TWI342902B - Tough diamonds and method of making thereof - Google Patents

Tough diamonds and method of making thereof Download PDF

Info

Publication number
TWI342902B
TWI342902B TW093120996A TW93120996A TWI342902B TW I342902 B TWI342902 B TW I342902B TW 093120996 A TW093120996 A TW 093120996A TW 93120996 A TW93120996 A TW 93120996A TW I342902 B TWI342902 B TW I342902B
Authority
TW
Taiwan
Prior art keywords
single crystal
diamond
crystal diamond
diamonds
hardness
Prior art date
Application number
TW093120996A
Other languages
English (en)
Other versions
TW200504254A (en
Inventor
Russell J Hemley
Ho-Kwang Mao
Chih Shiue Yan
Original Assignee
Carnegie Inst Of Washington
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carnegie Inst Of Washington filed Critical Carnegie Inst Of Washington
Publication of TW200504254A publication Critical patent/TW200504254A/zh
Application granted granted Critical
Publication of TWI342902B publication Critical patent/TWI342902B/zh

Links

Classifications

    • 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

Landscapes

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

Description

1342902 九、發明說明 【發明所屬之技術領域】 本發明係關於鑽石，且更特別的是，關於一種在沉積 室中使用微波電駿化學氣相沈積法（Microwave Plasma Chemical Vapor Deposition, MPCVD)製造之堅 |刃鑽石。 【先前技術】 合成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、且對廣多種電磁輻射具有透明 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》不過，鑽石可能因 破裂韌度低而對許多應用而言並不適合。 至少在最近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B. V. Spitsyn等 人於"Vapor Growth of Diamond on Diamond and Other Surfaces", Journal of Crystal Growth, vol. 52, pp. 219-226中之報導，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 8 00- 1 200°C之溫度下進行。氫氣的包括使用是要在鑽石形 成核及成長時防止石墨的形成。用此技術據報有至高達1 微米/小時之成長速率。 隨後的硏究，例如，Kamo等人在"Diamond Synthesis from Gas Phase in Microwave Plasma" ' Journal of Crystal 1342902
Growth > vol. 62，pp. 642-644中所報導者，證實使用微 波電漿化學氣相沈積法（Μ P C V D )以3 0 〇至7 0 0瓦（W )的 微波電力’ 2.45 GHz的頻率’於1-8千巴斯卡（Kpa)的壓 力和800- 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μ P C V D 方法據報可達3微米/小時之最大成長速率。 於上述諸方法與許多最近報導出的方法中，於某些例 子中，鑽石的破裂韌度比天然鑽石佳。特別者，只製出或 只長出多晶形式鑽石之較高成長速率方法已知能製造出破 裂韌度高於天然鑽石的鑽石。除了已經過退火的某些高壓 高熱（ΗΡΗΤ)合成鑽石之外，大部份鑽石都具有低於！ i MPa m1/2之破裂韌度。 【發明內容】 因此，本發明係有關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 積系統中製造具有增加破裂韌度的鑽石所用裝置與方法。 於以下的說明中將提出本發明的額外特性與優點，且 部份可由說明而明顯得知，或可由本發明之實施中得知。 本發明諸目標與其他優點將可藉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而實現及獲得。 爲達成此等及其他的優點且根據本發明目的，如所具 -6- 1342902 體實施且廣泛說明者’由微波電黎化學氣相沈積法長成之 單晶鑽石具有50-90 GPa的硬度與15-20 MPa ml/2的破裂 韌度。 在另一具體實例中，單晶鑽石具有18·20 MPa ml/2之 破裂韌度。 根據本發明另一具體實例’一種成長單晶鑽石之方法 包括將—晶種鑽石置於一固持器中’及於約1 0 0 0 ° C至約 1100°C之溫度下成長一單晶鑽石使得該單晶鑽石具有11-20 MPa m1/2之破裂韌度。 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欲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C V D -長成的單晶鑽石係以 2 0 02年1 1月6曰提出申請的美國專利申請第1〇/2 8 8,499 號’名稱爲"Apparatus and Method for Diamond Production"中所述裝置予以長成，該專利以引用方式倂入 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。本申請 案之發明人也是美國專利申請第1〇/288,499號之發明 m2902 入。 於lb型 {100}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/小時）及增進平滑{ 100}面的成長，於一 CVD室 內’在 N2/CH4 = 0.2-5.0%、CH4/H2 = 12-20。/。、120-220 托（torr)總壓力和900 - 1 5 00。(：之氣氛中，用微波感應電 漿成長單晶鑽石。拉曼光譜（Raman spectra )顯示出少鼍 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。(：與>1400°C產生褐鑽。光致發光（PL)光譜 顯示有氮空位（nitr〇gen-vacanCy，N-V )雜質。厚度至高 達4.5毫米之單晶鑽石係以比習知多晶CVD成長法高兩 個數量級的成長速率製造。 圖1係檢驗鑽石硬度和破裂韌度所用壓痕計之圖。用 圖1所示壓痕計1對微波電漿 CVD-長成的單晶鑽石進行 韋克士硬度（Vickers hardness)和破裂籾度之檢驗。圖1之 壓痕計1有一座落在底座3上之衝擊材料2。該衝擊材料 2可爲碳化矽、鑽石、或某些其他硬材料。該衝擊材料有 一帶有角錐韋克士壓痕計形狀之面，其中該角錐韋克士壓 痕計形狀的邊具有136°之角度。 壓痕計施加一點荷重於受檢驗鑽石2之上直到該受檢 驗鑽石2中形成壓痕或裂痕爲止。爲防止壓痕計的彈性變 形，乃在受檢驗鑽石的<1〇〇>方向中之{ 100}面上將荷 重從1變異至3公斤。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。以光學顯微術測量壓痕的尺 -8- 1342902 寸與伴隨壓痕的裂痕之尺寸。 經由測量壓痕的長度D與高度h ’可由下面的公式 (1 )定出受檢驗鑽石之硬度Hv :
Hv = 1.8 54 X P/D2 Ρ爲壓痕計上所用於受檢驗鑽石中形成壓痕的最大荷 重。D爲壓痕計在受檢驗鑽石中形成的最長裂痕之長度， 而h爲受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於下面的方程式（2 ) 中，可定出受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)，其假設爲looo GPa。P爲壓痕計在受檢驗鑽石中形成壓痕所用的最大荷 重。d爲受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| + d2)/2。c爲受檢驗鑽石中徑向裂 痕的平均長度，如圖2所示，使得c = (Cl + c2)/2。 圖3爲顯示微波電漿 CVD-長成的單晶鑽石與iia型 天然鑽石在硬度與韌度上比較之圖。圖3所示的微波電獎 C V D -長成的單晶鑽石係在約1 3 0 (Γ C的溫度下長成者以達 到高成長速率。如圖3所示者，該微波電發 CVD -長成的 單晶鑽石具有相對於天然Iia鑽石高出許多的6-18 MPa m1/2之破裂韌度。大部分微波電漿CVD-長成的單晶鑽石 具有比就Iia型天然鑽石所報導的破裂韌度範圍（如圖3中 -9- Π42902 虛線方形1 〇所示者）及就多晶CVD鑽石所報導的破裂韌 度範圍（如圖3中虛線方形20所示者）爲高之破裂韌度。 圖3中所呈現的微波電漿CVD-長成的單晶鑽石於50-90 GPa硬度下具有11-18 MPa m1/2之破裂韌度。 圖3中所呈現的微波電漿 CVD-長成的單晶鑽石所具 破裂韌度之差異顯得與加工溫度頗有關聯。因此，本案發 名人乃在特定加工溫度範圍之內成長其他的微波電漿 C VD-長成的單晶鑽石。換言之，係將一晶種鑽石置於一 固持器之內並於一特定加工溫度範圍之內成長單晶鑽石。 然後對此等其他微波電漿 CVD-長成的單晶鑽石進行相同 的硬度和破裂韌度檢驗。 圖4係顯示出在不同溫度下形成之微波電漿CVD長 成的單晶鑽石與Ila型天然鑽石所具硬度與韌度的比較之 圖。更具體言之，圖4顯示出分別在高於1 300°C、1150° C-1250°C、和1000°C-110(TC下形成的微波電漿CVD長成 的單晶鑽石所具硬度與韌度。如圖4中所示，在1 000°C-1100°C下長成的微波電漿CVD長成的單晶鑽石具有於 60-70 GPa硬度下之約18-20 MPa m1/2的破裂韌度。 雖然單晶鑽石的成長速率較爲慢，可以在1〇〇〇° Ο-ΐ 1 00°C 下製造 出具有 1 8-20 MPa m 1/2 的高 破裂韌 度之單 晶鑽石。沒有其他鑽石（不論合成或天然者）業經報導具有 此高破裂韌度。再者，於更高溫度，例如1 1 5 0- 1 3 5 0°C， 之下長成的鑽石可能不一定會達到高破裂韌度，不過會傾 向於具有高硬度，使得此等鑽石可用於其他用途。 -10- 1342902 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 而應廣泛地解讀爲落於其如所附申請專利範圍所界定的旨 意與範圍之內，因此所有落在申請專利範圍所具境界之內 的改變和修改，或此等境界的等效內容都欲爲後附申請專 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係一種用於檢驗鑽石硬度和破裂韌度之壓痕計 (indenter)之圖。 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。 圖3係顯示出微波電漿C V D長成的單晶鑽石與11 a 型天然鑽石所具硬度與韌度的比較之圖。 圖4係顯示出在不同的溫度下形成的微波電漿CVD 長成的單晶鑽石與型天然鑽石所具硬度與韌度的比較 之圖。 -11 -

Claims (1)

1| T342902 修iL 補定 十、申請專利範圍 1. 一種藉微波電漿化學氣相沈積法長成的單晶鑽 石，其具有5 0-90 GPa之硬度與11-20 MPa m1/2之破裂韌 度。 2.根據申請專利範圍第1項之單晶鑽石，其中該破 裂动度爲 18-20 MPa mi/2。 3 .根據申請專利範圍第1項之單晶鑽石，其中該硬 度爲 60-70 GPa。 4. 一種具有18-20 MPa mi/2破裂韌度之單晶鑽石。 5 ·根據申請專利範圍第4項之單晶鑽石，其具有60-70 GPa之硬度。 6. —種利用微波電漿化學氣相沈積法成長單晶鑽石 之方法，其包括： 將一晶種鑽石置於一固持器中：及 於約1 000°C至約1100°C之溫度下，在n2/CH4 = 0.2-5.0% 且 CH4/H2 = 12-20%而總壓力爲 1 20-220 托（torr) 的氣氛中成長單晶鑽石使得該單晶鑽石具有1 1-20 MPa m1/2之破裂韌度。 7. 根據申請專利範圍第6項之方法’其中該單晶鑽 石的成長導致一具有60-70 GPa的硬度之單晶鑽石。 -12-
TW093120996A 2003-07-14 2004-07-14 Tough diamonds and method of making thereof TWI342902B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US48643503P 2003-07-14 2003-07-14

Publications (2)

Publication Number Publication Date
TW200504254A TW200504254A (en) 2005-02-01
TWI342902B true TWI342902B (en) 2011-06-01

Family

ID=34079231

Family Applications (3)

Application Number Title Priority Date Filing Date
TW093120995A TWI345000B (en) 2003-07-14 2004-07-14 Ultrahard diamonds and method of making thereof
TW093120998A TWI371506B (en) 2003-07-14 2004-07-14 Annealing single crystal chemical vapor deposition diamonds
TW093120996A TWI342902B (en) 2003-07-14 2004-07-14 Tough diamonds and method of making thereof

Family Applications Before (2)

Application Number Title Priority Date Filing Date
TW093120995A TWI345000B (en) 2003-07-14 2004-07-14 Ultrahard diamonds and method of making thereof
TW093120998A TWI371506B (en) 2003-07-14 2004-07-14 Annealing single crystal chemical vapor deposition diamonds

Country Status (14)

Country Link
US (7) US7157067B2 (zh)
EP (3) EP1664373A4 (zh)
JP (3) JP2007531679A (zh)
KR (3) KR101111690B1 (zh)
CN (3) CN100402421C (zh)
AU (3) AU2004258192B2 (zh)
BR (3) BRPI0412536A (zh)
CA (3) CA2532384C (zh)
HK (3) HK1093334A1 (zh)
IL (4) IL173102A0 (zh)
RU (3) RU2323281C2 (zh)
TW (3) TWI345000B (zh)
WO (3) WO2005007936A2 (zh)
ZA (3) ZA200600883B (zh)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2328563C2 (ru) * 2002-09-06 2008-07-10 Элемент Сикс Лимитед Цветные алмазы
US7157067B2 (en) * 2003-07-14 2007-01-02 Carnegie Institution Of Washington Tough diamonds and method of making thereof
EP1723086B2 (en) * 2003-12-12 2011-09-14 Element Six Limited Method of incoporating a mark in cvd diamond
BRPI0515347A (pt) * 2004-09-10 2008-07-22 Carnegie Inst Of Washington diamante de cristal único cvd ultra-resistente e crescimento tridimensional do mesmo
JP5002982B2 (ja) * 2005-04-15 2012-08-15 住友電気工業株式会社 単結晶ダイヤモンドの製造方法
US8641999B2 (en) * 2005-07-11 2014-02-04 SCIO Diamond Technology Corporation Carbon grit
TWI410538B (zh) * 2005-11-15 2013-10-01 Carnegie Inst Of Washington 建基於以快速生長速率製造之單晶ｃｖｄ鑽石的新穎鑽石的用途／應用
JP5284575B2 (ja) * 2006-10-31 2013-09-11 住友電気工業株式会社 ダイヤモンド単結晶及びその製造方法
EP2215291A1 (en) * 2007-10-02 2010-08-11 Carnegie Institution Of Washington Low pressure method annealing diamonds
US9487858B2 (en) * 2008-03-13 2016-11-08 Board Of Trustees Of Michigan State University Process and apparatus for diamond synthesis
WO2009137020A1 (en) * 2008-05-05 2009-11-12 Carnegie Institution Of Washington Ultratough single crystal boron-doped diamond
US20100028556A1 (en) * 2008-05-09 2010-02-04 Apollo Diamond Gemstone Corporation Chemical vapor deposition colored diamond
US20100126406A1 (en) * 2008-11-25 2010-05-27 Yan Chih-Shiue Production of Single Crystal CVD Diamond at Rapid Growth Rate
US20100192474A1 (en) * 2009-01-30 2010-08-05 Lehigh University Ultrahard stishovite nanoparticles and methods of manufacture
US9017632B2 (en) 2009-06-26 2015-04-28 Element Six Technologies Limited Diamond material
CA2765804C (en) * 2009-06-26 2014-07-29 Element Six Limited Method for making fancy orange coloured single crystal cvd diamond and product obtained
CN101705478B (zh) * 2009-12-04 2011-06-01 北京科技大学 一种提高自支撑金刚石膜强度的方法
WO2011146460A1 (en) 2010-05-17 2011-11-24 Carnegie Institution Of Washington Production of large, high purity single crystal cvd diamond
SG179318A1 (en) * 2010-09-27 2012-04-27 Gemesis Company S Pte Ltd Method for growing white color diamonds by using diborane and nitrogen in combination in a microwave plasma chemical vapor deposition system
GB201121642D0 (en) 2011-12-16 2012-01-25 Element Six Ltd Single crtstal cvd synthetic diamond material
GB201205743D0 (en) * 2012-03-30 2012-05-16 Element Six Ltd Pressure cartridge
JP5527628B2 (ja) * 2012-04-09 2014-06-18 住友電気工業株式会社 ダイヤモンド単結晶
US9469918B2 (en) 2014-01-24 2016-10-18 Ii-Vi Incorporated Substrate including a diamond layer and a composite layer of diamond and silicon carbide, and, optionally, silicon
US11753740B2 (en) * 2019-11-18 2023-09-12 Shin-Etsu Chemical Co., Ltd. Diamond substrate and method for manufacturing the same
CN111778553A (zh) * 2020-07-29 2020-10-16 哈尔滨工业大学 用于提升cvd单晶金刚石品质的籽晶连续减薄等离子体退火方法
CN113816737B (zh) * 2021-09-09 2022-10-11 四川大学 一种高效制备透明金刚石材料的方法

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3913280A (en) 1971-01-29 1975-10-21 Megadiamond Corp Polycrystalline diamond composites
US3745623A (en) 1971-12-27 1973-07-17 Gen Electric Diamond tools for machining
JP2620252B2 (ja) * 1987-09-17 1997-06-11 住友電気工業株式会社 窒素含有硬質炭素膜の製造方法
US4985226A (en) * 1988-06-20 1991-01-15 Sumitomo Electric Industries, Ltd. Hole-burning material and production thereof
JP2921063B2 (ja) * 1990-08-22 1999-07-19 住友電気工業株式会社 高品質ダイヤモンドの気相合成方法
JP3077206B2 (ja) * 1991-01-10 2000-08-14 住友電気工業株式会社 ダイヤモンド膜及びその製造方法
US5397428A (en) * 1991-12-20 1995-03-14 The University Of North Carolina At Chapel Hill Nucleation enhancement for chemical vapor deposition of diamond
US5443032A (en) * 1992-06-08 1995-08-22 Air Products And Chemicals, Inc. Method for the manufacture of large single crystals
RU2006538C1 (ru) * 1992-07-14 1994-01-30 Акционерное общество "Компакт Лтд" Способ выращивания алмазов
EP0671482A1 (en) * 1994-03-11 1995-09-13 General Electric Company Toughened chemically vapor deposited diamond
JP3484749B2 (ja) * 1994-04-04 2004-01-06 住友電気工業株式会社 ダイヤモンドの合成法
US5451430A (en) * 1994-05-05 1995-09-19 General Electric Company Method for enhancing the toughness of CVD diamond
JP3728465B2 (ja) * 1994-11-25 2005-12-21 株式会社神戸製鋼所 単結晶ダイヤモンド膜の形成方法
US5653800A (en) * 1995-08-03 1997-08-05 Eneco, Inc. Method for producing N-type semiconducting diamond
JPH0948694A (ja) * 1995-08-04 1997-02-18 Kobe Steel Ltd 単結晶ダイヤモンド膜の形成方法
RU2099283C1 (ru) * 1996-06-05 1997-12-20 Закрытое акционерное общество "Техно-ТМ" Покрытие на основе алмазоподобного материала и способ его получения
JP3125046B2 (ja) * 1997-11-21 2001-01-15 工業技術院長 ダイヤモンド単結晶薄膜製造方法
US6582513B1 (en) 1998-05-15 2003-06-24 Apollo Diamond, Inc. System and method for producing synthetic diamond
AU1198900A (en) * 1998-10-01 2000-04-17 Uab Research Foundation, The A process for ultra smooth diamond coating on metals and uses thereof
RU2288302C2 (ru) 2000-06-15 2006-11-27 Элемент Сикс (Пти) Лтд. Монокристаллический алмаз, полученный методом химического осаждения из газовой фазы, и способ его получения
RU2202513C1 (ru) * 2001-10-03 2003-04-20 Санкт-Петербургский государственный электротехнический университет Способ выращивания слоя твердого углерода
UA81614C2 (ru) * 2001-11-07 2008-01-25 Карнеги Инститьюшн Ов Вашингтон Устройство для изготовления алмазов, узел удержания образца (варианты) и способ изготовления алмазов (варианты)
US6811610B2 (en) * 2002-06-03 2004-11-02 Diamond Innovations, Inc. Method of making enhanced CVD diamond
US7157067B2 (en) * 2003-07-14 2007-01-02 Carnegie Institution Of Washington Tough diamonds and method of making thereof
JP4547493B2 (ja) * 2006-02-08 2010-09-22 独立行政法人産業技術総合研究所 ダイヤモンド単結晶の製造方法及びダイヤモンド単結晶

Also Published As

Publication number Publication date
CA2532227A1 (en) 2005-01-27
AU2004258191A1 (en) 2005-01-27
AU2004258191B2 (en) 2009-03-12
IL173101A0 (en) 2006-06-11
RU2324764C2 (ru) 2008-05-20
WO2005007936A2 (en) 2005-01-27
HK1095611A1 (en) 2007-05-11
JP2007523819A (ja) 2007-08-23
US7713507B2 (en) 2010-05-11
ZA200600885B (en) 2007-04-25
US20060144322A9 (en) 2006-07-06
US20050034650A1 (en) 2005-02-17
CA2532362A1 (en) 2005-01-27
EP1664373A2 (en) 2006-06-07
AU2004258193A1 (en) 2005-01-27
US20070077192A1 (en) 2007-04-05
WO2005007937A3 (en) 2006-02-02
TWI371506B (en) 2012-09-01
RU2006104555A (ru) 2006-08-27
CA2532362C (en) 2012-06-26
US7115241B2 (en) 2006-10-03
KR20060035757A (ko) 2006-04-26
US7754180B2 (en) 2010-07-13
RU2323281C2 (ru) 2008-04-27
TW200504254A (en) 2005-02-01
EP1663866A2 (en) 2006-06-07
CN1942610B (zh) 2010-06-09
US20050011433A1 (en) 2005-01-20
IL173102A0 (en) 2006-06-11
AU2004258192A1 (en) 2005-01-27
WO2005007935A2 (en) 2005-01-27
RU2006104552A (ru) 2006-09-10
EP1664394B1 (en) 2017-11-22
US7309477B2 (en) 2007-12-18
CN1853001A (zh) 2006-10-25
TW200502444A (en) 2005-01-16
AU2004258192B2 (en) 2008-12-04
BRPI0411984A (pt) 2006-08-29
HK1093334A1 (en) 2007-03-02
BRPI0412647A (pt) 2006-09-26
CA2532384A1 (en) 2005-01-27
WO2005007935A3 (en) 2006-02-02
KR20060063887A (ko) 2006-06-12
US20080241049A1 (en) 2008-10-02
US7157067B2 (en) 2007-01-02
EP1663866A4 (en) 2010-05-05
IL173100A (en) 2010-12-30
CN1823008A (zh) 2006-08-23
IL207054A (en) 2011-12-29
RU2006104551A (ru) 2006-07-27
CA2532384C (en) 2014-04-01
US20050025886A1 (en) 2005-02-03
EP1664394A2 (en) 2006-06-07
KR101151768B1 (ko) 2012-06-15
KR20060126891A (ko) 2006-12-11
BRPI0412536A (pt) 2006-09-19
CN100402421C (zh) 2008-07-16
TWI345000B (en) 2011-07-11
AU2004258193B2 (en) 2010-09-16
HK1101705A1 (en) 2007-10-26
JP2007531680A (ja) 2007-11-08
ZA200600883B (en) 2007-04-25
IL173101A (en) 2011-02-28
US20070290408A1 (en) 2007-12-20
KR101277228B1 (ko) 2013-06-26
WO2005007936A3 (en) 2006-07-20
KR101111690B1 (ko) 2012-02-17
CN100519831C (zh) 2009-07-29
RU2325323C2 (ru) 2008-05-27
JP2007531679A (ja) 2007-11-08
EP1664373A4 (en) 2010-05-05
JP4960090B2 (ja) 2012-06-27
JP4846578B2 (ja) 2011-12-28
ZA200600884B (en) 2007-03-28
WO2005007937A2 (en) 2005-01-27
TW200513552A (en) 2005-04-16
EP1664394A4 (en) 2010-05-05
CN1942610A (zh) 2007-04-04
IL173100A0 (en) 2006-06-11
US20060185583A1 (en) 2006-08-24
IL207054A0 (en) 2010-12-30

Similar Documents

Publication Publication Date Title
TWI342902B (en) Tough diamonds and method of making thereof
US7594968B2 (en) Ultratough CVD single crystal diamond and three dimensional growth thereof
JP2013532109A (ja) 大形、高純度、単結晶のｃｖｄダイヤモンドの生成
Neto et al. Diamond/WC bilayer formation mechanism by hot-filament CVD

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees