TWI458852B - High colour diamond - Google Patents

High colour diamond Download PDF

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TWI458852B
TWI458852B TW095122494A TW95122494A TWI458852B TW I458852 B TWI458852 B TW I458852B TW 095122494 A TW095122494 A TW 095122494A TW 95122494 A TW95122494 A TW 95122494A TW I458852 B TWI458852 B TW I458852B
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diamond
nitrogen
cvd
diamond layer
concentration
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TW200710259A (en
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Stephen David Williams
Daniel James Twitchen
Philip Maurice Martineau
Geoffrey Alan Scarsbrook
Ian Friel
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Element Six Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/006—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterized by the colour of the layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/10—Heating of the reaction chamber or the substrate
    • C30B25/105—Heating of the reaction chamber or the substrate by irradiation or electric discharge
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A method of producing CVD diamond having a high colour, which is suitable for optical applications, for example. The method includes adding a gaseous source comprising a second impurity atom type to counter the detrimental effect on colour caused by the presence in the CVD synthesis atmosphere of a first impurity atom type. The described method applies to the production of both single crystal diamond and polycrystalline diamond.

Description

高色度鑽石High color diamond 發明領域Field of invention

本發明係有關適於光學應用之高色度的CVD鑽石，包括高色度等級的寶石。特定言之，本發明有關一添加一包含一第二雜質原子類型的氣態源以對抗CVD合成大氣中出現一第一雜質原子類型所造成對於色度的有害效應之方法。The present invention relates to high chroma CVD diamonds suitable for optical applications, including high chroma grade gemstones. In particular, the present invention relates to a method of adding a gaseous source comprising a second impurity atom type to counteract the deleterious effects on chromaticity caused by the presence of a first impurity atom type in the CVD synthesis atmosphere.

所描述的方法係適用於製造單晶鑽石及多晶鑽石，特別是單晶鑽石。The described method is suitable for the manufacture of single crystal diamonds and polycrystalline diamonds, especially single crystal diamonds.

此處所參照的所有文件皆以引用方式併入本文中。All documents referred to herein are hereby incorporated by reference.

發明背景Background of the invention

藉由CVD將諸如鑽石等材料沉積在一基材上之方法現今已被良好地建立且已在專利案及其他文獻中廣泛地加以描述。若要將鑽石沉積在一基材上，該方法一般係包含提供一氣體混合物，其在解離時可提供原子形式的氫或鹵素(譬如F、Cl)及C或含碳根及其他反應物種，譬如CHx 、CFx ，其中x為1至4。此外，可出現含氧源，亦可能出現用於氮或硼之供源。譬如，氮可以諸如N2 、NH3 、空氣及N2 H4 等許多形式導入合成電漿中。許多程序中，亦出現諸如氦、氖或氬等惰性氣體。因此，一典型源氣體混合物將含有碳氫化合物Cx Hy ，其中x及y可各為1至10，或鹵氫化合物Cx Hy Halz ，其中x及x可各為1至10而y可為0至10，且視需要包含下列一或多者：COx ，其中x可為0.5至2，O2 、H2 、N2 、NH3 、B2 H6 及一惰性氣體。各氣體可以其天然同位比值出現，或可人工式控制相對同位比值。譬如，氫可以氘或氚出現，而碳可以1 2 C或1 3 C出現。Methods for depositing materials such as diamonds onto a substrate by CVD are well established today and have been extensively described in patents and other literature. To deposit a diamond on a substrate, the method generally comprises providing a gas mixture that provides atomic hydrogen or halogen (such as F, Cl) and C or carbonaceous and other reactive species upon dissociation. For example, CH x , CF x , where x is 1 to 4. In addition, oxygen-containing sources may be present, and sources for nitrogen or boron may also be present. For example, nitrogen can be introduced into the synthetic plasma in many forms such as N 2 , NH 3 , air, and N 2 H 4 . In many procedures, inert gases such as helium, neon or argon also occur. Thus, a typical source gas mixture will contain a hydrocarbon C x H y , where x and y may each be from 1 to 10, or a halogen hydrogen compound C x H y Hal z , where x and x may each be from 1 to 10 and y can be from 0 to 10, and optionally contains one or more of the following: CO x , where x can be from 0.5 to 2, O 2 , H 2 , N 2 , NH 3 , B 2 H 6 and an inert gas. Each gas may appear in its natural equipotential ratio, or the relative equipotential ratio may be manually controlled. For example, hydrogen can appear as ruthenium or osmium, and carbon can occur at 1 2 C or 1 3 C.

源氣體混合物的解離通常係由一諸如微波、RF(射頻)能等能量源、一以火焰、熱絲或噴注為基礎的技術所引發，而依此產生的反應性氣體物種係得以沉積在一基材上且形成鑽石。Dissociation of the source gas mixture is usually initiated by an energy source such as microwave, RF (radio frequency) energy, a technique based on flame, hot wire or jet, and the resulting reactive gas species are deposited A diamond is formed on a substrate.

單晶CVD鑽石具有一系列應用，包括電子裝置及高工程光學裝置。可對於各應用特別定製鑽石的性質，如此一來對於合成程序的細節及材料的製造成本構成了限制。國際專利案WO 01/96634號係描述適於電子應用之高純度鑽石的合成，其因為沉積程序的氣相中且隨後在固體中之低雜質位準亦顯示出低吸收且適於製造“高色度”鑽石(亦即，具有接近於無雜質鑽石的理論極限的吸收之材料，且因此通常提供等同於D到優於K的天然鑽石色度等級之色度，其為美國寶石協會(GIA)色尺上之色度等級，請見“鑽石等級ABC”，V.Pagel－Theisen，第九版，2001，61頁)。然而，提供用以達成該發明的方法中所使用低氮位準所需要的控制程度將具有經濟懲罰代價。Single crystal CVD diamonds have a range of applications, including electronics and highly engineered optics. The nature of the diamond can be tailored to each application, thus limiting the details of the synthesis process and the cost of manufacturing the material. International Patent Publication No. WO 01/96634 describes the synthesis of high purity diamonds suitable for electronic applications, which also exhibit low absorption due to the low impurity levels in the gas phase of the deposition process and subsequently in the solids and are suitable for manufacturing "high" Chroma" diamond (ie, a material that has an absorption close to the theoretical limit of an impurity-free diamond, and therefore generally provides a chromaticity equivalent to the natural diamond color scale of D to better than K, which is the Gem Society of America (GIA) The chroma level on the color scale, see "Diamond Grade ABC", V. Pagel-Theisen, Ninth Edition, 2001, p. 61). However, the degree of control required to provide the low nitrogen levels used in the method of achieving the invention will be costly.

表1中顯示身為最廣泛使用且熟知的鑽石色尺之美國寶石協會(GIA)的色尺。表1得自‘鑽石等級ABC，手冊’，Verena Pagel－Theisen，第九版2001，比利時安托布的Rubin and Son n.v.出版，61頁。藉由與標準作比較來決定色度。鑽石的色度決定係為一主觀程序且只可由熟習該技術者可靠地進行。Table 1 shows the American Gemstone (GIA) color ruler, the most widely used and well-known diamond ruler. Table 1 is available from 'Diamond Grade ABC, Handbook', Verena Pagel-Theisen, Ninth Edition 2001, Rubin and Sonn. v., Antoine, Belgium, 61 pages. The chromaticity is determined by comparison with the standard. The chromaticity determination of a diamond is a subjective procedure and can only be reliably performed by those skilled in the art.

表2顯示身為最廣泛使用的清澈度尺之美國寶石協會(GIA)的清澈度尺。表2得自“鑽石等級ABC，手冊”，Verena Pagel－Theisen，第九版2001，比利時安托布的Rubin and Son n.v.出版，61頁。其考慮到一經切割鑽石上的內部及外部瑕疵。一般而言，在適當照明下由一有經驗的評等師輔以10x放大鏡或擴大鏡來檢查所尋找的缺陷類型。Table 2 shows the clarity of the American Gem Society (GIA), the most widely used clearing ruler. Table 2 is available from "Diamond Grade ABC, Handbook", Verena Pagel-Theisen, Ninth Edition 2001, Rubin and Sonn. v., Antoine, Belgium, 61 pages. It takes into account the internal and external flaws on a cut diamond. In general, the type of defect sought is checked by an experienced evaluator with a 10x magnifying glass or an enlarged mirror under appropriate illumination.

“高清澈度”在此處係指表2所界定至少為SI 1、較佳至少VS 2之清澈度。By "high-definition clarity" it is meant herein the clarity of at least SI 1, preferably at least VS 2 as defined in Table 2.

GIA鑽石寶石評等系統係為鑽石寶石最廣泛使用的評等尺度且一般被視為定義性評等尺度。對於此申請案之目的，所有寶石色度等級係基於GIA色度等級，而諸如清澈度等其他寶石性質係同樣地基於GIA評等系統。對於鑽石的一給定品質，亦即具有已知吸收特徵的材料，寶石色度亦隨著所產生寶石的尺寸及切割而變，隨著石體變大而移至較差色度(朝向字母中的Z之色度)。為了使色度系統能夠應用作為一材料性質，因此需要進一步固定寶石之切割的類型及尺寸。除非另外指明，此說明書中所提供的所有GIA色度等級皆針對一標準化0.5 ct圓形明亮式切割。The GIA Diamond Gem Rating System is the most widely used rating for diamond gemstones and is generally considered a defining rating. For the purposes of this application, all gem color ratings are based on GIA chroma levels, while other gemstone properties such as clarity are based on the GIA rating system. For a given quality of diamond, that is, a material with known absorption characteristics, the chromaticity of the gem varies with the size and cutting of the gemstone produced, and moves to a poorer chromaticity as the stone becomes larger (toward the letter) The chroma of Z). In order for the chromaticity system to be applied as a material property, it is necessary to further fix the type and size of the gems to be cut. All GIA shade levels provided in this specification are for a standardized 0.5 ct round brilliant cut unless otherwise indicated.

不同於成長具有高色度的高純度層，其中將精細控制雜質位準添加至程序之有色寶石的合成請見WO 03/052177及WO 03/052174。這些技術提供一用以製造通常位於頻譜的藍或棕部分之一色度範圍的CVD鑽石層及CVD鑽石寶石之方法。Unlike the development of high purity layers with high chroma, the synthesis of colored gemstones with fine control of impurity levels added to the procedure is described in WO 03/052177 and WO 03/052174. These techniques provide a method for fabricating CVD diamond layers and CVD diamond gems that are typically in the chromaticity range of one of the blue or brown portions of the spectrum.

氮係為CVD鑽石程序中的一顯著雜質。在早先提及的先前技藝中強調其在決定材料色度及品質上所扮演關鍵角色之程度。氮很普遍存在，形成大氣中的很大部份，且常成為氣體供應的主要污染物，即便是指定為“高純度者”亦然。利用WO 01/96634所描述的方法自高純度氣體供應將氮移除至合成高色度鑽石所需要之程度將很昂貴，其將影響最終材料的成本，且需要找出更可容忍雜質之替代性合成方法，其適於製造製造寶石及其他選定光學裝置所需要之高色度的厚層。Nitrogen is a significant impurity in the CVD diamond program. The extent to which it plays a key role in determining the color and quality of materials is emphasized in the prior art mentioned earlier. Nitrogen is very common and forms a large part of the atmosphere and is often a major contributor to gas supply, even if it is designated as “high purity”. The degree required to remove nitrogen from a high purity gas supply to a synthetic high chromal diamond using the method described in WO 01/96634 would be expensive, would affect the cost of the final material, and would require an alternative to more tolerable impurities. A synthetic method suitable for the manufacture of thick layers of high chroma required for the manufacture of gemstones and other selected optical devices.

含有以足堪提供可觀察頻譜儀特性的充分濃度出現之單替代氮形式的氮之鑽石係稱為1b鑽石。頻譜儀特性係包括處於270奈米的一吸收係數最大值，及對於較長波長，近似300奈米至500奈米間之吸收係數的逐漸減小，其中一寬廣吸收頻帶的跡象位於近似365奈米處。可在諸如第1圖的頻譜A等一型1b高壓高溫鑽石的吸收頻譜中看見這些特性。雖然單替代氮對於吸收頻譜在紫外光中具有最大的效應，延伸至頻譜的可見區域中者係為較弱吸收而影響到類型1b鑽石的色度且賦予其一特徵黃/棕色。A diamond containing a single alternative nitrogen form of nitrogen present at a sufficient concentration to provide observable spectrometer characteristics is referred to as a 1b diamond. The spectrum analyzer characteristics include a maximum absorption coefficient at 270 nm, and a gradual decrease in absorption coefficient between approximately 300 nm and 500 nm for longer wavelengths, where a broad absorption band is located at approximately 365 nm. Meter. These characteristics can be seen in the absorption spectrum of a type 1b high pressure high temperature diamond such as spectrum A of Fig. 1. Although a single replacement nitrogen has the greatest effect on the absorption spectrum in ultraviolet light, the weaker absorption in the visible region of the spectrum affects the chromaticity of the type 1b diamond and imparts a characteristic yellow/brown color.

在出現氮時成長之均質磊晶CVD鑽石的UV/可見吸收頻譜通常係含有來自具有上述頻譜特徵的單替代氮之一貢獻。除了單替代氮外，在出現氮時成長之均質磊晶CVD鑽石一般係含有氮空缺中心形式之部分的氮。當N－V中心為電性中立[N－V]0 時，其導致具有位於575奈米的零聲子線之吸收。當N－V中心帶負電[N－V]－ 時，其導致具有位於637奈米的零聲子線之吸收及一具有位於近似570奈米的吸收最大值之聲子頻帶之相關聯的系統。室溫下，N－V中心之此兩電荷狀態的吸收頻帶係合併成從約500奈米至640奈米之一寬廣頻帶。此吸收頻帶係位於可見頻譜的黃部分中，且當其為強烈時結晶可展現一互補粉紅/紫色。The UV/visible absorption spectrum of a homogeneous epitaxial CVD diamond grown in the presence of nitrogen typically contains one contribution from a single replacement nitrogen having the above spectral characteristics. In addition to a single replacement of nitrogen, homogeneous epitaxial CVD diamonds that grow in the presence of nitrogen typically contain nitrogen in the form of a central portion of the nitrogen vacancy. When the N-V center is electrically neutral [N-V] 0 , it results in absorption with a zero phonon at 575 nm. When the N-V center is negatively charged [N-V] - , it results in an absorption system with a zero phonon absorption at 637 nm and an associated system with a phonon band at an absorption maximum of approximately 570 nm. . At room temperature, the absorption bands of the two charge states of the N-V center are combined into a broad band from about 500 nm to 640 nm. This absorption band is located in the yellow portion of the visible spectrum, and when it is intense, the crystallization can exhibit a complementary pink/purple color.

出現氮所成長之低品質均質磊晶CVD鑽石的UV/可見頻譜亦可顯現從頻譜的紅至藍區且進入紫外光之測量吸收的一逐漸升高。亦可能有來自散射之貢獻。與單替代氮相關者除外，頻譜一般不含其他特性。此吸收頻譜提供一不良的棕色且此鑽石常含有清楚可見的石墨性內含物。The UV/visible spectrum of low-quality homogeneous epitaxial CVD diamonds with nitrogen growth can also appear to gradually increase from the red to blue region of the spectrum and into the measured absorption of ultraviolet light. There may also be contributions from scattering. Except for those associated with single replacement nitrogen, the spectrum generally does not contain other characteristics. This absorption spectrum provides a poor brown color and this diamond often contains clearly visible graphite inclusions.

出現氮所成長的較高品質均質磊晶CVD鑽石之吸收頻譜係含有在天然、HPHT合成鑽石或低品質CVD鑽石中未出現之額外貢獻。其包括定心於近似350奈米及510奈米之兩寬廣頻帶。The absorption spectrum of higher quality homogeneous epitaxial CVD diamonds with the growth of nitrogen contains additional contributions that are not found in natural, HPHT synthetic diamonds or low quality CVD diamonds. It includes centering on two broad bands of approximately 350 nm and 510 nm.

位於近似350奈米的頻帶係不同於普通類型1b的該頻譜區域中之寬廣頻帶且以依據相對於單替代氮具有回應性之中心濃度而定的程度來扭曲普通類型1b鑽石的頻譜。The frequency band located at approximately 350 nm is different from the wide frequency band in the spectral region of the general type 1b and distorts the spectrum of the ordinary type 1b diamond to the extent that it is responsive to a central concentration responsive to a single replacement nitrogen.

類似地，定心於近似510奈米處之頻帶係可重疊於有關負氮空缺中心之吸收及有關單替代氮之可見吸收。Similarly, a band centered at approximately 510 nm can overlap the absorption of the negative nitrogen vacancy center and the visible absorption of the single replacement nitrogen.

對於吸收頻譜的各種不同貢獻之重疊係會造成位於近似350及510奈米的頻帶導致吸收頻譜中之寬廣肩部而非顯著最大值。然而，對於吸收的這些貢獻係在眼睛對於小差異很敏感之400至600奈米頻譜區域的波長對於鑽石的相對吸收係數具有一很顯著效應。因此，其對於鑽石的認知色度造成重要貢獻。The overlap of the various contributions to the absorption spectrum results in a frequency band at approximately 350 and 510 nm resulting in a broad shoulder in the absorption spectrum rather than a significant maximum. However, these contributions to absorption have a very significant effect on the relative absorption coefficient of the diamond at wavelengths in the 400 to 600 nm spectral region where the eye is sensitive to small differences. Therefore, it makes an important contribution to the cognitive color of diamonds.

這些頻帶的頻譜中之寬度及位置可能改變。利用頻譜的二次微分最容易確定峰值最大值的位置。已經發現，出現氮、及缺乏根據本發明所使用的任何第二雜質所成長的均質磊晶CVD鑽石之吸收頻譜一般係可被解構成下列近似組份。The width and position in the spectrum of these bands may vary. It is most easy to determine the position of the peak maximum using the second derivative of the spectrum. It has been found that the absorption spectrum of homogeneous epitaxial CVD diamonds in which nitrogen is present and which lacks any second impurities used in accordance with the present invention can generally be decomposed into the following approximate components.

1)單替代氮組份，其具有概括位於0.4公分－ 1 至10公分－ 1 範圍內處於270奈米的一吸收係數，及概括位於0.04公分－ 1 至1公分－ 1 間處於425奈米的一吸收係數。1) a single set of alternative parts of nitrogen, having positioned 0.4 cm summarizes - 1-10 cm - an absorption coefficient in the range of 1 to 270 nm, and summarized located 0.04 cm - 1-1 cm - 1 at 425 nm An absorption coefficient.

2)具有近似1 eV的FWHM之處於3.54 eV(350奈米)＋/－0.2 eV的一吸收頻帶及在其中心對於吸收頻譜概括為1至8公分－ 1 的最大貢獻。2) An absorption band of 3.54 eV (350 nm) +/- 0.2 eV with a FWHM of approximately 1 eV and a maximum contribution of 1 to 8 cm - 1 at the center for the absorption spectrum.

3)具有近似1 eV的FWHM之處於2.43 eV(510奈米)＋/－0.4 eV的一吸收頻帶及在其中心對於吸收頻譜概括為0.2至4公分－ 1 的最大貢獻。3) An absorption band of 2.43 eV (510 nm) +/- 0.4 eV with a FWHM of approximately 1 eV and a maximum contribution of 0.2 to 4 cm - 1 at the center for the absorption spectrum.

4)發現具有下列近似形式的波長依存性之經測量吸收係數(以公分－ 1 為單位)的一小殘留波長依存性組份：c x(以微米為單元的波長)－ 3 ，其中c<0.2以使處於510奈米之此組份的貢獻概括小於1.5公分－ 1 。4) A small residual wavelength-dependent component of the wavelength-dependent measured absorption coefficient (in centimeters - 1 ) having the following approximate form: cx (wavelength in micrometers) - 3 , where c < 0.2 at 510 nm so that the contribution of this component is less than 1.5 cm summarized --1.

第1圖顯示一棕CVD鑽石層的吸收頻譜(曲線B)及其可被分解成之組份。此頻譜分解的第一步驟係為減除一型1b HPHT合成鑽石的頻譜(曲線A)，其尺度係使殘留物未顯示270奈米特性。殘留頻譜則可分解成一c x λ－ 3 組份(曲線C)及上述類型的兩重疊頻帶(曲線D)。Figure 1 shows the absorption spectrum (curve B) of a brown CVD diamond layer and its components that can be broken down into components. The first step in this spectral decomposition is to subtract the spectrum of the type 1b HPHT synthetic diamond (curve A) in such a way that the residue does not exhibit a 270 nm characteristic. The residue can be decomposed into a spectrum cx λ - 3 two overlapping frequency band component (curve C) and of the type described above (curve D).

已發現可藉由上述組份的總和來良好地指定利用一系列不同程序所成長之CVD鑽石的UV/可見頻譜的比值，不同案例中對於組份具有不同加權因子。基於指定頻譜形狀之目的，以下列方式提供不同組份的貢獻。It has been found that the ratio of the UV/visible spectrum of CVD diamonds grown using a range of different procedures can be well specified by the sum of the above components, with different weighting factors for the components in different cases. The contributions of the different components are provided in the following manner for the purpose of specifying the shape of the spectrum.

270奈米：類型1b組份之峰值270奈米吸收係數係自一用以連接延伸於近似範圍235奈米至325奈米上方之270奈米特性的類型1b頻譜任一側之斜坡基線來測量。270 nm: The peak 270 nm absorption coefficient of type 1b component is measured from a slope baseline on either side of the Type 1b spectrum used to connect the 270 nm characteristic extending above the approximate range of 235 nm to 325 nm. .

350奈米：此頻帶的峰值吸收係數貢獻。350 nm: The peak absorption coefficient contribution of this band.

510奈米：此頻帶的峰值吸收係數貢獻。510 nm: The peak absorption coefficient contribution of this band.

斜坡：c x λ－ 3 組份對於510奈米處的吸收吸數之貢獻。Slope: contribution of the cx λ - 3 component to the absorbance at 510 nm.

本發明係為一種用以製造一具有高色度的CVD鑽石層之方法，包含：提供一基材；提供一CVD合成大氣，其中存在有一包含對於所產生鑽石層的色度具有一有害效應之一第一雜質原子類型之第一氣體；及將一包含一第二雜質原子類型的第二氣體添加至該合成大氣中，其中該等第一及第二雜質原子類型並不相同；選擇該第二雜質原子類型的類型及數量以降低該對於第一雜質原子類型所造成的色度之有害效應藉以產生一具有高色度的鑽石層；及該等第一及第二雜質原子類型係獨立地為氮或在元素狀態中為固體之原子。The present invention is a method for producing a CVD diamond layer having a high chroma, comprising: providing a substrate; providing a CVD synthesis atmosphere in which one of the inclusions has a detrimental effect on the chromaticity of the diamond layer produced. a first gas of a first impurity atom type; and a second gas containing a second impurity atom type added to the synthesis atmosphere, wherein the first and second impurity atom types are not the same; The type and number of two impurity atom types to reduce the detrimental effect of the chromaticity caused by the first impurity atom type to thereby produce a diamond layer having a high chroma; and the first and second impurity atom types are independently It is an atom of nitrogen or a solid in the elemental state.

本發明亦為一種用以製造一CVD鑽石層之方法，包含：提供一基材；提供一CVD合成大氣，其中存在有大於300 ppb之未刻意添加之一濃度的氮；及將一包含一並非氮的第二雜質原子類型的第二氣體添加至該合成大氣中，其中該第二雜質原子類型係以一降低氮所造成對於色度的有害效應之量以一受控制方式添加藉以產生一具有高色度之鑽石層；及該第二雜質原子類型在元素狀態中為固體。The present invention is also a method for fabricating a CVD diamond layer, comprising: providing a substrate; providing a CVD synthesis atmosphere in which more than 300 ppb of undesired addition of a concentration of nitrogen is present; and a second gas of a second impurity atom type of nitrogen is added to the synthesis atmosphere, wherein the second impurity atom type is added in a controlled manner by a quantity that reduces the detrimental effect on chromaticity caused by nitrogen a high chroma diamond layer; and the second impurity atom type is a solid in the element state.

本發明又為一種用以製造一CVD鑽石層之方法，包含以下步驟：提供一基材；及將一含矽氣態源添加至一CVD合成大氣中。The invention further relates to a method for making a CVD diamond layer comprising the steps of: providing a substrate; and adding a gaseous source containing helium to a CVD synthesis atmosphere.

本發明又為一種CVD鑽石層，其由前述申請專利範圍任一項之方法所製造。The invention is further a CVD diamond layer produced by the method of any of the preceding claims.

本發明係為一種CVD鑽石層，其包含選自矽、硫或磷之一雜質原子類型，其中該鑽石層具有高色度。The present invention is a CVD diamond layer comprising one of the impurity atom types selected from the group consisting of ruthenium, sulfur or phosphorus, wherein the diamond layer has a high chroma.

本發明亦為一種CVD鑽石層，其中該鑽石層的大部份容積係包含選自矽、硫或磷之從101 5 至2 x 101 8 原子/立方公分的一雜質原子類型。The present invention is also one kind of CVD diamond layer wherein the majority volume of the diamond-based layer selected from the group comprising silicon, sulfur or phosphorus from 1015 to 2-type impurity atom x 10 1 8 atoms / cubic centimeter.

本發明又為一種CVD鑽石層，其根據申請專利範圍第1至33項中任一項之方法所製造以用來作為一光學元件。The invention is also a CVD diamond layer which is manufactured as an optical component according to the method of any one of claims 1 to 33.

本發明係為一種CVD鑽石層，其根據申請專利範圍第1至33項中任一項之方法所製造以用來作為一電性或電子元件。The present invention is a CVD diamond layer manufactured according to the method of any one of claims 1 to 33 for use as an electrical or electronic component.

本發明亦為一種CVD鑽石層，其根據申請專利範圍第1至33項中任一項之方法所製造，其具有大於0.1公厘之一厚度。The present invention is also a CVD diamond layer which is produced according to the method of any one of claims 1 to 33 which has a thickness of more than 0.1 mm.

本發明又為一種CVD單晶鑽石層，其根據申請專利範圍第1、2、4至22及24至31項中任一項之方法以一寶石形式所製造。The present invention is also a CVD single crystal diamond layer which is produced in the form of a gemstone according to the method of any one of claims 1, 2, 4 to 22 and 24 to 31.

本發明又為一種用以製造一具有高色度的CVD鑽石層之方法中之一充足數量的一氣態源之使用方式，其中該氣態源包含一第二雜質原子類型以對抗一第一雜質原子類型對於鑽石色度之有害效應。The invention further relates to a method for producing a sufficient amount of a gaseous source in a method for fabricating a CVD diamond layer having a high chroma, wherein the gaseous source comprises a second impurity atom type to counter a first impurity atom The detrimental effect of type on diamond color.

本發明又為一種CVD鑽石製造方法中之一矽氣態源之使用方式，其中該氣態源係添加至一包含一基材及一鑽石合成大氣之反應室以使該矽對抗一第一雜質原子類型之有害效應。The invention further relates to a method for using a gaseous source in a CVD diamond manufacturing method, wherein the gaseous source is added to a reaction chamber comprising a substrate and a diamond synthetic atmosphere to make the crucible against a first impurity atom type Harmful effects.

圖式簡單說明Simple illustration

此處參照下列圖式來描述本發明，其中：第1圖顯示一橙棕CVD鑽石層之UV/可見吸收頻譜的頻譜分解，代表出現氮而未施加本發明方法所成長的一典型CVD鑽石層。頻譜A顯示一類型1b HPHT合成鑽石，頻譜B顯示橙棕CVD鑽石的一原始頻譜，頻譜C顯示一具有(波長)－ 3 依存性之頻譜組份，而頻譜D顯示一由兩寬廣吸收頻帶構成之頻譜組份；第2圖顯示藉由785奈米雷射激勵在77 K所記錄之一經矽摻雜CVD鑽石樣本之一光致發光頻譜；及第3圖顯示範例7所描述的一樣本之一低放大率光學顯微影像。The invention is described herein with reference to the following drawings in which: Figure 1 shows a spectral decomposition of the UV/visible absorption spectrum of an orange-brown CVD diamond layer, representing a typical CVD diamond layer grown without the application of the method of the invention. . Spectrum A shows a type 1b HPHT synthetic diamond, spectrum B shows an original spectrum of orange-brown CVD diamonds, spectrum C shows a spectral component with (wavelength) - 3 dependence, and spectrum D shows a mixture of two broad absorption bands. Spectral component; Figure 2 shows the photoluminescence spectrum of one of the erbium-doped CVD diamond samples recorded at 77 K by 785 nm laser excitation; and Figure 3 shows the same as described in Example 7. A low magnification optical microscopy image.

發明的詳細描述Detailed description of the invention

第一實施例中，本發明提供一用於製造一具有高色度的CVD鑽石層之方法，包含：(i)提供一基材；(ii)提供一CVD合成大氣，其中存在有一包含對於所產生鑽石層的色度具有有害效應之一第一雜質原子類型之第一氣體；及(iii)將一包含一第二雜質原子類型的第二氣體添加至合成大氣中，其中第一及第二雜質原子類型並不相同；選擇第二雜質原子類型的類型及數量以降低對於第一雜質原子類型所造成的色度之有害效應藉以產生一具有高色度的鑽石層；及第一及第二雜質原子類型係獨立地為氮或在室溫及壓力下於元素狀態中為固體之原子。In a first embodiment, the present invention provides a method for fabricating a CVD diamond layer having high chroma, comprising: (i) providing a substrate; (ii) providing a CVD synthesis atmosphere, wherein there is a Generating a first layer of a first impurity atom type having a chromaticity of the diamond layer; and (iii) adding a second gas comprising a second impurity atom type to the synthesis atmosphere, wherein the first and second The types of impurity atoms are not the same; the type and amount of the second impurity atom type are selected to reduce the detrimental effect on the chromaticity caused by the first impurity atom type to produce a diamond layer having a high chroma; and the first and second The impurity atom type is independently nitrogen or an atom which is solid in an elemental state at room temperature and pressure.

利用此方式，本發明的方法係能夠提供一具有高色度之CVD鑽石層，其中合成大氣係包含一具有一將防止產生高色度鑽石的第一雜質原子類型之氣體。譬如，在包含氮的合成大氣中出現一氣體通常係將造成合成鑽石具有一黃/棕色，而在包含硼的合成大氣中出現一氣體則通常將造成合成鑽石具有藍色。In this manner, the method of the present invention is capable of providing a CVD diamond layer having a high chroma, wherein the synthetic atmosphere comprises a gas having a first impurity atom type that will prevent the generation of high chroma diamonds. For example, the presence of a gas in a synthetic atmosphere containing nitrogen will generally result in a yellow/brown synthetic diamond, while the presence of a gas in a synthetic atmosphere containing boron will generally result in a synthetic blue color.

本發明中依據鑽石材料的形式及其應用而以兩不同方式來定義“高色度”用語。此處所用的“高色度”定義係為最適用於所產生的鑽石層形式及其應用者。當鑽石為一圓形明亮式形式時(亦即，當鑽石為一寶石形式時)，一般使用GIA色尺。當鑽石為使用於科技應用之一板等形式時，材料概括就其吸收特徵予以定義。亦使用吸收特徵來界定多晶鑽石。In the present invention, the term "high chroma" is defined in two different ways depending on the form of the diamond material and its application. The definition of "high chroma" as used herein is best suited to the form of the diamond layer produced and its application. When the diamond is in the form of a round brilliant form (i.e., when the diamond is in the form of a gemstone), a GIA ruler is generally used. When a diamond is used in the form of a board for scientific applications, the material summary defines its absorption characteristics. Absorbing features are also used to define polycrystalline diamonds.

因此，當本發明的鑽石層為一寶石形式時，高色度概括係被定義為如對於0.5 ct圓形明亮所決定之美國寶石協會(GIA)寶石鑽石色尺(如上述)上優於K的色度。此色度等級係被熟練鑽石評等員認知為接近無色或無色。該鑽石可具有優於J、較佳優於I、較佳優於H、較佳優於G、較佳優於F、或較佳優於E之色度。本發明的鑽石層具有“很高色度”，其中色度如對於0.5 ct圓形明亮式所決定在GIA寶石鑽石色尺上係為D至F。Thus, when the diamond layer of the present invention is in the form of a gemstone, the high chroma outline is defined as superior to K on the GIA gem diamond ruler (as described above) as determined for a 0.5 ct round brightness. Chromaticity. This colorimetric level is perceived by the skilled diamond evaluator as being nearly colorless or colorless. The diamond may have a chromaticity better than J, preferably better than I, preferably better than H, preferably better than G, preferably better than F, or preferably better than E. The diamond layer of the present invention has a "very high chroma" in which the chromaticity is determined to be D to F on the GIA gemstone diamond color scale as determined for a 0.5 ct round brilliant pattern.

對於科技應用及對於本發明的多晶鑽石層，“高色度”概括被定義為材料的大部份容積在電磁頻譜的近紫外光及可見部分中之下列特定波長(亦即位於近似270奈米至800奈米範圍中之波長)於室溫測量時係具有下列吸收係數之至少一者：(i)在270奈米，小於2.9公分－ 1 ，較佳小於1.9公分－ 1 ，較佳小於1.0公分－ 1 ，較佳小於0.40公分－ 1 ；(ii)在350奈米，小於1.5公分－ 1 ，較佳小於0.90公分－ 1 ，較佳小於0.50公分－ 1 ，較佳小於0.20公分－ 1 ；(iii)在520奈米，小於0.45公分－ 1 ，較佳小於0.30公分－ 1 ，較佳小於0.14公分－ 1 ，較佳小於0.06公分－ 1 ；及(iv)在700奈米，小於0.18公分－ 1 ，較佳小於0.12公分－ 1 ，較佳小於0.06公分－ 1 ，較佳小於0.03公分－ 1 。For technical applications and for the polycrystalline diamond layer of the present invention, the "high chroma" generalization is defined as the majority of the volume of the material at the following specific wavelengths in the near-ultraviolet and visible portions of the electromagnetic spectrum (ie, located approximately 270 奈The wavelength in the range of meters to 800 nm) has at least one of the following absorption coefficients when measured at room temperature: (i) at 270 nm, less than 2.9 cm - 1 , preferably less than 1.9 cm - 1 , preferably less than 1.0 cm - 1, preferably less than 0.40 cm --1; (II) at 350 nm, of less than 1.5 cm - 1, preferably less than 0.90 cm - 1, preferably less than 0.50 cm - 1, preferably less than 0.20 cm --1 (iii) at 520 nm, less than 0.45 cm - 1 , preferably less than 0.30 cm - 1 , preferably less than 0.14 cm - 1 , preferably less than 0.06 cm - 1 ; and (iv) at 700 nm, less than 0.18 cm - 1, preferably less than 0.12 cm - 1, preferably less than 0.06 cm - 1, preferably less than 0.03 cm --1.

本發明的材料可在720至750奈米範圍中具有敏銳的吸收特性，但其對於色度少有貢獻且因此未受限於這些定義。The materials of the present invention may have sharp absorption characteristics in the range of 720 to 750 nm, but they contribute less to chromaticity and are therefore not limited by these definitions.

為了求出吸收係數，首先必須自所測量的吸收頻譜減去反射損失。當減除反射損失時，務必考慮到反射係數的頻譜依存性。這可藉由F.Peter在Z.Phys.15，358－368(1923)所提供自鑽石的折射率之波長依存性求出。利用一平行側式板的反射損失對於折射率之依存性之此及標準公式，可以波長的一函數來計算反射損失對於視吸收率之效應且自所測量頻譜予以減除而得以更精確地計算吸收係數頻譜。In order to find the absorption coefficient, the reflection loss must first be subtracted from the measured absorption spectrum. When subtracting the reflection loss, it is important to consider the spectral dependence of the reflection coefficient. This can be determined by the wavelength dependence of the refractive index of the diamond provided by F. Peter at Z. Phys. 15, 358-368 (1923). Using the dependence of the reflection loss of a parallel side plate on the refractive index and the standard formula, the effect of the reflection loss on the apparent absorption rate can be calculated as a function of the wavelength and can be more accurately calculated by subtracting the measured spectrum. Absorption coefficient spectrum.

或者，可利用如此說明書稍後所勾勒之CIELAB色度系統來定義“高色度”。此色度模擬系統得以自吸收頻譜決定出色度等級。Alternatively, "high chroma" can be defined using the CIELAB colorimetric system outlined later in this specification. This chroma simulation system is self-absorbing to determine the level of excellence.

此處所用的“大部份容積”用語係指至少50%的鑽石層、較佳至少55%、較佳至少60%、較佳至少70%、較佳至少80%、較佳至少90%、較佳至少95%的鑽石層。As used herein, the term "major volume" means at least 50% of the diamond layer, preferably at least 55%, preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%, Preferably at least 95% of the diamond layer.

第二氣體被精細地添加至CVD鑽石合成大氣。第二氣體較佳以一受控制方式添加。可控制第二氣體的出現以使第二氣體的濃度穩定而優於20%、較佳優於10%、較佳優於3%。The second gas is finely added to the CVD diamond synthesis atmosphere. The second gas is preferably added in a controlled manner. The presence of the second gas may be controlled to stabilize the concentration of the second gas to be better than 20%, preferably better than 10%, preferably better than 3%.

在不受限於任何特定理論下，咸信第二雜質原子類型係抑制第一雜質原子類型原本對於成長表面所具有的粗化效應。藉由使成長表面保持平坦，抑制了原本會劣化色度之一寬廣範圍的缺陷之攝入。將一包含一雜質原子類型(諸如氮)之氣態源添加至單晶CVD鑽石合成程序係會以一使表面粗度增加的方式來改變發生於鑽石成長表面上之反應，故對於該表面賦予較大之含有缺陷的傾向。當一雜質催化鑽石新層在一{100}表面的不同區域中之長晶時尤其如此，導致由具有可供包含不同缺陷的不同種類位址之傾斜狀豎板之梯台所組成的微階部之形成，諸如馬丁諾(Martineau)等人，Gems & Gemology，40(1)，2(2004)所描述。Without being bound by any particular theory, the second impurity atom type inhibits the coarsening effect that the first impurity atom type originally had on the growing surface. By keeping the growing surface flat, the ingestion of a defect that would otherwise degrade a wide range of chromaticity is suppressed. Adding a gaseous source containing an impurity atom type (such as nitrogen) to the single crystal CVD diamond synthesis program will change the reaction occurring on the diamond growth surface in such a way that the surface roughness is increased, so that the surface is given The tendency to have defects. This is especially true when an impurity catalyzes a new layer of diamond in a different region of a {100} surface, resulting in a microstep consisting of a terrace with inclined risers for different types of sites containing different defects. The formation is described, for example, by Martineau et al., Gems & Gemology, 40(1), 2 (2004).

具有可能潛在包括之許多種類的缺陷。譬如，可併入有單替代雜質缺陷。其包含一碳原子被一雜質原子之替代。氫總是出現在CVD成長環境中且可能變成併入在其本身上或連同一或多個雜質原子。空缺(通常由一碳原子佔據之鑽石晶格中未被佔據的位址)可能變成連同一或多個鄰近雜質原子(譬如氮空缺缺陷)、或一或多個氫原子(譬如空缺氫絡合物)被併入。部分缺陷絡合物係包含雜質原子、氫原子及空缺(譬如，氮空缺氫絡合物)。空缺的叢集可在具有或沒有經結合氫的情形下形成且在部分案例中可與雜質原子相關聯。There are many types of defects that may potentially be included. For example, a single replacement impurity defect can be incorporated. It contains a carbon atom replaced by an impurity atom. Hydrogen always appears in the CVD growth environment and may become incorporated into itself or with one or more impurity atoms. A vacancy (an unoccupied address in a diamond lattice usually occupied by one carbon atom) may become one or more adjacent impurity atoms (such as nitrogen vacancies) or one or more hydrogen atoms (such as vacancy hydrogen complexes) ()) is incorporated. Partially defective complexes contain impurity atoms, hydrogen atoms, and vacancies (for example, nitrogen vacancy hydrogen complexes). The cluster of vacancies can be formed with or without bound hydrogen and in some cases can be associated with impurity atoms.

一般發現，一旦表面被粗化時併入之寬廣範圍缺陷組係對於材料的光學及電子性質具有不良效應。譬如，缺陷組係可含有部分因為其譬如在頻譜可見區域中吸入光之方式而將對於材料提供不良光學性質者。因為其降低載體活動力及壽命而將劣化電子性質。It has generally been found that a wide range of defect groups incorporated once the surface is roughened has an adverse effect on the optical and electronic properties of the material. For example, a defect set may contain a portion that would provide poor optical properties to the material because it would, for example, draw light in the visible region of the spectrum. Electronic properties will be degraded because it reduces carrier activity and lifetime.

咸信本發明背後之一一般機制係在於一含有一第一雜質原子類型之氣態源會被添加一含有一第二雜質原子類型之第二氣態源所抑制而抑制了第一雜質原子類型原本對於成長表面所具有的粗化效應之有害效應。藉由抑制表面的粗化，第二雜質的添加亦抑制了上文所勾勒將劣化所成長材料的性質之寬廣範圍缺陷的併入。One of the general mechanisms behind the invention is that a gaseous source containing a first impurity atom type is inhibited by the addition of a second gaseous source containing a second impurity atom type to suppress the first impurity atom type. The detrimental effect of the roughening effect of the growing surface. By suppressing the roughening of the surface, the addition of the second impurity also inhibits the incorporation of a wide range of defects outlined above which degrade the properties of the grown material.

在出現兩雜質原子類型情形下，其中成長發生於一平坦表面上，兩雜質原子類型將概括被併入但比起對於一粗表面上的成長所觀察者具有更低效率。然而，當諸如添加第二雜質原子類型的緣故使成長發生於一平坦表面上時根本未觀察到上述許多缺陷(譬如，空缺叢集及氫相關缺陷)。結果係為兩雜質原子類型可以可測量的適度濃度被併入鑽石材料中但不具有對於所產生鑽石層性質(諸如其光學傳輸)具有最強負面效應之寬廣範圍的缺陷。In the case of two impurity atom types, where growth occurs on a flat surface, the two impurity atom types will be summarized in general but have lower efficiency than those observed for growth on a rough surface. However, many of the above-mentioned defects (such as vacancy clusters and hydrogen-related defects) are not observed at all when growth occurs on a flat surface such as the addition of the second impurity atom type. The result is that a moderate concentration of two impurity atom types can be incorporated into the diamond material without having a broad range of defects with the strongest negative effects on the properties of the diamond layer produced, such as its optical transmission.

亦相信本發明的方法可額外地以一第二一般原理為基礎，其中併入兩雜質原子類型的方式係使其彼此相互補償。就本身而言，選擇兩雜質原子類型而使得在鑽石層的特定濃度範圍內，其對於所需要的材料性質並無顯著不良效應。根據該技藝中的先前教導，將具有一假設在於如此將排除通常與將使色度及其他性質劣化之一範圍的缺陷相關聯之來自使用氮之補償的任何利益。然而，鑒於添加一第二雜質原子類型將使缺陷減少之上文所勾勒的第一一般原理，兩雜質原子類型之間的相互補償效應將有額外優點。這一般係部分地因為一雜質原子類型補償另一者在其缺乏時所具有之效應且反之亦然所致。可利用氮及硼的範例來顯示補償。替代性氮及硼藉由本身來分別提供鑽石黃/棕及藍色。然而，本申請案的發明人已經發現，當以近似相同濃度一起提供時，因為替代性氮缺陷將電子捐至替代性硼缺陷且所產生的經離子化缺陷不導致顯著光學吸收，可產生無色材料。It is also believed that the method of the present invention may additionally be based on a second general principle in which the two impurity atom types are incorporated in such a way as to compensate each other. For its part, the two impurity atom types are chosen such that within a particular concentration range of the diamond layer, there is no significant adverse effect on the desired material properties. In accordance with the prior teachings in this art, there will be a hypothesis that such an advantage would be excluded from the compensation of the use of nitrogen that would normally be associated with a defect that would degrade one of the chromaticity and other properties. However, in view of the first general principle outlined above, the addition of a second impurity atom type will reduce the defect, the mutual compensation effect between the two impurity atom types will have additional advantages. This is generally due in part to the fact that one impurity atom type compensates for the effect that the other has in its absence and vice versa. Examples of nitrogen and boron can be used to show compensation. Alternative nitrogen and boron provide diamond yellow/brown and blue, respectively, by themselves. However, the inventors of the present application have discovered that when provided together at approximately the same concentration, colorless color defects can be produced because the alternative nitrogen defects donate electrons to the alternative boron defects and the resulting ionized defects do not result in significant optical absorption. material.

對於給定一組的成長條件(諸如基材溫度、壓力及電漿溫度)，發明人已經發現，在表面粗化及所成長鑽石變棕色之前具有可被CVD鑽石合成程序所容忍之一低限值氮濃度。然而，低限值氮濃度傾向於低到要需要顯著時間及費用來避免併入會影響材料的光學及其他性質之缺陷。For a given set of growth conditions (such as substrate temperature, pressure, and plasma temperature), the inventors have discovered that there is a lower limit that can be tolerated by the CVD diamond synthesis program before the surface is roughened and the grown diamond turns brown. Value nitrogen concentration. However, the low limit nitrogen concentration tends to be low enough to require significant time and expense to avoid the incorporation of defects that would affect the optical and other properties of the material.

本發明的發明人已經發現，將一第二雜質原子類型(諸如硼或矽)添加至成長氣體會將低限值氮濃度顯著地增加至當相對較少注意到氮消除時成長環境中有可能出現之位準。這可讓鑽石在出現相對較高濃度的氮下成長而不劣化因為併入諸如空缺叢集及氫相關缺陷等缺陷而原本將導致之光學及其他性質。此外，已經驚人地發現，即便氮及第二雜質原子類型皆可能顯著地併入所成長鑽石中，仍可能具有此作用。The inventors of the present invention have found that the addition of a second impurity atom type (such as boron or ruthenium) to a growing gas will significantly increase the low limit nitrogen concentration to a potential growth environment when relatively little attention is paid to nitrogen elimination. The level of occurrence. This allows diamonds to grow without the presence of relatively high concentrations of nitrogen without degrading the optical and other properties that would otherwise be caused by incorporating defects such as vacancy clusters and hydrogen-related defects. Furthermore, it has been surprisingly found that even though both nitrogen and the second impurity atom type may be significantly incorporated into the grown diamond, this effect may still be present.

先前技藝(WO 2005/061400)中已知將特定摻雜物刻意地添加至CVD單晶鑽石的合成大氣藉以對於單晶CVD鑽石提供一“標籤”，亦即一來源或指紋標記。選擇摻雜物以使來源或指紋標記在正常觀視條件下不易被偵測或不影響鑽石材料的認知品質但在諸如曝露於光或輻射或一指定波長等指定條件下可加以偵測或成為可偵測。It is known in the prior art (WO 2005/061400) to intentionally add a specific dopant to the synthetic atmosphere of a CVD single crystal diamond to provide a "tag" for the single crystal CVD diamond, ie a source or fingerprint. The dopant is selected such that the source or fingerprint is not readily detectable or affects the cognitive quality of the diamond material under normal viewing conditions but can be detected or become specified under specified conditions such as exposure to light or radiation or a specified wavelength. Detectable.

相對地，本發明有關使用一第二雜質原子類型來對抗對於CVD合成大氣中所出現之一第一雜質原子類型的色度之有害效應。利用此方式，即便CVD合成大氣包含原本將產生並無高色度的鑽石之一第一雜質原子類型量，本發明能夠產生一具有高色度之CVD鑽石。這具有僅藉由添加一特定類型及數量的第二雜質原子即不再需要採取特殊步驟來消除已知會自合成大氣負面地影響鑽石色度之雜質原子類型之優點。因此，CVD鑽石的合成可被簡化且在時間及成本上更有效率。In contrast, the present invention relates to the use of a second impurity atom type to counteract the deleterious effects of chromaticity of one of the first impurity atom types occurring in the CVD synthesis atmosphere. In this manner, the present invention is capable of producing a CVD diamond having a high chroma, even if the CVD synthesis atmosphere contains a first impurity atom type amount which is originally one of diamonds having no high chroma. This has the advantage that by simply adding a particular type and amount of second impurity atoms, no special steps are required to eliminate the type of impurity atoms known to negatively affect the chroma of the diamond from the synthetic atmosphere. Therefore, the synthesis of CVD diamonds can be simplified and more efficient in time and cost.

本發明的方法所產生之CVD鑽石層可為單晶。The CVD diamond layer produced by the method of the present invention can be a single crystal.

或者，CVD鑽石層可為多晶。多晶CVD鑽石係為此技藝已知。其概括成長在一非鑽石基材(譬如，矽、碳化矽、鎢、鉬及其他碳化物形成金屬)上。合併一其中使成長速率隨著晶體學方向而變之成長機構之來自多重隨機定位及定向式核心之成長係導致其中顆粒具有或多或少對準於單一晶體學方向的成長方向(譬如平行於<100>或<110>)、但垂直於成長方向隨機地定向(亦即，位於層的平面中)之多晶層。此碟係由熟習該技術者描述為具有一“索線紋路”。Alternatively, the CVD diamond layer can be polycrystalline. Polycrystalline CVD diamonds are known for this skill. It is generalized on a non-diamond substrate (eg, tantalum, tantalum carbide, tungsten, molybdenum, and other carbide forming metals). Combining a growth from a multi-random localization and a directional core in which the growth rate changes with crystallographic orientation results in a particle having a growth direction that is more or less aligned with a single crystallographic direction (eg, parallel to <100> or <110>), but a polycrystalline layer that is randomly oriented perpendicular to the growth direction (ie, in the plane of the layer). This dish is described by those skilled in the art as having a "wire pattern".

或者，CVD鑽石層可為異質磊晶性。異質磊晶CVD鑽石層為此技藝所熟知。其一般成長在包括矽、碳化矽、鈦化鍶及銥等非鑽石材料的單晶基材上。絡合間層結構時常使用於基材與CVD鑽石層之間以控制應變及降低熱膨脹不匹配的衝擊。異質磊晶鑽石層的核心初始係由與基材的一特定定向關係所形成且隨後成長至或多或少位於相同晶體學定向中之鑽石的“分域”內，通常對於單晶基材中的一方向呈現一確定關係。分域通常由低角度邊界所分隔。對於數十微米厚的層已經據報具有數百微米的側向尺寸之分域。Alternatively, the CVD diamond layer can be heteroepitaxial. Heterogeneous epitaxial CVD diamond layers are well known in the art. It is generally grown on single crystal substrates comprising non-diamond materials such as tantalum, tantalum carbide, tantalum niobium and niobium. Complex interstitial structures are often used between the substrate and the CVD diamond layer to control strain and reduce thermal expansion mismatch shocks. The core of the heteroepitary diamond layer is initially formed by a specific orientation relationship with the substrate and subsequently grown into a "domain" of diamonds that are more or less in the same crystallographic orientation, typically for single crystal substrates. One direction presents a certain relationship. The subdomains are usually separated by low angle boundaries. Layers of tens of microns thick have been reported to have a lateral dimension of hundreds of microns.

本發明的方法中，第一雜質原子類型較佳為氮而第二雜質原子類型選自矽、硼、磷或硫。利用此方式，添加一包含矽、硼、磷或硫雜質原子類型之氣態源係可對抗氮原本將對於鑽石色度所造成之有害效應。更佳，第二雜質原子類型係為矽且因此矽雜質原子係對抗氮雜質原子對於鑽石之有害效應。或者，第二雜質原子類型係為硼且因此硼雜質原子係對抗氮雜質原子對於鑽石色度之有害效應。In the method of the present invention, the first impurity atom type is preferably nitrogen and the second impurity atom type is selected from the group consisting of ruthenium, boron, phosphorus or sulfur. In this way, the addition of a gaseous source system containing atomic types of bismuth, boron, phosphorus or sulfur impurities can counteract the deleterious effects that nitrogen would otherwise have on diamond chromaticity. More preferably, the second impurity atom type is ruthenium and thus the ruthenium impurity atom is resistant to the harmful effects of the nitrogen impurity atom on the diamond. Alternatively, the second impurity atom type is boron and thus the boron impurity atom is resistant to the detrimental effect of the nitrogen impurity atom on the diamond color.

或者，第一雜質原子類型為矽、硼、磷或硫而第二雜質原子類型為氮。利用此方式，添加一含有氮雜質原子的氣態源係可對抗矽、硼、磷或硫將對於鑽石色度之有害效應。更佳，第一雜質原子類型為矽且因此氮雜質原子係對抗矽雜質原子對於鑽石色度之有害效應。或者，第一雜質原子類型為硼且因此氮雜質原子係對抗硼雜質原子對於鑽石色度之有害效應。Alternatively, the first impurity atom type is yttrium, boron, phosphorus or sulfur and the second impurity atom type is nitrogen. In this way, the addition of a gaseous source containing nitrogen impurity atoms can counteract the deleterious effects of bismuth, boron, phosphorus or sulfur on the color of the diamond. More preferably, the first impurity atom type is 矽 and thus the nitrogen impurity atom is resistant to the detrimental effect of the erbium impurity atom on the diamond color. Alternatively, the first impurity atom type is boron and thus the nitrogen impurity atom is resistant to the detrimental effect of the boron impurity atom on the diamond color.

若是第一或第二雜質原子類型為氮，第一或第二氣體可為任何含有氮之氣態物種諸如N2 、NH3 (氨)、N2 H4 (聯氨)及HCN(氰化氫)等。第一或第二氣體較佳為N2 、NH3 或N2 H4 。第一或第二氣體較佳為N2 或NH3 ，第一或第二氣體較佳為N2 。合成大氣中出現之氮係以身為總氣體容積的分子比例之分子性氮(亦即N2 )的百萬分之份(ppm)或十億分之份(ppb)計算。因此，以分子性氮(N2 )添加之100 ppb的氮等同於200 ppb的氮原子或200 ppb的氨(NH3 )。If the first or second impurity atom type is nitrogen, the first or second gas may be any gaseous species containing nitrogen such as N 2 , NH 3 (ammonia), N 2 H 4 ( hydrazine), and HCN (hydrogen cyanide) )Wait. The first or second gas is preferably N 2 , NH 3 or N 2 H 4 . The first or second gas is preferably N 2 or NH 3 , and the first or second gas is preferably N 2 . The nitrogen present in the synthetic atmosphere is calculated in parts per million (ppm) or parts per billion (ppb) of molecular nitrogen (i.e., N 2 ) which is the molecular proportion of the total gas volume. Thus, 100 ppb of nitrogen added with molecular nitrogen (N 2 ) is equivalent to 200 ppb of nitrogen or 200 ppb of ammonia (NH 3 ).

對於氮以外之雜質添加，以ppm或ppb為單位的氣相濃度係指以較佳氣態物種添加之雜質的合成大氣中之濃度。For the addition of impurities other than nitrogen, the gas phase concentration in ppm or ppb means the concentration in the synthetic atmosphere of the impurities added by the preferred gaseous species.

若第一或第二雜質原子類型為硼，第一或第二氣體較佳為B2 H6 、BCl或BH3 。第一或第二氣體較佳為B2 H6 。If the first or second impurity atom type is boron, the first or second gas is preferably B 2 H 6 , BCl or BH 3 . The first or second gas is preferably B 2 H 6 .

若第一或第二雜質原子類型為矽，第一或第二氣體較佳為SiH4 、或Si2 H6 。第一或第二氣體較佳為SiH4 。If the first or second impurity atom type is ruthenium, the first or second gas is preferably SiH 4 or Si 2 H 6 . The first or second gas is preferably SiH 4 .

若第一或第二雜質原子類型為磷，第一或第二氣體較佳為H2 S。If the first or second impurity atom type is phosphorus, the first or second gas is preferably H 2 S.

若第一或第二雜質原子類型為磷，第一或第二氣體較佳為PH3 。If the first or second impurity atom type is phosphorus, the first or second gas is preferably PH 3 .

對於矽、硼、硫及磷，如果使用較佳物種(亦即，B2 H6 、SiH4 、H2 S及PH3 )除外的氣態物種來將雜質原子類型添加至合成環境，在決定合成環境中之該物種的濃度時必須顧及所添加的分子物種中之雜質原子類型的原子數。For bismuth, boron, sulphur and phosphorus, if a gaseous species other than the preferred species (ie, B 2 H 6 , SiH 4 , H 2 S, and PH 3 ) is used to add the impurity atom type to the synthetic environment, the synthesis is determined. The concentration of this species in the environment must take into account the number of atoms of the impurity atom type in the added molecular species.

以氣體將雜質原子類型添加至合成大氣。雖然氮除外皆可能以單一元素固體來添加所有雜質原子類型，卻不可能或極難以精確且可複製地控制作出此等添加之速率。譬如，已經藉由使固體硼曝露於合成大氣來作出硼的添加；其亦適用於其中已經使用固體表面之矽。然而，因為一雜質原子類型的氣態源可以一高度純粹形式製備、以一載體氣體重力測定式稀釋、然後作後製造分析以精確地決定確切濃度，本發明的方法中係使用雜質原子類型的氣態源。已知氣體濃度，可利用諸如質量流控制器等氣體計量裝置來添加精密及可複製性添加。The impurity atom type is added to the synthetic atmosphere by a gas. Although it is possible to add all impurity atom types with a single element solid, it is not possible or extremely difficult to accurately and reproducibly control the rate at which such additions are made. For example, the addition of boron has been made by exposing solid boron to the synthetic atmosphere; it is also suitable for use in which a solid surface has been used. However, since a gaseous source of an impurity atom type can be prepared in a highly pure form, diluted by a carrier gas gravimetric method, and then post-manufactured to accurately determine the exact concentration, the method of the present invention uses a gaseous atom type of impurity atom. source. Knowing the gas concentration, a gas metering device such as a mass flow controller can be used to add precision and reproducible additions.

第一雜質原子類型可為氮而第二雜質原子類型可為硫。第一雜質原子類型可為氮而第二雜質原子類型可為磷。第一雜質原子類型可為硫而第二雜質原子類型可為氮。第一雜質原子類型可為磷而第二雜質原子類型可為氮。第一雜質原子類型可為磷而第二雜質原子類型可為硫。第一雜質原子類型可為硫而第二雜質原子類型可為磷。第一雜質原子類型可為硼而第二雜質原子類型可為矽。第一雜質原子類型可為矽而第二雜質原子類型可為硼。第一雜質原子類型可為硼而第二雜質原子類型可為磷。第一雜質原子類型可為磷而第二雜質原子類型可為硼。第一雜質原子類型可為硼而第二雜質原子類型可為硫。第一雜質原子類型可為硫而第二雜質原子類型可為硼。第一雜質原子類型可為矽而第二雜質原子類型可為磷。第一雜質原子類型可為磷而第二雜質原子類型可為矽。第一雜質原子類型可為矽而第二雜質原子類型可為硫。第一雜質原子類型可為硫而第二雜質原子類型可為矽。The first impurity atom type may be nitrogen and the second impurity atom type may be sulfur. The first impurity atom type may be nitrogen and the second impurity atom type may be phosphorus. The first impurity atom type may be sulfur and the second impurity atom type may be nitrogen. The first impurity atom type may be phosphorus and the second impurity atom type may be nitrogen. The first impurity atom type may be phosphorus and the second impurity atom type may be sulfur. The first impurity atom type may be sulfur and the second impurity atom type may be phosphorus. The first impurity atom type may be boron and the second impurity atom type may be ruthenium. The first impurity atom type may be ruthenium and the second impurity atom type may be boron. The first impurity atom type may be boron and the second impurity atom type may be phosphorus. The first impurity atom type may be phosphorus and the second impurity atom type may be boron. The first impurity atom type may be boron and the second impurity atom type may be sulfur. The first impurity atom type may be sulfur and the second impurity atom type may be boron. The first impurity atom type may be ruthenium and the second impurity atom type may be phosphorus. The first impurity atom type may be phosphorus and the second impurity atom type may be ruthenium. The first impurity atom type may be ruthenium and the second impurity atom type may be sulphur. The first impurity atom type may be sulfur and the second impurity atom type may be ruthenium.

來自合成大氣的一雜質原子類型併入固體鑽石中之作用係高度地依據合成程序的確切細節而定。此等事物已經很詳細地描述於先前技藝中且為熟習該技術者所瞭解。會影響併入位準之參數係包括用來提供雜質原子的分子物種之本質、合成大氣的溫度、合成大氣的壓力、基材表面的溫度、表面的晶體學本質及對於合成系統之氣流條件。The role of an impurity atom type from the synthetic atmosphere incorporated into a solid diamond is highly dependent on the exact details of the synthesis procedure. These matters have been described in great detail in the prior art and are known to those skilled in the art. The parameters that affect the incorporation level include the nature of the molecular species used to provide the impurity atoms, the temperature of the synthetic atmosphere, the pressure of the synthetic atmosphere, the temperature of the surface of the substrate, the crystallographic nature of the surface, and the gas flow conditions for the synthesis system.

若是第一或第二氣體源包含氮，合成大氣中含氮氣體的濃度可大於300 ppb、大於500 ppb、大於600 ppb、大於1 ppm、大於2 ppm、大於3 ppm、大於5 ppm、大於10 ppm、大於20 ppm、大於30 ppm。含氮氣體之濃度可位於從300 ppb至30 ppm、500 ppb至20 ppm、600 ppb至10 ppm、1 ppm至5 ppm、或2 ppm至3 ppm的範圍中。If the first or second gas source comprises nitrogen, the concentration of the nitrogen-containing gas in the synthetic atmosphere may be greater than 300 ppb, greater than 500 ppb, greater than 600 ppb, greater than 1 ppm, greater than 2 ppm, greater than 3 ppm, greater than 5 ppm, greater than 10 Ppm, greater than 20 ppm, greater than 30 ppm. The concentration of the nitrogen-containing gas can range from 300 ppb to 30 ppm, 500 ppb to 20 ppm, 600 ppb to 10 ppm, 1 ppm to 5 ppm, or 2 ppm to 3 ppm.

若是第一或第二氣體源包含硼，合成大氣中含硼氣體的濃度可大於0.5 ppb、大於1.0 ppb、大於2 ppb、大於5 ppb、大於10 ppb、大於20 ppb、大於50 ppb、大於0.1 ppm、大於0.2 ppm。合成大氣中含硼氣體之濃度可從0.5 ppb至0.2 ppm、從1.0 ppb至0.1 ppm、從2 ppb至50 ppb、從10 ppb至20 ppb。合成大氣中含硼氣體的濃度可小於1.4 ppm、小於0.1 ppm、或小於0.05 ppm。If the first or second gas source comprises boron, the concentration of the boron-containing gas in the synthetic atmosphere may be greater than 0.5 ppb, greater than 1.0 ppb, greater than 2 ppb, greater than 5 ppb, greater than 10 ppb, greater than 20 ppb, greater than 50 ppb, greater than 0.1. Ppm, greater than 0.2 ppm. The concentration of boron-containing gases in the synthetic atmosphere can range from 0.5 ppb to 0.2 ppm, from 1.0 ppb to 0.1 ppm, from 2 ppb to 50 ppb, and from 10 ppb to 20 ppb. The concentration of the boron-containing gas in the synthetic atmosphere may be less than 1.4 ppm, less than 0.1 ppm, or less than 0.05 ppm.

若是第一或第二氣體源包含矽，合成大氣中含矽氣體的濃度可大於0.01 ppm、大於0.03 ppm、大於0.1 ppm、大於0.2 ppm、大於0.5 ppm、大於1 ppm、大於2 ppm、大於5 ppm、大於10 ppm、大於20 ppm。合成大氣中含矽氣體之濃度可從0.01 ppm至20 ppm、0.03 ppm至10 ppm、0.1 ppm至5 ppm、0.2 ppm至2 ppm、或0.5 ppm至1 ppm。If the first or second gas source comprises helium, the concentration of helium containing gas in the synthetic atmosphere may be greater than 0.01 ppm, greater than 0.03 ppm, greater than 0.1 ppm, greater than 0.2 ppm, greater than 0.5 ppm, greater than 1 ppm, greater than 2 ppm, greater than 5 Pppm, greater than 10 ppm, greater than 20 ppm. The concentration of helium containing gas in the synthetic atmosphere can range from 0.01 ppm to 20 ppm, 0.03 ppm to 10 ppm, 0.1 ppm to 5 ppm, 0.2 ppm to 2 ppm, or 0.5 ppm to 1 ppm.

次級離子質譜術(SIMS)測量已經顯示，對於成長氣體中的一給定矽濃度，若缺乏氮，成長鑽石中之矽濃度對於{111}、{110}或{113}成長係比對於{100}成長更高。對於{100}定向的一基材上之成長，雖然氣態矽雜質傾向於增加低限值氮濃度以供表面粗化，對於成長氣體之高濃度氮的添加係終將造成表面粗化且矽併入效率鉅幅地增高。當發生此作用時，SIMS測量係指示出鑽石中的矽濃度可顯著地超過氮的濃度且在此等案例中，鑽石將一般顯示負責吸收頻譜中945 nm的頻譜特性之高濃度的缺陷(目前咸信為一中立矽空缺缺陷)所導致之一灰色。一般而言，隨著氣態矽的濃度增加，對於{111}、{110}或{113}上成長的材料係比對於{100}成長更早認知到灰色。Secondary ion mass spectrometry (SIMS) measurements have shown that for a given concentration of germanium in a growing gas, if there is a lack of nitrogen, the concentration of germanium in the growing diamond is greater for {111}, {110}, or {113} growth ratios. 100} grows higher. For the growth of a substrate with {100} orientation, although gaseous helium impurities tend to increase the low limit nitrogen concentration for surface roughening, the addition of high concentration nitrogen to the growing gas will eventually cause surface roughening and enthalpy The efficiency of the entry has increased dramatically. When this occurs, the SIMS measurement indicates that the concentration of germanium in the diamond can significantly exceed the concentration of nitrogen and in these cases the diamond will generally exhibit a high concentration of defects responsible for the spectral properties of the 945 nm in the absorption spectrum (currently One of the grays caused by Xianxin as a neutral vacancy defect. In general, as the concentration of gaseous enthalpy increases, materials that grow on {111}, {110}, or {113} are grayer than earlier for {100} growth.

當矽為第一或第二雜質原子類型時，鑽石層的大部份容積中之矽濃度可能小於或等於2 x 101 8 原子/立方公分。鑽石層的大部份容積中之矽濃度可能位於從101 4 原子/立方公分至2 x 101 8 原子/立方公分、從3 x 101 4 原子/立方公分至101 7 原子/立方公分、從101 5 原子/立方公分至3 x 101 6 原子/立方公分、或從3 x 101 5 原子/立方公分至101 6 原子/立方公分之範圍中。鑽石層的大部份容積中之矽濃度可能大於101 3 原子/立方公分、大於101 4 原子/立方公分、大於3 x 101 4 原子/立方公分、大於101 5 原子/立方公分、大於3 x 101 5 原子/立方公分、大於101 6 原子/立方公分、大於3 x 101 6 原子/立方公分、大於101 7 原子/立方公分。When silicon is the first or second impurity atom type, the volume concentration of silicon in the majority of the diamond layer may be less than or equal to 2 x 10 1 8 atoms / cc. Most silicon concentration in volume of the diamond layer may be located from 1014 atoms / cc to 2 x 10 1 8 atoms / cm ^, from 3 x 10 1 4 atoms / cubic centimeter to 1017 atoms / cc , from 1015 atoms / cm ^ to 3 x 10 1 6 atoms / cubic centimeter, or from 3 x 10 1 5 atoms / cc to the range of 1016 atoms / cc in the. The concentration of radon in most of the diamond layer may be greater than 10 1 3 atoms/cm ^ 3 , greater than 10 1 4 atoms/cm ^ 3 , greater than 3 x 10 1 4 atoms/cm ^ 3 , greater than 10 1 5 atoms / cm ^ 3 , greater than 3 x 10 1 5 atoms / cm ^, greater than 1016 atoms / cc, is greater than 3 x 10 1 6 atoms / cm ^, greater than 1017 atoms / cc.

當氮為第一或第二雜質原子類型時，鑽石層的大部份容積中之氮濃度可能為從1 x 101 4 原子/立方公分至5 x 101 7 原子/立方公分、從5 x 101 5 原子/立方公分至2 x 101 7 原子/立方公分、或從1 x 101 6 原子/立方公分至5 x 101 6 原子/立方公分。鑽石層的大部份容積中之氮濃度可能大於2 x 101 5 原子/立方公分、大於5 x 101 5 原子/立方公分、大於101 6 原子/立方公分、大於3 x 101 6 原子/立方公分、大於101 7 原子/立方公分。When nitrogen is the first or second impurity atom type, the concentration of nitrogen in the volume of the diamond layer is most likely from 1 x 10 1 4 atoms / cc to 5 x 10 1 7 atoms / cm ^, from 5 x 1015 atoms / cc to 2 x 10 1 7 atoms / cubic centimeter, or from 1 x 10 1 6 atoms / cc to 5 x 10 1 6 atoms / cc. The volume of the nitrogen concentration in the diamond layer may be greater than most 2 x 10 1 5 atoms / cm ^, greater than 5 x 10 1 5 atoms / cm ^, greater than 1016 atoms / cc, is greater than 3 x 10 1 6 atoms / cubic centimeter, greater than 10 1 7 atoms / cubic centimeter.

當硼為第一或第二雜質原子類型時，鑽石層的大部份容積中之硼濃度可能為從101 4 原子/立方公分至101 8 原子/立方公分、從3 x 101 4 原子/立方公分至101 7 原子/立方公分、從101 5 原子/立方公分至101 6 原子/立方公分、或從3 x 101 5 原子/立方公分至101 6 原子/立方公分。鑽石層的大部份容積中之硼濃度可能大於101 3 原子/立方公分、大於101 4 原子/立方公分、大於3 x 101 4 原子/立方公分、大於101 5 原子/立方公分、大於3 x 101 5 原子/立方公分、大於101 6 原子/立方公分、大於3 x 101 6 原子/立方公分、大於101 7 原子/立方公分。When boron is the first or second impurity atom type, the volume of the boron concentration in the diamond layer may be from most 1014 atoms / cubic centimeter to 1018 atoms / cubic centimeter, from 3 x 10 1 4 atoms /cm ^ 3 to 10 1 7 atoms / cubic centimeter, from 10 1 5 atoms / cubic centimeter to 10 16 6 atoms / cubic centimeter, or from 3 x 10 15 5 atoms / cubic centimeter to 10 16 6 atoms / cubic centimeter. The volume of the boron concentration in the diamond layer may be greater than most 1013 atoms / cc, is greater than 1014 atoms / cc, is greater than 3 x 10 1 4 atoms / cm ^, greater than 1015 atoms / cc, greater than 3 x 10 1 5 atoms / cm ^, greater than 1016 atoms / cc, is greater than 3 x 10 1 6 atoms / cm ^, greater than 1017 atoms / cc.

通常，可利用次級離子質譜術(SIMS)來測量鑽石層中第一及第二雜質原子類型的濃度及任何其他雜質的濃度。雜質原子的偵測極限係依據所使用的SIMS條件而變。然而，對於本發明的第一及第二雜質原子類型之SIMS偵測極限通常位於101 4 至101 7 原子/立方公分之範圍中。特定言之，對於諸如硼及矽等元素而言，偵測極限通常約為101 5 原子/立方公分，而對於氮通常約為大於3 x 101 6 原子/立方公分。部分案例中，諸如燃燒分析、吸收、EPR等其他技術可提供更高敏感度。Typically, secondary ion mass spectrometry (SIMS) can be utilized to measure the concentration of the first and second impurity atom types in the diamond layer and the concentration of any other impurities. The detection limit of the impurity atoms varies depending on the SIMS conditions used. However, for the first and second impurity atom types of the present invention, detection limit of SIMS is typically in the range of 1014 - 7 at 1 to 10 / cm ^ of the. Certain words, for elements such as boron, silicon and the like, the detection limit is usually about 1015 atoms / cm ^, and for nitrogen usually about greater than 3 x 10 1 6 atoms / cc. In some cases, other technologies such as combustion analysis, absorption, EPR can provide higher sensitivity.

當第一及第二雜質原子類型分別為氮及矽、或反之為矽及氮時，鑽石層的大部份容積中之氮濃度較佳小於或等於2 x 101 7 原子/立方公分而鑽石層的大部份容積中之矽濃度較佳小於或等於2 x 101 8 原子/立方公分。利用此方式，可更易達成經合成鑽石中的高色度。When the first and second impurity atom types are nitrogen and silicon, or vice versa when silicon and nitrogen, the nitrogen concentration of the volume of the diamond layer most preferably less than or equal to 2 x 10 1 7 atoms / cc and the diamond the concentration of silicon in the majority volume of the layer is preferably less than or equal to 2 x 10 1 8 atoms / cc. In this way, high chroma in synthetic diamonds can be more easily achieved.

當第一及第二雜質原子類型分別為氮及矽、或反之為矽及氮時，鑽石層的大部份容積中之氮對於矽的濃度比值可能為1：20至20：1、1：10至10：1、1：9至9：1、1：8至8：1、1：7至7：1、1：6至6：1、1：5至5：1、1：4至4：1、1：3至3：1、1：2至2：1、較佳為1：1。When the first and second impurity atom types are nitrogen and helium, respectively, or vice versa, the concentration ratio of nitrogen to germanium in most of the diamond layer may be 1:20 to 20:1, 1: 10 to 10:1, 1:9 to 9:1, 1:8 to 8:1, 1:7 to 7:1, 1:6 to 6:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1, preferably 1:1.

當第一及第二雜質原子類型分別為氮及矽、或反之為矽及氮時，含氮氣體可能在合成大氣中以大於100 ppb、大於200 ppb、大於300 ppb之濃度出現，而含矽氣體可能在合成大氣中以大於10 ppb之濃度出現。When the first and second impurity atom types are nitrogen and helium, respectively, or vice versa, the nitrogen-containing gas may be present in the synthetic atmosphere at a concentration of more than 100 ppb, greater than 200 ppb, and greater than 300 ppb. The gas may appear in the synthetic atmosphere at concentrations greater than 10 ppb.

當第一及第二雜質原子類型分別為氮及硼、或反之為硼及氮時，鑽石層的大部份容積中氮濃度對於硼濃度之比值可能位於從1：2至2：1、從2：3至3：2、從3：4至4：3、從4：5至6：5、從9：10至11：10之範圍中，且該比值較佳為1：1。氮對於硼的比值較佳大於1：5。When the first and second impurity atom types are nitrogen and boron, respectively, or vice versa, the ratio of nitrogen concentration to boron concentration in most of the diamond layer may range from 1:2 to 2:1. 2:3 to 3:2, from 3:4 to 4:3, from 4:5 to 6:5, and from 9:10 to 11:10, and the ratio is preferably 1:1. The ratio of nitrogen to boron is preferably greater than 1:5.

當單替代硼及氮以近似相同濃度出現在鑽石中時，因為氮缺陷將電子捐至硼缺陷且所產生的離子化缺陷未導致顯著的光學吸收，故可產生無色材料。因此，不只硼在出現氮的情形下因為其抑制成長表面粗化之事實而對於成長具有一有利效應，併入鑽石之硼及氮可彼此補償以對於材料提供低光學吸收。When a single replacement of boron and nitrogen occurs in the diamond at approximately the same concentration, a colorless material can be produced because nitrogen defects donate electrons to boron defects and the resulting ionization defects do not result in significant optical absorption. Thus, not only does boron have a beneficial effect on growth in the presence of nitrogen because it inhibits the growth surface roughening, the boron and nitrogen incorporated into the diamond can compensate each other to provide low optical absorption for the material.

當第一及第二雜質原子類型分別為氮及硼、或反之為矽及氮時，含氮氣體可能在合成大氣中以大於100 ppb、較佳大於200 ppb、較佳大於300 ppb之濃度出現，而含硼氣體可能在合成大氣中以大於0.5 ppb之濃度出現。When the first and second impurity atom types are nitrogen and boron, respectively, or vice versa, the nitrogen-containing gas may be present in the synthetic atmosphere at a concentration greater than 100 ppb, preferably greater than 200 ppb, preferably greater than 300 ppb. And the boron-containing gas may appear in the synthetic atmosphere at a concentration greater than 0.5 ppb.

任意上述方法所產生之CVD鑽石層相較於一其中未添加含有第二雜質原子類型的第二氣體之方法較佳係具有一增加的經正規化自由激子強烈度。較佳具有在77 K測量的陰極發光頻譜中之一強烈自由激子發光，其中自由激子發光的積集強烈度係超過高純度條件下所成長的一均質磊晶CVD鑽石樣本之積集自由激子發光強烈度之0.3、較佳超過0.4、較佳超過0.5、較佳超過0.6、較佳超過0.7、較佳超過0.8、較佳超過0.9。The CVD diamond layer produced by any of the above methods preferably has an increased normalized exciton intensity compared to a method in which the second gas containing the second impurity atom type is not added. It is preferred to have one of the strong free exciton luminescence in the cathodoluminescence spectrum measured at 77 K, wherein the accumulation of free exciton luminescence is more than the accumulation of a homogeneous epitaxial CVD diamond sample grown under high purity conditions. The exciton luminescence intensity is 0.3, preferably more than 0.4, preferably more than 0.5, preferably more than 0.6, preferably more than 0.7, preferably more than 0.8, preferably more than 0.9.

任何上述方法所產生之CVD鑽石層相較於一其中未添加包含第二雜質原子類型的第二氣體之方法係可具有載體活動力、載體壽命、電荷收集距離及/或電荷收集效率之增加。所產生的鑽石層之電荷收集距離以1.0伏特/微米的施加電場測量時係可能大於100微米、大於150微米、大於200微米、大於300微米、大於500微米、或大於1000微米。一用以測量鑽石中電荷收集距離之方法係譬如描述於WO 01/96633號中。所產生鑽石層的載體活動力可為1200公分2 伏特－ 1 秒－ 1 、較佳1500公分2 伏特－ 1 秒－ 1 、較佳1800公分2 伏特－ 1 秒－ 1 、較佳2200公分2 伏特－ 1 秒－ 1 、較佳2500公分2 伏特－ 1 秒－ 1 。所產生的鑽石層之電荷收集效率較佳為30%、較佳50%、較佳70%、較佳80%、較佳90%、較佳95%、較佳97%。所產生鑽石層的載體壽命可大於1奈秒、大於3奈秒、大於10奈秒、大於30奈秒、或大於100奈秒。The CVD diamond layer produced by any of the above methods may have an increase in carrier activity, carrier lifetime, charge collection distance, and/or charge collection efficiency as compared to a method in which a second gas comprising a second impurity atom type is not added. The charge collection distance of the resulting diamond layer may be greater than 100 microns, greater than 150 microns, greater than 200 microns, greater than 300 microns, greater than 500 microns, or greater than 1000 microns as measured by an applied electric field of 1.0 volts/micron. A method for measuring the charge collection distance in a diamond is as described in WO 01/96633. The carrier activity of the resulting diamond layer may be 1200 cm 2 volts - 1 sec - 1 , preferably 1500 cm 2 volts - 1 second - 1 , preferably 1800 cm 2 volts - 1 second - 1 , preferably 2200 cm 2 volts - 1 second - 1 , preferably 2500 cm 2 volts - 1 second - 1 . The charge collection efficiency of the resulting diamond layer is preferably 30%, preferably 50%, preferably 70%, preferably 80%, preferably 90%, preferably 95%, preferably 97%. The carrier lifetime of the resulting diamond layer can be greater than 1 nanosecond, greater than 3 nanoseconds, greater than 10 nanoseconds, greater than 30 nanoseconds, or greater than 100 nanoseconds.

已知身為雜質之氮係會影響單晶CVD鑽石的電子性質，特別是電荷收集距離、載體活動力及載體壽命。若缺乏氮，單晶CVD鑽石的電子性質將會很好(譬如請見依斯柏格(Isberg)等人，Science，Vol.297，1970－1672頁，其中揭露了測量方法及結果)。隨著氮漸進地添加至合成大氣，所產生材料的電子性質係漸進地劣化。It is known that nitrogen as an impurity affects the electronic properties of single crystal CVD diamonds, particularly charge collection distance, carrier activity, and carrier lifetime. In the absence of nitrogen, the electronic properties of single crystal CVD diamonds will be very good (see, for example, Isberg et al., Science, Vol. 297, pp. 1970-1672, which discloses measurement methods and results). As the nitrogen is gradually added to the synthetic atmosphere, the electronic properties of the resulting material are progressively deteriorated.

先前實驗已經顯示在77 K測量處於235奈米之自由激子發射的強烈度係為電子性質之良好代理物(WO 01/96633)。利用此代理物，吾人能夠提供對於鑽石之經合併的氮及矽添加物之下列預期表現。Previous experiments have shown that the intensity of the free exciton emission at 235 nm measured at 77 K is a good agent of electronic properties (WO 01/96633). Using this agent, we are able to provide the following expected performance for the combined nitrogen and niobium additions to the diamond.

如果對於氮添加矽，氮對於電子性質之有害效應受到改良，其中隨著添加的矽濃度增加，改良量增加但改良速率減小，直到採行某比例之氮濃度為止，添加進一步的矽不再具有進一步改良效應在該點性質將開始再度劣化。If hydrazine is added to nitrogen, the harmful effects of nitrogen on the electronic properties are improved, and as the concentration of stront added increases, the amount of modification increases but the rate of improvement decreases until a certain proportion of nitrogen concentration is applied, and further enthalpy is added. There is a further improvement effect at which point the properties will begin to deteriorate again.

因此，將具有可對於固體中的一給定氮量添加之一最適矽量，但最適數值係依據所考慮的確切性質及所併入的氮量而定。發明人預期矽添加物相對於其在電子性質上的效應之最適數值係概括略小於使鑽石色度開始劣化(亦即，矽所造成的灰度開始變得明顯)之矽添加物。Thus, there will be one that is optimal for the addition of a given amount of nitrogen in the solid, but the optimum values will depend on the exact nature of the consideration and the amount of nitrogen incorporated. The inventors expect that the optimum value of the enthalpy additive relative to its effect on the electronic properties is generally less than the enthalpy additive that causes the diamond chromaticity to begin to degrade (i.e., the gradation caused by enthalpy begins to become apparent).

因此，含有一給定氮濃度及不同矽濃度(介於從恰高於零至穩超過最適值之間)的一系列鑽石係可能比起一原本相同之不含矽的鑽石具有可略微更好、遠為更好、相同或更差之電子性質。Therefore, a series of diamonds containing a given concentration of nitrogen and different concentrations of germanium (between just above zero and above the optimum) may be slightly better than an otherwise diamond-free diamond. Far better, the same or worse electronic properties.

本發明的一鑽石同樣地可能具有不良的電子性質(亦即，矽濃度穩超過最適值)，但如矽所造成的灰度之良好的光學性質尚未變成足以以一色變被認知或造成光學吸收頻譜之一顯著變化。A diamond of the present invention may likewise have poor electronic properties (i.e., the cerium concentration is stable above the optimum value), but the good optical properties of gradation such as yttrium have not become sufficient to be recognized or optically absorbed by one color change. One of the spectrum changes significantly.

一類似情況係有關於將硼添加至一含有鑽石之合成大氣。起初，硼係改良氮的有害效應而電子性質獲得改善。隨著所添加硼量的增加，或許當氮及硼量近似相等時，電子性質的改良將停止，且隨後藉由較高的添加速率而開始下降。可藉由一古典半導體補償模型來瞭解此表現。性質的改良及後續下降之速率預期遠比氮及矽的案例更為敏銳。A similar situation relates to the addition of boron to a synthetic atmosphere containing diamonds. Initially, boron improved the harmful effects of nitrogen and improved the electronic properties. As the amount of boron added increases, perhaps when the amounts of nitrogen and boron are approximately equal, the improvement in electronic properties will cease and then begin to decrease by a higher rate of addition. This performance can be understood by a classical semiconductor compensation model. The improvement in properties and the rate of subsequent decline are expected to be far more acute than in the case of nitrogen and helium.

包含第一雜質原子類型之第一氣體可能被刻意地添加至合成大氣。或者，第一氣體可無意地出現在合成大氣中，包括因為即便其影響所產生鑽石層的性質但其尚未被移除而出現在合成大氣中。合成大氣較佳係包含尚未刻意地添加之大於0.1 ppb、較佳大於1 ppb、較佳大於10 ppb之一濃度的第一氣體。此情況的一範例係為氮譬如以NH3 、空氣或N2 H4 形式留置在合成大氣中，且其被認為太昂貴或耗時而無法採行額外措施自合成大氣移除此等氣體。合成大氣較佳係包含尚未刻意被添加之大於300 ppb的濃度之含氮氣體。A first gas containing a first impurity atom type may be deliberately added to the synthesis atmosphere. Alternatively, the first gas may unintentionally appear in the synthetic atmosphere, including because it affects the nature of the diamond layer produced but it has not been removed and appears in the synthetic atmosphere. Preferably, the synthetic atmosphere comprises a first gas which has not been intentionally added at a concentration greater than 0.1 ppb, preferably greater than 1 ppb, preferably greater than 10 ppb. An example of this case to tie such NH 3, N 2 H 4 or air left in the form of nitrogen in the synthesis atmosphere, and it is considered too expensive or time-consuming and can not adopt additional measures to remove such gases from the synthesis atmosphere. Preferably, the synthetic atmosphere comprises a nitrogen-containing gas having a concentration of greater than 300 ppb that has not been intentionally added.

第一氣體可以一受控制方式或以一未受控制方式出現在合成大氣中。若是第一氣體以一未受控制方式出現，第一雜質類型原子可以鑽石合成所需要氣體之一者的一雜質出現。或者，若是以一受控制方式添加第一氣體，如此可只具有可導入合成大氣中之氣體量的一上限。或者，第一氣體的出現可受到控制以使第一氣體的濃度為穩定以優於20%、較佳優於10%、較佳優於3%。The first gas may be present in the synthetic atmosphere in a controlled manner or in an uncontrolled manner. If the first gas is present in an uncontrolled manner, the first impurity type atom may be present as an impurity of one of the gases required for diamond synthesis. Alternatively, if the first gas is added in a controlled manner, it may have only an upper limit of the amount of gas that can be introduced into the synthesis atmosphere. Alternatively, the presence of the first gas may be controlled such that the concentration of the first gas is stabilized to be better than 20%, preferably better than 10%, preferably better than 3%.

鑽石層較佳大於0.1公厘厚度、較佳大於0.5公厘厚度、較佳大於1公厘厚度、較佳大於2公厘厚度。The diamond layer is preferably greater than 0.1 mm thick, preferably greater than 0.5 mm thick, preferably greater than 1 mm thick, and preferably greater than 2 mm thick.

第一實施例的方法中：(1)基材可為一鑽石基材，其具有一大致無結晶缺陷之表面所以一顯露電漿蝕刻將顯露出與低於5 x 103 /平方公厘的缺陷相關之一表面蝕刻特性密度；(2)鑽石層的合成之時程可能至少為50小時；及/或(3)基材可包含多重分離的單晶鑽石基材。In the method of the first embodiment: (1) the substrate may be a diamond substrate having a surface substantially free of crystal defects so that a plasma etch will be revealed to be less than 5 x 10 3 /cm 2 . One of the surface etch characteristic densities associated with the defect; (2) the time course of synthesis of the diamond layer may be at least 50 hours; and/or (3) the substrate may comprise multiple separated single crystal diamond substrates.

該方法可包含至少一個、較佳至少兩個、較佳全部三個的特性(1)至(3)。該方法可包含特性(1)、特性(2)、特性(3)、特性(1)及(2)、特性(1)及(3)、特性(2)及(3)、特性(1)、(2)及(3)。The method may comprise at least one, preferably at least two, preferably all three of the characteristics (1) to (3). The method may include characteristics (1), characteristics (2), characteristics (3), characteristics (1) and (2), characteristics (1) and (3), characteristics (2) and (3), and characteristics (1). , (2) and (3).

利用一具有一大致無結晶缺陷的表面之鑽石基材，可大幅改良所成長鑽石的品質。特定言之，在所成長鑽石層中將出現較少個特性。The use of a diamond substrate having a surface that is substantially free of crystal defects can greatly improve the quality of the diamond being grown. In particular, fewer features will appear in the growing diamond layer.

基材可為諸如等上述1)中之單一鑽石基材。或者，基材可為複數個分離的單晶鑽石基材。複數個基材較佳呈側向分離。複數個單晶鑽石基材各可如上述特性1)大致無結晶缺陷。複數個側向分離的單晶鑽石基材可在大致相同的成長條件下同時地成長在相同合成系統中。The substrate may be a single diamond substrate such as in the above 1). Alternatively, the substrate can be a plurality of separate single crystal diamond substrates. The plurality of substrates are preferably laterally separated. Each of the plurality of single crystal diamond substrates may have substantially no crystal defects as described above. A plurality of laterally separated single crystal diamond substrates can be simultaneously grown in the same synthesis system under substantially the same growth conditions.

該方法可包含使用分離的多重單晶鑽石基材。較佳具有大於5、大於20、大於50、大於80、大於100、大於120、大於150、大於200個單晶基材。利用此等多重分離的單晶鑽石基材係可產生多重單晶鑽石層。或者，可產生在至少一方向中側向地延伸大於30公厘、較佳大於60公厘、較佳大於90公厘、較佳大於110公厘、較佳大於130公厘之多晶鑽石層。The method can include the use of a separate multiple single crystal diamond substrate. Preferably, it has greater than 5, greater than 20, greater than 50, greater than 80, greater than 100, greater than 120, greater than 150, and greater than 200 single crystal substrates. The use of such multiple-separated single crystal diamond substrates produces multiple single crystal diamond layers. Alternatively, a polycrystalline diamond layer extending laterally in at least one direction by more than 30 mm, preferably more than 60 mm, preferably more than 90 mm, preferably more than 110 mm, preferably more than 130 mm, may be produced. .

鑽石層的合成時程可至少為50小時、至少75小時、至少100小時、至少150小時。The diamond layer may have a synthetic time course of at least 50 hours, at least 75 hours, at least 100 hours, and at least 150 hours.

本發明的第二實施例中，提供有一製造一CVD鑽石層之方法，包含：(i)提供一基材；(ii)提供一CVD合成大氣，其中存在有大於300 ppb之未刻意添加的一氮濃度；及(iii)將一包含一並非氮的第二雜質原子類型之第二氣體添加至合成大氣中，In a second embodiment of the present invention, there is provided a method of making a CVD diamond layer comprising: (i) providing a substrate; (ii) providing a CVD synthesis atmosphere in which there is an unintentionally added one of greater than 300 ppb a nitrogen concentration; and (iii) adding a second gas comprising a second impurity atom type other than nitrogen to the synthesis atmosphere,

其中第二雜質原子類型係以一降低氮所造成對於色度的有害效應之數量以一受控制方式添加，藉以產生一具有高色度的鑽石層；及第二雜質原子類型在元素狀態中為固體。Wherein the second impurity atom type is added in a controlled manner by a reduced amount of chromogenic effects caused by nitrogen reduction, thereby producing a diamond layer having a high chroma; and the second impurity atom type is in the element state solid.

利用此方式，即便合成大氣包含在缺乏第二氣體時將對於所產生鑽石的色度具有不良效應使得所產生鑽石不具有高色度之一氮量，仍可產生一具有高色度的CVD鑽石層。第二實施例的方法係能夠合成高色度CVD鑽石而不必採取任何額外步驟來從合成大氣移除不良的氮。“高色度”用語係如先前所界定。鑽石層較佳具有很高色度，如先前所界定。In this way, even if the synthetic atmosphere is contained in the absence of the second gas, it will have an adverse effect on the chromaticity of the produced diamond so that the produced diamond does not have a high chroma one nitrogen, and a high chroma CVD diamond can be produced. Floor. The method of the second embodiment is capable of synthesizing high chroma CVD diamonds without having to take any additional steps to remove undesirable nitrogen from the synthetic atmosphere. The term "high chroma" is as previously defined. The diamond layer preferably has a very high chroma, as previously defined.

本發明的第二實施例中，CVD鑽石層可為單晶。或者，本發明的第二實施例中，CVD鑽石層可為多晶。In a second embodiment of the invention, the CVD diamond layer can be a single crystal. Alternatively, in a second embodiment of the invention, the CVD diamond layer may be polycrystalline.

上文所勾勒之本發明的方法之第一實施例的較佳特性係同樣地適用於本發明的方法之第二實施例，只要第一源氣體包含氮即可。The preferred features of the first embodiment of the method of the invention outlined above are equally applicable to the second embodiment of the method of the invention, as long as the first source gas comprises nitrogen.

特定言之，第二雜質原子類型可為硼、矽、磷或硫。第二雜質原子類型較佳為矽。In particular, the second impurity atom type may be boron, germanium, phosphorus or sulfur. The second impurity atom type is preferably ruthenium.

本發明的第二實施例之方法中，可以一未控制方式來添加未刻意添加至合成大氣之氮的濃度。除了未刻意添加至合成大氣之氮的濃度外，可將額外的氮刻意添加至合成大氣。In the method of the second embodiment of the present invention, the concentration of nitrogen that is not intentionally added to the synthetic atmosphere can be added in an uncontrolled manner. In addition to the concentration of nitrogen that is not intentionally added to the synthetic atmosphere, additional nitrogen can be deliberately added to the synthetic atmosphere.

本發明的第三實施例中，提供有一產生一CVD鑽石層之方法，包含以下步驟：(i)提供一基材；及(ii)將一含矽的氣態源添加至一CVD合成大氣中。In a third embodiment of the invention, a method of producing a CVD diamond layer is provided, comprising the steps of: (i) providing a substrate; and (ii) adding a gaseous source comprising ruthenium to a CVD synthesis atmosphere.

利用此方式，提供一經矽摻雜鑽石層。較佳，在本發明的第三實施例中，CVD鑽石層為單晶。或者，本發明的第三實施例中，CVD鑽石層為多晶。In this way, a tantalum doped diamond layer is provided. Preferably, in the third embodiment of the invention, the CVD diamond layer is a single crystal. Alternatively, in a third embodiment of the invention, the CVD diamond layer is polycrystalline.

第三實施例的方法中：(1)該層可成長至大於0.1公厘厚度；(2)該基材可為一具有一大致無結晶缺陷的表面之鑽石基材，使得一顯露電漿蝕刻將顯露出低於5 x 103 /平方公厘之與缺陷相關之一表面蝕刻特性密度；(3)單晶鑽石層的合成時程可至少為50小時；及/或(4)基材可包含多重分離的單晶鑽石基材。In the method of the third embodiment: (1) the layer can be grown to a thickness greater than 0.1 mm; (2) the substrate can be a diamond substrate having a surface substantially free of crystal defects, such that a plasma etching is exposed A surface etch characteristic density of less than 5 x 10 3 /cm ^ 2 associated with the defect will be revealed; (3) the synthesis time of the single crystal diamond layer can be at least 50 hours; and / or (4) the substrate can be A single crystal diamond substrate comprising multiple separations.

該方法可包含至少一個、至少兩個、至少三個、較佳全部四個特性(1)至(4)。該方法可包含特性(1)，特性(1)，特性(3)，特性(4)，特性(1)及(2)，特性(1)及(3)，特性(1)及(4)，特性(2)及(3)，特性(2)及(4)，特性(3)及(4)，特性(1)、(2)及(3)，特性(1)、(3)及(4)，特性(2)、(3)及(4)。The method may comprise at least one, at least two, at least three, and preferably all four characteristics (1) to (4). The method may include characteristics (1), characteristics (1), characteristics (3), characteristics (4), characteristics (1) and (2), characteristics (1) and (3), characteristics (1) and (4). , characteristics (2) and (3), characteristics (2) and (4), characteristics (3) and (4), characteristics (1), (2) and (3), characteristics (1), (3) and (4), characteristics (2), (3) and (4).

該層可成長至大於0.5公厘、大於1公厘、大於2公厘之一厚度。The layer can be grown to a thickness greater than 0.5 mm, greater than 1 mm, and greater than 2 mm.

鑽石層的合成時程可為至少50小時、至少75小時、至少100小時、至少150小時。The synthetic time course of the diamond layer can be at least 50 hours, at least 75 hours, at least 100 hours, at least 150 hours.

該方法可包含使用多重分離的單晶鑽石基材。較佳具有大於5、較佳大於20、較佳大於50個單晶基材。利用此等分離的單晶鑽石基材可產生多重單晶鑽石層。或者，可產生在至少一方向中側向地延伸大於30公厘、較佳大於60公厘、較佳大於90公厘、較佳大於110公厘、較佳大於130公厘之多晶鑽石層。The method can include the use of multiple isolated single crystal diamond substrates. It preferably has more than 5, preferably more than 20, preferably more than 50 single crystal substrates. Multiple single crystal diamond layers can be produced using such separate single crystal diamond substrates. Alternatively, a polycrystalline diamond layer extending laterally in at least one direction by more than 30 mm, preferably more than 60 mm, preferably more than 90 mm, preferably more than 110 mm, preferably more than 130 mm, may be produced. .

上文所勾勒之本發明的方法之第一實施例的較佳特性係同樣地適用於本發明的方法之第三實施例，只要第一或第二源氣體包含矽即可。The preferred features of the first embodiment of the method of the invention outlined above are equally applicable to the third embodiment of the method of the invention, as long as the first or second source gas comprises helium.

本發明的方法之第三實施例所產生之鑽石層的大部份101 4 原子/立方公分至2 x 101 8 原子/立方公分、從3 x 101 4 原子/立方公分至101 7 原子/立方公分、從101 5 原子/立方公分至3 x 101 6 原子/立方公分、從3 x 101 5 原子/立方公分至101 6 原子/立方公分、從2 x 101 7 原子/立方公分至2 x 101 8 原子/立方公分。Most diamond 1014 atomic layer of the third embodiment of the method of the present invention arising / cc to 2 x 10 1 8 atoms / cm ^, from 3 x 10 1 4 atoms / cc to 1017 atoms / cubic centimeter, from 1015 atoms / cm ^ to 3 x 10 1 6 atoms / cm ^, from 3 x 10 1 5 atoms / cubic centimeter to 1016 atoms / cubic centimeter, from 2 x 10 1 7 atoms /cubic centimeters to 2 x 10 1 8 atoms / cubic centimeter.

本發明的方法之第三實施例中，矽的添加可降低由於出現一雜質原子類型所造成對於所產生鑽石層的性質之有害效應。雜質原子類型較佳為氮。雜質原子類型可以一受控制或未受控制方式以一氣體被導入合成大氣中，如前文所述。雜質原子類型較佳為氮，且合成大氣包含大於300 ppb之未刻意添加的一氮濃度。In a third embodiment of the method of the present invention, the addition of niobium reduces the deleterious effects on the properties of the diamond layer produced due to the presence of an impurity atom type. The impurity atom type is preferably nitrogen. The impurity atom type can be introduced into the synthesis atmosphere as a gas in a controlled or uncontrolled manner, as previously described. The impurity atom type is preferably nitrogen, and the synthetic atmosphere contains an unintentionally added nitrogen concentration of more than 300 ppb.

該性質可為色度，而添加氮可產生一具有高色度的CVD鑽石層，其中“高色度”係如上文所定義。CVD鑽石層較佳具有很高色度，其中“很高色度”係如上文所定義。This property can be chromaticity, and the addition of nitrogen produces a CVD diamond layer with high chroma, where "high chroma" is as defined above. The CVD diamond layer preferably has a very high chroma, wherein "very high chroma" is as defined above.

該性質可為鑽石層的自由激子發射，而添加矽可產生一相較於一其中未添加矽之方法具有增加的經正規化自由激子強烈度之CVD鑽石層。可能具有在77 K測量的陰極發光頻譜中之一強烈自由激子發光，其中自由激子發光的積集強烈度係超過高純度條件下所成長的一均質磊晶CVD鑽石樣本之積集自由激子發光強烈度之0.3、較佳超過0.4、較佳超過0.5、較佳超過0.6、較佳超過0.7、較佳超過0.8、較佳超過0.9。This property can be a free exciton emission of the diamond layer, while the addition of germanium can result in a CVD diamond layer having an increased normalized exciton intensity compared to a method in which no germanium is added. There may be one strong free exciton luminescence in the cathodoluminescence spectrum measured at 77 K, where the accumulation of free exciton luminescence is more than the accumulation of a homogeneous epitaxial CVD diamond sample grown under high purity conditions. The sub-luminous intensity is 0.3, preferably more than 0.4, preferably more than 0.5, preferably more than 0.6, preferably more than 0.7, preferably more than 0.8, preferably more than 0.9.

該性質可為下列至少一者：載體活動力、載體壽命、電荷收集距離，而添加矽可產生一相較於一其中未添加矽之方法具有增加的載體活動力、載體壽命及/或電荷收集距離之CVD鑽石層。所產生的鑽石層之電荷收集距離以1.0伏特/微米的施加電場測量時係可能大於100微米、大於150微米、大於200微米、大於300微米、大於500微米、大於1000微米。所產生鑽石層的載體活動力可為1200公分2 伏特－ 1 秒－ 1 、較佳1500公分2 伏特－ 1 秒－ 1 、較佳1800公分2 伏特－ 1 秒－ 1 、較佳2200公分2 伏特－ 1 秒－ 1 、較佳2500公分2 伏特－ 1 秒－ 1 。所產生的鑽石層之電荷收集效率較佳為30%、較佳50%、較佳70%、較佳80%、較佳90%、較佳95%、較佳97%。所產生鑽石層的載體壽命可大於1奈秒、大於3奈秒、大於10奈秒、大於30奈秒、大於100奈秒。The property can be at least one of: carrier activity, carrier lifetime, charge collection distance, and the addition of hydrazine can result in increased carrier activity, carrier lifetime, and/or charge collection compared to a method in which strontium is not added. Distance to the CVD diamond layer. The charge collection distance of the resulting diamond layer may be greater than 100 microns, greater than 150 microns, greater than 200 microns, greater than 300 microns, greater than 500 microns, greater than 1000 microns as measured by an applied electric field of 1.0 volts/micron. The carrier activity of the resulting diamond layer may be 1200 cm 2 volts - 1 sec - 1 , preferably 1500 cm 2 volts - 1 second - 1 , preferably 1800 cm 2 volts - 1 second - 1 , preferably 2200 cm 2 volts - 1 second - 1 , preferably 2500 cm 2 volts - 1 second - 1 . The charge collection efficiency of the resulting diamond layer is preferably 30%, preferably 50%, preferably 70%, preferably 80%, preferably 90%, preferably 95%, preferably 97%. The carrier lifetime of the resulting diamond layer can be greater than 1 nanosecond, greater than 3 nanoseconds, greater than 10 nanoseconds, greater than 30 nanoseconds, and greater than 100 nanoseconds.

任何上述方法(亦即對於第一、第二及第三實施例)中，當CVD鑽石層為單晶時，鑽石層的大部份容積可具有下列特性的至少一者：a)在室溫測量之一吸收頻譜藉以使一標準0.5 ct圓形明亮式的色度將優於K；b)在室溫測量處於270奈米之小於1.9公分－ 1 的一吸收係數；c)在室溫測量處於350奈米之小於0.90公分－ 1 的一吸收係數；d)處於520奈米之小於0.30公分－ 1 的一吸收；或e)處於700奈米之小於0.12公分－ 1 的一吸收。In any of the above methods (i.e., for the first, second, and third embodiments), when the CVD diamond layer is a single crystal, a majority of the volume of the diamond layer can have at least one of the following characteristics: a) at room temperature One of the absorption spectra is measured so that a standard 0.5 ct circular brilliant chromaticity will be better than K; b) an absorption coefficient of less than 1.9 cm - 1 at 270 nm is measured at room temperature; c) measured at room temperature An absorption coefficient of less than 0.90 cm - 1 at 350 nm; d) an absorption of less than 0.30 cm - 1 at 520 nm; or e) an absorption of less than 0.12 cm - 1 at 700 nm.

鑽石層的大部份容積可包含至少55%、較佳至少60%、較佳至少70%、較佳至少80%、較佳至少90%、較佳至少95%的鑽石層。A majority of the volume of the diamond layer may comprise at least 55%, preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%, preferably at least 95% of the diamond layer.

單晶鑽石層可具有至少兩個、至少三個、至少四個、較佳全部五個特性(a)至(e)。鑽石層可具有特性a)及b)；特性a)及c)；a)及d)；a)及e)；b)及c)；b)及d)；b)及e)；c)及d)；c)及e)；d)及e)；a)、b)及c)；a)、b)及d)；a)、b)及e)；a)、c)及d)；a)、c)及e)；a)、d)及e)；b)、c)及d)；b)、c)及e)；b)、d)及e)；c)、d)及e)；a)、b)、c)及d)；a)、b)、c)及e)；a)、b)、d)及e)；a)、c)、d)及e)；b)、c)、d)及e)；或a)、b)、c)、d)及e)。The single crystal diamond layer may have at least two, at least three, at least four, and preferably all five characteristics (a) to (e). The diamond layer may have characteristics a) and b); characteristics a) and c); a) and d); a) and e); b) and c); b) and d); b) and e); And d); c) and e); d) and e); a), b) and c); a), b) and d); a), b) and e); a), c) and d ); a), c) and e); a), d) and e); b), c) and d); b), c) and e); b), d) and e); c), d) and e); a), b), c) and d); a), b), c) and e); a), b), d) and e); a), c), d) And e); b), c), d) and e); or a), b), c), d) and e).

較佳地，對於特性a)，鑽石層具有在室溫測量的一吸收頻譜藉以使一標準0.5 ct圓形明亮式的色度將優於J、較佳優於I、較佳優於H、較佳優於G、較佳優於F、較佳優於E、較佳為D。Preferably, for characteristic a), the diamond layer has an absorption spectrum measured at room temperature such that a standard 0.5 ct circular brilliant chromaticity will be better than J, preferably better than I, preferably better than H, Preferably, it is better than G, preferably better than F, preferably better than E, and more preferably D.

較佳地，對於特性b)，鑽石層具有小於1.0公分－ 1 ；較佳小於0.4公分－ 1 之在室溫測量處於270奈米的一吸收係數。Preferably, for characteristic b), the diamond layer has an absorption coefficient of less than 1.0 cm - 1 ; preferably less than 0.4 cm - 1 at room temperature measured at 270 nm.

較佳地，對於特性c)，鑽石層具有小於0.5公分－ 1 ；較佳小於0.2公分－ 1 之在室溫測量處於350奈米的一吸收係數。Preferably, for characteristic c), the diamond layer has an absorption coefficient of less than 0.5 cm - 1 ; preferably less than 0.2 cm - 1 at room temperature measured at 350 nm.

較佳地，對於特性d)，鑽石層具有小於0.14公分－ 1 ；較佳小於0.06公分－ 1 之在室溫測量處於520奈米的一吸收係數。Preferably, for characteristic d), the diamond layer has an absorption coefficient of less than 0.14 cm - 1 ; preferably less than 0.06 cm - 1 at room temperature measured at 520 nm.

較佳地，對於特性e)，鑽石層具有小於0.06公分－ 1 ；較佳小於0.03公分－ 1 之在室溫測量處於700奈米的一吸收係數。Preferably, for the characteristic E), the diamond layer has less than 0.06 cm --1; preferably less than 0.03 cm --1 measured at room temperature of the absorption coefficient at a 700 nm.

在任何上述方法中(亦即，有關第一、第二及第三實施例)，當CVD層為多晶時，鑽石層的大部份容積可具有至少一項下列特性：a)小於1.9公分－ 1 之在室溫測量處於270奈米的一吸收係數；b)小於0.90公分－ 1 之在室溫測量處於350奈米的一吸收係數；c)小於0.30公分－ 1 之處於520奈米的一吸收；及d)小於0.12公分－ 1 之處於700奈米的一吸收。In any of the above methods (i.e., with respect to the first, second, and third embodiments), when the CVD layer is polycrystalline, a majority of the volume of the diamond layer can have at least one of the following characteristics: a) less than 1.9 cm. --1 measured at room temperature in the 270 nm absorption coefficient a; b) is less than 0.90 cm --1 measured at room temperature in the 350 nm absorption coefficient a; c) is less than 0.30 cm --1 at 520 nm of an absorbent; and d) less than 0.12 cm --1 of absorption in a 700 nm.

多晶鑽石層可具有特性a)，特性b)，特性c)，特性d)，特性a)及b)，特性a)及c)，特性a)及d)，特性b)及c)，特性b)及d)，特性c)及d)，特性a)、b)及c)、特性a)、b)及d)，特性a)、c)及d)，特性b)、c)及d)，或特性a)、b)、c)及d)。The polycrystalline diamond layer may have characteristics a), properties b), properties c), properties d), properties a) and b), properties a) and c), properties a) and d), properties b) and c), Characteristics b) and d), characteristics c) and d), characteristics a), b) and c), characteristics a), b) and d), characteristics a), c) and d), characteristics b), c) And d), or characteristics a), b), c) and d).

較佳地，對於特性a)，鑽石層具有小於1.0公分－ 1 ；較佳小於0.4公分－ 1 之在室溫測量處於270奈米的一吸收係數。Preferably, for characteristic a), the diamond layer has an absorption coefficient of less than 1.0 cm - 1 ; preferably less than 0.4 cm - 1 at room temperature measured at 270 nm.

較佳地，對於特性b)，鑽石層具有小於0.5公分－ 1 ；較佳小於0.2公分－ 1 之在室溫測量處於350奈米的一吸收係數。Preferably, for characteristic b), the diamond layer has an absorption coefficient of less than 0.5 cm - 1 ; preferably less than 0.2 cm - 1 at room temperature measured at 350 nm.

較佳地，對於特性c)，鑽石層具有小於0.14公分－ 1 ；較佳小於0.06公分－ 1 之在室溫測量處於520奈米的一吸收係數。Preferably, for characteristic c), the diamond layer has an absorption coefficient of less than 0.14 cm - 1 ; preferably less than 0.06 cm - 1 at room temperature measured at 520 nm.

較佳地，對於特性d)，鑽石層具有小於0.06公分－ 1 ；較佳小於0.03公分－ 1 之在室溫測量處於700奈米的一吸收係數。Preferably, for the characteristics d), the diamond layer has less than 0.06 cm --1; preferably less than 0.03 cm --1 measured at room temperature of the absorption coefficient at a 700 nm.

在其中CVD為單晶之任何上述方法中，鑽石層較佳形成至一具有三個大於2公厘的正交維度之寶石中，其中至少一軸線設置為沿著<100>結晶方向或沿著寶石的主要對稱軸線。In any of the above methods wherein CVD is a single crystal, the diamond layer is preferably formed into a gemstone having three orthogonal dimensions greater than 2 mm, wherein at least one axis is disposed along the <100> crystallographic direction or along The main axis of symmetry of the gemstone.

根據本發明，提供有由上文揭露的任一方法所產生之一CVD鑽石層。According to the present invention, there is provided a CVD diamond layer produced by any of the methods disclosed above.

若是CVD層為單晶，鑽石層的大部份容積可自單一成長段形成。If the CVD layer is a single crystal, most of the volume of the diamond layer can be formed from a single growth section.

鑒於因為成長期間表面粗化降低使得任何上述本發明的方法所產生之鑽石層中的缺陷減少，鑽石層亦可具有改良的機械及化學性質，包括抗磨性及熱穩定度。一材料的磨耗性質係為一寬廣範圍的材料巨觀性質(譬如包括其硬度、強度、勁度、韌性、顆粒尺寸、熱傳導性、顆粒定向等)之間的很複雜交互作用之結果。此技藝中已知鑽石具有優異的磨耗性質且廣泛予以利用：將其使用在包括切割工具、岩石鑽孔(rock drill)、導線壓模(wire dies)及許多其他應用等之一寬廣應用範圍中作為一工具材料。In view of the reduced defects in the diamond layer produced by any of the above methods of the present invention due to reduced surface roughening during growth, the diamond layer may also have improved mechanical and chemical properties, including abrasion resistance and thermal stability. The wear properties of a material are the result of a very complex interaction between a broad range of material macroscopic properties, including, for example, hardness, strength, stiffness, toughness, particle size, thermal conductivity, particle orientation, and the like. Diamonds are known in the art to have excellent attrition properties and are widely used: they are used in a wide range of applications including cutting tools, rock drills, wire dies, and many other applications. As a tool material.

鑽石工具在特定應用中之效能係強烈地受其微結構所影響，且在特定單晶鑽石的案例中受到點及延伸缺陷密度所影響。一特定範例係為如WO2004/074557號所揭露之一導線抽引壓模，其中顯示藉由控制延伸缺陷密度來降低應變係對於改良磨耗性質特別有效。因為本發明的方法相較於使用概括相同方法但無添加第二雜質所製備之鑽石而言可對於單晶鑽石材料提供降低的點及延伸缺陷密度，可合理地預期本發明的材料將具有經改良的磨耗性質。The effectiveness of diamond tools in specific applications is strongly influenced by their microstructure and is affected by point and extended defect densities in the case of specific single crystal diamonds. A specific example is a wire drawing die as disclosed in WO 2004/074557, wherein it is shown that reducing the strain system by controlling the elongation defect density is particularly effective for improving the wear properties. Since the method of the present invention provides reduced dots and extended defect densities for single crystal diamond materials as compared to diamonds prepared using the same general method but without the addition of a second impurity, it is reasonable to expect that the materials of the present invention will have Improved wear properties.

根據本發明，亦提供一CVD鑽石層，其包含選自矽、硫或磷之一雜質原子類型，其中鑽石層具有高色度。According to the present invention, there is also provided a CVD diamond layer comprising one of the impurity atom types selected from the group consisting of ruthenium, sulfur or phosphorus, wherein the diamond layer has a high chroma.

根據本發明，提供一CVD鑽石層，其包含選自矽、硫或磷之一雜質原子類型，其中鑽石層的大部份容積中之雜質原子類型的濃度係為從101 4 至2 x 101 8 原子/立方公分。鑽石層的大部份容積中之矽濃度係可大於101 3 原子/立方公分、大於101 4 原子/立方公分、大於3 x 101 4 原子/立方公分、大於101 5 原子/立方公分、大於3 x 101 5 原子/立方公分、大於101 6 原子/立方公分、大於3 x 101 6 原子/立方公分、大於101 7 原子/立方公分。雜質原子類型的濃度可為從3 x 101 4 原子/立方公分至101 7 原子/立方公分、從101 5 原子/立方公分至3 x 101 6 原子/立方公分、或從3 x 101 5 原子/立方公分至101 6 原子/立方公分、從101 6 原子/立方公分至2 x 101 7 原子/立方公分、從2 x 101 6 原子/立方公分至101 7 原子/立方公分、大於2 x 101 7 原子/立方公分。CVD鑽石層的大部份容積較佳係包含從2X101 7 原子/立方公分至2 x 101 8 原子/立方公分之選自矽、硫或磷的雜質原子類型。雜質原子類型較佳為矽。CVD鑽石層可為單晶。或者，CVD鑽石層可為多晶。According to the present invention, there is provided a CVD diamond layer comprising an impurity atom type selected from the group consisting of ruthenium, sulfur or phosphorus, wherein the concentration of impurity atom types in a majority of the volume of the diamond layer is from 10 1 4 to 2 x 10 1 8 atoms / cubic centimeter. Most of the volume concentration of the silicon-based diamond layer may be greater than 1013 atoms / cc, is greater than 1014 atoms / cc, is greater than 3 x 10 1 4 atoms / cm ^, greater than 1015 atoms / cc , greater than 3 x 10 1 5 atoms / cm ^, greater than 1016 atoms / cc, is greater than 3 x 10 1 6 atoms / cm ^, greater than 1017 atoms / cc. The concentration of impurity atom type may be from 3 x 10 1 4 atoms / cubic centimeter to 1017 atoms / cubic centimeter, from 1015 atoms / cm ^ to 3 x 10 1 6 atoms / cubic centimeter, or from 3 x 10 15 atoms / cubic centimeter to 1016 atoms / cubic centimeter, from 1016 atoms / cc to 2 x 10 1 7 atoms / cm ^, from 2 X 1016 atoms / cubic centimeter to 1017 atoms / cc, is greater than 2 x 10 1 7 atoms / cc. Most preferred volume-based CVD diamond layer comprises from 2X10 1 7 atoms / cm ^ to impurity atom type selected from silicon, sulfur or phosphorus 2 x 10 1 8 atoms / cm ^ of. The impurity atom type is preferably ruthenium. The CVD diamond layer can be a single crystal. Alternatively, the CVD diamond layer can be polycrystalline.

光致發光頻譜術提供一用以偵測矽相關缺陷出現在鑽石中之敏感性方法。一般可藉由77K之633奈米HeNe雷射激勵來偵測737奈米的一矽相關光致發光線。本發明人的研究已經指示出，在77K以785奈米雷射輻射所激勵之經矽摻雜的鑽石之光致發光頻譜亦時常顯示946奈米的一條線。這一般伴隨著975奈米的另一條線。從前未曾報告這兩條光致發光線。第2圖顯示以785奈米雷射輻射所激勵之對於經矽摻雜鑽石之一典型光致發光頻譜。Photoluminescence spectroscopy provides a sensitive method for detecting the presence of defects associated with defects in diamonds. A 737 nm of a related photoluminescent line can generally be detected by a 77K 633 nm HeNe laser excitation. Studies by the inventors have indicated that the photoluminescence spectrum of ytterbium doped diamond excited by 785 nm laser radiation at 77 K also often shows a line of 946 nm. This is usually accompanied by another line of 975 nm. The two photoluminescent lines have not been reported before. Figure 2 shows a typical photoluminescence spectrum for a warp-doped diamond excited by 785 nm of laser radiation.

本發明亦已經利用EPR(電子超磁共振)調查經矽摻雜樣本。這提供一用以偵測及特徵化矽相關缺陷之敏感性方法。目前的偵測極限係容許測量低達一ppb的缺陷濃度。最近已經利用EPR來偵測及特徵化一中立矽空缺缺陷，且工作繼續進行以利用相同方式來識別其他矽相關缺陷。目前的結果提示946奈米光致發光線可能係為利用EPR所識別之中立矽空缺缺陷的一光學簽章。The present invention has also utilized EPR (Electron Ultra Magnetic Resonance) to investigate warp-doped samples. This provides a sensitive method for detecting and characterizing defects associated with defects. Current detection limits allow measurement of defect concentrations as low as one ppb. EPR has recently been utilized to detect and characterize a neutral vacancy defect, and work continues to identify other 矽 related defects in the same manner. The current results suggest that the 946 nm photoluminescence line may be an optical signature that utilizes the EPR to identify the neutral vacancy defect.

CVD鑽石層較佳具有高色度，其中“高色度”係如上文所定義。The CVD diamond layer preferably has a high chroma, wherein "high chroma" is as defined above.

CVD鑽石層較佳具有大於0.1公厘、較佳大於0.5公厘、較佳大於1公厘、較佳大於2公厘之厚度。The CVD diamond layer preferably has a thickness greater than 0.1 mm, preferably greater than 0.5 mm, preferably greater than 1 mm, preferably greater than 2 mm.

本發明的任何方法所產生之CVD鑽石層可在大於0.1立方公厘、較佳大於0.5立方公厘、較佳大於1立方公厘、較佳大於3.4立方公厘、較佳大於8立方公厘、較佳大於27立方公厘、較佳大於64立方公厘、較佳大於125立方公厘、較佳大於512立方公厘、較佳大於1000立方公厘之一容積上方具有小於1 x 10－3 、較佳小於1 x 10－ 4 、較佳小於3 x 10－ 4 、較佳小於1 x 10－ 5 之雙折射。可利用譬如Metripol裝備來特徵化雙折射。The CVD diamond layer produced by any of the methods of the present invention may be greater than 0.1 cubic centimeters, preferably greater than 0.5 cubic centimeters, preferably greater than 1 cubic centimeter, preferably greater than 3.4 cubic centimeters, and more preferably greater than 8 cubic centimeters. Preferably, it is greater than 27 cubic centimeters, preferably greater than 64 cubic centimeters, preferably greater than 125 cubic centimeters, preferably greater than 512 cubic millimeters, preferably greater than 1000 cubic millimeters, and one volume above one x 10- 3, preferably less than 1 x 10 - 4, preferably less than 3 x 10 - 4, preferably less than 1 x 10 - 5 of the birefringence. Available, such as Metripol Equipped to characterize birefringence.

對於一諸如無應力鑽石等等向性媒體，折射率係與光偏振方向獨立無關。如果一鑽石樣本被非均質地施加應力，因為成長應力或局部缺陷或者因為外部施加的壓力，折射率將為異向性。對於偏振方向之折射率變異可由具有一橢球的一般形式之一稱為光學指示率(optical indicatrix)之表面作為代表。任兩橢球軸線之間的差異係為沿第三者導引的光之線性雙折射。這可表示為包含未施應力材料的折射率、應力及光－彈性係數之一函數。For a directional medium such as a stress-free diamond, the refractive index is independent of the direction of polarization of the light. If a diamond sample is stressed in a heterogeneous manner, the refractive index will be anisotropic due to growth stress or local defects or due to externally applied pressure. The refractive index variation for the polarization direction can be represented by a surface having one of the general forms of an ellipsoid called optical indicatrix. The difference between the axes of any two ellipsoids is the linear birefringence of the light guided along the third. This can be expressed as a function of the refractive index, stress, and photo-elastic coefficient of the unstressed material.

Metripol(Oxford Cryosystems)提供一給定波長的折射率如何依據垂直於觀視方向之平面中的偏振方向而定之資訊。Metripol如何運作之一說明請見A.M.Glazer等人於Proc.R.Soc.Lond.A(1996)452，2751－2765。Metripol (Oxford Cryosystems) provides information on how the refractive index of a given wavelength depends on the direction of polarization in a plane perpendicular to the viewing direction. Metripol For a description of how this works, see AMGlazer et al., Proc. R. Soc. Lond. A (1996) 452, 2751-2765.

Metripol儀器係決定“慢軸線”的方向，亦即垂直於使折射率具有最大值之觀視方向的平面中之偏振方向。亦測量| sinδ |，其中δ為下式提供的相位移δ＝(2π/λ)△n LMetripol The instrument determines the direction of the "slow axis", that is, the direction of polarization in a plane perpendicular to the viewing direction that maximizes the refractive index. Also measured | sinδ |, where δ is the phase shift provided by: δ = (2π / λ) Δn L

其中λ為光的波長，L為試樣的厚度而△n為平行於慢及快軸線偏振(亦即雙折射)之光的折射率間之差異。△n L已知身為“光學阻滯”。Where λ is the wavelength of light, L is the thickness of the sample, and Δn is the difference between the refractive indices of light polarized parallel to the slow and fast axis (ie, birefringence). Δn L is known as "optical block".

對於第一階之阻滯，其中L＝0.6公厘而λ＝589.6奈米，則：當sinδ＝1且△n L＝λ/4，可推論出△n＝2.45 x 10－ 4 。For the first-order block, where L = 0.6 mm and λ = 589.6 nm, then: when sin δ = 1 and Δn L = λ / 4, Δn = 2.45 x 10 - 4 can be inferred.

當sinδ＝0.5且△n L＝λ/12，可推論出△n＝0.819 x 10－ 4 。When sin δ = 0.5 and Δn L = λ / 12, Δn = 0.819 x 10 - 4 can be inferred.

Metripol產生三色碼影像，其顯示a)“慢軸線”的空間變異，b)| sinδ |及c)操作波長之吸收率。Metripol A three color code image is produced which shows a) the spatial variability of the "slow axis", b) | sin δ | and c) the absorbance of the operating wavelength.

樣本係以已知厚度的光學板製備且在至少1.3公厘x1.3公厘、較佳2.5公厘x2.5公厘、更佳4公厘x4公厘的一區域上分析。Metripol| sinδ |影像隨後被分析且可對於整體受分析區域計算出整體分析區域上方的各訊框中之| sinδ |的最大值且使用這些數值來特徵化△n的最大值。The samples were prepared from optical plates of known thickness and analyzed on an area of at least 1.3 mm x 1.3 mm, preferably 2.5 mm x 2.5 mm, more preferably 4 mm x 4 mm. Metripol The sinδ | image is then analyzed and the maximum value of | sin δ | in each frame above the overall analysis area can be calculated for the overall analyzed area and these values used to characterize the maximum value of Δn.

正弦δ的表現係為一特定材料板之性質，此處藉由施加一最小厚度被拘限於有效厚度之板。可藉由將正弦δ資訊轉換回到在樣本厚度上方平均之平行於慢及快軸線作偏振之光的折射率之間的差異△n[ 平 均 ] 之一數值來獲得材料的一更基礎性質。The sinusoidal δ is expressed as a property of a particular material sheet, and is limited to a plate of effective thickness by applying a minimum thickness. △ difference between the information may be converted by a sinusoidal δ back above the average thickness of the sample parallel to the polarization of light for the slow and fast axes of the refractive index n [average level] values one obtains a more basic properties of the material .

儀器解析度及雜訊係對於| sinδ |數值及因此對於可由Metripol測量的阻滯Delta－nd設定一下限。這轉而在可測量雙折射上設定一下限，但此參數的極限係依據試樣厚度而定。供示範用，如果| sin delta |的下限為0.03，對於波長550奈米的光，這對應於一500微米厚度樣本之△n＝1.05x10－ 5 之可測量雙折射之一下限；或一3500微米厚度樣本之△n＝7.5x10－ 7 之可測量雙折射之一下限。Instrument resolution and noise system for | sinδ | values and therefore for Metripol The measured retardation Delta-nd sets a lower limit. This in turn sets a lower limit on the measurable birefringence, but the limit of this parameter depends on the thickness of the sample. Used for demonstration, if | sin delta | lower limit is 0.03, for light of 550 nm wavelength, which corresponds to a 500 micron thickness △ samples of n = 1.05x10 - 5 measurable lower limit of a birefringent; or a 3500 △ thickness of the sample of m n = 7.5x10 - 7 measurable lower limit of a birefringent.

可在實質能夠作容積測量之3正交方向中決定雙折射數值。這可能在諸如球形光學件等部分應用中特別重要。以測量為基礎且假設一3公厘路徑長度來計算下文界定的極限。The birefringence value can be determined in three orthogonal directions that are substantially capable of volume measurement. This may be particularly important in some applications such as spherical optics. The limits defined below are calculated on a measurement basis and assuming a 3 mm path length.

本發明的方法較佳係提供鑽石材料之製造藉以令雙折射測量在至少一個、較佳兩個、較佳全部三個正交方向中顯示△n數值而使得：△n較佳係在大於1x1公厘區域上方、較佳大於2x2公厘區域上方、較佳大於4x4公厘區域上方、較佳大於7x7公厘區域上方、較佳大於15x15公厘區域上方小於2x10－ 6 ；△n較佳係在大於1x1公厘區域上方、較佳大於2x2公厘區域上方、較佳大於4x4公厘區域上方、較佳大於7x7公厘區域上方、較佳大於15x15公厘區域上方小於5x10－ 6 ；△n較佳係在大於1x1公厘區域上方、較佳大於2x2公厘區域上方、較佳大於4x4公厘區域上方、較佳大於7x7公厘區域上方、較佳大於15x15公厘區域上方小於1x10－ 5 。Preferably, the method of the present invention provides for the manufacture of a diamond material such that the birefringence measurement exhibits a value of Δn in at least one, preferably two, preferably all three orthogonal directions such that: Δn is preferably greater than 1x1 Above the aliquot, preferably above 2x2 mm, preferably above 4x4 mm, preferably above 7x7 mm, preferably above 15x15 mm, less than 2x10 - 6 ; Δn is better 1x1 mm larger than the above area, preferably greater than 2x2 mm in the upper region, preferably greater than 4x4 mm in the upper region, preferably greater than 7x7 mm in the upper region, preferably greater than 15x15 mm upper region is smaller than 5x10 - 6; △ n in the preferred system is greater than the upper region of 1x1 mm, preferably greater than 2x2 mm in the upper region, preferably greater than 4x4 mm in the upper region, preferably greater than 7x7 mm in the upper region, preferably greater than 15x15 mm upper area is less than 1x10 - 5 .

若是雙折射數值對於一特定鑽石容積之三正交方向的各者位居一給定低限值以下，則對於此說明書目的而言，該容積視為具有一低於該低限值之雙折射數值。If the birefringence value is below a given low limit for each of the three orthogonal directions of a particular diamond volume, then for the purposes of this specification, the volume is considered to have a birefringence below the lower limit. Value.

本發明亦提供根據上文所勾勒的任何方法所產生之一CVD鑽石層以作為一光學元件之用。The invention also provides for the use of a CVD diamond layer as an optical component in accordance with any of the methods outlined above.

本發明亦提供根據上文所勾勒的任何方法所產生之一CVD鑽石層以作為一電性或電子元件之用。本發明亦提供根據上述任何方法所產生之一CVD鑽石層以作為一切割工具或導線抽引壓模或其他抗磨元件之用。The invention also provides for the use of a CVD diamond layer as an electrical or electronic component in accordance with any of the methods outlined above. The invention also provides a CVD diamond layer produced by any of the above methods for use as a cutting tool or wire drawing die or other anti-wear element.

本發明亦提供根據上文所勾勒的任何方法所產生之一CVD鑽石層，其中鑽石層具有大於0.1公厘、較佳大於0.5公厘、較佳大於1公厘、較佳大於2公厘的一厚度。The invention also provides a CVD diamond layer produced according to any of the methods outlined above, wherein the diamond layer has a thickness greater than 0.1 mm, preferably greater than 0.5 mm, preferably greater than 1 mm, preferably greater than 2 mm. a thickness.

本發明亦提供根據上文所勾勒的任何方法所產生之一CVD單晶鑽石層，其中鑽石層係為一寶石的形式。The invention also provides a CVD single crystal diamond layer produced according to any of the methods outlined above, wherein the diamond layer is in the form of a gemstone.

CVD單晶鑽石較佳具有大於2公厘的三個正交維度，其中至少一軸線係配置為沿著<100>晶體方向或沿著寶石的主要對稱軸線。三個正交維度較佳大於2.5公厘、較佳大於3.0公厘、較佳大於3.5公厘。CVD單晶鑽石較佳具有高清澈度，在GIA寶石評等尺上至少SI1的清澈度，如上文所定義。CVD單晶鑽石層在GIA寶石評等尺上較佳具有至少VS2、較佳至少VVS2、較佳至少VVS1的清澈度。The CVD single crystal diamond preferably has three orthogonal dimensions greater than 2 mm, wherein at least one of the axes is configured along the <100> crystal direction or along the major axis of symmetry of the gemstone. The three orthogonal dimensions are preferably greater than 2.5 mm, preferably greater than 3.0 mm, and more preferably greater than 3.5 mm. The CVD single crystal diamond preferably has a high definition clarity and at least SI1 clarity on the GIA gemstone scale, as defined above. The CVD single crystal diamond layer preferably has a clarity of at least VS2, preferably at least VVS2, preferably at least VVS1, on the GIA gemstone scale.

本發明的方法可用來製造CVD多晶鑽石，其中可改良譬如出現氮之有害效應。特定言之，可對抗具有少量的氮對於多晶鑽石的電性性質(諸如電荷收集效率及載體壽命)之有害效應。利用此方式，因為電性性質的改良，可使用含有氮的多晶鑽石作為一偵測器。這具有使偵測器能夠由含氮的多晶鑽石製成而非仰賴遠比合成更昂貴的“純”多晶鑽石之優點。The method of the present invention can be used to make CVD polycrystalline diamonds in which the deleterious effects of, for example, nitrogen can be improved. In particular, it can counteract the detrimental effects of having a small amount of nitrogen on the electrical properties of polycrystalline diamonds, such as charge collection efficiency and carrier lifetime. In this way, because of the improvement in electrical properties, a polycrystalline diamond containing nitrogen can be used as a detector. This has the advantage of enabling the detector to be made of nitrogen-containing polycrystalline diamonds rather than relying on "pure" polycrystalline diamonds that are far more expensive than synthetic.

本發明的方法所製造之多晶CVD鑽石係可用來作為一在電磁頻譜的遠紅外線部分具有低光學吸收之材料(其用來製造長波紅外線光學組件包括雷射離開窗及飛彈的成像圓頂，及其他用途)。利用本發明的方法可製造此等比目前可能者具有更好效能之組件。The polycrystalline CVD diamonds produced by the method of the present invention can be used as a material having low optical absorption in the far infrared portion of the electromagnetic spectrum (which is used to fabricate long-wave infrared optical components including imaging domes for laser exit windows and missiles, And other uses). Components that are more efficient than currently possible can be fabricated using the method of the present invention.

本發明的方法所製造之多晶鑽石亦可用來作為一在電磁頻譜的微波部分中具有低介電損失之材料(其使用於高供電迴旋管之離開窗口)且作為一其中很重視熱傳導之材料(使用於熱管理應用中)。The polycrystalline diamond produced by the method of the present invention can also be used as a material having a low dielectric loss in the microwave portion of the electromagnetic spectrum (which is used in the exit window of a high-powered gyrotron) and as a material in which heat conduction is highly valued. (used in thermal management applications).

本發明的任何方法所製造之鑽石層係較佳具有高的晶性品質。就單晶鑽石而言，“高晶性品質”可允許出現雜質原子及相關聯的點缺陷但對於會影響材料使用於光學應用之排差束或其他延伸缺陷出現則具有限制，譬如造成過度散射、或色度、或強度或可處理性降低至低於預定光學應用所需要者。就多晶鑽石而言，“高晶性品質”係指材料在顆粒邊界中具有一可忽略含量的非鑽石碳及其他缺陷。此等缺陷對於材料在光學及其他應用中之可使用性具有顯著影響且因此為不良的作用。The diamond layer produced by any of the methods of the present invention preferably has a high crystalline quality. In the case of single crystal diamonds, "high crystalline quality" may allow the presence of impurity atoms and associated point defects but may be limited for the presence of differential beams or other extended defects that may affect the use of the material in optical applications, such as causing excessive scattering. , or the chromaticity, or intensity or handleability, is reduced below what is required for the intended optical application. In the case of polycrystalline diamonds, "high crystalline quality" refers to materials having a negligible amount of non-diamond carbon and other defects in the grain boundaries. These defects have a significant impact on the workability of the material in optical and other applications and are therefore undesirable.

本發明亦提供使用一含有第二雜質原子類型之足量的氣態源以對抗一用以製造一具有高色度的CVD鑽石層之方法中對於第一雜質原子類型的色度之有害效應，其中高色度如上文所定義。有關氣態源的較佳特性及就本發明的方法之第一、第二及第三實施例所界定之第一及第二雜質原子類型係同樣地適用於此用途。The present invention also provides for the use of a sufficient amount of a gaseous source containing a second impurity atom type to counteract a deleterious effect on the chromaticity of a first impurity atom type in a method for fabricating a CVD diamond layer having a high chroma. High chroma is as defined above. Preferred properties relating to the gaseous source and the first and second impurity atom types as defined in the first, second and third embodiments of the method of the invention are equally applicable to this use.

本發明亦提供使用矽的一氣態源以添加至一包含一基材及一鑽石合成大氣之反應室故使矽在一CVD鑽石製造方法中對抗第一雜質原子類型的有害效應。有關本發明的方法之第二實施例中所界定之氣態源、矽及第一雜質原子類型之較佳特性係同樣適用於此用途。The present invention also provides for the use of a gaseous source of ruthenium to add to a reaction chamber comprising a substrate and a diamond synthetic atmosphere such that the ruthenium adversely affects the first impurity atom type in a CVD diamond manufacturing process. The preferred characteristics of the gaseous source, hydrazine and first impurity atom type as defined in the second embodiment of the method of the invention are equally applicable to this use.

本發明所提供所有方法、鑽石層及用途中，所產生的鑽石層中可能存在有額外雜質。任何額外雜質(不包括氫)的總濃度係小於5 ppm、較佳小於2 ppm、較佳小於1 ppm、較佳小於0.5 ppm、較佳小於0.2 ppm。鑽石層中任何單晶額外雜質(不包括氫)的濃度係為2 ppm或更小、較佳1 ppm或更小、較佳0.5 ppm或更小、較佳0.2 ppm或更小、較佳0.1 ppm或更小。In all methods, diamond layers and uses provided by the present invention, additional impurities may be present in the diamond layer produced. The total concentration of any additional impurities (excluding hydrogen) is less than 5 ppm, preferably less than 2 ppm, preferably less than 1 ppm, preferably less than 0.5 ppm, preferably less than 0.2 ppm. The concentration of any single crystal additional impurities (excluding hydrogen) in the diamond layer is 2 ppm or less, preferably 1 ppm or less, preferably 0.5 ppm or less, preferably 0.2 ppm or less, preferably 0.1. Ppm or less.

根據本發明，一用以製造如前文定義的“高色度”、低光學吸收單晶CVD鑽石之方法係包括提供一鑽石基材、提供一包括或出現顯著的一或多個氣態雜質位準的源氣體、解離源氣體以產生一含有顯著位準的一或多個氣態雜質之合成大氣、且容許鑽石基材上之均質磊晶鑽石成長之步驟。In accordance with the present invention, a method for making a "high chroma", low optical absorption single crystal CVD diamond as defined above includes providing a diamond substrate providing a level of one or more gaseous impurities comprising or exhibiting significant The source gas, the source gas is dissociated to produce a synthetic atmosphere containing a significant level of one or more gaseous impurities, and the step of allowing the homogeneous epitaxial diamond on the diamond substrate to grow.

所謂“低光學吸收”係指一材料在可見頻譜中吸收很少。特定言之，如果至少50%的鑽石層(大部份容積)在300至1000微米間的所有波長皆具有小於20公分－ 1 之吸收係數，則一鑽石層具有低的光學吸收。一具有低光學吸收之鑽石層係可在270奈米具有小於2公分－ 1 的吸收係數，及/或在350奈米小於1.5公分－ 1 的吸收係數，及/或在520奈米小於1公分－ 1 的吸收係數。所有吸收係數皆在室溫下測量。By "low optical absorption" is meant a material that absorbs little in the visible spectrum. In particular, a diamond layer has low optical absorption if at least 50% of the diamond layer (most of the volume) has an absorption coefficient of less than 20 cm - 1 at all wavelengths between 300 and 1000 microns. A diamond layer having low optical absorption may have an absorption coefficient of less than 2 cm - 1 at 270 nm, and/or an absorption coefficient of less than 1.5 cm - 1 at 350 nm, and/or less than 1 cm at 520 nm. - 1 absorption coefficient. All absorption coefficients were measured at room temperature.

氣態雜質(如下文所定義)較佳選自包括下列各物的群組：N、B、Si、P及S，特別是較佳至少包括N。The gaseous impurities (as defined below) are preferably selected from the group consisting of N, B, Si, P and S, and particularly preferably at least N.

本發明的一較佳實施例中，對於單獨能夠製造本發明之所需要的高色度、低光學吸收CVD鑽石材料而言，第一氣態雜質且特別是氮的位準並非最適。本發明的此實施例中，至少到不超過上限的程度，合成大氣中第一氣態雜質的位準可能為穩定、或經決定，而一第二氣態雜質以一受控制方式導入合成大氣中，該第二雜質係經選擇且以一適當量提供藉以降低對於第一雜質的色度之效應。In a preferred embodiment of the invention, the level of the first gaseous impurity, and particularly the nitrogen, is not optimal for high chroma, low optical absorption CVD diamond materials that are capable of producing the present invention alone. In this embodiment of the invention, at least to the extent that the upper limit is not exceeded, the level of the first gaseous impurity in the synthetic atmosphere may be stabilized or determined, and a second gaseous impurity is introduced into the synthetic atmosphere in a controlled manner. The second impurity is selected and provided in an appropriate amount to reduce the effect on the chromaticity of the first impurity.

第二氣態雜質較佳選自包括下列各物的群組：N、B、Si、S及P。The second gaseous impurity is preferably selected from the group consisting of N, B, Si, S, and P.

本發明的單晶CVD鑽石材料除了在一具有顯著氣態雜質位準之合成大氣中成長外，本身可包括顯著雜質位準同時維持所需要的高色度及低光學吸收特徵。The single crystal CVD diamond material of the present invention, in addition to being grown in a synthetic atmosphere having significant gaseous impurity levels, may itself include significant impurity levels while maintaining the desired high chroma and low optical absorption characteristics.

特定言之，本發明之單晶CVD鑽石材料較佳含有顯著位準之雜質N、B或Si的一或多者、且特別至少為N。In particular, the single crystal CVD diamond material of the present invention preferably contains one or more of the significant levels of impurities N, B or Si, and in particular at least N.

本發明的單晶CVD鑽石材料較佳亦具有高清澈度，特別是如此處所界定。The single crystal CVD diamond material of the present invention preferably also has a high definition clarity, particularly as defined herein.

CVD鑽石材料較佳係成長在大致無結晶缺陷之一鑽石基材的表面上。Preferably, the CVD diamond material is grown on the surface of a diamond substrate that is substantially free of crystal defects.

本發明延伸至在結晶結構中含有顯著雜質位準之高色度、低光學吸收、及較佳高清澈度、單晶CVD鑽石。The invention extends to high chroma, low optical absorption, and preferably high definition, single crystal CVD diamonds containing significant impurity levels in the crystalline structure.

本發明的單晶CVD鑽石係適合用於諸如鑽石窗、鑽石透鏡及鉆等光學應用中，且用以定型成一寶石，特別是一高色度等級之寶石。The single crystal CVD diamond of the present invention is suitable for use in optical applications such as diamond windows, diamond lenses and drills, and is used to shape a gemstone, particularly a high chroma grade gemstone.

本發明的方法所產生之CVD鑽石所身處之應用係包括光學應用，諸如紅外線傳輸窗、及其中務必作應力控制及盡量減少雙折射之標準具、刀刃、諸如肖特基二極體等電子組件、及輻射偵測器。The application of the CVD diamond produced by the method of the present invention includes optical applications such as infrared transmission windows, etalons for which stress control and birefringence are to be minimized, blades, electrons such as Schottky diodes Components, and radiation detectors.

上述本發明的方法係可供製造適合光學及寶石應用之高色度、低光學吸收單晶CVD鑽石。上述本發明的方法亦可供製造高色度、低光學吸收多晶CVD鑽石。在一含有顯著位準的一或多個氣態雜質且特別是其中出現的一氣態雜質為氮之合成大氣中進行CVD程序。儘管或特定案例中正因為含有顯著位準的一或多個雜質且此等雜質包括氮、矽及硼，高色度、低光學吸收單晶CVD鑽石係適合使用於光學及寶石應用中。時常視為以一特定形式或一特定程度出現在高品質高純度CVD鑽石中之鑽石的特定性質亦藉由在成長程序中出現雜質予以修改或被併入鑽石內，本發明進一步可供製造具有這些經修改性質之高色度的鑽石材料。The above described method of the present invention is useful for the manufacture of high chroma, low optical absorption single crystal CVD diamonds suitable for optical and gemstone applications. The above described method of the invention is also useful for the manufacture of high chroma, low optical absorption polycrystalline CVD diamonds. The CVD procedure is carried out in a synthetic atmosphere containing one or more gaseous impurities of significant level and in particular a gaseous impurity in which nitrogen gas is present. High-color, low optical absorption single crystal CVD diamonds are suitable for use in optical and gemstone applications, although or in certain cases because of one or more impurities that contain significant levels and such impurities include nitrogen, helium, and boron. The particular properties of diamonds that are often considered to be present in a high quality, high purity CVD diamond in a particular form or to a particular extent are also modified or incorporated into the diamond by the presence of impurities in the growth process, and the invention is further These modified high chroma diamond materials.

一特定範例係為將矽添加至一含氮之CVD鑽石合成大氣，已顯示其將增加經正規化FE強烈度，及因此預期將其他電子性質顯著地改良朝向已經在缺乏氮情形下測量之數值。此外，由於成長期間降低表面粗化所導致鑽石中缺陷的降低係預計可改良數個其他機械及化學性質，包括抗磨性及熱穩定度。預期熱穩定度特別會在如退火期間有可能發生之不具有穩定化壓力之條件下受到改良，。A particular example is the addition of niobium to a nitrogen-containing CVD diamond synthesis atmosphere, which has been shown to increase the normalized FE intensity, and thus is expected to significantly improve other electronic properties toward values already measured in the absence of nitrogen. . In addition, the reduction in defects in diamonds due to reduced surface roughening during growth is expected to improve several other mechanical and chemical properties, including abrasion resistance and thermal stability. It is expected that the thermal stability will be improved particularly in the case where it is possible to have a stabilizing pressure, such as during annealing.

本發明的鑽石材料可有利地具有“高色度”及“低光學吸收”，如前文所定義。The diamond material of the present invention may advantageously have "high chroma" and "low optical absorption" as defined above.

高色度的鑽石可以數種方式特徵化。對於一寶石應用中所使用材料較佳且最具界定性方式係為自該材料製備一寶石，及寶石色度的特徵化。特定言之，本發明可供製造將形成圓形明亮式的一0.5 ct CVD鑽石寶石之一數量及尺寸之材料，其具有以優於K、更佳優於J、更佳優於I、更佳優於H、更佳優於G、更佳優於F、最佳優於E的天然鑽石色尺為基礎之一色度。本文中“優於”係指較高色度或較低吸收側之一色度，亦即朝向設有D色度石體之側，在優於E色度的案例中係指D色度或完全無色鑽石。High chroma diamonds can be characterized in several ways. The preferred and most defined way for a material used in a gemstone application is to prepare a gemstone from the material and characterize the color of the gemstone. In particular, the present invention can be used to manufacture a material of a number and size of a 0.5 ct CVD diamond gemstone that will form a round brilliant shape, which has a better than K, better than J, better than I, and more Better than H, better than G, better than F, best better than E, the natural diamond color ruler is based on one color. By "better" in this context is meant one of the higher chroma or lower absorption side, ie towards the side with the D color stone body, in the case of better than the E color, the D color or complete Colorless diamonds.

本申請案全文中，鑽石的色度係指美國寶石協會(GIA)色尺，如前述。GIA色尺係經過從D至Z，及較高字母。“高色度”習知係為位於字母下端從D至優於K之色度範圍。GIA色尺係很廣泛地使用於全球鑽石業中[請見“鑽石評等ABC”，V.Pagel－Theisen，第9版，2001，頁61及64－83，如何決定色度的說明]。基本上，藉由相對於先前已決定色度之鑽石標準比較鑽石來決定色度等級。使用“無色”來描述鑽石色度似乎是異常的，但“無色”係指未輔助或輕微輔助人眼之偵測低限值：諸如頻譜儀等光學儀器係能夠偵測導致遠低於其可被人眼認知為一色彩之鑽石中色彩之吸收特性。因此，將人眼認知為無色之一鑽石視為在一色尺上具有一位置將是完全合理的方式。Throughout this application, the chromaticity of a diamond refers to the GIA color scale, as described above. The GIA ruler passes from D to Z, and the higher letters. The "high chroma" convention is the range of chromaticities from D to better than K at the lower end of the letter. The GIA ruler system is widely used in the global diamond industry [see "Diamond Ratings ABC", V. Pagel-Theisen, 9th Edition, 2001, pages 61 and 64-83, how to determine the chromaticity description]. Basically, the chroma level is determined by comparing the diamonds against the diamond standard of the previously determined chroma. The use of “colorless” to describe diamond chromaticity seems to be abnormal, but “colorless” refers to undetected or slightly assisted human eye detection low limits: optical instruments such as spectrometers are capable of detecting far below them. The absorption of color in a diamond that is recognized by the human eye as a color. Therefore, it would be perfectly reasonable to treat the human eye as a colorless diamond as having a position on a color ruler.

因為對於相同光學吸收係數而言，一較大寶石具有一較低色度等級，在此色度定義中需要參照寶石的一特定尺寸以適當地識別一鑽石材料的色度。然而，請瞭解此參照一寶石尺寸並未將本發明限於任何特定尺寸或切割之寶石。若是材料為一不同尺寸及/或切割的寶石之形式，或無法以一寶石形式、且更佳一圓形明亮式切割寶石製造，此處提供了均等圓形明亮式切割色度之色度計算的適當方法。Since a larger gemstone has a lower chromaticity level for the same optical absorption coefficient, a specific size of the gemstone is required in this chromaticity definition to properly identify the chromaticity of a diamond material. However, it is understood that this reference to a gem size does not limit the invention to any particular size or cut gemstone. If the material is in the form of a different size and/or cut gemstone, or cannot be made in a gemstone form, and a better round brilliant cut gemstone, the chromaticity calculation of the uniform round brilliant cut chroma is provided here. The appropriate method.

對於其他光學應用，關鍵參數一般係為橫越應用中的相關光學範圍之光學吸收係數。特定言之，波長270奈米、350奈米、及500奈米之鑽石的吸收係數係具有特定相干性，由正常處理條件下常見雜質導致之缺陷所產生，且時常對於材料色度或吸收扮演一顯著角色而可能限制其用途。因此，上述本發明的CVD鑽石材料亦較佳將具有一個、更佳兩個、最佳全部可在光學吸收頻譜中觀察之下列特徵：(i)、(ii)、(iii)、(iv)：i)在300至1000奈米之間的所有波長於室溫測量之一吸收係數，其小於2公分－ 1 、更佳小於1公分－ 1 ，更佳小於0.5公分－ 1 、且最佳小於0.2公分－ 1 ；ii)270奈米之一吸收係數，其小於2公分－ 1 、更佳小於1公分－ 1 、更佳小於0.5公分－ 1 、且最佳小於0.2公分－ 1 ；iii)350奈米之一吸收係數，其小於1.5公分－ 1 、更佳小於0.75公分－ 1 、更佳小於0.3公分－ 1 、且最佳小於0.15公分－ 1 ；iv)520奈米之一吸收係數，其小於1公分－ 1 、更佳小於0.5公分－ 1 、更佳小於0.2公分－ 1 、且最佳小於0.1公分－ 1 。For other optical applications, the key parameters are generally the optical absorption coefficients across the relevant optical range in the application. In particular, the absorption coefficients of diamonds with wavelengths of 270 nm, 350 nm, and 500 nm are specific coherence, resulting from defects caused by common impurities under normal processing conditions, and often play a role in material color or absorption. A significant role may limit its use. Accordingly, the CVD diamond material of the present invention described above will preferably have one, preferably two, and most preferably the following features that can be observed in the optical absorption spectrum: (i), (ii), (iii), (iv) : i) all wavelengths between 300 to 1000 nm in one of the absorption coefficient measured at room temperature, which is smaller than 2 cm - 1, more preferably less than 1 cm - 1, more preferably less than 0.5 cm - 1, and most preferably less than 0.2 cm - 1 ; ii) one absorption coefficient of 270 nm, which is less than 2 cm - 1 , more preferably less than 1 cm - 1 , more preferably less than 0.5 cm - 1 , and most preferably less than 0.2 cm - 1 ; iii) 350 one nm absorption coefficient, which is smaller than 1.5 cm - 1, more preferably less than 0.75 cm - 1, more preferably less than 0.3 cm - 1, and most preferably less than 0.15 cm --1; IV) one of the absorption coefficient 520 nm, which Less than 1 cm - 1 , more preferably less than 0.5 cm - 1 , more preferably less than 0.2 cm - 1 , and most preferably less than 0.1 cm - 1 .

上述本發明的CVD鑽石材料亦將較佳具有一個、更佳兩個、更佳三個、更佳四個、且最佳全部可在層的大部份容積中觀察的下列特徵(1)、(2)、(3)、(4)、(5)，其中大部份容積係包含至少50%、較佳至少55%、較佳至少60%、較佳至少70%、較佳至少80%、較佳至少90%且最佳至少95%之該層的整體容積：1)小於150微米、較佳小於100微米、更佳小於50微米、更佳小於20微米、更佳小於10微米、且最佳小於5微米之一電荷收集距離，所有電荷收集距離係在1伏特/微米的一施加場及300K測量。或者，大於100微米、較佳大於150微米、較佳大於200微米、較佳大於300微米、較佳大於500微米、較佳大於1000微米之一電荷收集距離(雖然大部份應用可獲益自一高電荷收集距離，需要很高速偵測器之部分應用係獲益自低電荷收集距離，特別是可連同使用本發明的一較佳方法獲得之高結晶品質)；2)大於0.05 ppm、更佳大於0.1 ppm、更佳大於0.2 ppm、更佳大於0.5 ppm、更佳大於1 ppm、更佳大於2 ppm、更佳大於5 ppm、最佳大於10 ppm的至少一雜質(排除氫)之一位準(雜質濃度譬如可藉由次級離子質譜術(SIMS)、輝光放電質譜術(GDMS)或燃燒質譜術(CMS)、電子超磁共振(EPR)及IR(紅外線)吸收來測量)。此外，可在基線減除之後自270奈米的吸收特性峰值決定出未經補償的單替代氮濃度(相對於自燃燒分析作破壞性分析的樣本所獲得之標準值予以校準)；3)大於0.2 ppm、更佳大於0.5 ppm、更佳大於1 ppm、更佳大於2 ppm、更佳大於5 ppm、更佳大於10 ppm、更佳大於20 ppm之一總雜質濃度(排除氫)(雜質濃度可如上測量)；4.1)在77 K測量的陰極發光頻譜中之弱自由激子發光，其中自由激子發光的積集強烈度較佳不超過0.5、更佳不超過0.2、更佳不超過0.1、最佳不超過0.05之對於高純度條件下成長的一均質磊晶CVD鑽石樣本(譬如WO 01/96634所顯露者)之積集自由激子發光強烈度。或者，在77K測量的陰極發光頻譜中之一強烈自由激子發光，其中自由激子發光的積集強烈度較佳超過0.5、較佳超過0.6、較佳超過0.7、較佳超過0.8、較佳超過0.9之對於在高純度條件下成長的一均質磊晶CVD鑽石樣本之積集自由激子發光強烈度；或4.2)在室溫下193奈米ArF受激準分子雷射所激勵之自由激子發射的強度係使得對於自由激子發射的量子生產率小於10－ 4 、更佳小於10－ 5 、且更佳小於10－ 6 。或者，自由激子發射大於10－ 6 、較佳大於10－ 5 、較佳大於10－ 4 。自由激子發射亦可由上述帶隙輻射、譬如由來自一ArF受激準分子雷射之193奈米輻射所激勵。利用此方式所激勵之光致發光頻譜中的強烈自由激子發射之出現係指示出大致不存在排差及雜質；5)EPR中，在g＝2.0028超過1 x 101 6 原子公分－ 3 、更佳超過2 x 101 6 原子公分－ 3 、更佳超過5 x 101 6 原子公分－ 3 、更佳超過1 x 101 7 原子公分－ 3 、更佳超過2 x 101 7 原子公分－ 3 、最佳超過5 x 101 7 原子公分－ 3 之一自旋密度。或者，自旋密度較佳小於5 x 101 7 原子公分－ 3 、較佳小於2 x 101 7 原子公分－ 3 、較佳小於1 x 101 7 原子公分－ 3 、較佳小於5 x 101 6 原子公分－ 3 、較佳小於2 x 101 6 原子公分－ 3 、較佳小於1 x 101 6 原子公分－ 3 (單晶鑽石中，此線係有關晶格缺陷濃度且通常在不良品質均質磊晶鑽石中為大但在使用一高純度成長程序之高色度CVD鑽石中則為小)。The CVD diamond material of the present invention described above will preferably have one, more preferably two, more preferably three, more preferably four, and most preferably the following features (1) that can be observed in most of the volume of the layer, (2), (3), (4), (5), wherein a majority of the volume comprises at least 50%, preferably at least 55%, preferably at least 60%, preferably at least 70%, preferably at least 80% Preferably, at least 90% and optimally at least 95% of the overall volume of the layer: 1) less than 150 microns, preferably less than 100 microns, more preferably less than 50 microns, more preferably less than 20 microns, more preferably less than 10 microns, and Optimal charge collection distance of less than 5 microns, all charge collection distances are measured at an applied field of 1 volt/micron and measured at 300K. Or a charge collection distance greater than 100 microns, preferably greater than 150 microns, preferably greater than 200 microns, preferably greater than 300 microns, preferably greater than 500 microns, and preferably greater than 1000 microns (although most applications may benefit from A high charge collection distance requires that some applications of very high speed detectors benefit from low charge collection distances, especially high crystal quality that can be achieved with a preferred method of the invention; 2) greater than 0.05 ppm, more One of at least one impurity (excluding hydrogen) preferably greater than 0.1 ppm, more preferably greater than 0.2 ppm, more preferably greater than 0.5 ppm, more preferably greater than 1 ppm, still more preferably greater than 2 ppm, more preferably greater than 5 ppm, and most preferably greater than 10 ppm The level (impurity concentration can be measured, for example, by secondary ion mass spectrometry (SIMS), glow discharge mass spectrometry (GDMS) or combustion mass spectrometry (CMS), electronic ultra-magnetic resonance (EPR), and IR (infrared) absorption). In addition, uncompensated single-substitute nitrogen concentrations (calibrated against standard values obtained from destructively analyzed samples from combustion analysis) can be determined from baseline peaks at 270 nm after baseline subtraction; 3) greater than 0.2 ppm, more preferably more than 0.5 ppm, more preferably more than 1 ppm, more preferably more than 2 ppm, more preferably more than 5 ppm, more preferably more than 10 ppm, more preferably more than 20 ppm, one total impurity concentration (excluding hydrogen) (impurity concentration) Can be measured as above); 4.1) weak free exciton luminescence in the cathodoluminescence spectrum measured at 77 K, wherein the accumulation of free exciton luminescence is preferably not more than 0.5, more preferably not more than 0.2, more preferably not more than 0.1. Preferably, no more than 0.05 is a free exciton luminescence intensity accumulated for a homogeneous epitaxial CVD diamond sample grown under high purity conditions (as disclosed by WO 01/96634). Alternatively, one of the cathode luminescence spectra measured at 77K is strongly free exciton luminescence, wherein the intensity of accumulation of free exciton luminescence is preferably more than 0.5, preferably more than 0.6, preferably more than 0.7, preferably more than 0.8, preferably. Excessive exciton luminescence intensity over 0.9 for a homogeneous epitaxial CVD diamond sample grown under high purity conditions; or 4.2) free radical excitation by a 193 nm ArF excimer laser at room temperature The intensity of the sub-emission is such that the quantum productivity for free exciton emission is less than 10 - 4 , more preferably less than 10 - 5 , and even more preferably less than 10 - 6 . Alternatively, the free exciton emission is greater than 10 - 6 , preferably greater than 10 - 5 , preferably greater than 10 - 4 . The free exciton emission can also be excited by the above-described bandgap radiation, such as by 193 nm radiation from an ArF excimer laser. The appearance of strong free exciton emission in the photoluminescence spectrum excited by this method indicates that there is substantially no difference in emissions and impurities; 5) in EPR, more than 1 x 10 16 6 centimeters - 3 at g = 2.0028, More preferably more than 2 x 10 1 6 atomic centimeters - 3 , more preferably more than 5 x 10 1 6 atomic centimeters - 3 , more preferably more than 1 x 10 1 7 atomic centimeters - 3 , more preferably more than 2 x 10 1 7 atomic centimeters - 3 , optimally more than 5 x 10 1 7 atomic centimeters - 3 one spin density. Alternatively, the spin density is preferably less than 5 x 10 1 7 atoms cm - 3 and preferably less than 2 x 10 1 7 atoms cm - 3 and preferably less than 1 x 10 1 7 atoms cm - 3 and preferably less than 5 x 10 1 6 atomic centimeters - 3 , preferably less than 2 x 10 1 6 atomic centimeters - 3 , preferably less than 1 x 10 1 6 atomic centimeters - 3 (in single crystal diamonds, this line is related to lattice defect concentration and is usually poor The quality of the homogeneous epitaxial diamond is large but is small in high chroma CVD diamonds using a high purity growth procedure).

該層的大部份容積較佳係自單一成長段形成。Most of the volume of the layer is preferably formed from a single growth section.

上述本發明的一關鍵係在於成長發生於一使用一含有至少一氣態雜質、更佳含有至少兩氣態雜質的氣體混合物之CVD反應器中。本發明的較佳方法係在於其中至少一氣態雜質至少部分地產生而無刻意添加，但因為藉由處理源極氣體或對於真空環境的修改來進一步降低其位準之困難或成本，而在其中刻意添加一第二雜質或可供程序取用以改良第一雜質的效應。此說明書中，一氣態雜質係為並非碳之任意元素，其在室溫及壓力下的正常元素狀態為固體但可採行氣態形式且可被添加，或另外以一處理氣體混合物中的一氣體出現，或可經由氣態形式譬如自反應器的壁或自反應器容積內的其他固體元素在程序內被轉移，其中該元素可(i)被併入鑽石晶格中，或(ii)可與鑽石的成長表面交互作用及修改所形成鑽石的品質，或(iii)與程序中出現之其他氣態物種交互作用藉以影響程序的結果。A key aspect of the above described invention is that growth occurs in a CVD reactor using a gas mixture containing at least one gaseous impurity, more preferably at least two gaseous impurities. Preferably, the method of the present invention resides in wherein at least one gaseous impurity is at least partially produced without intentional addition, but because of the difficulty or cost of further reducing its level by treating the source gas or modifying the vacuum environment, Deliberately adding a second impurity or a procedure available to improve the effect of the first impurity. In this specification, a gaseous impurity is any element other than carbon, and its normal elemental state at room temperature and pressure is solid but can be taken in gaseous form and can be added, or otherwise treated as a gas in a gas mixture. Occurs, or may be transferred within the program via a gaseous form such as from the wall of the reactor or from other solid elements within the reactor volume, where the element may (i) be incorporated into the diamond lattice, or (ii) The diamond's growth surface interacts and modifies the quality of the diamond formed, or (iii) interacts with other gaseous species present in the program to influence the outcome of the program.

上述發明的較佳方法中，其中一氣態雜質至少部分地產生而無刻意添加，程序中其濃度一般使其如果以唯一氣態雜質出現，其將被併入鑽石晶格中或與鑽石的成長表面交互作用，或與程序中出現的其他氣態物種交互作用藉以顯著地影響程序的結果，且特別是劣化色度或增加材料的光學吸收。氣態雜質的定義確切地排除了貴氣體、鹵素、氧及氫，且特別包括諸如B、P、S、Si等元素。此外，作為對於雜質的元素狀態在室溫下為一固體之條件之一特定且唯一的例外，在此說明書中任何形式的氮(譬如，N2 、NH2 )亦視為一氣態雜質。In a preferred method of the above invention, wherein a gaseous impurity is at least partially produced without intentional addition, the concentration of the program is generally such that if it occurs as a single gaseous impurity, it will be incorporated into the diamond lattice or with the diamond's growth surface. Interactions, or interactions with other gaseous species present in the program, can significantly affect the results of the program, and in particular degrade the color or increase the optical absorption of the material. The definition of gaseous impurities specifically excludes noble gases, halogens, oxygen, and hydrogen, and specifically includes elements such as B, P, S, Si, and the like. Further, as a specific and unique exception to the condition that the elemental state of the impurity is a solid at room temperature, any form of nitrogen (e.g., N 2 , NH 2 ) in this specification is also regarded as a gaseous impurity.

特定言之，氮的出現已知會影響成長程序。先前，高純度鑽石、或無色鑽石的製造係顯示WO 01/96634所描述的電子性質已經需要將氮位準控制至小於300 ppb。此說明書內，高於300 ppb的氮(以N2 測量，或對於諸如NH3 等其他形式的氮之均等物)因此係為一氣態雜質。In particular, the emergence of nitrogen is known to affect growth processes. Previously, the manufacture of high purity diamonds or colorless diamonds showed that the electronic properties described in WO 01/96634 had to be controlled to a nitrogen level of less than 300 ppb. Within this specification, nitrogen above 300 ppb (in N 2 measurements, or to equivalents of nitrogen such as NH 3 other forms) is tied to a gaseous impurities.

因此，上述發明的方法係提供用以自一成長程序來製造高色度鑽石之構件，其含有大於300 ppb、更佳大於500 ppb、更佳大於1 ppm、更佳大於2 ppm、更佳大於5 ppm、更佳大於10 ppm、最佳大於20 ppm或更高的濃度之氮。Accordingly, the method of the above invention provides means for fabricating high chroma diamonds from a growth process comprising greater than 300 ppb, more preferably greater than 500 ppb, more preferably greater than 1 ppm, even more preferably greater than 2 ppm, more preferably greater than Nitrogen at a concentration of 5 ppm, more preferably greater than 10 ppm, optimally greater than 20 ppm or higher.

如前述，較佳至少氮以一氣態雜質出現在合成大氣中。因此，上述本發明的方法可以兩不同方式使用，第一者中氮位準受到小心地控制，而第二較佳方法中氮位準只被控制至使其保持低於顯著高於製造高色度鑽石時正常所需要者的某低限值之程度。As mentioned above, preferably at least nitrogen is present in the synthetic atmosphere as a gaseous impurity. Thus, the above described method of the invention can be used in two different ways, with the nitrogen level in the first being carefully controlled, while in the second preferred method the nitrogen level is only controlled to remain below the manufacturing high color. The degree to which a low limit is required for normal diamonds.

在氮受到小心控制之第一方法中，其首要利益在於其中未受控制的雜質並非氮，且可使用氮來降低其效應。譬如，一CVD室中的硼污染很具持續性，即便低位準的硼亦會對於所合成鑽石添加顯著藍色。然而，可利用氮添加物的小心控制(以N2 或任何其他含N氣體的形式)來補償此硼且降低其對於鑽石色度之效應。此外，可能有一使所添加氮亦修改且特別是降低攝入固體中的硼量之效應。熟習該技術者將瞭解此技術可施加至並非硼之污染物。In the first method in which nitrogen is carefully controlled, its primary advantage is that the uncontrolled impurities are not nitrogen, and nitrogen can be used to reduce its effect. For example, boron contamination in a CVD chamber is very continuous, even if low levels of boron add significant blue to the synthesized diamond. However, the use of carefully controlled nitrogen additions (in the form of N 2 or any other N containing gas) to compensate this boron and reduce its effect to the color of the diamond. In addition, there may be an effect of modifying the added nitrogen and, in particular, reducing the amount of boron in the ingested solids. Those skilled in the art will appreciate that this technique can be applied to contaminants that are not boron.

然而，上述發明的一較佳方法係應付以高於高色度鑽石合成之正常所需要者的位準出現之氮的較常見問題。譬如，可選擇使用含有顯著氮雜質位準之處理氣體，或者處理室可具有一小洩漏，或氮可由其他構件進入程序中。在此等案例中，氮位準的降低可能很昂貴。However, a preferred method of the above invention is to cope with the more common problem of nitrogen occurring at a level higher than that required for normal color synthesis of high chroma diamonds. For example, a process gas containing significant levels of nitrogen impurities may be selected, or the process chamber may have a small leak, or nitrogen may enter the process by other components. In these cases, the reduction in nitrogen levels can be expensive.

藉由將選定的氣態雜質小心添加至成長程序的氣相中，其中這些雜質可能影響成長程序，且其本身可被併入鑽石中，可以降低成長程序中出現的氮對於所產生鑽石色度之影響。特定言之，對於色度的利益可導因於併入可用以補償氮之刻意添加的雜質，或者其可降低成長期間氮的攝入，或其可簡單地降低氮對於鑽石色度之有害效應，或者其可提供這些效應的一合併。By carefully adding selected gaseous impurities to the gas phase of the growth process, which may affect the growth process and which itself can be incorporated into the diamond, the nitrogen present in the growth process can be reduced for the color of the diamond produced. influences. In particular, the benefit to chromaticity may be due to the incorporation of impurities that may be used to compensate for the deliberate addition of nitrogen, or it may reduce nitrogen uptake during growth, or it may simply reduce the deleterious effects of nitrogen on diamond chromaticity. Or it can provide a merger of these effects.

為此，上述本發明的方法之一特佳實施例係包括用以修改氮對於成長程序及/或鑽石所產生色度的效應、且特別是降低若在於其以下氮若以唯一氣態雜質出現則將發生之鑽石的光學吸收藉以改良其色度之一氣態雜質的受控制式添加。此氣態雜質可為B、Si、S、P的任一者，但不在此限。此氣態雜質更佳為B或Si、且最佳為Si。To this end, a preferred embodiment of one of the above-described methods of the present invention includes modifying the effect of nitrogen on the chromaticity produced by the growth process and/or the diamond, and in particular reducing if the nitrogen below it is present as the only gaseous impurity. The optical absorption of the diamond that occurs will be used to improve the controlled addition of gaseous impurities, one of its chromaticities. This gaseous impurity may be any of B, Si, S, and P, but is not limited thereto. This gaseous impurity is more preferably B or Si, and is most preferably Si.

因此，一種此等選定雜質為硼，其譬如可以二硼烷形式添加至氣相中。若出現有硼，氮攝入可依據精密濃度及成長條件而降低，且硼可補償被攝入的氮。此外，硼似乎可降低被攝入的氮對於鑽石色度之有害效應。硼的一項困難係在於過多的硼將使鑽石著成藍色，所以需要對於氮位準來最適化硼位準且小心予以控制。Thus, one such selected impurity is boron, which may be added to the gas phase, for example, in the form of diborane. In the presence of boron, nitrogen intake can be reduced depending on precise concentrations and growth conditions, and boron can compensate for the nitrogen being ingested. In addition, boron appears to reduce the deleterious effects of nitrogen intake on diamond color. One difficulty with boron is that too much boron will make the diamond blue, so it is necessary to optimize the boron level for the nitrogen level and carefully control it.

如同一般所熟知，CVD鑽石成長中氮的併入比值一般遠低於硼。結果，當目標在對於併入固體中的氮及硼位準達成一平衡程度以達成補償時，添加至氣相之硼位準可能遠低於所出現的氮位準、且較佳更小10倍因數、更佳更小30倍因數、最佳更小100倍因數。鑒於需要至少某程度地平衡硼與氮，因為雜質的相對攝入在成長段之間變動，當自材料產生的最終物件被限定至一單一鑽石成長段時，此方法具有最好功效且因此偏好此方法。As is well known, the ratio of nitrogen incorporation in CVD diamond growth is generally much lower than boron. As a result, when the target achieves a degree of equilibrium for the nitrogen and boron levels incorporated into the solid to achieve compensation, the boron level added to the gas phase may be much lower than the nitrogen level present, and preferably less 10 Double factor, better 30 times smaller factor, best smaller 100 times factor. In view of the need to balance boron and nitrogen to at least some extent, since the relative uptake of impurities varies between growth stages, this method has the best efficacy and therefore preference when the final object from the material is limited to a single diamond growth stage. This method.

譬如二硼烷或部分其他含硼氣體形式之刻意添加的硼較佳係以大於0.5 ppb(十億分之一份，或氣相中出現的每109 個分子之二硼烷分子數，如同入進氣流中在解離前出現者)、更佳大於0.1 ppb、更佳大於2 ppb、更佳大於5 ppb、更佳大於10 ppb、更佳大於20 ppb、更佳大於50 ppb、最佳大於0.1 ppb的濃度提供。Deliberately added boron, such as diborane or some other boron-containing gas, is preferably greater than 0.5 ppb (parts per billion, or the number of diborane molecules per 10 9 molecules present in the gas phase, as Preferably, the influent stream appears before dissociation), more preferably greater than 0.1 ppb, more preferably greater than 2 ppb, more preferably greater than 5 ppb, more preferably greater than 10 ppb, more preferably greater than 20 ppb, more preferably greater than 50 ppb, optimal Provided at concentrations greater than 0.1 ppb.

當氮以一雜質出現在程序中時，刻意添加至程序以改良色度之一特佳雜質係為矽。矽當出現時已知係被攝入鑽石中且特別在出現氮時已知形成737奈米發光中心。此中心未影響鑽石的可見色度。然而，此發明揭露以適當濃度添加至氣相之譬如矽烷形式的矽係會造成以一氣態雜質出現的任何氮對於鑽石色度所具有的效應之鉅幅降低。該機制可能係為降低氮攝入或簡單地降低氮攝入通常所產生的缺陷中心之一者，或可能具有補償效應，但這對於先前報告為鑽石中的p型摻雜物之矽而言將令人驚訝。然而，在矽的案例中，相較於對於色度的有利效應而對於所觀察色度並無任何有害效應之所需要的最小值，添加額外的矽將具有遠為更大的餘裕，使得該程序比硼更易施加。因此相較於使用硼而言係偏好使用矽。特定言之，因為可添加充分的Si直到所需要的全部成長段皆呈現所需要程度的無色為止，較不需要將產物限於來自單一成長段之材料。When nitrogen is present in the program as an impurity, it is deliberately added to the program to improve one of the chromaticities. When 矽 occurs, it is known that the system is ingested into the diamond and is known to form a 737 nm luminescence center especially when nitrogen is present. This center does not affect the visible color of the diamond. However, this invention discloses that the addition of a lanthanide in the form of a decane at a suitable concentration to the gas phase results in a substantial reduction in the effect of any nitrogen present as a gaseous impurity on the color of the diamond. This mechanism may be one of the centers of defects typically produced by reducing nitrogen intake or simply reducing nitrogen uptake, or may have a compensatory effect, but this is the case for previously reported p-type dopants in diamonds. It will be amazing. However, in the case of 矽, the additional minimum 添加 will have a much larger margin than the minimum required for the observed chromaticity without any detrimental effect on the observed chromaticity, so that The program is easier to apply than boron. Therefore, it is preferred to use hydrazine compared to the use of boron. In particular, because sufficient Si can be added until all of the desired growth stages exhibit the desired degree of colorlessness, it is less desirable to limit the product to materials from a single growth stage.

達成此效應所需要的矽摻雜物之精密濃度將部分地依據諸如程序功率、壓力、基材溫度等其他程序條件而定，但熟習該技術者將能夠使此處所提供的條件適應於其自身特定合成系統而無不當困難。The precise concentration of germanium dopant required to achieve this effect will depend, in part, on other process conditions such as program power, pressure, substrate temperature, etc., but those skilled in the art will be able to adapt the conditions provided herein to themselves. Specific synthetic systems without undue difficulty.

譬如矽烷或部分其他含矽氣體形式之刻意添加的矽較佳係以大於0.01 ppm(百萬分之一或每106 之份數，均等矽烷分子：所有氣體分子出現在解離前的入進氣流中)、更佳大於0.03 ppm、更佳大於0.1 ppm、更佳大於0.2 ppm、更佳大於0.5 ppm、更佳大於1 ppm、更佳大於2 ppm、更佳大於5 ppm、更佳大於10 ppm、最佳大於20 ppm的濃度提供。Deliberately added hydrazines such as decane or some other hydrazine-containing gas form are preferably greater than 0.01 ppm (parts per million or every 10 6 parts, equal decane molecules: all gas molecules appear in the intake before dissociation More preferably in the stream), more than 0.03 ppm, more preferably more than 0.1 ppm, more preferably more than 0.2 ppm, more preferably more than 0.5 ppm, more preferably more than 1 ppm, more preferably more than 2 ppm, more preferably more than 5 ppm, more preferably more than 10 A concentration of ppm, optimally greater than 20 ppm is provided.

CVD鑽石材料本身較佳包括顯著位準之一種、或較佳不只一種雜質，其中雜質可為下列一或多者：a)固相的硼，處於大於101 4 原子公分－ 3 、較佳大於3 x 101 4 原子公分－ 3 、較佳大於101 5 原子公分－ 3 、更佳大於3 x 101 5 原子公分－ 3 、更佳大於101 6 原子公分－ 3 、更佳大於3 x 101 6 原子公分－ 3 、最佳大於101 7 原子公分－ 3 之濃度；b)固態的矽，處於大於101 4 原子公分－ 3 、較佳大於3 x 101 4 原子公分－ 3 、較佳大於101 5 原子公分－ 3 、更佳大於3 x 101 5 原子公分－ 3 、更佳大於101 6 原子公分－ 3 、更佳大於3 x 101 6 原子公分－ 3 、最佳大於101 7 原子公分－ 3 之濃度；c)固態的氮，處於大於5 x 101 5 原子公分－ 3 、較佳大於101 6 原子公分－ 3 、更佳大於3 x 101 6 原子公分－ 3 、最佳大於101 7 原子公分－ 3 之濃度。較佳氮出現在至少另一雜質旁邊，該另一雜質更佳為B或Si且滿足對於上述硼及矽之判別標準，且最佳為Si且滿足對於上述矽的判別標準。雖然處於這些位準之氮在CVD鑽石中為已知，但未知其連同在高色度、且特別是在高清澈度及顯著尺寸之高色度寶石中。The CVD diamond material itself preferably comprises a significant level, or preferably more than one impurity, wherein the impurities may be one or more of the following: a) solid phase boron, greater than 10 1 4 atomic centimeters - 3 , preferably greater than 3 x 10 1 4 atomic centimeters - 3 , preferably greater than 10 1 5 atomic centimeters - 3 , more preferably greater than 3 x 10 1 5 atomic centimeters - 3 , more preferably greater than 10 1 6 atomic centimeters - 3 , more preferably greater than 3 x 10 1 6 atomic centimeters - 3 , optimally greater than 10 1 7 atomic centimeters - 3 concentration; b) solid enthalpy, greater than 10 1 4 atomic centimeters - 3 , preferably greater than 3 x 10 1 4 atomic centimeters - 3 , Preferably greater than 10 1 5 atomic centimeters - 3 , more preferably greater than 3 x 10 1 5 atomic centimeters - 3 , more preferably greater than 10 1 6 atomic centimeters - 3 , more preferably greater than 3 x 10 1 6 atomic centimeters - 3 , optimal greater than 1017 atoms cm - 3 the concentration; c) solid nitrogen is greater than 5 x 10 1 5 atoms cm - 3, preferably greater than 1016 atoms cm - 3, more preferably greater than 3 X 1016 atoms cm - 3 , optimally greater than 10 1 7 atomic centimeters - 3 concentration. Preferably, the nitrogen is present next to at least one other impurity, and the other impurity is more preferably B or Si and satisfies the criterion for the above-mentioned boron and bismuth, and is preferably Si and satisfies the criterion for the above-mentioned enthalpy. Although nitrogen at these levels is known in CVD diamonds, it is not known to be associated with high chroma gems of high chroma, especially in high definition and significant size.

熟習該技術老將瞭解上述方法的實施例原則上可施用至鑽石中雜質的許多其他組合，譬如硼及硫或硼及磷、或矽及硫、或矽及磷，但成長程序中出現會影響色度之身為一未經控制雜質之這些雜質的一者是遠為較少見的現象。Those skilled in the art will appreciate that embodiments of the above methods can in principle be applied to many other combinations of impurities in diamonds, such as boron and sulfur or boron and phosphorus, or antimony and sulfur, or antimony and phosphorus, but will appear in the growth process. One of these impurities, which is an uncontrolled impurity, is a far less common phenomenon.

因為刻意添加的雜質可能降低未經控制雜質之攝入，可以相較於並無刻意添加的摻雜物所達成者來改良所產生材料的電子性質，但其通常將不超過自諸如WO 01/96634中所揭露者等高純度程序所獲得者。此文中，經改良的電子性質可包括增加的活動力、壽命、電荷收集距離及類似物。Since deliberately added impurities may reduce the intake of uncontrolled impurities, the electronic properties of the resulting material may be improved compared to those not intentionally added, but typically will not exceed those from, for example, WO 01/ Those obtained by the high purity program such as those disclosed in 96634. In this context, improved electronic properties may include increased activity, lifetime, charge collection distance, and the like.

上述發明的鑽石層較佳具有“高晶性品質”。本文中“高晶性品質”可容許出現雜質原子及相關聯的點缺陷，但譬如藉由造成過度散射、或色彩、或強度降低或可處理性低於預定光學應用所需要者而對於會影響光學應用的材料使用之排差束或其他延伸缺陷構成了限制。The diamond layer of the above invention preferably has a "high crystal quality". "High crystalline quality" herein may permit the presence of impurity atoms and associated point defects, but may be affected, for example, by causing excessive scattering, or color, or reduced intensity or handleability lower than required for a predetermined optical application. The use of differential beams or other extended defects in materials used in optical applications constitutes a limitation.

上述發明的另一態樣係為本發明的高色度CVD鑽石可以一寶石的形式製備。此等寶石可具有高品質。寶石品質評等中，四個關鍵品質參數之一者係為鑽石寶石的清澈度。所使用的清澈度等級一般係為GIA(美國寶石協會)所界定者且在從FL(無瑕疵)、IF、VVS1(很很輕微內含物)、VVS2、VS1(很輕微內含物)、VS2、SI1(輕微內含物)、SI2、I1(不完美)、I2及I3尺度上運作。清澈度係為寶石中不存在可見瑕疵，在CVD鑽石成長程序中常利用不良基材製備及/或不純程序氣體來在鑽石中產生使清澈度劣化之內含物或其他特性。Another aspect of the above invention is that the high chroma CVD diamond of the present invention can be prepared in the form of a gemstone. These stones can be of high quality. One of the four key quality parameters in the gem quality rating is the clarity of the diamond gemstone. The clarity levels used are generally defined by GIA (American Gem Society) and are from FL (no flaw), IF, VVS1 (very very slight inclusions), VVS2, VS1 (very slight inclusions), VS2, SI1 (slight inclusions), SI2, I1 (imperfect), I2 and I3 scale operations. The clarity is such that no visible defects are present in the gemstone, and poor substrate preparation and/or impure process gases are often used in CVD diamond growth procedures to produce inclusions or other characteristics in the diamond that degrade clarity.

在寶石中希望具有高清澈度、特別是連同高色度，但先前尚未知悉具有在程序中或後續材料中出現顯著雜質情形下製造高色度及高清澈度材料之方法。特定言之，本發明的方法提供在一出現顯著氣態雜質、且在一較佳實施例中在固體中含有顯著位準之該等氣態雜質的一或多者之程序中成長之高色度的材料，其中清澈度優於I1、更佳優於SI1、更佳優於VS2、更佳優於VS1、更佳優於VVS2、更佳優於VVS1、最佳為無瑕疵。It is desirable to have high definition in gemstones, particularly in conjunction with high chroma, but it has not previously been known to produce high chroma and high definition materials in the presence of significant impurities in the process or in subsequent materials. In particular, the method of the present invention provides high chroma growth in the process of one or more of the presence of significant gaseous impurities and, in a preferred embodiment, a significant level of such gaseous impurities in the solid. The material, wherein the clarity is better than I1, better than SI1, better than VS2, better than VS1, better than VVS2, better than VVS1, and most preferably no flaw.

上述發明提供一層高色度、低光學吸收且較佳亦高清澈度鑽石之CVD單晶鑽石材料，其具有較佳大於0.1公厘、更佳大於0.2公厘、更佳大於0.5公厘、更佳大於1公厘、更佳大於2公厘、更佳大於2.5公厘、更佳大於3公厘、最佳大於3.5公厘之厚度，其中該層含有顯著雜質或在出現顯著氣態雜質下成長。The above invention provides a CVD single crystal diamond material having a high chroma, low optical absorption, and preferably high definition diamond, preferably having a thickness of more than 0.1 mm, more preferably more than 0.2 mm, more preferably more than 0.5 mm, more Preferably, the thickness is more than 1 mm, more preferably more than 2 mm, more preferably more than 2.5 mm, more preferably more than 3 mm, most preferably more than 3.5 mm, wherein the layer contains significant impurities or grows in the presence of significant gaseous impurities. .

上述發明進一步提供以一寶石形式拋光的上述單晶鑽石層所產生之一CVD鑽石，其特徵在於具有大於2公厘、較佳大於2.5公厘、更佳大於3.0公厘之三個正交維度，其中至少一軸線配置為沿著<100>晶體方向或沿著石體的主要對稱軸線。鑽石將具有高品質且可具有上述特徵的一或多者。The above invention further provides a CVD diamond produced by the single crystal diamond layer polished in the form of a gemstone, characterized by having three orthogonal dimensions of greater than 2 mm, preferably greater than 2.5 mm, and more preferably greater than 3.0 mm. At least one of the axes is configured along the <100> crystal direction or along the main axis of symmetry of the stone body. The diamond will have one or more of high quality and may have the above characteristics.

對於上述本發明的均勻高色度單晶CVD鑽石材料之製造而言，成長務必發生於一大致無結晶缺陷之鑽石表面上。本文中，缺陷主要係指排差及微裂痕，但亦包括雙邊界、點缺陷、低角邊界及對於晶體結構之任何其他擾亂。基材較佳為一低雙折射型Ia天然、Ib或IIa高壓力/高溫度合成鑽石或一CVD合成單晶鑽石。缺陷可以兩方式劣化材料，產生應力、裂痕及相關聯的較佳位址以供色度缺陷形成，及負面地影響雜質的局部攝入。因為排差操作係發生於厚層成長期間，基材內及成長的早期階段期間之排差控制特別重要。For the manufacture of the uniform high chroma single crystal CVD diamond material of the present invention described above, growth must occur on the surface of a diamond having substantially no crystal defects. In this context, defects mainly refer to displacement and micro-cracks, but also include double boundaries, point defects, low-angle boundaries, and any other disturbances to the crystal structure. The substrate is preferably a low birefringence type Ia natural, Ib or IIa high pressure/high temperature synthetic diamond or a CVD synthetic single crystal diamond. Defects can degrade materials in two ways, creating stresses, cracks, and associated preferred addresses for chrominance defect formation, and negatively affecting localized uptake of impurities. Because the differential operation occurs during thick layer growth, the differential control during the substrate and during the early stages of growth is particularly important.

缺陷密度最容易在使用一經最適化的電漿或化學蝕刻以顯露缺陷(稱為一顯露電漿蝕刻)(譬如利用下述類型的一簡短電漿蝕刻)之後藉由光學評價予以特徵化。可顯露出兩類型的缺陷：1)對於基材材料品質為本徵者。選定的天然鑽石中，這些缺陷的密度可低達50/平方公厘，更典型數值為102 /平方公厘，在其他案例中可為106 /平方公厘或更大。The defect density is most easily characterized by optical evaluation after the use of an optimized plasma or chemical etch to reveal defects (referred to as a reveal plasma etch) (e.g., using a short plasma etch of the type described below). Two types of defects can be revealed: 1) the quality of the substrate material is intrinsic. In selected natural diamonds, the density of these defects can be as low as 50/cm 2 , more typically 10 2 /cm 2 , and in other cases 10 6 /mm ^ 2 or more.

2)拋光所導致者，包括排差結構及沿著拋光線形成顫響軌道(有時稱為撞響軌道)之微裂痕。其密度可在一樣本上顯著地變動，典型數值介於從102 /平方公厘、至不良拋光區域或樣本中的大於104 /平方公厘之間。2) Caused by polishing, including the differential structure and the formation of micro-cracks along the polishing line to form a trembling track (sometimes referred to as a bump track). The density can vary significantly from sample to sample, with typical values ranging from 10 2 /cm 2 to less than 10 4 /cm 2 in poorly polished areas or samples.

缺陷的較佳低密度係使得如上述與缺陷相關之表面蝕刻特性的密度低於5 x 103 /平方公厘、更佳低於102 /平方公厘。The preferred low density of the defects is such that the density of the surface etch characteristics associated with the defects as described above is less than 5 x 10 3 /cm 2 , more preferably less than 10 2 /cm 2 .

因此可藉由小心製備基材來盡量地減少位於或低於發生CVD成長處的基材表面之缺陷。由於各階段會影響當一基材完成時終將形成基材表面的平面處之材料內的缺陷密度，此處製備係包括自礦收回物(在天然鑽石案例中)或合成(在合成材料案例中)施加至材料之任何程序。特定處理步驟可包括諸如機械鋸切、研磨及拋光(在此申請案中，經特定最適化以產生低缺陷位準)等習知鑽石程序、及諸如雷射處理或離開植入及掘除技術、化學/機械拋光、及液體與電漿化學處理技術等較不習知的技術。此外，應盡量減少表面RQ (刻筆輪廓計所測量的表面輪廓與扁平部之均方根差，較佳在0.08公厘長度上測量)，任何電漿蝕刻前之典型數值不大於數奈米，亦即小於10奈米。Therefore, defects at or below the surface of the substrate where CVD growth occurs can be minimized by carefully preparing the substrate. Since each stage affects the density of defects in the material at the plane where the surface of the substrate will eventually form when the substrate is completed, the preparation here includes self-mineral reclaimed material (in the case of natural diamonds) or synthetic (in the case of synthetic materials) Medium) Any procedure applied to the material. Specific processing steps may include conventional diamond procedures such as mechanical sawing, grinding and polishing (in this application, specifically optimized to produce low defect levels), and such as laser processing or exit implant and excavation techniques. Lesser-known techniques such as chemical/mechanical polishing, and liquid and plasma chemical processing techniques. In addition, the surface R Q should be minimized (the root mean square difference between the surface profile measured by the stylus profilometer and the flat portion, preferably measured over 0.08 mm), and the typical value before any plasma etch is no more than a few Meter, that is, less than 10 nm.

盡量減少基材的表面損害之一特定方法係包括其上發生均質磊晶鑽石成長之表面上的一現場電漿蝕刻。原則上，此蝕刻不需位於現場，亦不需緊接在成長程序之前，但如果位於現場將可達成最大利益，因為如此可避免任何進一步物理損害或化學污染之危險。當成長程序亦以電漿為基礎時，現場蝕刻一般亦最為方便。電漿蝕刻可使用與沉積或鑽石成長程序類似的條件，但不存在任何含碳源氣體且概括處於一略微較低溫度以提供更好的蝕刻速率控制。譬如，其可由下列一或多者所組成：(i)一氧蝕刻，其主要使用氫且依需要包括少量的Ar及一所需要少量的O2 。典型的氧蝕刻條件為50至450 x 102 帕壓力，一含有1至4%氧含量、0至30%氬含量且其餘為氫之蝕刻氣體，所有百分比皆基於體積，600至1100℃的一基材溫度(較典型為800℃)及3至60分鐘的一典型時程；(ii)一氫蝕刻，其類似於(i)但不存在有氧；(iii)可使用不只以氬、氫及氧為基礎之替代性蝕刻方法，譬如，使用鹵素、其他惰性氣體或氮者。One particular method of minimizing surface damage to the substrate is a field plasma etch on the surface on which the growth of the homogeneous epitaxial diamond occurs. In principle, this etch does not need to be on site and does not need to be in front of the growth process, but it will be of maximum benefit if located at the site, as this avoids any further physical or chemical contamination hazards. When the growth process is also based on plasma, on-site etching is generally the most convenient. Plasma etching can use conditions similar to those of deposition or diamond growth procedures, but there are no carbon source gases present and are generally at a slightly lower temperature to provide better etch rate control. For example, it may be composed of one or more of the following: (i) an oxygen etch, which primarily uses hydrogen and, if desired, a small amount of Ar and a small amount of O 2 required . Typical oxygen etching conditions are 50 to 450 x 10 2 Pa pressure, an etching gas containing 1 to 4% oxygen content, 0 to 30% argon content and the balance being hydrogen, all percentages based on volume, 600 to 1100 ° C Substrate temperature (typically 800 ° C) and a typical time course of 3 to 60 minutes; (ii) hydrogen etching, similar to (i) but no aerobic; (iii) can be used not only argon, hydrogen And oxygen-based alternative etching methods, such as the use of halogens, other inert gases or nitrogen.

一般而言，蝕刻係包含一氧蝕刻，然後為一氫蝕刻，然後藉由導入碳源氣體而直接移至合成。選擇蝕刻時間/溫度藉以能夠移除來自處理的留存表面損害，且移除任何表面污染物，但不形成高度粗化表面且不沿諸如與表面相交且因此造成深凹坑之排差等延伸缺陷作廣泛地蝕刻。由於蝕刻具侵略性，此階段之室設計及材料選擇務必使其組件不讓材料被電漿轉移成氣相或轉移至基材表面。位於氧蝕刻後之氫蝕刻係對於結晶缺陷較不具特定性，而弄圓將侵蝕性攻擊此等缺陷之氧蝕刻所造成的稜角且提供一較平順、更好的表面以供後續成長。In general, the etch process involves an oxygen etch followed by a hydrogen etch followed by direct transfer to synthesis by introduction of a carbon source gas. The etch time/temperature is selected to be able to remove residual surface damage from the process and remove any surface contaminants, but does not form a highly roughened surface and does not extend along defects such as intersections with the surface and thus causing deep pits. Widely etched. Due to the aggressiveness of the etch, the chamber design and material selection at this stage must be such that the assembly does not allow the material to be transferred into the gas phase by the plasma or transferred to the surface of the substrate. Hydrogen etching after oxygen etching is less specific to crystalline defects, and rounding will aggressively attack the edges caused by oxygen etching of such defects and provide a smoother, better surface for subsequent growth.

其上發生CVD鑽石成長之鑽石基材的表面較佳係為{100}、{110}、{113}或{111}表面。由於處理拘限，實際樣本表面定向會與這些理想定向相差最高5。、部分案例中最高相差10°，但由於其會負面地影響可複製性故較不理想。The surface of the diamond substrate on which the CVD diamond grows is preferably a {100}, {110}, {113} or {111} surface. Due to processing constraints, the actual sample surface orientation will differ from these ideal orientations by a maximum of 5. In some cases, the highest difference is 10°, but it is less than ideal because it will negatively affect the reproducibility.

上述本發明的方法可與諸如退火等後成長處理作進一步合併。本文中，退火可發生於一溫度及壓力範圍，從低達1000℃－1800℃溫度的近大氣退火，及1200℃－3000℃範圍溫度的石墨或鑽石穩定區域中之高壓力退火。The above method of the present invention can be further combined with post-growth treatment such as annealing. In this context, annealing can occur at a temperature and pressure range, from near atmospheric annealing at temperatures as low as 1000 ° C to 1800 ° C, and high pressure annealing in graphite or diamond stabilizing regions at temperatures ranging from 1200 ° C to 3000 ° C.

對於色度具有三個視覺屬性：色調、光度及飽和。色調係為可使其被分類成紅、綠、藍、黃、黑或白、或位於這些基本色調的相鄰對或三件組之間的一色調之色屬性(Stephen C.Hofer，有色鑽石之收集及分類，1998，Ashland Press，紐約)。There are three visual attributes for chromaticity: hue, luminosity, and saturation. Hue is a color attribute that allows it to be classified as red, green, blue, yellow, black or white, or between adjacent pairs or groups of three basic tones (Stephen C. Hofer, colored diamonds) Collection and Classification, 1998, Ashland Press, New York).

白、灰及黑物件係在從明亮到陰暗的一光度尺上予以差別化。光度係為以從白開始漸進式經過灰的較暗位準且以黑終結的一中立消色差尺由類似性程度所界定之色屬性。White, gray and black objects are differentiated from a light to dark shade. The luminosity is a color attribute defined by the degree of similarity by a neutral achromatic ruler that progressively passes through the darker level of gray and ends in black.

飽和係為由與相同光度的一消色差色之差異程度所界定之色屬性。其亦為一對應於色強度之描述性用語。鑽石業使用諸如強烈、強力及逼真等形容詞來代表視覺評估之不同飽和程度。CIELAB色系中，飽和係為脫離中立色軸之程度(由飽和＝[(a＊ )2 ＋(b＊ )2 ]1 /2 所界定，見下文)。光度係為與飽和分開認知之一視覺品質。The saturation is a color attribute defined by the degree of difference from an achromatic color of the same luminosity. It is also a descriptive term corresponding to color intensity. The diamond industry uses adjectives such as strong, powerful and realistic to represent the different degrees of saturation of visual assessment. In the CIELAB color system, the saturation is the degree of departure from the neutral color axis (defined by saturation = [(a * ) 2 + (b * ) 2 ] 1 / 2 , see below). The luminosity is a visual quality that is perceived separately from saturation.

在具有特定吸收性質的材料已經成長至一有限厚度之案例中，能夠自該材料的一薄平行側板上所進行之吸收頻譜測量來預測若其自具有相同吸收係數頻譜之均勻材料的一較厚板片拋光則一圓形明亮式將為何色會是有用的方式。此處描述用以達成此作用之一簡單例行方式。此例行方式的第一階段係為材料的一平行側板與其在頻譜的可見區中相距其測量透射比之CIELAB色品座標的偏差。In cases where materials with specific absorption properties have grown to a finite thickness, absorption spectra measurements from a thin parallel side plate of the material can be used to predict a thicker uniform material if it has the same absorption coefficient spectrum. The polishing of the plate is a round bright style, which will be a useful way. A simple routine to achieve this is described here. The first stage of this routine is the deviation of a parallel side panel of material from its CIELAB chromaticity coordinates that measure its transmittance in the visible region of the spectrum.

一物件的認知色係依據物件的透射比/吸收頻譜、照明源的頻譜功率分佈及觀察者眼睛的響應曲線而定。此說明書中所引用的CIELAB色品度座標已經以下述方式求出。The perceived color of an object depends on the transmittance/absorption spectrum of the object, the spectral power distribution of the illumination source, and the response curve of the observer's eye. The CIELAB chromaticity coordinates quoted in this specification have been found in the following manner.

利用一標準D65照射頻譜及眼睛的標準(紅、綠及藍)響應曲線(G.Wyszecki及W.S.Stiles，John Wiley，紐約－倫敦－雪梨，1967)鑽石的一平行側板之CIE L＊ a＊ b色品度座標已經利用下列關係自其透射頻譜求出(350奈米及800奈米之間，具有一1奈米資料間隔)。CIE L * a * b color of a parallel side panel of a diamond using a standard D65 illumination spectrum and eye standard (red, green, and blue) response curves (G. Wyszecki and WSStiles, John Wiley, New York-London-Sydney, 1967) The coordinates have been derived from their transmission spectrum using the following relationship (between 350 nm and 800 nm with a 1 nm data gap).

Sλ ＝波長λ之透射比Lλ ＝照射之頻譜功率分佈xλ ＝眼睛的紅響應函數yλ ＝眼睛的綠響應函數zλ ＝眼睛的藍響應函數X＝Σλ [Sλ xλ Lλ ]/Y0 Y＝Σλ [Sλ yλ Lλ ]/Y0 Z＝Σλ [Sλ zλ Lλ ]/Y0 其中Y0 ＝Σλ yλ Lλ L＊ ＝116(Y/Y0 )1 / 3 －16＝光度(對於Y/Y0 >0.008856)a＊ ＝500[(X/X0 )－(Y/Y0 )1 / 3 ](對於X/X0 >0.008856，Y/Y0 >0.008856)b＊ ＝200[(Y/Y0 )－(Z/Z0 )1 / 3 ](對於Z/Z0 >0.008856)C＊ ＝(a＊ 2 ＋b＊ 2 )1 / 2 ＝飽和hab＝arctan(b＊ /a＊ )＝灰調角S λ = transmittance of wavelength λ L λ = spectral power distribution of illumination x λ = red response function of the eye y λ = green response function of the eye z λ = blue response function of the eye X = Σ λ [S λ x λ L λ ] / Y 0 Y = λ λ [S λ y λ L λ ] / Y 0 Z = Σ λ [S λ z λ L λ ] / Y 0 where Y 0 = Σ λ y λ L λ L * = 116 ( Y/Y 0 ) 1 / 3 -16=luminosity (for Y/Y 0 >0.008856)a * =500[(X/X 0 )-(Y/Y 0 ) 1 / 3 ] (for X/X 0 > 0.008856,Y/Y 0 >0.008856)b * =200[(Y/Y 0 )-(Z/Z 0 ) 1 / 3 ](for Z/Z 0 >0.008856)C * =(a * 2 +b * 2 ) 1 / 2 = saturated hab = arctan (b * / a * ) = gray adjustment angle

這些等式的修改版本必須使用在X/X0 、Y/Y0 及Z/Z0 之極限外。修改版本係在Commission Internationale de L’Eclairage(Colormetry(1986))所準備的一技術報告中提供。Modified versions of these equations must be used outside the limits of X/X 0 , Y/Y 0, and Z/Z 0 . The modified version is provided in a technical report prepared by Commission Internationale de L'Eclairage (Colormetry (1986)).

以a＊ 對應於x軸而b＊ 對應於y軸將a＊ 及b＊ 座標描繪在一圖形上將是正常的方式。正a＊ 及b＊ 值分別對應於色調的紅及黃組份。負a＊ 及b＊ 值分別對應於綠及藍組份。圖形的正象限則覆蓋介於從黃經過橙至紅的色調，飽和(C＊ )由相距原點的距離提供。It would be normal for a * to correspond to the x-axis and b * to correspond to the y-axis to depict a * and b * coordinates on a graph. The positive a * and b * values correspond to the red and yellow components of the hue, respectively. The negative a * and b * values correspond to the green and blue components, respectively. The positive quadrant of the graphic covers the hue from yellow to orange to red, and the saturation (C * ) is provided by the distance from the origin.

可以預測具有一給定吸收係數頻譜之鑽石的a＊ b＊ 座標將隨著光徑長度變化而如何改變。為了具有此作用，首先必須自經測得的吸收頻譜減除反射損失。然後縮放吸收度以容許具有一不同路徑長度且隨後加回反射損失。吸收頻譜可轉換至一透射頻譜用以求出新厚度之CIELAB座標。利用此方式，可以模型來模擬色調、飽和及光度對於光徑長度之依存性以瞭解每單位厚度具有給定吸收性質之鑽石色度將如何依據光徑長度而定。It can be predicted how the a * b * coordinate of a diamond having a given absorption coefficient spectrum will change as the length of the optical path changes. In order to have this effect, the reflection loss must first be subtracted from the measured absorption spectrum. The absorbance is then scaled to allow for a different path length and then the return loss is added back. The absorption spectrum can be converted to a transmission spectrum to find the CIELAB coordinates for the new thickness. In this way, the model can be used to simulate the dependence of hue, saturation, and luminosity on the length of the optical path to understand how the chromaticity of the diamond with a given absorption property per unit thickness will depend on the length of the optical path.

因為吸收係數朝向較短波長逐漸升高，大部份CVD材料為棕色。一般已經以一可使經拋光石體的桌台平行於與CVD材料所沉積之鑽石基材的介面之定向藉由均質磊晶CVD材料來產生CVD合成圓形明亮式。基材移除及所產生板片的頂及底面作拋光之後，吸收/透射頻譜已經收集以上述方式決定的飽和值。以受限於此等板片厚度的深度來拋光圓形明亮式(一“深度受限圓形明亮式”)時，已經在對於平行側板片的經模型模擬的飽和與經訓練鑽石評等員利用下列轉換式：D＝0、E＝1、F＝2、G＝3、H＝4等所判斷自GIA等級所求出之所產生完成石體的數值色度等級之間發現一近似線性關係。對於中至弱的飽和，已知棕/泛棕深度受限CVD圓形明亮式的數值色度等級及自板片的吸收/透射頻譜以模型模擬出之飽和(C＊ )之間的實證關係遵守下列近似關係式：圓形明亮式數值色度等級＝2 x C＊ Since the absorption coefficient gradually increases toward shorter wavelengths, most of the CVD material is brown. The CVD synthetic circular bright form has generally been produced by a homogeneous epitaxial CVD material in a direction that allows the polished stone body table to be oriented parallel to the interface of the diamond substrate deposited with the CVD material. After the substrate is removed and the top and bottom surfaces of the resulting sheet are polished, the absorption/transmission spectrum has collected the saturation values determined in the manner described above. Saturated and trained diamond critics who have been modeled for parallel side plates when polishing round brilliant shapes (a "depth-limited round brilliant") at a depth limited by the thickness of the plates An approximate linearity is found between the numerical chromaticity levels of the finished stone bodies determined from the GIA level, using the following transformation formulas: D=0, E=1, F=2, G=3, H=4, etc. relationship. For medium to weak saturation, the numerical relationship between the brown/pan-brown depth-limited CVD circular bright numerical chromaticity level and the absorption/transmission spectrum from the plate is modeled to saturate (C * ). Observe the following approximate relationship: round brilliant numerical chroma level = 2 x C *

觀察到的線性係由下列論點所支撐。色度模擬工作已經顯示出，對於具有給定吸收性質的材料，對於低至中飽和，路徑長度與利用上文勾勒的例行方式自吸收/透射頻譜求出的C＊ 值之間具有一近似線性關係。在給定的觀視及照明條件下，自一圓形明亮式抵達一觀視者眼睛的光之平均路徑長度應與石體的線性維度成正比。接著在對於一平行側板片之飽和與對於自該板片所產生的一深度受限圓形明亮式之飽和間應有一近似線性關係。先前的工作已經暗示，一經拋光石體的色度等級與其飽和之間具有一近似線性關係。綜言之，這暗示一深度受限圓形明亮式的色度等級與自其所拋光之平行側板片的吸收/透射頻譜所求出之飽和之間應有一近似線性關係。The observed linearity is supported by the following arguments. Chroma simulation work has shown that for materials with a given absorption property, for low to medium saturation, the path length has an approximation between the C * values obtained using the routine self-absorption/transmission spectrum outlined above. Linear relationship. Under a given viewing and lighting condition, the average path length of light that reaches a viewer's eye from a round brilliant form should be proportional to the linear dimension of the stone body. There should then be an approximately linear relationship between saturation for a parallel side panel and saturation for a depth limited circular bright pattern produced from the panel. Previous work has suggested that there is an approximately linear relationship between the chroma level of a polished stone and its saturation. In summary, this implies that there should be an approximately linear relationship between the depth-limited circular bright chromaticity level and the saturation obtained from the absorption/transmission spectrum of the parallel side plates it is polished.

從上文討論應可得知，若是製造一相對較薄的板，可以自對於該板所測量的吸收/透射頻譜預測，如果自一具有相同吸收係數頻譜之均勻材料的較厚板片拋光，一圓形明亮式將為何色。為了達成此作用，首先必須自測得的吸收頻譜減除反射損失。然後縮放吸收度以容許具有一不同路徑長度且隨後加回反射損失。然後吸收頻譜可轉換成一透射頻譜用以求出對於新厚度之CIELAB座標(譬如，對於一0.5 ct圓形明亮式近似為3.2公厘或對於一1 ct圓形明亮式近似為3.8公厘)。當減除反射損失時，務必考慮到反射係數的頻譜依存性。其可自F.Peter在Z.Phys.15，358－368(1923)所提供之鑽石折射率的波長依存性求出。利用一平行側板的反射損失對於折射率之依存性之此及標準公式，可以波長之一函數來計算反射損失對於視吸收度之效應且自測得的頻譜減除以容許更精確地計算吸收係數頻譜。It should be understood from the above discussion that if a relatively thin plate is fabricated, it can be predicted from the absorption/transmission spectrum measured for the plate if a thicker plate of uniform material having the same absorption coefficient spectrum is polished, What is the color of a round bright style? In order to achieve this, the reflection loss must first be subtracted from the measured absorption spectrum. The absorbance is then scaled to allow for a different path length and then the return loss is added back. The absorption spectrum can then be converted to a transmission spectrum to find the CIELAB coordinates for the new thickness (e.g., approximately 3.2 mm for a 0.5 ct circular bright approximation or 3.8 mm for a 1 ct circular bright approximation). When subtracting the reflection loss, it is important to consider the spectral dependence of the reflection coefficient. It can be determined from the wavelength dependence of the refractive index of the diamond provided by F. Peter in Z. Phys. 15, 358-368 (1923). Using the dependence of the reflection loss of a parallel side plate on the refractive index and the standard formula, the effect of the reflection loss on the apparent absorbance can be calculated as a function of the wavelength and the self-measured spectral subtraction can be used to allow a more accurate calculation of the absorption coefficient. Spectrum.

現在參照下列非限制性範例來描述本發明。這些範例各者中，除非另外指明，為了控制氮且因此將本發明的利用予以特徵化，利用淨化器及高純度氣體源從入進氣流移除氮，所以在未刻意添加氮摻雜物源的情形下氣流含有小於100 ppb的N2 。然後通常利用氫中100 ppm的N2 之一混合物將氮加回到程序中，此氣體混合物提供程序氣體中氮位準的良好控制，特別是0.5至20 ppm範圍尤然。熟習該技術者將瞭解，利用較低純度氣體或較差真空實行方式會容易導致程序中的氮雜質位準，特別是在1至20 ppm或更大範圍中尤然，此等案例中氮將不是刻意添加的雜質，而是由於較差控制或節省成本所出現者。The invention will now be described with reference to the following non-limiting examples. In each of these examples, unless otherwise specified, in order to control nitrogen and thus characterize the utilization of the present invention, nitrogen is removed from the inlet gas stream using a purifier and a high purity gas source, so nitrogen dopants are not intentionally added. In the case of a source, the gas stream contains less than 100 ppb of N 2 . Then 100 ppm hydrogen typically utilize one of N 2 mixture of nitrogen was added back to the program, the provider of this gas mixture of nitrogen gas level well controlled, especially in the range of 0.5 to 20 ppm, especially natural. Those skilled in the art will appreciate that the use of lower purity gases or poorer vacuum implementations can easily lead to levels of nitrogen impurities in the process, especially in the range of 1 to 20 ppm or greater, where nitrogen will not be Deliberately added impurities, but due to poor control or cost savings.

範例1Example 1

根據WO 01/96634所描述之方法來製備適於合成單晶CVD鑽石之lb HPHT基材，其具有{100}主面。A lb HPHT substrate suitable for the synthesis of single crystal CVD diamond having a {100} major face is prepared according to the method described in WO 01/96634.

這些基材利用一高溫鑽石硬銲材料被硬銲至一鎢基材上。將其導入一微波電漿CVD反應器中且以WO 01/96634中所描述的一般形式但利用下述特定合成條件開始一蝕刻及成長循環。These substrates are brazed to a tungsten substrate using a high temperature diamond brazing material. This was introduced into a microwave plasma CVD reactor and an etching and growth cycle was initiated in the general form described in WO 01/96634 using the specific synthesis conditions described below.

利用氫中100 ppm N2 的一混合物將氮添加至程序中。利用氫中20 ppm或100 ppm的B2 H6 將硼雜質添加至程序。Nitrogen was added to the program using a mixture of 100 ppm N 2 in hydrogen. Boron impurities were added to the procedure using 20 ppm or 100 ppm of B 2 H 6 in hydrogen.

製備出兩組樣本。Two sets of samples were prepared.

樣本組1－1Sample group 1-1

第一成長階段包含200/250/4500 sccm(標準立方公分每分鐘)之處於200 x 102 帕的CH4 /Ar/H2 及850℃的一基材溫度而未添加摻雜物。這是一控制層的高純度高色度成長以示範程序控制。The first growth stage comprised 200/250/4500 sccm (standard cubic centimeters per minute) of CH 4 /Ar/H 2 at 200 x 10 2 Pa and a substrate temperature of 850 ° C without the addition of dopants. This is a control layer of high purity and high chroma growth controlled by an exemplary program.

第二成長階段與上述第一階段相同，其中添加1 ppm的N2 。此階段係評估作為唯一氣態雜質之1.0 ppm氮的效應。The second growth phase is the same as the first phase described above, with 1 ppm of N 2 added . This phase evaluates the effect of 1.0 ppm nitrogen as the sole gaseous impurity.

樣本組1－2Sample group 1-2

第一成長階段係重覆對於組1－1的第一成長階段之條件。The first growth phase repeats the conditions for the first growth phase of Group 1-1.

第二成長階段與上述第一階段相同，其中添加0.003 ppm B2 H6 且添加1 ppm N2 。The second growth stage was the same as the first stage described above, with 0.003 ppm B 2 H 6 added and 1 ppm N 2 added .

成長期間完成時，自反應器移除且處理以產生一範圍的測試件之樣本(特別是成長的橫剖面切片)，而第二階段成長層的獨立板通常係為2至3公厘厚。橫剖面切片可確認，在各案例中第一階段成長基本上係為無色高純度成長，而第二階段成長在樣本組1－1中顯著為棕色，第二階段成長在添加硼的第二程序中幾乎為無色。Upon completion of the growth period, the reactor is removed and processed to produce a range of samples of the test piece (especially the growing cross-sectional slice), while the separate plates of the second stage growth layer are typically 2 to 3 mm thick. Cross-sectional sectioning confirmed that in the first case, the growth of the first stage was basically colorless and high-purity growth, while the growth of the second stage was significantly brown in the sample group 1-1, and the second stage was the second procedure of adding boron. It is almost colorless.

利用下列一般成長條件產生數個進一步的樣本：200/250/4500 sccm(標準立方公分每分鐘)處於200 x 102 帕的CH4 /Ar/H2 及850℃的基材溫度，添加0.003 ppm的B2 H6 ，添加1 ppm的N2 ，但對於不同成長參數作出小的變異且特別是使溫度變動＋/－100℃，B及N濃度在兩方向具有5倍因數之相對比值(譬如，相對於氮較高及較低的硼)，及＋/－100 x 102 帕的壓力。結論係為，相對於氮過多的B產生藍材料，相對於氮過少的B產生棕材料，B及N之間的最適平衡係隨著諸如壓力及溫度等其他程序參數具有某程度變動。然而，可藉由將一最適位準的硼添加至程序、匹配於所使用的特定成長條件而令氮在產生棕色或光學吸收性鑽石方面之有害效應獲得改良且大體停止。Several further samples were generated using the following general growth conditions: 200/250/4500 sccm (standard cubic centimeters per minute) at a substrate temperature of 200 x 10 2 Pa CH 4 /Ar/H 2 and 850 ° C with 0.003 ppm added B 2 H 6 , adding 1 ppm of N 2 , but making small variations for different growth parameters and especially making the temperature change +/- 100 ° C, the B and N concentrations have a relative ratio of 5 times in both directions (eg , relative to nitrogen with higher and lower boron), and a pressure of +/- 100 x 10 2 Pa. The conclusion is that B is a blue material with respect to excessive nitrogen, and a brown material is produced with respect to B with too little nitrogen. The optimum balance between B and N varies to some extent with other program parameters such as pressure and temperature. However, the deleterious effects of nitrogen on the production of brown or optically absorptive diamonds can be improved and substantially stopped by the addition of an optimum level of boron to the process, matching the particular growth conditions employed.

範例2Example 2

如同範例1中來製備1b HPHT鑽石基材且將其安裝至一鎢碟上。將此碟導入一微波電漿CVD反應器中且以WO 01/96634所描述的一般形式開始一蝕刻及成長循環，但利用下述特定合成條件。A 1b HPHT diamond substrate was prepared as in Example 1 and mounted on a tungsten dish. The dish was introduced into a microwave plasma CVD reactor and an etching and growth cycle was initiated in the general form described in WO 01/96634, but with the specific synthesis conditions described below.

利用氫中100 ppm的N2 之一混合物將氮添加至程序中。利用氫中通常為500 ppm的SiH4 將矽雜質添加至程序。製備兩組樣本。Nitrogen was added to the program using a mixture of 100 ppm of N 2 in hydrogen. The cerium impurity is added to the procedure using SiH 4 , typically 500 ppm in hydrogen. Two sets of samples were prepared.

樣本組2－1Sample group 2-1

第一成長階段包含36/0/600 sccm(標準立方公分每分鐘)之處於250 x 102 帕的CH4 /Ar/H2 及810℃的一基材溫度而未添加摻雜物。這是一控制層的高純度高色度成長以示範程序控制。The first growth stage comprised 36/0/600 sccm (standard cubic centimeters per minute) of CH 4 /Ar/H 2 at 250 x 10 2 Pa and a substrate temperature of 810 ° C without the addition of dopants. This is a control layer of high purity and high chroma growth controlled by an exemplary program.

第二成長階段與上述第一階段相同，其中添加2.0 ppm的氮。此階段係評估作為唯一氣態雜質之2.0 ppm氮的效應。The second growth phase is the same as the first phase described above, with 2.0 ppm of nitrogen added. This phase evaluates the effect of 2.0 ppm nitrogen as the sole gaseous impurity.

樣本組2－2Sample group 2-2

第一成長階段係重覆對於組2－1的第一成長階段之條件。The first growth phase repeats the conditions for the first growth phase of Group 2-1.

第二成長階段與上述第一階段相同，其中添加0.03 ppm的矽烷且添加2.0 ppm的氮。The second growth stage was the same as the first stage described above, with 0.03 ppm of decane added and 2.0 ppm of nitrogen added.

成長期間完成時，自反應器移除且處理以產生一範圍的測試件之樣本(特別是成長的橫剖面切片)，而第二階段成長層的獨立板通常係為2至3公厘厚。橫剖面切片可確認，在各案例中第一階段成長基本上係為無色高純度成長，而第二階段成長在樣本組2－1中顯著為棕色，第二階段成長在添加矽的第二程序中幾乎為無色。Upon completion of the growth period, the reactor is removed and processed to produce a range of samples of the test piece (especially the growing cross-sectional slice), while the separate plates of the second stage growth layer are typically 2 to 3 mm thick. Cross-section slicing confirmed that in the first case, the first stage of growth was basically colorless and high-purity growth, while the second stage of growth was significantly brown in sample group 2-1, and the second stage grew in the second procedure of adding bismuth. It is almost colorless.

利用下列一般成長條件產生數個進一步的樣本：36/0/600 sccm(標準立方公分每分鐘)處於250 x 102 帕的CH4 /Ar/H2 及810℃的基材溫度，添加0至5 ppm的矽烷，且添加0至10 ppm的氮，但對於不同成長參數亦作出小的變異且特別是使溫度變動＋/－100℃，及＋/－100 x 102 帕的壓力。特定言之，測試下列組合，以0.2：1、1：1、5：10的ppm記錄下矽烷/氮濃度。在各案例中，矽烷的效應在於抑制鑽石中原本會產生的任何棕色著色。此外，抑制棕色著色所需要之過多的矽並未產生任何有害色度或鑽石成長中的其他變化。因為矽烷的濃度不重要，且氣相的氮濃度位準或其他程序參數的精密值變得遠為較不重要，這提供使用Si作為氣態雜質在降低對於氮的有害效應方面優於B之一額外優點。Several further samples were generated using the following general growth conditions: 36/0/600 sccm (standard cubic centimeters per minute) at a substrate temperature of 250 x 10 2 Pa CH 4 /Ar/H 2 and 810 ° C, adding 0 to 5 ppm of decane, with 0 to 10 ppm of nitrogen added, but with small variations for different growth parameters and especially for temperature fluctuations of +/- 100 ° C, and pressures of +/- 100 x 10 2 Pa. Specifically, the following combinations were tested and the decane/nitrogen concentration was recorded at a ppm of 0.2:1, 1:1, 5:10. In each case, the effect of decane is to inhibit any brown coloration that would otherwise be produced in the diamond. In addition, the excessive enthalpy required to inhibit brown coloration does not produce any harmful color or other changes in diamond growth. Since the concentration of decane is not important, and the precise value of the nitrogen concentration level or other program parameters of the gas phase becomes far less important, this provides one of the advantages over B in reducing the harmful effects on nitrogen using Si as a gaseous impurity. Additional advantages.

範例3Example 3

如同範例1中來製備1b HPHT鑽石基材且將其安裝至一鎢碟上。將此碟導入一微波電漿CVD反應器中且以WO 01/96634所描述的一般形式開始一蝕刻及成長循環，但利用下述特定合成條件：成長條件為36/0/600 sccm(標準立方公分每分鐘)之處於250 x 102 帕的CH4 /Ar/H2 及810℃的一基材溫度，且有0.25 ppm的矽烷濃度及2 ppm的氮濃度。繼續成長直到CVD層厚度為2公厘為止。成長程序終止之後，移除樣本且處理一者以產生單晶CVD鑽石之一獨立平行側板。處理另一者以產生一{100}橫剖面切片。獨立CVD板的特徵化提供下列結果：a)在板的各側上四個地方進行SIMS測量，指示出具有近似6 x 101 5 公分－ 3 (34 ppb)均勻Si濃度。A 1b HPHT diamond substrate was prepared as in Example 1 and mounted on a tungsten dish. The dish was introduced into a microwave plasma CVD reactor and an etching and growth cycle was initiated in the general form described in WO 01/96634, but with the following specific synthesis conditions: growth conditions of 36/0/600 sccm (standard cube) The centimeters per minute is at a substrate temperature of 250 x 10 2 Pa C 4 /Ar/H 2 and 810 ° C with a decane concentration of 0.25 ppm and a nitrogen concentration of 2 ppm. Continue to grow until the CVD layer thickness is 2 mm. After the growth procedure is terminated, the sample is removed and processed to produce one of the individual parallel side plates of the single crystal CVD diamond. The other is processed to produce a {100} cross-sectional slice. Characterized CVD separate plate following results: a) SIMS measurements carried out in four places on each side of the plate, indicating approximately 6 x 10 1 5 cm having - 3 (34 ppb) uniform Si concentration.

b)在室溫進行UV/可見/NIR吸收頻譜術測量，指示出對於300奈米與1000奈米間的所有波長，吸收係數小於0.15公分－ 1 。270奈米的吸收係數為0.18公分－ 1 ，且在基線減除之後，270奈米特性的峰值吸收係數為0.036公分－ 1 ，指示出近似24 ppb之未經補償氮的濃度。350奈米及520奈米的吸收係數分別為0.10及0.07公分－ 1 。b) UV/visible/NIR absorption spectroscopy measurements at room temperature indicating an absorption coefficient of less than 0.15 cm - 1 for all wavelengths between 300 nm and 1000 nm. 270 nm absorption coefficient of 0.18 cm - 1, and, after baseline subtraction, the peak 270 nm absorption coefficient characteristic of 0.036 cm - 1, indicating that the concentration of uncompensated nitrogen of approximately 24 ppb. 350 nm and 520 nm absorption coefficient of 0.10 and 0.07 cm --1.

c)對於此種類材料所產生的一0.5 ct圓形明亮式之CIELAB色品度座標係利用早先描述方法自吸收頻譜術資料作估計且發現係為：L＊ ＝87.9，a＊ ＝－0.13，b＊ ＝1.07，C＊ ＝1.08c) A 0.5 ct round brilliant CIELAB chromaticity coordinate system generated for this type of material is estimated using the self-absorption spectroscopy data described earlier and found to be: L * = 87.9, a * = -0.13, b * =1.07, C * =1.08

利用早先描述的方法，可推導出一具有這些色品度座標的石體將具有一FGIA色度等級。Using the method described earlier, it can be inferred that a stone body having these chromaticity coordinates will have a FGIA chromaticity level.

d)在77K進行吸收頻譜術，指示出一具有6.02 meV．公分－ 1 的積集吸收係數之強烈737奈米特性。d) Perform absorption spectrum at 77K, indicating that it has 6.02 meV. Cm - 1 absorption coefficient product set of strong 737 nm feature.

e)在77K以633奈米激勵進行光致發光頻譜術，指示出737奈米之Si相關特性的拉曼正規化強烈度為4。e) Photoluminescence spectroscopy was performed at 77 K with a excitation of 633 nm, indicating a Raman normalization intensity of 4 for the Si-related property of 737 nm.

f)在77K以514奈米激勵進行光致發光頻譜術，指示出具有下列拉曼正規化強烈度之575、637及737奈米的光致發光特性： f) Photoluminescence spectroscopy with a 514 nm excitation at 77 K, indicating photoluminescence characteristics of 575, 637 and 737 nm with the following Raman normalization intensity:

g)在77K以325奈米激勵進行光致發光頻譜術，指示出533奈米及575奈米之光致發光特性。g) Photoluminescence spectroscopy at 77 K with 325 nm excitation, indicating photoluminescence characteristics of 533 nm and 575 nm.

橫剖面切片的特徵化係提供下列結果：a)SIMS測量再度指示出對於主導<100>段之近似6 x 101 5 公分－ 3 (34 ppb)的一Si濃度。對於已由源自基材的{100}邊緣面成長所形成之次要<100>段測得顯著較高的Si濃度。部分區域中，光學顯微術指示為接近無色，發現Si濃度高於101 8 公分－ 3 (5.7 ppm)。A cross-sectional slice of the feature lines following results: a) SIMS measurements again indicated a dominant <100> Segment of approximately 6 x 10 1 5 cm for - a Si concentration of 3 (34 ppb) of. A significantly higher Si concentration was measured for the secondary <100> segment that had been formed by the {100} edge face growth from the substrate. Subarea, optical microscopy indicated a nearly colorless, the Si concentration was found above 1,018 cm - 3 (5.7 ppm).

b)以633奈米激勵在77K收集的光致發光頻譜係顯示737奈米之一強烈Si相關特性，其具有對於主導<100>段近似4的一拉曼正規化強烈度且在次要<100>段中升高至幾乎40。b) The photoluminescence spectrum collected at 77K with 633 nm excitation shows a strong Si-related property of 737 nm, which has a Raman normalization intensity of approximately 4 for the dominant <100> segment and is secondary < 100> increased to almost 40 in the segment.

c)CVD材料的發光影像，其以上述帶隙激勵生成，由橙紅發光所主導。c) A luminescence image of the CVD material, which is generated by the above-described band gap excitation, dominated by orange-red illumination.

範例4Example 4

如同範例1中製備1b HPHT鑽石基材且將其安裝至一鎢碟上。將此碟導入一微波電漿CVD反應器中且以WO 01/96634所描述的一般形式開始一蝕刻及成長循環，但利用下述特定合成條件：成長條件為36/0/600 sccm(標準立方公分每分鐘)之處於250 x 102 帕的CH4 /Ar/H2 及810℃的一基材溫度，且有0.25 ppm的矽烷濃度及1 ppm的氮濃度。繼續成長直到CVD層厚度為0.7公厘為止。成長程序終止之後，移除樣本且處理一者以產生單晶CVD鑽石之一獨立平行側板。處理另一者以產生一{100}橫剖面切片。獨立CVD板的特徵化提供下列結果：a)在板的各側上四個地方進行SIMS測量，指示出具有近似5 x 101 5 公分－ 3 (28 ppb)的均勻Si濃度。A 1b HPHT diamond substrate was prepared as in Example 1 and mounted on a tungsten dish. The dish was introduced into a microwave plasma CVD reactor and an etching and growth cycle was initiated in the general form described in WO 01/96634, but with the following specific synthesis conditions: growth conditions of 36/0/600 sccm (standard cube) The centimeters per minute is at a substrate temperature of 250 x 10 2 Pa C 4 /Ar/H 2 and 810 ° C with a decane concentration of 0.25 ppm and a nitrogen concentration of 1 ppm. Continue to grow until the CVD layer thickness is 0.7 mm. After the growth procedure is terminated, the sample is removed and processed to produce one of the individual parallel side plates of the single crystal CVD diamond. The other is processed to produce a {100} cross-sectional slice. Characterized CVD separate plate following results: a) SIMS measurements carried out in four places on each side of the plate, indicating approximately having 5 x 10 1 5 cm - uniform Si concentration of 3 (28 ppb) of.

b)在室溫進行UV/可見/NIR吸收頻譜術測量，指示出對於300奈米與1000奈米間的所有波長，吸收係數小於0.5公分－ 1 。270奈米的吸收係數為0.5公分－ 1 ，且在基線減除之後，270奈米特性的峰值吸收係數為0.074公分－ 1 ，指示出近似50 ppb之未經補償氮的濃度。350奈米及520奈米的吸收係數分別為0.32及0.28公分－ 1 。b) UV/visible/NIR absorption spectroscopy measurements at room temperature indicating an absorption coefficient of less than 0.5 cm - 1 for all wavelengths between 300 nm and 1000 nm. The absorption coefficient of 270 nm is 0.5 cm - 1 , and after the baseline subtraction, the peak absorption coefficient of the 270 nm characteristic is 0.074 cm - 1 , indicating an uncompensated nitrogen concentration of approximately 50 ppb. 350 nm and 520 nm were 0.32 and absorption coefficient of 0.28 cm --1.

c)對於此種類材料所產生的一0.5 ct圓形明亮式之CIELAB色品度座標係利用早先描述方法自吸收頻譜術資料作估計且發現係為：L＊ ＝84.0，a＊ ＝－0.19，b＊ ＝－0.43，C＊ ＝0.47c) A 0.5 ct round brilliant CIELAB chromaticity coordinate system generated for this type of material is estimated using the self-absorption spectroscopy data described earlier and found to be: L * = 84.0, a * = -0.19, b * =-0.43, C * =0.47

利用早先描述的方法，可推導出一具有這些色品度座標的石體將具有一E GIA色度等級。Using the method described earlier, it can be inferred that a stone body having these chromaticity coordinates will have an E GIA chromaticity level.

d)在77K進行吸收頻譜術，指示出一具有5.41 meV．公分－ 1 的積集吸收係數之強烈737奈米特性。d) Perform absorption spectrum at 77K, indicating that it has 5.41 meV. Cm - 1 absorption coefficient product set of strong 737 nm feature.

e)在77K以633奈米激勵進行光致發光頻譜術，指示出737奈米之Si相關特性的拉曼正規化強烈度為近似0.90。e) Photoluminescence spectroscopy was performed with a 633 nm excitation at 77 K, indicating a Raman normalization intensity of approximately 0.99 nm for the Si-related property of approximately 0.90.

f)在77K以514奈米激勵進行光致發光頻譜術，指示出具有下列拉曼正規化強烈度之575、637及737奈米的光致發光特性： f) Photoluminescence spectroscopy with a 514 nm excitation at 77 K, indicating photoluminescence characteristics of 575, 637 and 737 nm with the following Raman normalization intensity:

g)在77K以325奈米激勵進行光致發光頻譜術，指示出533奈米及575奈米之光致發光特性。g) Photoluminescence spectroscopy at 77 K with 325 nm excitation, indicating photoluminescence characteristics of 533 nm and 575 nm.

橫剖面切片的特徵化係提供下列結果：a)SIMS測量再度指示出對於主導<100>段之近似5 x 101 5 公分－ 3 (28 ppb)的一Si濃度。對於已由源自基材的{100}邊緣面成長所形成之次要<100>段測得顯著較高的Si濃度。部分區域中，光學顯微術指示為接近無色，發現Si濃度高於101 8 公分－ 3 (5.7 ppm)。Wherein a cross-sectional slice of the system provides the following results: a) SIMS measurements again indicated for the dominant <100> Segment of approximately 5 x 10 1 5 cm - 3 (28 ppb) of a Si concentration. A significantly higher Si concentration was measured for the secondary <100> segment that had been formed by the {100} edge face growth from the substrate. Subarea, optical microscopy indicated a nearly colorless, the Si concentration was found above 1,018 cm - 3 (5.7 ppm).

b)以633奈米激勵在77K收集的光致發光頻譜係顯示737奈米之一強烈Si相關特性，其具有對於主導<100>段近似1的一拉曼正規化強烈度且在次要<100>段中升高至幾乎4。b) The photoluminescence spectrum collected at 77K with 633 nm excitation shows a strong Si-related property of 737 nm, which has a Raman normalization intensity of approximately 1 for the dominant <100> segment and is secondary < 100> increased to almost 4 in the segment.

c)CVD材料的發光影像，其以上述帶隙激勵生成，由橙紅發光所主導。c) A luminescence image of the CVD material, which is generated by the above-described band gap excitation, dominated by orange-red illumination.

範例5Example 5

一層式單晶CVD鑽石樣本在六不同階段中成長在一{100}HPHT合成基材上。氣體流率為36/600 sccm(標準立方公分每分鐘)的CH4 /H2 且基材溫度為810℃。供應氮及矽烷以在程序氣體中對於成長程序的不同階段提供下表3所列濃度。成長終止於CVD成長的總厚度為1.4公厘時。A one-layer single crystal CVD diamond sample was grown on a {100} HPHT synthetic substrate in six different stages. The gas flow rate was 36/600 sccm (standard cubic centimeters per minute) of CH 4 /H 2 and the substrate temperature was 810 °C. Nitrogen and decane are supplied to provide the concentrations listed in Table 3 below for different stages of the growth procedure in the process gas. Growth ends at a total thickness of 1.4 mm when CVD is grown.

一{100}經拋光橫剖面切片係自樣本被處理藉以能夠研究層的性質。當切片在一光學傳輸顯微鏡下觀視時，CVD成長為均勻無色。然而，利用上述帶隙激勵所記錄之切片的發光影像中可清楚地辨別對應於不同成長階段之不同的層。其亦可容易在利用一配備有一牛津(Oxford)儀器低放大陰極發光成像系統之掃描電子顯微鏡所記錄之陰極發光影像中予以識別。利用一MonoCL光譜儀來測量電子束激勵下各層所發射之235奈米自由激子發光的強烈度。表3列出氣相矽及氮濃度，利用SIMS所測量之所產生的矽濃度及相對於高純度CVD鑽石的一標準樣本所測量之自由激子發光強烈度。A {100} polished cross-section slice is processed from the sample to enable the study of the properties of the layer. When the sections were viewed under an optical transmission microscope, the CVD grew to be uniform and colorless. However, different layers corresponding to different growth stages can be clearly discerned in the luminescence image of the slice recorded by the above-described band gap excitation. It can also be readily identified in a cathodoluminescence image recorded by a scanning electron microscope equipped with an Oxford instrument low magnification cathodoluminescence imaging system. A MonoCL spectrometer was used to measure the intensity of the 235 nm free exciton luminescence emitted by each layer under electron beam excitation. Table 3 lists the gas phase enthalpy and nitrogen concentrations, the enthalpy concentration produced by SIMS and the free exciton luminescence intensity measured relative to a standard sample of high purity CVD diamond.

此範例顯示，即便含有顯著濃度的矽且在出現通常將造成材料顯現很弱自由激子發射的一氮濃度之情形下成長，所成長的鑽石顯現驚人強烈的自由激子發光(相對於一高純度鑽石標準所顯示者測量)。在藉由較高氣相氮濃度所達成之最高的矽濃度，自由激子發射係顯著地較弱，但材料仍橫越頻譜可見區域具有很低的吸收係數且因此為無色。吸收係數頻譜係得自吸收度測量(減除經計算的反射損失頻譜之後)且對於橫越樣本的所有位置發現350至800奈米中的吸收係數小於0.9公分－ 1 且唯有在737奈米升高至高於0.7公分－ 1 。This example shows that even with a significant concentration of yttrium and growing in the presence of a nitrogen concentration that would normally cause the material to exhibit a weak free exciton emission, the growing diamond exhibits a surprisingly strong free exciton luminescence (relative to a high As measured by the purity diamond standard). At the highest enthalpy concentration achieved by the higher gas phase nitrogen concentration, the free exciton emission system is significantly weaker, but the material still traverses the spectrally visible region with a very low absorption coefficient and is therefore colorless. The absorption coefficient spectrum is derived from the absorbance measurement (after subtracting the calculated reflection loss spectrum) and the absorption coefficient in the 350 to 800 nm is found to be less than 0.9 cm - 1 for all positions across the sample and only at 737 nm. Raise to above 0.7 cm - 1 .

範例6Example 6

一層式單晶CVD鑽石樣本在五不同階段中成長在一{100}HPHT合成基材上。氣體流率為36/600 sccm(標準立方公分每分鐘)的CH4 /H2 且基材溫度為883℃。供應氮及矽烷以在程序氣體中對於成長程序的不同階段提供下表4所列濃度。成長終止於CVD成長的總厚度為1.2公厘時。A one-layer single crystal CVD diamond sample was grown on a {100} HPHT synthetic substrate in five different stages. The gas flow rate was 36/600 sccm (standard cubic centimeters per minute) of CH 4 /H 2 and the substrate temperature was 883 °C. Nitrogen and decane are supplied to provide the concentrations listed in Table 4 below for different stages of the growth procedure in the process gas. Growth ends at a total thickness of 1.2 mm when CVD is grown.

一{100}經拋光橫剖面切片係自樣本被處理藉以能夠研究層的性質。利用上述帶隙激勵所記錄之切片的發光影像中可清楚地辨別對應於不同成長階段之不同的層。其亦可容易在利用一配備有一牛津(Oxford)儀器低放大陰極發光成像系統之SEM所記錄之陰極發光影像中予以識別。利用一MonoCL光譜儀來測量電子束激勵下各層所發射之235奈米自由激子發光的強烈度。表4列出氣相矽及氮濃度，利用SIMS測量之所產生的矽濃度及相對於高純度CVD鑽石的一標準樣本所測量之自由激子發光強烈度。A {100} polished cross-section slice is processed from the sample to enable the study of the properties of the layer. Different layers corresponding to different growth stages can be clearly discerned in the luminescence image of the slice recorded by the above-described band gap excitation. It can also be readily identified in a cathodoluminescence image recorded by an SEM equipped with an Oxford instrument low magnification cathodoluminescence imaging system. A MonoCL spectrometer was used to measure the intensity of the 235 nm free exciton luminescence emitted by each layer under electron beam excitation. Table 4 lists the gas phase enthalpy and nitrogen concentrations, the enthalpy concentration produced by SIMS measurement and the intensity of the free exciton luminescence measured relative to a standard sample of high purity CVD diamond.

當切片在一光學傳輸顯微鏡下觀視時，已經發現略微灰色的最後層除外，CVD成長係為均勻無色。在77 K的吸收頻譜術係指示出，除了737奈米的熟知Si相關線之外，此最後層亦顯示近似945.3奈米、830.1及856.8奈米之吸收線及這些線與近似750奈米之間之吸收的廣泛升高。因為橫越整個可見頻譜觀察到此較高位準的吸收，導致灰色外觀。吸收係數頻譜係得自吸收度測量(減除經計算的反射損失頻譜之後)。對於前四層樣本內之所有位置，發現吸收係數在350至800奈米之間小於1公分－ 1 ，只在737奈米升高至高於0.8公分－ 1 。對於最後層，發現吸收係數位於0.9公分－ 1 至2.1公分－ 1 之間，只在737奈米升高至高於1.5公分－ 1 。When the sections were viewed under an optical transmission microscope, it was found that except for the slightly gray final layer, the CVD growth was uniform and colorless. At 77 K, the absorption spectrum indicates that in addition to the well-known Si-related lines of 737 nm, this last layer also shows absorption lines of approximately 945.3 nm, 830.1 and 856.8 nm and these lines and approximately 750 nm. The wide increase in absorption between the two. This higher level of absorption is observed across the entire visible spectrum, resulting in a gray appearance. The absorption coefficient spectrum is derived from the absorbance measurement (after subtracting the calculated reflection loss spectrum). For all positions in the first four samples, the absorption coefficient was found to be less than 1 cm - 1 between 350 and 800 nm, and only increased from 737 nm to above 0.8 cm - 1 . For the final layer, the absorption coefficient was found located 0.9 cm - 1 to 2.1 cm - between 1 only rises above 737 nm in the 1.5 cm - 1.

範例7Example 7

一層式單晶CVD鑽石樣本在四不同階段中成長在一{100}HPHT合成基材上。所使用的氣體流率為250/60/4000 sccm的CH4 /Ar/H2 且基材溫度為825℃。表5列出對於各成長階段所供應之N2 及B2 H6 處理氣體濃度，以及樣本各層中原子氮及硼的對應濃度(如SIMS所測量)。所沉積的CVD材料總厚度為1.0公厘。A one-layer single crystal CVD diamond sample was grown on a {100} HPHT synthetic substrate in four different stages. The gas flow rate used was CH 4 /Ar/H 2 of 250/60/4000 sccm and the substrate temperature was 825 °C. Table 5 lists the N 2 and B 2 H 6 process gas concentrations supplied for each growth stage, as well as the corresponding concentrations of atomic nitrogen and boron in each layer of the sample (as measured by SIMS). The total thickness of the deposited CVD material is 1.0 mm.

自樣本處理一{100}經拋光橫剖面切片以研究該等層。第3圖顯示此樣本的一低放大光學顯微鏡影像，其中顯示CVD成長階段。A {100} polished cross-sectional slice was taken from the sample to study the layers. Figure 3 shows a low magnification optical microscope image of this sample showing the CVD growth phase.

對應於第一成長階段之層係在對於高純度CVD鑽石成長之程序條件下進行，且就本身而言此薄的初始層具有高色度。對於後續成長階段，氣相的氮位準係設定在一仿傚一未受控制空氣洩漏至氣體系統中之位準，其中此洩漏的大小將導入充分氮以導致很差的晶性品質CVD材料。第3圖顯示，儘管程序氣體混合物中出現高的氮濃度，在對應於第二及第三成長階段之層中維持了合理色度及良好的晶性。這是由於添加至程序之受控制的二硼烷量所致，其改良了氮的負面效應。特定言之，併入材料內的硼係抑止過度表面粗化及後續材料劣化且此外提供了氮捐體的補償。第四成長階段中，程序氣體混合物中的二硼烷此時係低於表面粗化受到抑止之位準且其中併入材料中之硼完全地補償了氮。因此，材料轉變為黑色且具有不良的晶性性質。材料中測得的硼及氮濃度增加可由增加的表面粗度予以解釋，其導致雜質攝入值之一般增加。The layer corresponding to the first growth stage is carried out under the procedural conditions for the growth of high purity CVD diamond, and as such, this thin initial layer has a high chroma. For subsequent growth stages, the nitrogen level of the gas phase is set to the level at which an uncontrolled air leaks into the gas system, where the size of this leak will introduce sufficient nitrogen to result in a poor crystalline quality CVD material. Figure 3 shows that, despite the high nitrogen concentration in the process gas mixture, reasonable color and good crystallinity are maintained in the layers corresponding to the second and third growth stages. This is due to the amount of diborane added to the program, which improves the negative effects of nitrogen. In particular, the boron incorporated into the material inhibits excessive surface roughening and subsequent material degradation and additionally provides compensation for the nitrogen donor. In the fourth growth phase, the diborane in the process gas mixture is now below the level at which the surface roughening is inhibited and the boron incorporated into the material completely compensates for the nitrogen. Therefore, the material changes to black and has poor crystalline properties. The increase in boron and nitrogen concentrations measured in the material can be explained by the increased surface roughness, which results in a general increase in the impurity uptake value.

範例8Example 8

一層式單晶CVD鑽石樣本在七不同階段中成長於一{100}HPHT合成基材上。所使用的氣體流率為250/60/4000 sccm的CH4 /Ar/H2 且基材溫度為805℃。表6列出對於各成長階段所供應之N2 及B2 H6 程序氣體濃度，以及各層樣本中原子氮及硼的對應濃度(如SIMS所測量)。所沉積的CVD材料總厚度為1.2公厘。A one-layer single crystal CVD diamond sample was grown on a {100} HPHT synthetic substrate in seven different stages. The gas flow rate used was CH 4 /Ar/H 2 of 250/60/4000 sccm and the substrate temperature was 805 °C. Table 6 lists the N 2 and B 2 H 6 process gas concentrations supplied for each growth stage, as well as the corresponding concentrations of atomic nitrogen and boron in each sample (as measured by SIMS). The total thickness of the deposited CVD material was 1.2 mm.

此範例中，儘管程序氣體混合物中之二硼烷的一固定濃度可能歸因於諸如溫度等反應器條件的小變化，併入材料中的硼係以成長時間的一函數穩態地增加。成長的各層中，併入材料中之硼係大於氮的併入，故達成氮捐體的完全補償。因此，類似於範例6，材料能夠容忍相對較高的氮量而無劣化，只要維持氮捐體的完全補償即可。In this example, although a fixed concentration of diborane in the process gas mixture may be due to small changes in reactor conditions such as temperature, the boron incorporated into the material increases steadily as a function of growth time. In each of the growing layers, the boron incorporated into the material is greater than the incorporation of nitrogen, thus achieving complete compensation for the nitrogen donor. Thus, similar to Example 6, the material can tolerate a relatively high amount of nitrogen without degradation as long as the full compensation of the nitrogen donor is maintained.

利用配備有一牛津(Oxford)儀器陰極發光(CL)系統之一SEM系統，在樣本各層中測量激子頻率。在液體氮溫度記錄下頻譜，且自各頻譜計算出硼束縛激子強烈度對於自由激子強烈度之比值。此外，將自由激子強烈度與高純度CVD鑽石的一標準樣本中之自由激子強烈度作比較。硼束縛激子強烈度係如同預期與材料中增加的硼濃度具有交叉相關性。此外，相對於高純度標準樣本之自由激子強烈度係以增高的硼併入之一函數而減小，其與硼束縛激子強烈度的增加呈現一致。顯然相對於標準高純度樣本之自由激子強烈度係高達如同材料中氮位準所提供者。譬如，對於一無硼、但只有0.08 ppm的氮之CVD樣本，已經測得相對於標準高純度樣本之<10%的一自由激子強烈度。這是硼在出現高氮位準時的改良效應之進一步證據：硼的效應係為防止與高氮攝入相關聯之表面粗化，其抑止了普通將熄滅自由激子強烈度之其他點缺陷的攝入。Exciton frequencies were measured in each layer of the sample using an SEM system equipped with an Oxford Instrument Cathodoluminescence (CL) system. The spectrum is recorded at liquid nitrogen temperature and the ratio of boron bound exciton intensity to free exciton intensity is calculated from each spectrum. In addition, the exciton intensity is compared to the free exciton intensity in a standard sample of high purity CVD diamond. The boron bound exciton intensity is as expected to have a cross-correlation with the increased boron concentration in the material. Furthermore, the free exciton intensity relative to the high purity standard sample is reduced by a function of increased boron incorporation, which is consistent with the increase in boron bound exciton intensity. It is clear that the free exciton intensity relative to standard high purity samples is as high as the nitrogen level in the material. For example, for a boron-free, but only 0.08 ppm nitrogen CVD sample, a free exciton intensity of <10% relative to a standard high purity sample has been measured. This is further evidence of the improved effect of boron in the presence of high nitrogen levels: the effect of boron is to prevent surface roughening associated with high nitrogen uptake, which inhibits other point defects that would normally extinguish the excitability of free excitons. Ingestion.

相對於其中尚未出現氮之案例，此上述補償效應亦導致高色度材料。表6的層6中，其中氣相氮降低至1 ppm，相較於層5及7的相對較高色度，該層由於著有藍色而顯著可見。This compensating effect also results in high chroma materials compared to the case where nitrogen has not yet appeared. In layer 6 of Table 6, where the gas phase nitrogen is reduced to 1 ppm, the layer is significantly visible due to the presence of blue, as compared to the relatively higher chroma of layers 5 and 7.

範例9Example 9

製備一50公厘直徑鉬基材以供成長一多晶CVD鑽石層。開始成長之前，利用氣體色層分析術測量來決定成長環境具有2.5 ppm的未受控制氮濃度。此氮濃度通常將導致不良品質的一多晶鑽石層。作出成為100 ppm位於氫中的矽烷之矽烷添加以使氣相中的矽濃度近似為1.5 ppm。利用在880℃溫度及200 x 102 帕壓力具有600/10/23 sccm的H2 /Ar/CH4 氣體組成物、H2 中9.5 sccm的100 ppm SiH4 添加(等同於氣相中的~1.5 ppm矽)之一電漿輔助式CVD程序開始成長。A 50 mm diameter molybdenum substrate was prepared for growth of a polycrystalline CVD diamond layer. Before starting to grow, gas chromatograph measurements were used to determine the uncontrolled nitrogen concentration of 2.5 ppm in the growing environment. This nitrogen concentration will generally result in a polycrystalline diamond layer of poor quality. A decane addition to 100 ppm of decane in hydrogen was made to approximate the ruthenium concentration in the gas phase to 1.5 ppm. Addition of H 2 /Ar/CH 4 gas composition of 600/10/23 sccm at a temperature of 880 ° C and a pressure of 200 x 10 2 Pa, 9.5 sccm of 100 ppm SiH 4 in H 2 (equivalent to ~ in the gas phase) One of the 1.5 ppm 矽) plasma-assisted CVD programs began to grow.

成長持續超過75小時且以利用具有尖鉆的一測微計測量時以近似500微米厚度移除一多晶層。該層外觀為淡灰色且判斷結晶品質為良好而無證據顯示具有孔隙。The growth lasted for more than 75 hours and a polycrystalline layer was removed with a thickness of approximately 500 microns when measured with a micrometer with sharp diamonds. The appearance of the layer was light gray and the crystal quality was judged to be good without evidence of porosity.

自該層雷射切割數個10 x 10公厘正方形且作處理藉以可測量光學性質。材料在可見波長為透明且具有一輕微灰色。Optical properties were measured by laser cutting a few 10 x 10 mm squares from the layer. The material is transparent at the visible wavelength and has a slight gray color.

C＊ ．．．飽和C * . . . saturation

zλ ．．．眼睛的藍響應函數z λ . . . Blue response function of the eye

hab．．．灰調角Hab. . . Gray adjustment angle

△n．．．平行於慢及快軸線偏振(亦即雙折射)之光的折射率間之差異△n. . . Difference in refractive index of light parallel to slow and fast axis polarization (ie, birefringence)

L．．．試樣的厚度L. . . Thickness of sample

Lλ ．．．照射之頻譜功率分佈L λ . . . Spectral power distribution of illumination

Sλ ．．．波長λ之透射比S λ . . . Transmittance of wavelength λ

△n．．．L光學阻滯△n. . . L optical retardation

xλ ．．．眼睛的紅響應函數x λ . . . Red response function of the eye

δ．．．相位移δ. . . Phase shift

yλ ．．．眼睛的綠響應函數y λ . . . Green response function of the eye

λ．．．光的波長λ. . . Wavelength of light

第1圖顯示一橙棕CVD鑽石層之UV/可見吸收頻譜的頻譜分解，代表出現氮而未施加本發明方法所成長的一典型CVD鑽石層。頻譜A顯示一類型1b HPHT合成鑽石，頻譜B顯示橙棕CVD鑽石的一原始頻譜，頻譜C顯示一具有(波長)－ 3 依存性之頻譜組份，而頻譜D顯示一由兩寬廣吸收頻帶構成之頻譜組份；第2圖顯示藉由785奈米雷射激勵在77 K所記錄之一經矽摻雜CVD鑽石樣本之一光致發光頻譜；及第3圖顯示範例7所描述的一樣本之一低放大率光學顯微影像。Figure 1 shows the spectral decomposition of the UV/visible absorption spectrum of an orange-brown CVD diamond layer, representing the presence of nitrogen without the application of a typical CVD diamond layer grown by the method of the present invention. Spectrum A shows a type 1b HPHT synthetic diamond, spectrum B shows an original spectrum of orange-brown CVD diamonds, spectrum C shows a spectral component with (wavelength) - 3 dependence, and spectrum D shows a mixture of two broad absorption bands. Spectral component; Figure 2 shows the photoluminescence spectrum of one of the erbium-doped CVD diamond samples recorded at 77 K by 785 nm laser excitation; and Figure 3 shows the same as described in Example 7. A low magnification optical microscopy image.

Claims (29)

一種用以形成一CVD鑽石之方法，該方法包含：(i)提供一基材；(ii)提供一CVD合成大氣，其中存在有一以氮分子數計算濃度大於300ppb之含氮氣體；及(iii)將一包含硼或矽之氣體添加至該CVD鑽石合成大氣中，其中該硼或矽係以一受控制之方式添加至該CVD鑽石合成大氣中，以降低由氮所造成對於該單晶CVD鑽石之色度的有害效應，以產生單晶CVD鑽石，在單晶CVD鑽石中單晶CVD鑽石之至少80%的大部份容積具有以下特徵(a)至(e)之至少一種：(a)一吸收頻譜，在室溫測量所以該標準0.5ct圓形明亮式的色度將優於美國寶石協會(GIA)寶石鑽石色尺上K的色度；(b)在室溫測量處於270奈米之小於2.9公分-1 的一吸收係數；(c)在室溫測量處於350奈米之小於1.5公分-1 的一吸收係數；(d)在室溫測量處於520奈米之小於0.45公分-1 的一吸收係數；或(e)在室溫測量處於700奈米之小於0.18公分-1 的一吸收係數，其中該單晶CVD鑽石具有一大於0.1公厘之厚度，其中該單晶CVD鑽石之主要容積中之氮濃度係大於5x 1015 原子/立方公分，而其中該單晶CVD鑽石之主要容積中之硼或矽之濃度係大於1014 原子/立方公分。A method for forming a CVD diamond, the method comprising: (i) providing a substrate; (ii) providing a CVD synthesis atmosphere in which a nitrogen-containing gas having a concentration of nitrogen molecules greater than 300 ppb is present; and (iii Adding a gas containing boron or lanthanum to the CVD diamond synthesis atmosphere, wherein the boron or lanthanum is added to the CVD diamond synthesis atmosphere in a controlled manner to reduce the CVD caused by nitrogen for the single crystal CVD The detrimental effect of the chromaticity of the diamond to produce a single crystal CVD diamond in which at least 80% of the volume of the single crystal CVD diamond has at least one of the following characteristics (a) to (e): (a An absorption spectrum, measured at room temperature, so the standard 0.5 ct round brilliant chromaticity will be superior to the chromaticity of K on the GIA gem diamond ruler; (b) measured at room temperature at 270 奈An absorption coefficient of less than 2.9 cm -1 for rice; (c) an absorption coefficient of less than 1.5 cm -1 at 350 nm measured at room temperature; (d) less than 0.45 cm at 520 nm measured at room temperature - an absorption coefficient of 1; or (e) an absorption at 0.18 cm -1 of less than 700 nm measured at room temperature The main volume number, wherein the single crystal CVD diamond having a thickness greater than 0.1 mm, the volume of which is mainly in the single crystal CVD diamond of greater than the concentration of nitrogen-based 5x 10 15 atoms / cm ^, and wherein the single crystal CVD diamond of The concentration of boron or cerium in the medium is greater than 10 14 atoms/cm 3 . 如申請專利範圍第1項之方法，其中矽係被加入該CVD鑽石合成大氣中。 The method of claim 1, wherein the lanthanide is added to the CVD diamond synthesis atmosphere. 如申請專利範圍第2項之方法，其中該鑽石層的大部份容積中氮的濃度係小於或等於2 x 1017 原子/立方公分，而該鑽石層的大部份容積中矽的濃度小於或等於2 x 1018 原子/立方公分。The method of claim 2, wherein a concentration of nitrogen in a majority of the volume of the diamond layer is less than or equal to 2 x 10 17 atoms/cm 3 , and a concentration of germanium in a majority of the volume of the diamond layer is less than Or equal to 2 x 10 18 atoms / cubic centimeter. 如申請專利範圍第2項之方法，其中該鑽石層的大部份容積中氮濃度對於矽濃度之比值係為從1：20至20：1。 The method of claim 2, wherein the ratio of the concentration of nitrogen to the concentration of cerium in the majority of the volume of the diamond layer is from 1:20 to 20:1. 如申請專利範圍第2項之方法，其中該含氮氣體係以大於300ppb的一濃度出現在該合成大氣中，且該含矽氣體以大於10ppb的一濃度出現在該合成大氣中。 The method of claim 2, wherein the nitrogen-containing system is present in the synthesis atmosphere at a concentration greater than 300 ppb, and the helium-containing gas is present in the synthesis atmosphere at a concentration greater than 10 ppb. 如申請專利範圍第1項之方法，其中硼被加入至該CVD鑽石合成大氣中。 The method of claim 1, wherein boron is added to the CVD diamond synthesis atmosphere. 如申請專利範圍第6項之方法，其中該鑽石層的大部份容積中氮濃度對於硼濃度之比值係為從1：2至2：1。 The method of claim 6, wherein the ratio of the concentration of nitrogen to the concentration of boron in the majority of the volume of the diamond layer is from 1:2 to 2:1. 如申請專利範圍第6項之方法，其中該含氮氣體係以大於300ppb的一濃度出現在該合成大氣中，且該含硼氣體以大於0.5ppb的一濃度出現在該合成大氣中。 The method of claim 6, wherein the nitrogen-containing system is present in the synthesis atmosphere at a concentration greater than 300 ppb, and the boron-containing gas is present in the synthesis atmosphere at a concentration greater than 0.5 ppb. 如申請專利範圍第1項之方法，其中該所產生的CVD鑽石層，相較於一其中未添加該含有一第二雜質原子類型的第二氣體之方法，係具有一增加的經正規化自由激子強度。 The method of claim 1, wherein the CVD diamond layer produced has an increased normalization freedom compared to a method in which the second gas containing a second impurity atom type is not added. Exciton intensity. 如申請專利範圍第1項之方法，其中該所產生的CVD鑽石層，相較於一其中未添加該含有一第二雜質原子類型的第二氣體之方法，係具有載體活動力、載體壽命及/或電荷收集距離之一增加。 The method of claim 1, wherein the CVD diamond layer produced has a carrier activity, a carrier lifetime, and a method in which the second gas containing a second impurity atom type is not added. / or one of the charge collection distances increases. 如申請專利範圍第1項之方法，其中該合成大氣係包含大於300ppb的一濃度之尚未刻意添加的該含氮氣體。 The method of claim 1, wherein the synthetic atmosphere comprises a concentration of greater than 300 ppb of the nitrogen-containing gas that has not been intentionally added. 如申請專利範圍第1項之方法，其中該第一氣體未以一受控制方式添加。 The method of claim 1, wherein the first gas is not added in a controlled manner. 如申請專利範圍第1項之方法，其中該方法包含下列特性的一或多者：(1)該基材為一具有一表面之鑽石，該表面大致上無結晶缺陷而使得一顯露電漿蝕刻將顯露出有關低於5 x 103 /平方公厘的缺陷之表面蝕刻特性的一密度；(2)該單晶鑽石層的合成時程為至少50小時；及(3)該基材包含多重的經分離單晶鑽石基材。The method of claim 1, wherein the method comprises one or more of the following characteristics: (1) the substrate is a diamond having a surface which is substantially free of crystal defects such that a plasma etching is exposed A density will be revealed for surface etch characteristics of defects below 5 x 10 3 /mm ^ 2 ; (2) the single diamond layer has a synthesis time of at least 50 hours; and (3) the substrate contains multiple Separated single crystal diamond substrate. 如申請專利範圍第1項之方法，其中該CVD鑽石層係為一單晶，且其中該鑽石層的大部份容積具有下列特性的至少一者：a)一吸收頻譜，在室溫測量所以一標準0.5ct圓形明亮式的色度將優於K；b)在室溫處於270奈米測量小於1.9公分-1 之一吸收係數；c)在室溫處於350奈米測量小於0.90公分-1 之一吸收係數； d)處於520奈米小於0.30公分-1 之一吸收；或e)處於700奈米小於0.12公分-1 之一吸收。The method of claim 1, wherein the CVD diamond layer is a single crystal, and wherein a majority of the volume of the diamond layer has at least one of the following characteristics: a) an absorption spectrum, measured at room temperature A standard 0.5 ct round brilliant chromaticity will be better than K; b) at 270 nm at room temperature measuring less than 1.9 cm -1 one absorption coefficient; c) at room temperature at 350 nm measuring less than 0.90 cm - 1 one absorption coefficient; d) at 520 nm less than 0.30 cm -1 absorption; or e) at 700 nm less than 0.12 cm -1 absorption. 如申請專利範圍第1項之方法，其中該CVD鑽石層係為一單晶且其中該鑽石層形成於一具有大於2公厘的三正交維度之寶石中，其中至少一軸線配置為沿著<100>結晶方向或沿著該寶石的主要對稱軸線。 The method of claim 1, wherein the CVD diamond layer is a single crystal and wherein the diamond layer is formed in a gemstone having a triple orthogonal dimension greater than 2 mm, wherein at least one axis is configured along <100> Crystallization direction or along the main axis of symmetry of the gemstone. 一種CVD鑽石層，其由申請專利範圍第1項之方法所製造。 A CVD diamond layer produced by the method of claim 1 of the patent application. 一種光學元件，其包含根據申請專利範圍第1項之方法所製造之CVD鑽石層。 An optical component comprising a CVD diamond layer produced according to the method of claim 1 of the patent application. 一種電性或電子元件，其包含根據申請專利範圍第1項之方法所製造之CVD鑽石層。 An electrical or electronic component comprising a CVD diamond layer produced according to the method of claim 1 of the patent application. 一種CVD鑽石層，其根據申請專利範圍第1項之方法所製造，其具有大於0.1公厘之一厚度。 A CVD diamond layer produced according to the method of claim 1 which has a thickness greater than 0.1 mm. 一種CVD單晶鑽石層，其根據申請專利範圍第1項之方法以一寶石形式所製造。 A CVD single crystal diamond layer produced in the form of a gemstone according to the method of claim 1 of the patent application. 如申請專利範圍第20項之CVD單晶鑽石層，其具有大於2公厘之三正交維度，其中至少一軸線配置為沿著<100>結晶方向或沿著該寶石的主要對稱軸線。 A CVD single crystal diamond layer according to claim 20, which has three orthogonal dimensions greater than 2 mm, wherein at least one axis is configured along the <100> crystallographic direction or along the major axis of symmetry of the gemstone. 如申請專利範圍第20項之CVD單晶鑽石層，其在GIA寶石評等尺度上具有至少SH之一清澈度。 A CVD single crystal diamond layer as claimed in claim 20, which has at least one of the clarity of SH on the GIA gem rating. 一種單晶CVD鑽石層，其中該單晶鑽石層之之至少80%的大部份容積具有以下特徵(a)至(e)之至少一種：(a)一吸收頻譜，在室溫測量所以該標準0.5ct圓形明亮 式的色度將優於美國寶石協會(GIA)寶石鑽石色尺上K的色度；(b)在室溫測量處於270奈米之小於2.9公分-1 的一吸收係數；(c)在室溫測量處於350奈米之小於1.5公分-1 的一吸收係數；(d)在室溫測量處於520奈米之小於0.45公分-1 的一吸收係數；或(e)在室溫測量處於700奈米之小於0.18公分-1 的一吸收係數，其中該單晶CVD鑽石具有一大於0.1公厘之厚度，其中該單晶CVD鑽石之主要容積中之氮濃度係大於5x 1015 原子/立方公分，而其中該單晶CVD鑽石之主要容積中之硼或矽之濃度係大於1014 原子/立方公分。A single crystal CVD diamond layer, wherein at least 80% of the volume of the single crystal diamond layer has at least one of the following characteristics (a) to (e): (a) an absorption spectrum, measured at room temperature The standard 0.5ct round brilliant chromaticity will be superior to the chromaticity of K on the GIA diamond diamond ruler; (b) the absorption coefficient at 270 nm below 2.9 cm -1 at room temperature (c) measuring an absorption coefficient of less than 1.5 cm -1 at 350 nm at room temperature; (d) measuring an absorption coefficient of less than 0.45 cm -1 at 520 nm at room temperature; or (e) Measuring an absorption coefficient of less than 0.18 cm -1 at 700 nm, wherein the single crystal CVD diamond has a thickness greater than 0.1 mm, wherein the nitrogen concentration in the main volume of the single crystal CVD diamond is greater than 5 x 10 15 atoms/cm 3 , and wherein the concentration of boron or lanthanum in the main volume of the single crystal CVD diamond is greater than 10 14 atoms/cm 3 . 如申請專利範圍第23項之CVD鑽石層，其中該鑽石層的大部份容積中含有由1015 至2 x 1018 原子/立方公分的矽。The CVD diamond layer of claim 23, wherein a majority of the volume of the diamond layer contains 15 from 10 15 to 2 x 10 18 atoms/cm 3 . 如申請專利範圍第23項之CVD鑽石層，其中矽係存在於該單晶CVD鑽石層中。 The CVD diamond layer of claim 23, wherein the lanthanide is present in the single crystal CVD diamond layer. 如申請專利範圍第23項之CVD鑽石層，其中該層具有一大於1公厘之厚度。 A CVD diamond layer according to claim 23, wherein the layer has a thickness greater than 1 mm. 如申請專利範圍第23項之CVD鑽石層，其中該層在一大於0.1立方公厘之容積下具有小於1 x 10-3 之一雙折射。The CVD diamond layer of claim 23, wherein the layer has a birefringence of less than 1 x 10 -3 at a volume greater than 0.1 cubic centimeters. 如申請專利範圍第23項之CVD鑽石層，其中該鑽石層係為一單晶。 The CVD diamond layer of claim 23, wherein the diamond layer is a single crystal. 如申請專利範圍第23項之CVD鑽石層，其中該硼之濃度係大於該氮之濃度。 The CVD diamond layer of claim 23, wherein the concentration of boron is greater than the concentration of the nitrogen.
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