TWI345000B - Ultrahard diamonds and method of making thereof - Google Patents

Ultrahard diamonds and method of making thereof Download PDF

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Publication number
TWI345000B
TWI345000B TW093120995A TW93120995A TWI345000B TW I345000 B TWI345000 B TW I345000B TW 093120995 A TW093120995 A TW 093120995A TW 93120995 A TW93120995 A TW 93120995A TW I345000 B TWI345000 B TW I345000B
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Taiwan
Prior art keywords
diamond
single crystal
crystal diamond
diamonds
microwave plasma
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TW093120995A
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English (en)
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TW200513552A (en
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Russell J Hemley
Ho-Kwang Mao
Chih Shiue Yan
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Carnegie Inst Of Washington
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    • 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
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/02—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/26—Preparation
    • 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
    • C23C16/274—Diamond only using microwave discharges
    • 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
    • C23C16/277—Diamond only using other elements in the gas phase besides carbon and hydrogen; using other elements besides carbon, hydrogen and oxygen in case of use of combustion torches; using other elements besides carbon, hydrogen and inert gas in case of use of plasma jets
    • 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
    • C23C16/279—Diamond only control of diamond crystallography
    • 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
    • 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
    • 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
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N5/00—Details of television systems
    • H04N5/76—Television signal recording
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B2220/00—Record carriers by type
    • G11B2220/20—Disc-shaped record carriers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B2220/00—Record carriers by type
    • G11B2220/60—Solid state media
    • G11B2220/65—Solid state media wherein solid state memory is used for storing indexing information or metadata
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N5/00—Details of television systems
    • H04N5/76—Television signal recording
    • H04N5/765—Interface circuits between an apparatus for recording and another apparatus
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N5/00—Details of television systems
    • H04N5/76—Television signal recording
    • H04N5/765—Interface circuits between an apparatus for recording and another apparatus
    • H04N5/775—Interface circuits between an apparatus for recording and another apparatus between a recording apparatus and a television receiver
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N5/00—Details of television systems
    • H04N5/76—Television signal recording
    • H04N5/78—Television signal recording using magnetic recording
    • H04N5/781—Television signal recording using magnetic recording on disks or drums
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N9/00—Details of colour television systems
    • H04N9/79—Processing of colour television signals in connection with recording
    • H04N9/80—Transformation of the television signal for recording, e.g. modulation, frequency changing; Inverse transformation for playback
    • H04N9/804—Transformation of the television signal for recording, e.g. modulation, frequency changing; Inverse transformation for playback involving pulse code modulation of the colour picture signal components
    • H04N9/8042—Transformation of the television signal for recording, e.g. modulation, frequency changing; Inverse transformation for playback involving pulse code modulation of the colour picture signal components involving data reduction
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N9/00—Details of colour television systems
    • H04N9/79—Processing of colour television signals in connection with recording
    • H04N9/80—Transformation of the television signal for recording, e.g. modulation, frequency changing; Inverse transformation for playback
    • H04N9/82—Transformation of the television signal for recording, e.g. modulation, frequency changing; Inverse transformation for playback the individual colour picture signal components being recorded simultaneously only
    • H04N9/8205—Transformation of the television signal for recording, e.g. modulation, frequency changing; Inverse transformation for playback the individual colour picture signal components being recorded simultaneously only involving the multiplexing of an additional signal and the colour video signal

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Plasma & Fusion (AREA)
  • Multimedia (AREA)
  • Signal Processing (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Television Signal Processing For Recording (AREA)

Description

1345000 (1) 九、發明說明 【發明所所屬之技術領域】 本發明係關於鑕石，且更特別的是’關於一種在沉積 室中使用微波電漿化學氣相沈積法（MPCVD )製造之超 硬鑽石。 【先前技術】 人造鑽石之大規模生產長久以來即爲硏究與工業兩者 之目標。鑽石，除了其珍寶性質之外，還是最硬的已知材 料、具有最高已知導熱率、且對對廣多種電磁輻射具有透 射性。因此，鑽石除了其作爲寶石之價値之外，因爲在許 多工業中有其廣泛應用範圍而具有價値。 最近20年以來，已有經由化學氣相沈積法（CVD )製 造少量鑽石之方法可用。據Β· V. Spitsyn等人於“Vapor Growth of Diamond on Diamond and Other Surfaces” Journal of Crystal Growth，v o ]. 52，p p . 2]9-226 中之幸| 導 ’該方法包括鑽石之CVD，係於一基板上經由使用甲烷 ，或另一種簡單烴氣體，與氫氣之組合於減壓和800至 1200 °C之溫度下進行。氫氣的包括入是要在鑽石核形成及 成長時防止石墨的形成。用此技術據報有高達I微米/時 之成長速率》 隨後的硏究，例如1 Kamo等人在“Diamond Synthesis from Gas Phase in microwave plasma，，，Journal of Crystal
Growth’ v〇l. 62，pp. 642-644中所報導者：證實使用微波 (2) (2)1345000 電漿化學氣相沈積法（MPCVD)可使用3 00至700瓦特的 微波電力，2.45 GHz的頻率，於1-8千巴斯卡（Kpa)的壓力 和8 0 0- 1 000°C之溫度下製造鑽石。於Kamo等人的方法中 係使用濃度爲1至3%的甲烷氣體。使用此M PCVD方法據 報可達3微米/時之最大成長速率。 天然鑽石具有在80- 1 20GPa間之硬度。大部份長成的 或人造的鑽石，不論方法爲何，都具有低於llOGpa的硬 度。除了經過退火的II a型天然鑽石之外，尙未報導過有 大於120GPa的硬度之鑽石》 【發明內容】 因此’本發明係針對一種製造鑽石之裝置與方法，其 可實質地消除因相關技藝之限制與缺點所導致的一或更多 項問題。 本發明之一項目標係有關一種在微波電漿化學氣相沈 積法系統中製造具有增加的硬度之鑕石所用裝置與方法。 本發明之另一目標爲提高單晶鑽石之光學特性。 於以下的說明中將提出本發明的額外特性與優點，且 部份可由說明獲得明白，或可由本發明之實施中得知。由 本發明文字說明與其申請專利範圍以及附圖所特別指出的 結構可實現及獲得本發明諸目標與其他優點。 爲達成此等及其他的優點且根據本發明目的，如所具 體實施且廣泛說明者，由微波電漿化學氣相沈積法成長且 於超過4.0GPa的壓力下退火並且加熱至超過]50(pC的溫 (3) (3)1345〇〇〇 度之單晶鑽石具有大於120GPa的硬度。 在另一具體貫例中’單晶鑽石有160-180GPa之硬度 0 根據本發明另一具體實例，一種製造硬單晶鑽石之方 法包括成長一單晶鑽石且於超過4.0GPa的壓力和超過 bOOt的溫度下退火使其具有超過l2〇GPa之硬度。 應瞭解者，前述一般說明與下面的詳細說明兩者均爲 示範性且爲說明性者且係打算對所申請的本發明提供進一 步解說者。 【實施方式】 較佳具體實例之詳細說明 至此要參考本發明較佳具體實例之細節，其結果都在 所附圖式中示出。 本申請案所稱之微波電漿CVD-長成的單晶鑽石係以 2002年11月6日提出申請的美國專利申請第1〇/2 88，499號 ’名稱爲 “Apparatus and Method for Diamond Production ”中所裝置予以長成，該專利以引文方式倂入本文。一般 而言，係將一晶種鑽石置於一固持器中，該固持器隨著鑽 石成長會移動該晶種鑽石/長成鑽石。此申請案之發明人 也是美國專利申請第】0/2 8 8 ;499號之發明人。 於lb型{]00}合成鑽石上沉積出微波電漿CVD-長成 ，厚度大於1毫米的單晶鑽石。爲提高成長率（50至150微 米/時）及增進平滑{]〇〇}表面的成長，於一CVD室，在 (4) (4)1345000 N2/CH4 = 0,2-5_0%、CH4/H2=]2-20%的氣圍內，1 20-22 0 托 (t〇rr)總壓力和900- 1 500 °C下，用微波感應電漿成長單晶 鑽石。拉曼光譜（Raman spectra)顯示出少量氫化非晶形 碳（a-C: H) 4 及含氮 a-C: H(N: a-C: H) 4 促成在 <950 °C與>1400 °C產生褐鑽。光致發光（PL)光譜顯示有氮空 位（nitrogen-vacancy) ( N-V)雜質。厚度達4.5毫米之 單晶鑽石係以比習知複晶CVD成長法更高兩個數量級的 成長速率製造。 微波電漿CVD-長成的單晶鑽石係在一使用皮帶式或 鐵鈷式裝置之反應容器內於超過4.0GPa，例如5-7GPa的 壓力下退火，且經加熱到1 5 0 0 °C例如1 8 0 0 - 2 9 0 0 °C的溫度1 至60分鐘。該反應容器可爲一匣（cell)，例如美國專利第 3,745,623號或第3,9 1 3,2 8 0號中所述者，彼等以引文方式 倂入本文。此一退火處理，可減少或消除微波電漿CVD-長成的單晶鑽石晶體內之顏色，且增亮lb型HPHT合成 種晶之色調。此外’經退火的微波電漿C V D -長成單晶鑽 石，經退火的CVD鑽石所具硬度（至少約140GPa )超過 下列諸鑽石之硬度：經退火或未經退火lb型HPHT合成 鑌石（~90GPa)、經退火la型天然鑽石（〜]〇〇GPa)、 Ila型天然鑽石（〜llOGPa)、及經退火Ila型天然鑽石（ 〜140GPa)與經燒結過的複晶鑽石（]20-l40GPa)。 實施例 # ] 用^/^比例的仏/^^在一微波CVD室中，於一黃色ib (5) (5)1345000 型HPHT合成鑽石上，在約1500 °C的溫度下成長一單晶 CVD鑽石。該微波電漿CVD -長成的單晶鑽石之尺寸爲一 平方厘米且厚度稍大於—毫米。該微波電漿CVD -長成的 單晶鑽石之顏色爲棕色。然後’將該棕色微波電漿CVD-長成的單晶鑽石置於反應容器中lb型HPHT合成晶種鑽 石上作爲樣品。 將該反應容器放置於習用的HPHT裝置中。首先，將 壓力增加到5. OGPa之壓力，然後提高溫度到高達2200 °C 。將樣品保持在此等退火條件下5分鐘，然後在釋放壓力 前，以約〗分鐘的時間降低溫度至室溫。 將該樣品從反應容器取出且於光學顯微鏡下檢查。該 棕色微波電漿CVD-長成的單晶鑽石已變成淺綠半透明顏 色且牢固地黏合於該黃色lb型HPHT合成鑽石。該lb型 HPHT合成鑽石所具黃色變成較淺黃色或更爲半透明的黃 色。其硬度爲約160GPa。 實施例 # 2 與上述實施例# I 一樣，不同處在於將退火條件維持i 小時。該棕色微波電漿CVD·長成的單晶鑽石變成淺綠色 ’其較實施例#1中所得的淺綠色更爲半透明，且保持牢固 地黏合於該lb型HPHT合成鑽石。該ib型HPHT合成鑽 石之黃顏色變成更淺的黃色或更爲半透明的黃色。其硬度 爲約 1 8 0 G P a。 (6) (6)1345000 實施例 # 3 在一微波CVD室中’使用5%比例的N2/CH4，於約 1 4 5 0 °C的溫度下，在一黃色lb型HPHT合成鑽石上成長 一單晶CVD鑽石。該微波電漿CVD-長成的單晶鑽石之尺 寸爲一平方厘米且其厚度稍大於一毫米。該微波電漿 CVD-長成的單晶鑽石之顏色爲淺棕色或黃色。換言之， —種不像上述實施例#1中經微波電漿CVD-長成的單晶鑽 石所具棕色一樣深的黃色或淺棕色。然後，將該黃色或淺 棕色微波電漿CVD-長成的單晶鑽石置於一反應容器中lb 型HPHT合成晶種鑽石上作爲樣品。其硬度大於〗60GPa。 該反應容器係置於習用的HP HT裝置中。將壓力增加 到約爲5.0GPa之壓力，然後快速提高溫度到高達約2000 °C。將樣品保持在此等退火條件下5分鐘，然後在釋放壓 力前，以約1分鐘的時間降低溫度至室溫。 從反應容器取出該樣品且於光學顯微鏡下檢查。該淺 棕色微波電漿CVD-長成的單晶鑽石已變成無色且保持牢 固地黏合於該黃色lb型HPHT合成鑽石上。該lb型 HP Η T合成鑽石之黃顏色也變成較淺的黃色或更爲半透明 的黃色。 實施例 #4 與實施例# 1 一樣，不同處在於將一無色微波電漿單晶 CVD-長成的鑽石至於N2/CH4 = 5°/。的氣圍內，在〜]20(TC的 溫度下退火。退火後，該微波電漿單晶CVD-長成的鑽石 -10 - (7) (7)1345000 爲藍色。此藍色微波電漿單晶CVD-長成的鑽石具有很高 的大於20MPamW2之韌度。其硬度爲約l40GPa。 實施例 # 5 與實施例#1一樣，不同處在於將一無色微波電漿單 晶CVD -長成的鑽石至於n2/CH4 = 〇.5%的氣圍內，在〜1200 °C的溫度下退火。退火後，該微波電漿單晶CVD -長成的 鑽石仍爲無色。此無色微波電漿單晶CVD_長成的鑽石具 有〜160GPa的硬度及〜i〇MPami/2的韌度》 圖]係檢驗鑽石硬度之鑽石壓痕計之圖。用圖丨所示鑽 石壓痕計1對經退火的微波電漿CVD·長成的單晶鑽石進行 韋克士硬度（Vickers hardness)檢驗。圖1之鑽石壓痕計1有 —座落在底座3上之衝擊材料2。該衝擊材料2可爲碳化矽 、鑽石、或其他硬材料。該衝擊材料2有一帶有一角錐韋 克士鑽石壓痕計形狀之面，其中該角錐韋克士鑽石壓痕計 形狀的邊之角度爲136°。 鑽石壓痕計施加一點荷重於檢驗鑽石2之上直到該檢 驗鑽石2中形成壓痕或裂痕爲止。爲防止鑽石壓痕計的彈 性變形’乃在檢驗鑽石的{]〇〇}方向中之<]〇〇>面上將荷重 從1變異至3公斤。以光學顯微術測量壓痕的尺寸與伴隨壓 痕的裂痕之尺寸。圖2爲在微波電漿CVD·長成的單晶鑽石 上造成的壓痕之圖形。 經由測里壓痕的長度D與局度h，可由下面的公式（ 1 )定出檢驗鑽石之硬度Hv : -11 - 1345000
(1 ) ： Hv- 1.8 5 4 X P/D2 Ρ爲鑽石壓痕計上所用於檢驗鑽石中形成壓痕的最大 荷重。D爲鑽石壓痕計在檢驗鑽石中形成的最長裂痕之長 度且h爲檢驗鑽石中的壓痕之深度，如圖1所示者。 使用方程式（1 )所得硬度Hv於下面的公式（2 )中 ，可定出檢驗鑽石之破裂韌度Kc: (2) : Kc = (0.016±0.004)(E/Hv)1/2(P/c3/2) E 爲楊氏模數（Young’s modulus)，其經假設爲 lOOOGPa。P爲鑽石壓痕計在檢驗鑽石中形成壓痕所用的 最大荷重。項d爲檢驗鑽石中的壓痕腔洞之平均長度，如 圖2中所示者，使得d = (d ,+^)/2。項c爲檢驗鑽石中徑向 裂痕的平均長度，如圖2所示，使得c = (Cl + c2)/2。 因爲測量硬度中的未確定性，所以也對其他鑽石實施 相同的檢驗。發現對其他鑽石的測量與所公布的對其他鑽 石之數據一致。韋克士硬度檢驗是在不同類型鑽石的（ 1〇〇)方向之面（]〇〇)上完成的。 以光學顯微術觀察時，經退火的微波電漿CVD-長成 的單晶鑕石所具經壓痕的表面明顯不同於其他（較軟的） 鑽石所具者。經退火的微波電漿CVD-長成的單晶鑽石呈 現沿著< ]1 〇 >或< ]Π >的方形裂痕圖樣，而沿著< ]〇 〇 >沒有 -12 - (9) 1345000 的 記 1 1 > '( ，的 形 漿 之 Ila 型 壓 進 退 明 單 計 下 與 la 韌 長 如 十字形裂痕線，且用角錐狀韋克士鑽石壓痕計在經退少 微波電漿CVD-長成的單晶鑽石表面上產生水印狀變形 號。相反地，經退火的Ila型天然鑽石沿著<1 10>或<1 有較少的方形裂痕圖樣，但是仍呈現較軟鑽石的十字形 100)裂痕。這種結果表示經退火的微波電漿CVD-長成 單晶鑽石比鑽石壓痕計更硬，且因鑽石壓痕計之塑性變 所致壓力造成較軟{111}面之滑動。 韋克士壓痕計典型地係在對未經退火的微波電 CVD-長成的單晶鑽石及lb型天然鑽石進行〜15次測量 後破裂。此外，韋克士壓痕計典型地係在對經退火的 型天然鑽石、經退火的la型天然鑽石、與經退火的lb HPHT合成鑽石進行〜5次測量之後破裂。不過，韋克士 痕計在對經退火的微波電漿CVD_長成的單晶鑽石只有 行一次或兩次測量之後就破裂。此等觀察進一步表明經 火的微波電漿CVD-長成的單晶鑽石比所測量的値所表 者更爲硬。確實，許多經退火的微波電漿CVD-長成的 晶鑽石就僅會損壞較軟的壓痕計。在此等情況中，壓痕 無法在經退火的微波電漿CVD -長成的單晶鑽石表面留 任何印痕。 圖3爲經退火的微波電漿CVD-長成的單晶鑽石， 1Ia型天然鑽石、經退火的Ila型天然鑽石、經退火的 型天然鑽石及經退火的lb型HPHT合成鑽石在硬度與 度上比較之圖。如圖3所示，該經退火的微波電漿CVD-成的單晶鑽石具有比Ila型天然鑽石遠較爲高的硬度， -13- (10) (10)1345000 圖3中虛線方形1 〇所不者。所有經退火的微波電獎C V D -長 成的單晶鑽石也具有比對多晶CVD鑽石所報導的硬度範 圍較高之硬度，如圖3中虛線方形2 0所示者。圖3中所呈現 的微波電漿CVD-長成的單晶鑽石於l4〇-〗80GPa硬度下具 有6_10MP a m 1/2之破裂韌度，這表示彼等可能更爲硬。 由於本發明可用數種形式具體實施而不違離本發明的 旨意或基本特性，所以也應瞭解者，上述具體實例，除非 另有指明，否則並不受限於前述說明部份之任何細節，反 而應廣泛地認爲是落於其如所附申請專利範圍所界定的旨 意與範圍之內，且因此所有落在申請專利範圍所具境界之 內的改變和修改，或此等境界的等效物都理應爲後附申請 專利範圍所涵蓋。 【圖式簡單說明】 所附諸圖式，於倂入本文中以提供對本發明的進一步 瞭解且構成本說明書之一部份之下，係用以闡明本發明具 體實例且與說明部分一起用來解釋本發明原理。 圖1係檢驗鑽石硬度所用之鑽石壓痕計（in d enter)之圖 ο 圖2爲在鑽石上造成的壓痕之圖形。 圖3係顯示出經退火的微波電漿CVD長成的單晶鑽石 ，與Ila型天然鑽石，經退火的Ila型天然鑽石，經退火 的la型天然鑽石和經退火的lb型HP HT等合成鑽石所具 硬度與韌度的比較之圖。 -14 - (11) (11)1345000 【主要元件符號說明】 1 :壓痕計 2 :衝擊材料 3，4 :底座 1 0，2 0 :虛線方形
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Claims (1)

1345000 1 年}月j日修正本 附件3A :第093 1 2099 5號申請專利範圍修正本 民國100年3月23日修正 十、申請專利範圍 1 · 一種單晶鑽石，其係經由微波電漿化學氣相沈積法 長成，在5至7GPa的壓力下退火且經加熱至1· 800至2900。C 的溫度而具有140至180GPa之硬度。 2. 根據申請專利範圍第1項之單晶鑽石，其中其破裂 韌度爲6至10 MPa m1/2。 3. —種製造硬單晶鑽石之方法，其包括： 成長一單晶鑽石；及 將該單晶鑽石於5至7GPa的壓力及1 800至2900°C的 溫度下退火以具有140至180GPa之硬度。 4·根據申請專利範圍第3項之方法，其中該單晶鑽石 的成長係包括微波電漿化學氣相沈積。 5 ·根據申請專利範圍第3項之方法，其中該單晶鑽石 的成長是在1^2/(：114 = 0.2-5.0%且（^4/只2=12-20%的環境 中且於120_22〇托（torr)的總壓力下發生。 6.根據申請專利範圍第3項之方法，其中該單晶鑽石 的成長是在900至1500 °C溫度之環境中發生。 7 ·根據申請專利範圍第3項之方法，其中該退火係持 續1至60分鐘。
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