucible comprises an active purification layer comprising a flux composition comprising colloidal cerium oxide, as exemplified above with respect to Figures 3 and 4 lining. The flux composition may also comprise one or more fluxing materials including, but not limited to, at least one of sodium carbonate (Na2CO3), calcium oxide (CaO), and calcium fluoride (CaF2), such an exemplary liner being described in Figure 5 above. The liner coated on the inner surface of the molten crucible may comprise a barrier layer comprising tantalum carbide particles bonded together with a colloidal cerium oxide binder, an active purification layer comprising colloidal cerium oxide, and optionally one or more flux materials The lining as described above with respect to Figures 6 and 7.

在204而言，襯裡可塗佈在定向凝固模具的內表面的至少一部分上。在一例示中，定向凝固模具的內表面上塗佈的襯裡包含一個屏障層，其包含以膠體氧化矽黏著劑結合在一起的碳化矽顆粒，如上述關於第1圖及第2圖。在另一例示中，定向凝固模具的內表面上塗佈的襯裡包含一個活性純化層，其包含具有膠體氧化矽的助熔劑組合物，如上述關於第3圖及第4圖的例示襯裡。助熔劑組合物亦可包含一個或多個助熔劑材料，包含但不限於，碳酸鈉(Na2CO3)、氧化鈣(CaO)、及氟化鈣(CaF2)，這樣的例示襯裡描述於上面第5圖。定向凝固模具的內表面上塗佈的襯裡，可包含含有以膠體氧化矽黏著劑結合在一起的碳化矽顆粒的屏障層、含有膠體氧化矽的活性純化層、以及選擇地一個或多個助熔劑材料，如上述關於第6圖及第7圖所述的襯裡。At 204, the liner can be coated on at least a portion of the inner surface of the directional solidification mold. In one example, the liner coated on the inner surface of the directional solidification mold comprises a barrier layer comprising tantalum carbide particles bonded together by a colloidal cerium oxide binder, as described above with respect to Figures 1 and 2. In another illustration, the liner coated on the inner surface of the directional solidification mold comprises an active purification layer comprising a flux composition having colloidal cerium oxide, such as the exemplary liners described above with respect to Figures 3 and 4. The flux composition may also comprise one or more fluxing materials including, but not limited to, sodium carbonate (Na2CO3), calcium oxide (CaO), and calcium fluoride (CaF2), such an exemplary liner as described in Figure 5 above. . The lining coated on the inner surface of the directional solidification mold may comprise a barrier layer comprising cerium carbide particles bonded together by a colloidal cerium oxide binder, an active purification layer containing colloidal cerium oxide, and optionally one or more fluxing agents Materials, such as the lining described above with respect to Figures 6 and 7.

在一些例示中，僅熔化坩堝的內表面上可被塗佈。在其他例示中，僅定向凝固模具的內表面可被塗佈。在其他的例示中，熔化坩堝的內表面及定向凝固模具的內表面均可被塗佈。In some illustrations, only the inner surface of the melting crucible can be coated. In other illustrations, only the inner surface of the directional solidification mold can be coated. In other examples, the inner surface of the fused crucible and the inner surface of the directional solidification mold may be coated.

在206而言，第一矽可在熔化坩堝的內部熔化，以提供第一熔融矽。第一矽可包含任何合適的等級純度矽。第一矽可至少部分地熔化。至少部分地熔化第一矽可包含完全地熔化的第一矽、幾乎完全地熔化的第一矽(超過約無論是99%、95%、90%、85%、或80%熔化的重量)、或部分地熔化的第一矽(小於約80%或更少熔化的重量)。該方法亦可包含從熔化坩堝傳送第一熔融矽至定向凝固模具，像是藉由將第一熔融矽澆進定向凝固模具中。At 206, the first crucible can be melted inside the melting crucible to provide a first melting crucible. The first crucible can comprise any suitable grade purity. The first crucible can be at least partially melted. At least partially melting the first crucible may comprise a first crucible that is completely melted, a first crucible that is nearly completely melted (more than about 99%, 95%, 90%, 85%, or 80% of the weight of the melt), Or a partially melted first crucible (less than about 80% or less of the melted weight). The method may also include transferring the first molten crucible from the crucible to the directional solidification mold, such as by pouring the first molten crucible into the directional solidification mold.

在208而言，若塗佈到坩堝的襯裡是一個活性純化襯裡，然後在第一熔融矽中的一個或多個污染物或雜質可與一個或多個襯裡的成分反應，以形成熔渣或浮渣。在一例示中，熔渣可形成於襯裡本身。In 208, if the liner applied to the crucible is an active purification liner, then one or more contaminants or impurities in the first melting crucible can react with one or more of the liner components to form a slag or scum. In one example, slag may be formed in the liner itself.

在210而言，第一熔融矽係在定向凝固模具中定向地凝固，以提供一種包含第二矽的錠。在一例示中，第一熔融矽可大致上在定向凝固模具的底部開始凝固，且大致上在定向凝固模具的頂部結束，以形成第二矽。定向凝固可能會導致第二矽的最後冷凍部分(last-to-freeze portion)比第二矽的早期冷凍部分(earlier frozen portions)包含更高的雜質濃度。第二矽除了最後冷凍部分以外的部分可包含比第二矽的最後冷凍部分還低的雜質濃度。第二矽可為一矽錠。矽錠可適用於裁切成太陽能晶圓，例如，用於太陽能電池的製造。At 210, the first molten tantalum is directionally solidified in a directional solidification mold to provide an ingot comprising the second tantalum. In an illustration, the first molten crucible may begin to solidify substantially at the bottom of the directional solidification mold and substantially terminate at the top of the directional solidification mold to form a second crucible. Directional solidification may result in a last-to-free portion of the second crucible containing a higher concentration of impurities than the earlier frozen portions of the second crucible. The second portion other than the last frozen portion may contain a lower impurity concentration than the last frozen portion of the second crucible. The second crucible can be a crucible. Bismuth ingots can be used for cutting into solar wafers, for example, for the manufacture of solar cells.

在一例示中，定向凝固可包含設置一頂部加熱器在定向凝固模具上。定向凝固模具可在添加熔融矽以前進行預熱。頂部加熱器可用於預熱定向凝固模具。預熱定向凝固模具可幫助防止在定向凝固模具的牆壁上的矽過度快速凝固。可使用頂部加熱器以熔化第一矽，形成第一熔融矽。可使用頂部加熱器以傳遞熱量給第一熔融矽。當矽在定向凝固模具中熔化時，頂部加熱器可傳遞熱量給第一熔融矽。頂部加熱器可用於控制第一熔融矽的頂部的熱。頂部加熱器可用來作為絕緣體，以控制在定向凝固模具的頂部之熱量損失量。第一矽可在裝置外部熔化，如在熔爐中的熔化坩堝，然後添加到定向凝固模具中。在一例示中，在裝置外部熔化的矽可在添加進定向凝固模具以前，使用頂部加熱器進一步加熱到所需溫度。In one example, directional solidification can include providing a top heater on the directional solidification mold. The directional solidification mold can be preheated before the addition of the molten crucible. The top heater can be used to preheat the directional solidification mold. Preheating the directional solidification mold can help prevent excessive rapid solidification of the crucible on the walls of the directional solidification mold. A top heater can be used to melt the first crucible to form a first molten crucible. A top heater can be used to transfer heat to the first melting crucible. When the crucible is melted in the directional solidification mold, the top heater can transfer heat to the first melting crucible. A top heater can be used to control the heat of the top of the first melting crucible. The top heater can be used as an insulator to control the amount of heat loss at the top of the directional solidification mold. The first crucible can be melted outside the device, such as a melting crucible in a furnace, and then added to a directional solidification mold. In one example, the crucible melted outside of the apparatus can be further heated to the desired temperature using a top heater prior to addition to the directional solidification mold.

在一例示中，頂部加熱器可包含一個感應加熱器，矽在添加進定向凝固模具以前可熔化。又或者，頂部加熱器可包含加熱元件以及感應加熱器。與熔融矽感應加熱可以更有效。感應可引起熔融矽的混合。在一些例示中，可以充分地調整電源，以最佳化混合量，過量的混合可增進雜質的分離，但也會在最終的矽錠中產生不希望的多孔隙。In one example, the top heater can include an induction heater that can be melted prior to being added to the directional solidification mold. Still alternatively, the top heater can include a heating element and an induction heater. Induction heating with molten helium can be more effective. Induction can cause mixing of the molten crucible. In some instances, the power supply can be adequately adjusted to optimize the amount of mixing, which can enhance the separation of impurities, but can also create undesirable porosity in the final tantalum ingot.

定向凝固可包含從定向凝固模具的底部將熱去除。熱的移除可以任何合適的方式發生。舉例來說，熱的移除可包含至少其中一個風扇橫跨定向凝固模具的底部，使周圍空氣冷卻定向凝固模具的底部，不論有沒有使用風扇，運行冷卻液以通過鄰進裝置底部的管件，通過貫穿裝置的底部之管件，通過貫穿位於裝置其上的材料之管件，或其組合。從定向凝固模具的底部將熱去除可使熱梯度在定向凝固的模具中建立，可提供大致上從定向凝固模具的底部到定向凝固模具的頂部，對於第一熔融矽的定向凝固之更好的控制。Directional solidification can include removing heat from the bottom of the directional solidification mold. Thermal removal can occur in any suitable manner. For example, the removal of heat may include at least one of the fans spanning the bottom of the directional solidification mold, allowing the ambient air to cool the bottom of the directional solidification mold, whether or not a fan is used, running the coolant to pass the tube at the bottom of the adjoining device, By means of a tubular member extending through the bottom of the device, through a tubular member that penetrates the material located thereon, or a combination thereof. The removal of heat from the bottom of the directional solidification mold allows the thermal gradient to be established in the directionally solidified mold, providing substantially the top from the bottom of the directional solidification mold to the top of the directional solidification mold, for better directional solidification of the first molten crucible control.

從定向凝固模具的底部將熱去除可在整個定向凝固的持續時間內進行。多個冷卻方法皆可以使用。例如，定向凝固模具的底部可以液體冷卻及以風扇冷卻。風扇冷卻可發生於部分的定向凝固，而液體冷卻發生於其他部分，具有在兩種冷卻方式之間的重疊或缺少其一的任何合適的量。以在兩種冷卻方式之間的重疊或缺少其一的任何合適的量。以液體冷卻可能會出現部分的定向凝固，而周圍空氣單獨冷卻另一部分。藉由設置定向凝固模具在一個冷卻的材料塊而冷卻，亦可發生於任何合適的定向凝固持續期間，包含任何合適的以任何適當的重疊量的冷卻方法之組合。冷卻定向凝固模具的底部可與熱添加至頂部同時進行，例如，當熱量添加至頂部以增加頂部的溫度時，維持頂部的溫度，或允許一個頂部的特定冷卻速率。加熱定向凝固模具的頂部、冷卻定向凝固模具的底部、及其組合之所有合適的之構造及方法，與任何合適的暫時重疊或缺乏的量包含作為本發明的例示。The removal of heat from the bottom of the directional solidification mold can be carried out for the entire duration of the directional solidification. Multiple cooling methods can be used. For example, the bottom of the directional solidification mold can be liquid cooled and cooled by a fan. Fan cooling can occur in partial directional solidification, while liquid cooling occurs in other portions, with any suitable amount of overlap or lack of one between the two cooling modes. With any suitable amount of overlap or lack of one between the two cooling modes. Partial directional solidification may occur with liquid cooling, while ambient air cools the other portion separately. Cooling by providing a directional solidification mold in a cooled block of material may also occur during any suitable duration of directional solidification, including any suitable combination of cooling methods in any suitable amount of overlap. Cooling the bottom of the directional solidification mold can be performed simultaneously with the addition of heat to the top, for example, when heat is added to the top to increase the temperature of the top, maintaining the temperature of the top, or allowing a specific cooling rate of the top. All suitable configurations and methods for heating the top of the directional solidification mold, cooling the bottom of the directional solidification mold, and combinations thereof, with any suitable temporary overlap or lack of inclusion, are included as examples of the invention.

定向凝固可包含使用頂部加熱器，以加熱矽到至少約1200°C，並緩慢冷卻矽的頂端溫度從約10至約16小時。定向凝固可包含使用頂部加熱器，以加熱矽至包含介於約1200°C及1600°C，並保持矽的頂端溫度大致恆定為約14小時。定向凝固可包含關閉頂部加熱器，使矽冷卻從約2至約60小時，然後從定向凝固模具移除頂端加熱器。Directional solidification can include the use of a top heater to heat the crucible to at least about 1200 ° C and slowly cool the top temperature of the crucible from about 10 to about 16 hours. Directional solidification can include the use of a top heater to heat the crucible to a temperature comprised between about 1200 ° C and 1600 ° C and maintaining the top end of the crucible substantially constant for about 14 hours. Directional solidification can include turning off the top heater, allowing the crucible to cool from about 2 to about 60 hours, and then removing the top heater from the directional solidification mold.

在212而言，第二矽可從定向凝固模具移除。矽可藉由任何合適的方法移除。舉例來說，矽可藉由顛倒定向凝固模具，並允許第二矽脫離定向凝固模具而移除。在另一個例示中，定向凝固裝置可分成兩個或多個部分，例如基本上能夠攔腰被分開形成兩半，允許第二矽從定向凝固模具中除去。At 212, the second crucible can be removed from the directional solidification mold.矽 can be removed by any suitable method. For example, the crucible can be removed by inverting the directional solidification mold and allowing the second crucible to exit the directional solidification mold. In another illustration, the directional solidification device can be divided into two or more portions, for example, substantially capable of forming the two halves separately, allowing the second crucible to be removed from the directional solidification mold.

在214而言，第二矽的一部分，例如，矽錠可被移除。較佳地，去除部分的第二矽導致整體增加所得到的矽錠的純度。舉例來說，該方法可包含除去從在至少一部分的最後冷凍部分的定向地凝固的第二矽。定向地凝固的矽之最後冷凍部分可為第二矽錠的頂部，因為它在底部到頂部的定向凝固過程中的定向。最大的雜質濃度一般可發生在固體矽的最後冷凍部分。卸下的最後冷凍部分，從而可從固體矽除去雜質，產生一個修剪的第二矽，其具有比第一矽具有較低的雜質濃度。除去部分的矽可包含用帶鋸(band saw)、線鋸(wire saw)、或任何合適的切割裝置來切割固體矽。除去部分的矽可包含珠粒噴擊法(shot blasting)或蝕刻。珠粒噴擊法或蝕刻亦可用於一般清除或移除第二矽的任何外表面，而不只是最後冷凍部分。移除部分的矽可包含除去最後冷凍的液體部分，如藉由從坩堝中澆注剩餘的液體。At 214, a portion of the second crucible, for example, the crucible ingot can be removed. Preferably, the removal of a portion of the second enthalpy results in an overall increase in the purity of the resulting bismuth ingot. For example, the method can include removing a second crucible that is solidified from the direction of at least a portion of the last frozen portion. The last frozen portion of the directionally solidified crucible can be the top of the second crucible because of its orientation during the directional solidification from bottom to top. The maximum impurity concentration generally occurs in the last frozen portion of the solid helium. The last frozen portion is removed so that impurities can be removed from the solid helium, resulting in a trimmed second crucible having a lower impurity concentration than the first crucible. Removing a portion of the crucible can include cutting the solid crucible with a band saw, a wire saw, or any suitable cutting device. The removed portion of the crucible may include shot blasting or etching. Bead blasting or etching can also be used to generally remove or remove any outer surface of the second crucible, rather than just the last frozen portion. Removing the portion of the crucible can include removing the last frozen liquid portion, such as by pouring the remaining liquid from the crucible.

在216而言，在移除第二矽錠的部分之後，例如，最後冷凍部分，矽錠可切割成一個或多個太陽能晶圓，使用例如，帶鋸(band saw)、線鋸(wire saw)、或任何合適的切割裝置。At 216, after removing the portion of the second bismuth ingot, for example, the last frozen portion, the bismuth ingot can be cut into one or more solar wafers using, for example, a band saw, a wire saw ), or any suitable cutting device.

實施例Example

為了更佳地闡述本文揭露的方法及裝置，一系列非限制性的實施例於此提供：To better illustrate the methods and apparatus disclosed herein, a series of non-limiting embodiments are provided herein:

實施例1包含用於容納熔融矽混合物的坩堝，坩堝包含至少一個耐火材料，其具有至少一個內表面，以界定用於接收熔融矽的內側，及設置在內表面的襯裡，襯裡包含以膠體矽結合在一起的碳化矽顆粒。Embodiment 1 includes a crucible for containing a molten crucible mixture, the crucible comprising at least one refractory material having at least one inner surface defining an inner side for receiving the molten crucible, and a liner disposed on the inner surface, the liner comprising a colloidal crucible The tantalum carbide particles are combined.

實施例2包含如實施例1之坩堝，其中襯裡40%的重量是碳化矽且60%的重量是膠體氧化矽。Example 2 comprises a crucible as in Example 1 wherein 40% by weight of the liner is tantalum carbide and 60% by weight is colloidal tantalum oxide.

實施例3包含如實施例1或2其中之一的坩堝，其中襯裡防止或減少從至少一個耐火材料而來容納在物體內側的熔融矽的汙染物。Embodiment 3 comprises a crucible according to any one of embodiments 1 or 2, wherein the liner prevents or reduces contaminants of the molten crucible contained in the inside of the object from the at least one refractory material.

實施例4包含如實施例3之坩堝，其中襯裡防止熔融矽被硼、磷、或鋁至少其中之一汙染。Embodiment 4 comprises a crucible as in Example 3, wherein the liner prevents the molten crucible from being contaminated by at least one of boron, phosphorus, or aluminum.

實施例5包含如實施例1至4其中任何一個之坩堝，其中碳化矽顆粒具有小於或等於約3.5公釐(millimeters)的尺寸。Embodiment 5 comprises, as in any one of embodiments 1 to 4, wherein the niobium carbide particles have a size of less than or equal to about 3.5 millimeters.

實施例6包含如實施例1至5其中任何一個之坩堝，其中膠體氧化矽包含懸浮於液相中的氧化矽顆粒，氧化矽顆粒具有包含介於10奈米(nanometers)及30奈米之尺寸。Embodiment 6 includes the crucible of any one of embodiments 1 to 5, wherein the colloidal cerium oxide comprises cerium oxide particles suspended in a liquid phase, and the cerium oxide particles have a size of between 10 nanometers and 30 nanometers. .

實施例7包含如實施例1至6其中任何一個之坩堝，其中襯裡具有包含從2公釐至10公釐之厚度。Embodiment 7 comprises a crucible as in any one of embodiments 1 to 6, wherein the liner has a thickness of from 2 mm to 10 mm.

實施例8包含如實施例1至7其中任何一個之坩堝，其中至少一個耐火材料包含氧化鋁。Embodiment 8 comprises, as in any one of embodiments 1 to 7, wherein at least one refractory material comprises alumina.

實施例9包含如實施例1至8其中任何一個之坩堝，其中坩堝係用於熔化第一矽，以形成熔融矽。Embodiment 9 comprises, as in any one of embodiments 1 to 8, wherein the lanthanide is used to melt the first ruthenium to form a fused ruthenium.

實施例10包含如實施例1至9其中任何一個之坩堝，其中坩堝係用作為定向凝固的模具。Embodiment 10 comprises a crucible as in any of Embodiments 1 to 9, wherein the oxime is used as a mold for directional solidification.

實施例11包含用於純化矽的方法，該方法包含在熔化坩堝的內側熔化第一矽，以提供第一熔融矽，熔化坩堝包含第一耐火材料，其具有至少一個第一內表面，界定熔化坩堝的內側，在定向凝固模具中定向地凝固第一熔融矽，以提供第二矽，定向凝固模具包含第二耐火材料，具有至少一個第二內表面，界定定向凝固模具的內側，並以襯裡，其包含藉由膠體氧化矽結合在一起的碳化矽顆粒，塗佈到至少一部分的第一內表面及第二內表面至少其中之一。Embodiment 11 includes a method for purifying a crucible, the method comprising melting a first crucible on an inner side of a molten crucible to provide a first molten crucible, the molten crucible comprising a first refractory material having at least one first inner surface defining melting The inner side of the crucible is directionally solidified in the directional solidification mold to provide a second crucible, the directional solidification mold comprising a second refractory material having at least one second inner surface defining the inner side of the directional solidification mold and lining And comprising at least one of the first inner surface and the second inner surface of at least a portion of the tantalum carbide particles bonded together by the colloidal cerium oxide.

實施例12包含如實施例11之方法，其中襯裡40%的重量是碳化矽且60%的重量是膠體氧化矽。Example 12 comprises the method of Example 11, wherein 40% by weight of the liner is tantalum carbide and 60% by weight is colloidal cerium oxide.

實施例13包含如實施例11或12其中之一的方法，其中襯裡防止或減少從至少一個耐火材料而來容納在物體內側的熔融矽的汙染物。Embodiment 13 includes the method of any one of embodiments 11 or 12, wherein the liner prevents or reduces contaminants of the molten crucible contained in the inner side of the object from the at least one refractory material.

實施例14包含如實施例13之坩堝，其中襯裡防止熔融矽被硼、磷、或鋁至少其中之一汙染。Embodiment 14 comprises the crucible of Example 13, wherein the liner prevents the molten crucible from being contaminated by at least one of boron, phosphorus, or aluminum.

實施例15包含如實施例11至14其中任何一個之方法，其中碳化矽顆粒具有一小於或等於約3.5公釐(millimeters)的尺寸。Embodiment 15 includes the method of any one of embodiments 11 to 14, wherein the niobium carbide particles have a size of less than or equal to about 3.5 millimeters.

實施例16包含如實施例11至15其中任何一個之方法，其中膠體氧化矽包含懸浮於液相中的氧化矽顆粒，氧化矽顆粒具有一包含介於10奈米(nanometers)及30奈米之尺寸。Embodiment 16 includes the method of any one of embodiments 11 to 15, wherein the colloidal cerium oxide comprises cerium oxide particles suspended in a liquid phase, and the cerium oxide particles have a content of between 10 nanometers and 30 nanometers. size.

實施例17包含如實施例11至16其中任何一個之方法，其中襯裡具有包含從2公釐至10公釐之厚度。Embodiment 17 includes the method of any one of embodiments 11 to 16, wherein the liner has a thickness of from 2 mm to 10 mm.

實施例18包含如實施例11至17其中任何一個之方法，其中熔化坩堝的第一耐火材料包含氧化鋁。Embodiment 18 includes the method of any one of embodiments 11 to 17, wherein the first refractory material that melts the ruthenium comprises alumina.

實施例19包含如實施例11至18其中任何一個之方法，其中定向凝固模具的第二耐火材料包含氧化鋁。Embodiment 19 includes the method of any one of embodiments 11 to 18, wherein the second refractory material of the directional solidification mold comprises alumina.

實施例20包含如實施例11至19其中任何一個之方法，其中定向凝固模具的第二耐火材料包含碳化矽及磷黏著劑。Embodiment 20 includes the method of any one of embodiments 11 to 19, wherein the second refractory material of the directional solidification mold comprises tantalum carbide and a phosphorus binder.

實施例21包含如實施例11至20其中任何一個之方法，其中以襯裡塗佈到至少一部分的第一內表面及第二內表面至少其中之一，其包含以襯裡塗佈至少一部分的每一個第一內表面及至少一部分的第二內表面。Embodiment 21 includes the method of any one of embodiments 11 to 20, wherein the liner is applied to at least one of the at least one of the first inner surface and the second inner surface, the outer layer comprising at least a portion of the liner coated a first inner surface and at least a portion of the second inner surface.

例示Illustration

被襯裡30塗佈的熔化坩堝10包含含有氧化鋁的耐火材料12，其被配置以防止或減少雜質汙染物從耐火材料12至坩堝10內的熔融矽2。襯裡30包含從膠體氧化矽藉由黏著劑34約束在一起的碳化矽顆粒32。碳化矽顆粒32係由聯合礦產公司(Allied Mineral Products, Inc.)，哥倫布市，俄亥俄州，美國，商品名奈米科技碳化矽(NANOTEK SiC)所出售的市售碳化矽而形成。用於形成黏著劑34的膠體氧化矽是市售的膠體氧化矽，如威仕邦(WesBond)公司，威明頓(Wilmington)，德拉瓦州，美國，商品名BINDZIL 2040所出售的膠體氧化矽。碳化矽顆粒32及膠體氧化矽黏著劑34混合在一起，其重量比率約60重量%是碳化矽顆粒32以及約40重量%是氧化矽。The enthalpy 10 coated by the liner 30 comprises a refractory material 12 comprising alumina that is configured to prevent or reduce the melting enthalpy of impurity contaminants from the refractory material 12 to the crucible 10. Liner 30 comprises tantalum carbide particles 32 bound together by colloidal cerium oxide by an adhesive 34. Tantalum carbide particles 32 are formed from commercially available tantalum carbide sold by Allied Mineral Products, Inc., Columbus, Ohio, USA, under the trade name NANOTEK SiC. The colloidal cerium oxide used to form the adhesive 34 is a commercially available colloidal cerium oxide such as the colloidal cerium oxide sold under the trade name BINDZIL 2040 by WesBond, Wilmington, Delaware, USA. . The cerium carbide particles 32 and the colloidal cerium oxide binder 34 are mixed together, and the weight ratio thereof is about 60% by weight of the cerium carbide particles 32 and about 40% by weight is cerium oxide.

碳化矽顆粒32及膠體氧化矽黏著劑34的混合物，藉由漆塗(painting)或刷塗(brushing)方法塗佈到坩堝10的內表面20。混合物的三個塗層塗佈至內表面20，而該三個塗層被允許在空氣中乾燥約6小時。產生的襯裡30具有從約4公釐至約5公釐的厚度。A mixture of the cerium carbide particles 32 and the colloidal cerium oxide binder 34 is applied to the inner surface 20 of the crucible 10 by a painting or brushing method. Three coatings of the mixture were applied to the inner surface 20, and the three coatings were allowed to dry in air for about 6 hours. The resulting liner 30 has a thickness of from about 4 mm to about 5 mm.

坩堝10係用於熔化矽，以形成熔融矽2，然後經由定向凝固(如上所述)，將其倒入用於純化熔融矽2的定向凝固模具中。一個特定的坩堝10及襯裡30使用於熔融矽2的1至4次之間的鑄造(例如，1至4次個別的熔化的固體矽的批量，以形成熔融矽2)。在定向凝固模具的襯裡的一個例示中，在每一個錠定向凝固以後，襯裡30被刷新。在1至4次鑄件以後，坩堝10的襯裡30可被刷新，如藉由除去任何殘存的之前的襯裡30，接著經由相同的上述之塗佈及乾燥法，再塗佈一個新的襯裡30。The crucible 10 is used to melt the crucible to form a molten crucible 2, which is then poured into a directional solidification mold for purifying the molten crucible 2 by directional solidification (described above). A particular crucible 10 and liner 30 is used for casting between 1 and 4 times of melting crucible 2 (e.g., 1 to 4 batches of individual molten solid crucibles to form a molten crucible 2). In one illustration of the lining of the directional solidification mold, the liner 30 is refreshed after each ingot is directionally solidified. After 1 to 4 castings, the liner 30 of the crucible 10 can be refreshed, such as by removing any remaining previous liner 30, and then applying a new liner 30 via the same coating and drying process described above.

第11圖顯示一個特定污染物的水準，在矽錠裡的硼這個案例，在使用坩堝10來定向凝固之後的結果的一個例示。第11圖顯示硼的濃度，每百萬分之一重(ppmw)，係從個別的熔化及定向凝固的運行而測定，在本文中稱為「鑄件(castings)」。隔距300的左側的鑄件是沒有襯裡的熔化坩堝的結果，例如，其中熔融矽2可與氧化鋁折射材料直接接觸。在矽中的硼水準，在被坩堝10熔化以前，正被饋送到坩堝10，在矽中的硼水準是已知的不超過約0.25百萬分之一重(ppmw)的硼。因此，如果在所得到的矽錠之硼水準大於0.25百萬分之一重(ppmw)的硼，則增加的硼假定為從坩堝10內而來，且最有可能從耐火材料12而來。Figure 11 shows the level of a particular contaminant, the case of boron in the ingot, and an example of the results after using the crucible 10 for directional solidification. Figure 11 shows the concentration of boron, measured in parts per million (ppmw), from individual melting and directional solidification operations, referred to herein as "castings." The casting on the left side of the gauge 300 is the result of a lining-free melting crucible, for example, where the molten crucible 2 can be in direct contact with the alumina refractive material. The boron level in the crucible is being fed to crucible 10 before being melted by crucible 10, and the boron level in the crucible is known to be no more than about 0.25 parts per million (ppmw) of boron. Thus, if the boron level of the resulting antimony ingot is greater than 0.25 parts per million (ppmw) of boron, the increased boron is assumed to be from the crucible 10 and is most likely to come from the refractory material 12.

如第11圖所示，隔距300的左側的鑄件(例如，由在不含屏障襯裡的熔化坩堝裡熔化的矽製得的那些鑄件)一般具有硼水準高於0.25百萬分之一重(ppmw)，並且在大多數情況下，大於0.30百萬分之一重(ppmw)，其值選擇作為一產品矽錠的硼水準的上部門檻。隔距300的右側的鑄件(例如，由在包含屏障襯裡30的熔化坩堝10裡熔化的矽製得的那些鑄件)基本上均低於0.30百萬分之一重(ppmw)的門檻，大部分係低於0.25百萬分之一重(ppmw)的值。第11圖顯示襯裡30可作為硼從坩堝10通至熔融矽2的一個屏障。類似的圖顯示磷的濃度在所得的矽錠陶醉，襯裡30亦可作為磷從坩堝10通至熔融矽2的一個屏障。As shown in Fig. 11, the castings on the left side of the gauge 300 (e.g., those made from tantalum melted in a melting crucible without a barrier liner) generally have a boron level above 0.25 parts per million ( Ppmw), and in most cases greater than 0.30 parts per million (ppmw), the value chosen as the upper level of the boron level of a product. The castings on the right side of the gauge 300 (e.g., those made from tantalum melted in the melting crucible 10 containing the barrier liner 30) are substantially below the threshold of 0.30 parts per million (ppmw), most of which are It is less than 0.25 parts per million (ppmw). Figure 11 shows that the liner 30 acts as a barrier to the passage of boron from the crucible 10 to the melting crucible 2. A similar diagram shows that the concentration of phosphorus is intoxicated by the resulting bismuth ingot, and the lining 30 can also serve as a barrier to the passage of phosphorus from the crucible 10 to the melting crucible 2.

上面的詳細說明包括參考附圖，以形成一部分的詳細說明。藉由圖解的方式，圖顯示出本發明可實施的具體的實施例。這些實施例，參照本文亦稱為「例示」。這些例示可包含除了那些已顯示或已描述的以外的元件。然而，本案發明人還考慮所提供的例子中，只顯示或描述那些元件。此外，本案發明人亦考慮例示使用那些已顯示或已描述的元件(或其一個或多個態樣)的任何組合或排列，不是就一個特定的例示而言(或其一個或多個態樣)，就是就其他的例示而言(或其一個或多個態樣)而在本文顯示或敘述。The above detailed description includes reference to the accompanying drawings, and, The drawings show specific embodiments that can be implemented by the present invention. These embodiments are also referred to herein as "exemplary." These illustrations may include elements other than those already shown or described. However, the inventors of the present invention have also considered that only those elements are shown or described in the examples provided. Moreover, the inventors of the present invention are also contemplated to exemplify any combination or arrangement of elements (or one or more aspects thereof) that have been shown or described, not in a particular example (or one or more aspects thereof) Is shown or described herein in terms of other examples (or one or more aspects thereof).

如果併入參考而在此文件與任何文件之間有不一致的用法，其以本文中的用法控制。If there is an inconsistent usage between this file and any of the files if incorporated into the reference, it is controlled by the usage herein.

在本文中，用詞「一(a)」或「一個(an)」的使用，在專利文獻中是常見的，包括一個或多於一個，獨立於任何其他「至少一個(at least one)」或「一個或多個(one or more)」的實例或用法。在本文中，用詞「或(or)」是用來指非排他性，除非另有說明，像是「A或B」包含「A但不是B」、「B但不是A」以及「A和B」。在本文中，用詞「包括(including)」及「在其中(in which)」用作淺顯的英語，分別與用詞「包含(comprising)」及「其中(wherein)」相當。另外，在下面的申請專利範圍裡，用詞「包括(including)」及「包含(comprising)」係開放式用法，也就是說，系統、設備、物品、成分、配方、或過程包含除了那些列出的以外的元件，在申請專利範圍內的用詞仍被視為落入申請專利範圍的範疇內。此外，在下面的申請專利範圍中，用詞「第一(first)」、「第二(second)」、及「第三(third)」等僅僅用來作為標籤，並不試圖強加數字的要求在它們的目標物上。In this context, the use of the words "a" or "an" is common in the patent literature, including one or more than one, independent of any other "at least one". Or an instance or usage of "one or more". In this context, the word "or" is used to mean non-exclusive, unless otherwise stated, such as "A or B" contains "A but not B", "B but not A" and "A and B" "." In this paper, the words "including" and "in which" are used in plain English, respectively, which are equivalent to the words "comprising" and "wherein". In addition, in the scope of the following claims, the terms "including" and "comprising" are used in an open manner, that is, systems, devices, articles, ingredients, recipes, or processes include those in addition to those listed. The use of the elements other than the ones that are within the scope of the patent application is still considered to fall within the scope of the patent application. In addition, in the scope of the following patent application, the words "first", "second", and "third" are used merely as labels and do not attempt to impose numerical requirements. On their target.

本文所描述的方法的例示可以至少一部分是機器或電腦執行。某些例示可包含可操作來配置一電子裝置以執行如上述例子中描述的方法之指令編碼的電腦可讀取媒體(computer-readable medium)或機器可讀媒體(machine-readable medium)。這種方法的實現可包含代碼(code)，像是微代碼(microcode)、組合語言代碼(assembly language code)、更高級別語言代碼(higher-level language code)，或類似者。這樣的代碼可包含用於執行各種方法的電腦可讀指令。代碼可形成電腦程序產品的一部分。進一步，在一個例示中，如在執行過程中，或在其他時間，代碼可以被明確地儲存於一種或多種依電性(volatile)、非短暫性的、或非易失性的(non-volatile)有形的電腦可讀取媒體。這些有形的電腦可讀取媒體的例示可包含但不限於，硬碟(hard disks)、移動式磁片(removable magnetic disk)、移動式光碟(removable optical disk)(例如，光碟(compact disk, CD)及數位光碟(digital video disk, DVD))、卡式磁帶(magnetic cassettes)、記憶卡或記憶條(memory cards or sticks)、隨機存取記憶體(random access memories, RAMs)、唯讀記憶體(read only memories, ROMs)，等類似者。The illustration of the methods described herein can be performed at least in part by a machine or computer. Some examples may include a computer-readable medium or a machine-readable medium operable to configure an electronic device to perform the instruction encoding of the method as described in the above examples. Implementations of such methods may include code, such as microcode, assembly language code, higher-level language code, or the like. Such code may include computer readable instructions for performing various methods. The code can form part of a computer program product. Further, in one illustration, as during execution, or at other times, the code may be explicitly stored in one or more of a volatile, non-transitory, or non-volatile (non-volatile) ) Tangible computer readable media. Examples of such tangible computer readable media may include, but are not limited to, hard disks, removable magnetic disks, removable optical disks (eg, compact disks (CDs). ) and digital video disk (DVD), magnetic cassettes, memory cards or sticks, random access memories (RAMs), read-only memory (read only memories, ROMs), and so on.

以上的敘述旨在說明性的，並非限制性的。例如，在上述實施例(或其一個或多個態樣)可相互組合使用。藉由所屬技術領域中具有通常知識者依據檢閱以上的敘述後，可使用其他例示。提供的摘要符合37 C.F.R. §1.72(b)，允許讀者快速地確定公開的技術的性質。申請時理解摘要不會被用來解釋或限制申請專利範圍的範疇或含義。另外，在上面的詳細說明中，各種特徵可被組合在一起，以簡化本公開。一個沒有被權利要求的揭露特徵，不應該解釋為意思是對任何一個申請專利範圍是必須的。相反地，本發明的專利標的(subject matter)可存在於不超過一個特定的公開的例示中的所有特徵。因此，下面的申請專利範圍在此併入詳細說明中，以作為範例或例示，每個申請專利範圍依據自己的作為一個單獨的例示，可預期的是這樣的例示可以各種組合或排列彼此結合。本發明的範圍應當參考所附的申請專利範圍，以及同等於這些給予的申請專利範圍的全部範疇。The above description is intended to be illustrative, and not restrictive. For example, the above embodiments (or one or more aspects thereof) can be used in combination with each other. Other examples may be used by reviewing the above description by those of ordinary skill in the art. The summary provided is in accordance with 37 C.F.R. § 1.72(b), allowing the reader to quickly ascertain the nature of the disclosed technology. The abstract is not used to explain or limit the scope or meaning of the scope of the patent application. In addition, in the above detailed description, various features may be combined together to simplify the disclosure. An uncovered feature that is not claimed is not to be construed as meaning that it is necessary for any patent application. Conversely, the subject matter of the present invention may be present in all features in no more than one particular disclosed embodiment. The scope of the following claims is hereby incorporated by reference in its entirety in the claims of The scope of the invention should be determined by reference to the appended claims and the scope of the claims.

2．．．熔融矽2. . . Melting enthalpy

10．．．坩堝10. . . crucible

12．．．耐火材料12. . . Refractory

14．．．厎部14. . . Crotch

16．．．側面16. . . side

18．．．內側18. . . Inside

20．．．內表面20. . . The inner surface

22．．．上表面twenty two. . . Upper surface

24．．．內表面twenty four. . . The inner surface

30．．．襯裡30. . . lining

2-2．．．坩堝內表面之襯裡的一部分2-2. . . Part of the lining of the inner surface

Claims (10)

一種用於容納熔融矽混合物的坩堝，其包含：
至少一耐火材料，具有至少一內表面，界定用於接收熔融矽的一內側；以及

一襯裡，係設置於該內表面，該襯裡包含複數個碳化矽顆粒，係藉由一膠體氧化矽而黏結在一起。
A crucible for containing a molten crucible mixture comprising:
At least one refractory material having at least one inner surface defining an inner side for receiving the molten crucible;

A lining is disposed on the inner surface, and the lining comprises a plurality of cerium carbide particles bonded together by a colloidal cerium oxide.
如申請專利範圍第1項所述之坩堝，其中包含至少其一：
該碳化矽顆粒具有小於或等於約3.5公釐的尺寸；

該膠體氧化矽包含複數個氧化矽顆粒懸浮在液相；以及

該氧化矽顆粒具有介於10奈米及30奈米的尺寸。
As stated in item 1 of the scope of patent application, it contains at least one of:
The niobium carbide particles have a size of less than or equal to about 3.5 mm;

The colloidal cerium oxide comprises a plurality of cerium oxide particles suspended in a liquid phase;

The cerium oxide particles have a size of between 10 nm and 30 nm.
如申請專利範圍第1項所述之坩堝，其中包含至少其一：
該襯裡具有包含從2公釐至10公釐的厚度；

該至少一耐火材料包含氧化鋁；

該坩堝設置用於熔化一第一矽，以形成該熔融矽；以及

該坩堝設置作為用於定向凝固的一模具。
As stated in item 1 of the scope of patent application, it contains at least one of:
The liner has a thickness comprising from 2 mm to 10 mm;

The at least one refractory material comprises alumina;

The crucible is configured to melt a first crucible to form the molten crucible;

This crucible is provided as a mold for directional solidification.
一種用於純化矽的方法，該方法包含：
熔化在一熔化坩堝的一內側的一第一矽，以提供一第一熔融矽，該熔化坩堝包含一第一耐火材料，其具有至少一第一內表面，以界定該熔化坩堝的該內側；

定向地凝固在一定向凝固模具內的該第一熔融矽，以提供一第二矽，該定向凝固模具包含一第二耐火材料，其具有至少一第二內表面，以界定該定向凝固模具的一內側；以及

將包含藉由一膠體氧化矽而黏結在一起的複數個碳化矽顆粒的一襯裡，塗佈到該第一內表面及該第二內表面之至少其中之一的至少一部分。
A method for purifying hydrazine, the method comprising:
Melting a first crucible on an inner side of a melting crucible to provide a first melting crucible comprising a first refractory material having at least a first inner surface to define the inner side of the melting crucible;

Directly solidifying the first molten crucible in a directional solidification mold to provide a second crucible, the directional solidification mold comprising a second refractory material having at least a second inner surface to define the directional solidification mold One inside;

A liner comprising a plurality of niobium carbide particles bonded together by a colloidal cerium oxide is applied to at least a portion of at least one of the first inner surface and the second inner surface.
如申請專利範圍第4項所述之方法，其中該碳化矽顆粒具有小於或等於約3.5公釐的尺寸。The method of claim 4, wherein the niobium carbide particles have a size of less than or equal to about 3.5 mm. 如申請專利範圍第4項所述之方法，其中
該膠體氧化矽包含複數個氧化矽顆粒懸浮在液相，該氧化矽顆粒具有包含介於10奈米及30奈米的尺寸。
The method of claim 4, wherein the colloidal cerium oxide comprises a plurality of cerium oxide particles suspended in a liquid phase, the cerium oxide particles having a size of between 10 nm and 30 nm.
如申請專利範圍第4項所述之方法，其中該襯裡具有包含從2公釐至10公釐的厚度。The method of claim 4, wherein the liner has a thickness of from 2 mm to 10 mm. 如申請專利範圍第4項所述之方法，其中該熔化坩堝之該第一耐火材料包含氧化鋁。The method of claim 4, wherein the first refractory material of the enthalpy of fusion comprises alumina. 如申請專利範圍第4項所述之方法，其中該定向凝固模具之該第二耐火材料包含氧化鋁。The method of claim 4, wherein the second refractory material of the directional solidification mold comprises alumina. 如申請專利範圍第4項所述之方法，其中該定向凝固模具之該第二耐火材料包含碳化矽及一磷黏著劑。The method of claim 4, wherein the second refractory material of the directional solidification mold comprises niobium carbide and a phosphorus binder.