CN113186597B - Low-cost, large-size and high-quality single crystal diamond as well as preparation method and application thereof - Google Patents
Low-cost, large-size and high-quality single crystal diamond as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN113186597B CN113186597B CN202010037077.1A CN202010037077A CN113186597B CN 113186597 B CN113186597 B CN 113186597B CN 202010037077 A CN202010037077 A CN 202010037077A CN 113186597 B CN113186597 B CN 113186597B
- Authority
- CN
- China
- Prior art keywords
- single crystal
- crystal diamond
- deposition
- diamond
- another preferred
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 183
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 176
- 239000013078 crystal Substances 0.000 title claims abstract description 164
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 238000000151 deposition Methods 0.000 claims description 44
- 230000008021 deposition Effects 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 238000005229 chemical vapour deposition Methods 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 238000002834 transmittance Methods 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 238000001069 Raman spectroscopy Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 230000000052 comparative effect Effects 0.000 description 20
- 239000007789 gas Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- -1 ethylene, propylene, acetylene Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009643 growth defect Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
- 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
- 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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention relates to a low-cost, large-size and high-quality single crystal diamond as well as a preparation method and application thereof. Specifically, the single crystal diamond has the characteristics of low cost, large size, high quality, high purity and high hardness, and can effectively expand the application range of the single crystal diamond.
Description
Technical Field
The invention relates to the field of materials, in particular to a low-cost, large-size and high-quality single crystal diamond as well as a preparation method and application thereof.
Background
The single crystal diamond has the advantages of super hardness, high heat conductivity, high electron mobility, excellent optical performance, high chemical stability and the like, and has great application prospect in the industrial and high-tech fields such as machining, optics, microelectronics, quantum computers and the like. However, natural diamond is rare, the production cost and the post-processing cost are high, and large-scale application is difficult to realize. Therefore, the artificial synthesis of diamond has been a hot spot of research, and the existing synthesis methods mainly include a high temperature high pressure method (HTHP), a chemical vapor deposition method (CVD), and the like. The traditional HTHP method has severe requirements on equipment, and usually adopts catalysts such as iron, nickel and the like for synthesis, so that the prepared diamond has low purity, many defects, small size, high cost and the like, and is difficult to meet the performance requirements of the related fields. The CVD single crystal diamond has the advantages of simple equipment, large preparation area, few defects and the like, and is the main development direction of large-size artificial single crystal diamond synthesis. At present, a single crystal diamond is prepared by a CVD method mainly by a hot filament CVD method, a microwave plasma CVD method, a direct current injection CVD method and the like, and researchers prepare single crystal diamond products with higher quality through a series of researches on deposition parameters, growth rate, mechanical properties, optical properties and the like of the single crystal diamond in the CVD process. However, the above method still has the disadvantages of low growth rate (such as 5-8 μm), poor growth uniformity, low quality (FWHM is generally 5-7cm -1), small size (typically <10mm x10 mm), high production cost, and the like, and still has difficulty in meeting the current low-cost, high-quality and large-size application requirements of CVD single crystal diamond.
Therefore, there is a need in the art to develop a single crystal diamond and a method for preparing the same that have low cost, high quality and large size, thereby overcoming the disadvantages of the prior art and improving the performance to expand the application range of the single crystal diamond.
Disclosure of Invention
The invention aims to provide a single crystal diamond with low cost, large size and high quality and a preparation method thereof.
In a first aspect of the present invention, there is provided a single crystal diamond having a Raman peak full width at half maximum FWHM value of 2.9 to 3.5cm -1.
In another preferred example, the content of the crystalline carbon element in the single crystal diamond is equal to or more than 99.9wt%.
In another preferred example, the single crystal diamond is a single crystal structure.
In another preferred example, the atomic percent of carbon atoms in the single crystal diamond is 100% based on the total number of atoms making up the single crystal diamond.
In another preferred embodiment, the single crystal diamond is free of graphite.
In another preferred example, the graphite content in the single crystal diamond is 0wt%.
In another preferred embodiment, the single crystal diamond has a crystalline carbon element content of greater than or equal to 99.99wt%, preferably greater than or equal to 99.999wt%, more preferably greater than or equal to 99.9999wt%, preferably 100wt%, based on the total weight of the single crystal diamond product.
In another preferred example, the single crystal diamond has a Raman peak full width at half maximum FWHM value of 3.0 to 3.3cm -1, preferably 3.0 to 3.1cm -1.
In another preferred embodiment, the single crystal diamond has a hardness of 90-120GPa.
In another preferred example, the upper limit of hardness of the single crystal diamond is selected from the group consisting of: 120GPa, 115GPa and 110GPa.
In another preferred example, the lower limit of hardness of the single crystal diamond is selected from the group consisting of: 90GPa, 95GPa, 100GPa and 108GPa.
In another preferred embodiment, the single crystal diamond has an infrared transmittance of 68% or more.
In another preferred example, the single crystal diamond has an upper limit of infrared transmittance selected from the group consisting of: 71%, 70.5% and 70%.
In another preferred example, the single crystal diamond has a lower limit of infrared transmittance selected from the group consisting of: 68%, 68.5%, 69%, 70%.
In another preferred example, the single piece of single crystal diamond has a length of 3-5mm, a width of 3-5mm, and a thickness of 1-3mm; and/or
The whole dimension of the single crystal diamond is 50-80mm in length, 50-80mm in width and 1-3mm in thickness.
In another preferred example, the single crystal diamond has the dimensions shown in the following table:
in another preferred example, the single crystal diamond has one or more features selected from the group consisting of:
1) The single crystal diamond comprises 20 to 60 single crystal diamond pieces, preferably 22 to 45, more preferably 25 to 40, most preferably 28 to 35;
2) The length of the single crystal diamond is 50-80mm, preferably 52-65mm, more preferably 53-60mm, most preferably 54-58mm;
3) The single crystal diamond has a width of 50-80mm, preferably 52-65mm, more preferably 53-60mm, most preferably 54-58mm;
4) The thickness of the single crystal diamond is 2-2.5mm;
5) The single crystal diamond consists of single oriented (100) plane carbon crystals.
In another preferred example, the single crystal diamond pieces are placed at intervals of 1-3mm.
In a second aspect of the present invention, there is provided a method of producing a single crystal diamond according to the first aspect of the present invention, comprising the steps of:
1) Providing a matrix material;
2) Depositing the single crystal diamond according to the first aspect of the present invention on the surface of the base material by chemical vapor deposition;
wherein the deposition atmosphere of the deposition is as follows: carbon source, hydrogen and argon.
In another preferred example, the substrate material is type Ib single crystal diamond.
In another preferred embodiment, the length of the individual matrix material is 1-8mm, preferably-2-7 mm, more preferably 3-6mm, most preferably 4-5mm.
In another preferred embodiment, the width of the individual matrix material is 1-8mm, preferably 2-7mm, more preferably 3-6mm, most preferably 4-5mm.
In another preferred embodiment, the thickness of the individual matrix material is 0.5-2mm, preferably 0.7-1.5mm, more preferably 0.8-1.2mm.
In another preferred embodiment, step 1) is preceded by the further step of:
a-1) carrying out impurity removal treatment on the matrix material;
a-2) carrying out surface cleaning treatment on the substrate;
a-3) drying the base material.
In another preferred embodiment, the material used for the impurity removal treatment is selected from the group consisting of: concentrated nitric acid, concentrated sulfuric acid, potassium nitrate, or a combination thereof.
In another preferred embodiment, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 0.5-5, preferably 0.8-3, more preferably 1-2.
In another preferred example, the surface cleaning treatment is ultrasonic cleaning.
In another preferred embodiment, the cleaning agent used in the surface cleaning treatment is selected from the group consisting of: alcohol, acetone, deionized water, or combinations thereof.
In another preferred embodiment, the time of the ultrasonic cleaning is 30 to 100 minutes, preferably 40 to 80 minutes, more preferably 50 to 60 minutes.
In another preferred embodiment, the temperature of the ultrasonic cleaning is 50-150 ℃, preferably 70-120 ℃, more preferably 90-100 ℃.
In another preferred embodiment, the temperature of the drying process is 70-110 ℃, preferably 80-105 ℃.
In another preferred embodiment, the drying treatment is for a period of 5 to 15 hours.
In another preferred embodiment, the method further comprises, before step 2), the steps of:
b-1) preheating the matrix material.
In another preferred embodiment, the preheating temperature is 45-70 ℃, preferably 50-60 ℃.
In another preferred embodiment, step b-1) is to preheat the substrate material and form a plasma by introducing hydrogen and an inert gas under vacuum.
In another preferred embodiment, in step b-1), the vacuum is a vacuum of 10Pa or less, preferably 0.01 to 0.1Pa.
In another preferred embodiment, in step b-1), the preheating is carried out at a heating rate of 3-6deg.C/min.
In another preferred embodiment, the deposition atmosphere for the deposition is as follows: the flow rate of the carbon source is 5-40sccm, the flow rate of the hydrogen is 500-800sccm, and the flow rate of the argon is 5-15sccm.
In another preferred embodiment, the carbon source is a gas selected from the group consisting of: methane, ethane, propane, butane, ethylene, propylene, acetylene, or combinations thereof.
In another preferred embodiment, the carbon source is selected from the group consisting of: 10-35sccm, 15-30sccm, and 18-25sccm.
In another preferred embodiment, the hydrogen flow rate is selected from the group consisting of: 450-800sccm, 550-750sccm, 580-650sccm.
In another preferred embodiment, the argon flow is selected from the group consisting of: 5-15sccm and 6-12sccm.
In another preferred embodiment, the deposition is performed at a deposition temperature of 960-1100 ℃; and/or
The deposition time of the deposition is 10-80 hours, preferably 20-70 hours, more preferably 30-60 hours; and/or
The deposition pressure of the deposition is 0.05 Pa to 30000Pa.
In another preferred embodiment, the deposition pressure of the deposition is 0.08 to 25000Pa.
In another preferred embodiment, the deposition is performed at a deposition temperature of 970-1000 ℃.
In another preferred example, the deposition temperature refers to a temperature that the base material has at the time of deposition.
In another preferred embodiment, the preheat temperature is raised to the deposition temperature at a heating rate of 6-10 ℃/min.
In another preferred embodiment, step 2) is optionally followed by the step of:
3) Cooling the product obtained in step 2) to obtain the single crystal diamond according to the first aspect of the present invention.
In another preferred embodiment, the cooling process of step 3) includes the steps of:
c-1) stopping introducing the carbon source, and reducing the system to a first cooling temperature at a cooling rate of 3-6 ℃/min;
c-2) stopping introducing argon, and then reducing the system to a second cooling temperature;
c-3) stopping the hydrogen supply and subsequently reducing the system to a third cooling temperature.
In another preferred embodiment, in step c-1), the hydrogen flow is 200-800sccm, preferably 500-700sccm, more preferably 550-650sccm.
In another preferred embodiment, in step c-1), the flow rate of argon is 5-15sccm, preferably 6-12sccm, more preferably 8-10sccm.
In another preferred embodiment, the first cooling temperature is 450-600 ℃, preferably 500-550 ℃.
In another preferred embodiment, the second cooling temperature is 150-400 ℃, preferably 200-350 ℃.
In another preferred embodiment, the third cooling temperature is 25-40 ℃, such as room temperature.
In a third aspect of the present invention there is provided a diamond article comprising or consisting of a single crystal diamond according to the first aspect of the present invention.
In another preferred embodiment, the article comprises:
A base material; and
A deposited layer of single crystal diamond according to the first aspect of the present invention composited on the surface of the base material.
In another preferred embodiment, the article is selected from the group consisting of: cutter, electronic product, optical product.
In another preferred embodiment, the deposited layer is chemically bonded to the base material.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Drawings
Fig. 1 is a photograph of a CVD glow plasma morphology of single crystal diamond 1 obtained in example 1.
Fig. 2 is a photograph of the single crystal diamond 1 obtained in example 1 during the growth process.
Fig. 3 is a macroscopic photograph of single crystal diamond 1 obtained in example 1.
Fig. 4 shows the infrared transmittance value of the single crystal diamond 1 obtained in example 1.
Detailed Description
The present inventors have studied intensively for a long time, and developed a CVD single crystal diamond of low cost, large size and high quality for the first time and a method for producing the same. The single crystal diamond prepared by the method has large size, high quality and low cost, and the preparation area can be further enlarged by improving the CVD equipment, and the size of the prepared single crystal diamond can be further increased. On this basis, the inventors completed the present invention.
Terminology
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, the term "single crystal" refers to a single oriented structural entity in which atoms in the product produced are strictly formed according to the rule of crystal packing.
As used herein, the term "HPHT" refers to the production of diamond under conditions of high temperature and pressure.
As used herein, the term "type Ia single crystal diamond" refers to a diamond product formed under conditions of high temperature and high pressure in nature, characterized by single crystal diamond containing nitrogen element impurities, the nitrogen element being in a condensed state distribution within the diamond-like structure.
As used herein, the term "type Ib single crystal diamond" refers to a diamond product formed under conditions of high temperature and high pressure in nature, and is characterized by single crystal diamond containing nitrogen element impurities, wherein the nitrogen element is dispersed in the diamond-like structure.
As used herein, the term "type IIa single crystal diamond" refers to a diamond product formed under high temperature and high pressure conditions in nature, and is characterized by a single crystal diamond free of nitrogen impurities, having an infrared transmittance of 71.4%, a hardness of 120GPa, and a Raman peak full width at half maximum FWHM value of 4.8cm -1.
As used herein, the term "type IIb single crystal diamond" refers to a diamond product formed under conditions of high temperature and high pressure in nature, characterized as single crystal diamond containing boron element impurities.
As used herein, the term "single crystal diamond seed" refers to type Ib single crystal diamond prepared using the HPHT process, a substrate material for use in growing single crystal diamond by the dc glow CVD process.
As used herein, the terms "single crystal diamond seed" and "seed" may be used interchangeably.
As used herein, the terms "comprising," "including," and "containing" are interchangeable, and include not only closed-ended definitions, but also semi-closed, and open-ended definitions. In other words, the term includes "consisting of … …", "consisting essentially of … …".
As used herein, the term "FWHM" refers to the value of the half-width of the raman peak profile of a product after testing using raman spectroscopy, the smaller the value indicating a higher purity of the test sample.
As used herein, the term "GPa" refers to the hardness number units of single crystal diamond measured using a nanoindenter.
As used herein, the term "CVD system" refers to a direct current glow plasma vapor deposition furnace.
As used herein, the term "plasma" refers to a chemically reactive gas state formed after the reaction gases are ionized during CVD.
As used herein, the term "carbon source" refers to a feedstock that provides elemental carbon in a coating.
As used herein, the term "sccm" is a unit of volumetric flow, i.e., english standard-state cubic CENTIMETER PER minutes.
As used herein, the term "ppm" refers to a volume concentration unit, english PARTS PER MILL ion.
As used herein, the term "infrared transmittance" refers to a means of characterization of the transparency and defect content of single crystal diamond using infrared light, with a larger value indicating a higher transparency and a lower defect content for single crystal diamond.
The invention provides a single crystal diamond and a preparation method thereof, wherein the method is a direct current glow plasma CVD method, and a single crystal diamond product with low cost, high quality and large size is obtained by improving the density, uniformity and size of plasma, and carbon element in the single crystal diamond is in a single crystal structure.
The single crystal diamond product of the invention has a single crystal structure containing only carbon elements. In the single crystal diamond product, the length of the single crystal diamond is about 30 to 100mm, preferably 40 to 70mm; the single crystal diamond product has a width of 30-100mm, preferably 40-70mm.
In the invention, the thickness of the single crystal diamond product is mainly influenced by the deposition time, and a person skilled in the art can obtain the maximum value of the thickness by regulating the preparation time, and on the basis of considering the quality of the diamond product, the thickness of the single crystal diamond product is typically 2-2.5mm.
In another preferred embodiment, the purity of the methane is 99.9999%.
In another preferred embodiment, the hydrogen has a purity of 99.9999%.
In another preferred embodiment, the argon gas has a purity of 99.9999%
The invention also provides a preparation method of the low-cost, large-size and high-quality monocrystalline diamond product, which comprises the following steps:
(1) Providing a substrate;
(2) And performing chemical vapor deposition on the surface of the substrate by a direct current glow plasma chemical vapor deposition method in the presence of a carbon source, hydrogen and argon, so as to form the single crystal diamond product on the surface of the substrate.
And (3) preprocessing the substrate in the step (1), so that nucleation and growth of diamond grains on the surface of the substrate are facilitated. In a preferred embodiment, in the step (1), the substrate is a pretreated substrate, and the pretreatment includes the steps of: (a) And sequentially carrying out impurity removal, surface cleaning and drying treatment on the surface of the base material.
In another preferred embodiment, in the step (a), the following materials are selected for impurity removal: concentrated nitric acid, concentrated sulfuric acid, potassium nitrate, or a combination thereof. In another preferred embodiment, the impurity removing material is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio of the two is 1:1-1:5, preferably 1:1-1:3, and more preferably 1:1-1:2.
After the impurity removal is finished, in order to prevent residual acid liquor on the surface of the matrix, defects, amorphous phases or polycrystal and the like are caused in the growth process of diamond grains. The surface needs to be cleaned. In a preferred embodiment, in the step (a), the cleaning solution used for surface cleaning includes (but is not limited to): alcohol, acetone, deionized water, or combinations thereof. In another preferred embodiment, the water includes (but is not limited to): distilled water, deionized water, or a combination thereof. In another preferred embodiment, the time of the ultrasonic cleaning is 50-60 minutes. In another preferred embodiment, the temperature of the ultrasonic cleaning is 90-100 ℃. After the cleaning is finished, the substrate is required to be subjected to vacuum drying treatment so as to prevent secondary residue of the cleaning liquid. In another preferred embodiment, in the step (a), the temperature of the drying is 70-100 ℃. In another preferred embodiment, in the step (a), the drying time is 5 to 10 hours.
In another preferred embodiment, the method further comprises a step (3) of cooling the coating obtained in step (2), the cooling step comprising:
(3-1) first stage Cooling Process: stopping introducing the carbon source, adjusting the flow of the auxiliary gas to 200-600sccm, cooling to 500-550 ℃ at a cooling rate of 2-5 ℃/min.
(3-2) Second stage Cooling Process: when the temperature is reduced to 500-550 ℃, stopping introducing argon; and when the temperature is reduced to 200-300 ℃, stopping introducing auxiliary gas, and then cooling to room temperature.
In a preferred embodiment of the present invention, the method for preparing a single crystal diamond product comprises the steps of:
1. Placing the substrate in a CVD device, vacuumizing to a vacuum degree of 1 x 10 -3-10-1 Pa, and introducing auxiliary gas (such as mixed gas of hydrogen and argon, wherein the flow rate of the hydrogen is 200-800sccm, and the flow rate of the argon is 2-40 sccm). Starting a heating program of the gas circuit system, wherein the heating temperature is 50-55 ℃, and the heating rate is 3-6 ℃/min;
2. Heating to 960-1000 ℃ at a speed of 5-10 ℃/min, and introducing carbon source gas with a flow rate of 10-40sccm; the deposition time is 40-45h, and the deposition pressure is 0.08-25000Pa;
3. And after the deposition is finished, entering a controllable cooling program, stopping introducing the carbon source, and adjusting the flow of the auxiliary gas to 200-600sccm at a cooling rate of 2-5 ℃/min. When the temperature is reduced to 500-550 ℃, stopping introducing argon; and (3) stopping introducing auxiliary gas when the temperature is reduced to 200-300 ℃, and then cooling to room temperature to obtain the single crystal diamond product.
The single crystal diamond product can improve the growth rate and the growth uniformity of diamond by regulating and controlling the shape of plasma and the concentration of reaction raw materials, obviously reduce defects and graphite phases generated in the preparation process, and further increase the size of the prepared single crystal diamond, improve the quality of the diamond and obviously reduce the production cost by changing the concentration of gas plasma and the area of a deposition area.
Compared with the prior art, the invention has the following main advantages:
(1) The single crystal diamond product has the characteristics of high hardness, high wear resistance, large size, high purity, forbidden bandwidth, high mobility, large heat conductivity and the like, and is suitable for the fields of precision machining tools, electronic power devices, optical devices and the like. Meanwhile, the single crystal diamond product has low production cost, simple process and strong controllability, and is suitable for industrial production.
(2) The preparation method of the single crystal diamond product has the advantages of high growth rate (such as 20-30 mu m/h), good growth uniformity, few defects, large product size, simple equipment and low production cost. The obtained diamond product has extremely high hardness and extremely high purity, and can realize large-scale preparation of large-size monocrystalline diamond under the condition of low cost.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described herein are presented for illustrative purposes only.
Example 1 preparation of Single Crystal Diamond 1 by direct Current glow plasma CVD method
1. The surface of HPHT Ib type diamond seeds with the size of 4mm 1mm is subjected to impurity removal by using a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 1:1, then is subjected to ultrasonic cleaning by using deionized water and acetone, is dried at 90-100 ℃ for 10 hours, and is placed in a CVD device.
2. The CVD device is vacuumized to 1 x 10 -2 Pa, hydrogen and argon are filled, the flow rate of the hydrogen is 600sccm, and the flow rate of the argon is 10sccm. And starting a preheating program of the gas circuit system, setting the preheating temperature to 55 ℃ and the preheating speed to 5 ℃/min.
3. The method for preparing the large-size single crystal diamond product by the direct current glow plasma chemical vapor deposition method comprises the following steps: the heating program of the CVD system is started, the heating temperature is set to 970 ℃, and the heating rate is 8 ℃/min. The CVD device is heated to 970 ℃ and enters a deposition procedure, methane, hydrogen and argon are introduced, the flow rate of the methane is 30sccm, the flow rate of the hydrogen is 600sccm, the flow rate of the argon is 10sccm, the deposition time is 40h, and the deposition pressure is 20000Pa.
4. Stopping introducing methane, and regulating the flow of the auxiliary gas (hydrogen and argon) to 200-600sccm, wherein the cooling rate is 5 ℃/min. When the temperature is reduced to 500-550 ℃, stopping introducing argon; and when the temperature is reduced to 200-300 ℃, stopping introducing auxiliary gas (hydrogen), and then cooling to room temperature to obtain the single crystal diamond 1.
The single crystal diamond 1 obtained in example 1 was subjected to CVD process observation, raman, infrared transmittance, hardness, and the like, and the measurement results are shown in fig. 1 to 4.
Fig. 1 is a photograph of a CVD glow plasma morphology of single crystal diamond 1 obtained in example 1.
Fig. 1 shows: in the growth process of the single crystal diamond 1 obtained in example 1, the glow plasma formed was large in area, high in plasma density and uniform in distribution.
Fig. 2 is a photograph of the single crystal diamond 1 obtained in example 1 during the growth process.
Fig. 2 shows: the obtained single crystal diamond product has even and smooth surface, small roughness and no obvious growth defect.
Laser Raman spectrum testing
Laser raman spectroscopy can identify the lattice structure of a substance. For single crystal diamond, the raman spectrum can reliably detect the content of non-diamond SP 2 bond carbon phase (the diamond is SP 3 bond carbon) in the single crystal diamond, and then the purity of the single crystal diamond product can be known through the full width at half maximum value FWHM of the raman spectrum.
The full width at half maximum FWHM of the Raman spectrum of the single crystal diamond 1 obtained in example 1 was 3.0cm -1, which is smaller than the full width at half maximum (fwhm=4.8 cm -1) of HPHT IIa diamond, indicating that the quality of the diamond product was superior to HPHT IIa diamond.
Fig. 3 is a macroscopic photograph of single crystal diamond 1 obtained in example 1.
Fig. 3 shows: the single crystal diamond 1 obtained in example 1 was larger in size, and the single crystal diamond product was 4mm by 1mm in size; the single crystal diamond product has high purity and high transparency.
In practice, the single crystal diamond described in example 1 contained 24 single crystal diamonds, so the size of the single crystal diamond obtained was 58mm by 2.3mm.
Hardness test
The method comprises the following steps: hardness comparison test was performed on the single crystal diamond 1 prepared in example 1.
The hardness testing method comprises the following steps: the hardness value of the single crystal diamond 1 is tested by adopting a nano indentation instrument, and the test mode is as follows: the diamond pressure head is vertically pressed into a micro-area on the surface of the test sample, and the maximum loading load is: 400mN, load resolution: 30nN, the minimum load achievable: 1.5 μN, displacement resolution: 0.003nm, the achievable self-small displacement: 0.04nm, maximum displacement achievable: each sample was tested 3 times at 250 μm and the results averaged.
The average hardness value of the single crystal diamond 1 obtained in example 1 was found to be about 110GPa.
Transmittance test
The single crystal diamond product of example 1 was subjected to transmittance testing using infrared spectroscopy. The infrared spectrum has extremely high sensitivity to the chemical bond characteristics of carbon bonds, the types of defects and the distribution thereof, and is an effective method for measuring the defects in the single crystal diamond.
The method comprises the following steps: the single crystal diamond 1 prepared in example 1 was subjected to an infrared transmittance test. And testing the infrared transmittance of the single crystal diamond product by adopting a Fourier infrared spectrometer. The infrared wavelength of the test instrument is 4000-500cm -1.
Fig. 4 shows the infrared transmittance value of the single crystal diamond 1 obtained in example 1.
Fig. 4 shows: the infrared transmittance of the single crystal diamond 1 obtained in example 1 was 70%.
The single crystal diamond is a large-area sheet product formed by connecting single crystal seeds (100) after epitaxial growth.
Comparative examples 1 to 7 preparation of single crystal diamonds C1 to C5
The CVD diamond products C1 to C7 described in comparative examples 1 to 7 were prepared in a similar manner to example 1 except that the parameters during the coating preparation process were changed as in table 1, and FWHM values, hardness values, product sizes, infrared transmittance, etc. of the resultant diamond were characterized and measured in the same manner as in example 1, and the results are shown in table 1.
Table 1 determination and characterization of properties of single crystal diamonds prepared in example 1 and comparative examples 1-7
Comparison of example 1 and comparative examples 1 to 7
The hardness values of the single crystal diamonds prepared in example 1 and comparative examples 1 to 7 were compared, and the results are shown in table 1; as can be seen from Table 1, the single crystal diamond product prepared in example 1 has a hardness value of 110GPa, which is significantly greater than the diamond products prepared in comparative examples 1-7 (e.g., the hardness value of 105GPa for comparative example 6).
The single crystal diamonds prepared in example 1 and comparative examples 1 to 7 were compared in size and the results are shown in table 1. As can be seen from table 1, the single crystal diamond prepared in example 1 had a size of 58mm by 2.3mm and a thickness significantly greater than that of comparative examples 1 to 7 (as in comparative example 6, the size was 58mm by 1.9 mm).
The results of comparing the raman peak full width at half maximum FWHM values of the single crystal diamonds prepared in example 1 and comparative examples 1 to 7 are shown in table 1. As can be seen from Table 1, the single crystal diamond prepared in example 1 has a Raman peak full width at half maximum FWHM value of 3.0cm -1, which is significantly smaller than that of comparative examples 1 to 7 (as in comparative example 6, the FWHM value is 3.2cm -1).
The single crystal diamonds prepared in example 1 and comparative examples 1 to 7 were compared in infrared transmittance values, and the results are shown in table 1. As can be seen from Table 1, the single crystal diamond 1 prepared in example 1 had an infrared transmittance value of 70% which is significantly larger than that of comparative examples 1 to 7 (as in comparative example 6, the infrared transmittance value was 69.4%).
Comparative examples 1 and 6 show that: the increase in argon content and growth temperature increased the energy density and uniformity of the reactant gases, and thus increased the growth rate and quality of the single crystal diamond of example 1.
Therefore, the single crystal diamond 1 prepared in example 1 of the present invention has a larger size, extremely high hardness and quality (e.g., high purity) as compared to comparative examples 1 to 7.
EXAMPLE 2 Single Crystal diamond 2
The process is identical to example 1, except that: the hydrogen flow rate was 800sccm.
The result shows that the diamond product is still in a single crystal structure, the Raman peak full width at half maximum FWHM value is 3.1cm -1, the hardness value is 106GPa, the size is 58mm, 2.0mm and the infrared transmittance is 69.6%.
EXAMPLE 3 Single Crystal diamond 3
The process is identical to example 1, except that: the argon flow was 6sccm.
The result shows that the diamond product is still in a single crystal structure, the Raman peak full width at half maximum FWHM value is 3.1cm -1, the hardness value is 108GPa, the size is 58mm, 2.0mm, and the infrared transmittance is 69.8%.
The hardness, size and infrared transmittance of examples 1-3 are obviously higher than those of comparative examples 1-7, and the Raman peak full width at half maximum FWHM value is obviously lower than those of comparative examples 1-7, which shows that the single crystal diamond products prepared in examples 1-3 have extremely high hardness, large size and extremely high purity.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (13)
1. A method for producing a single crystal diamond, comprising the steps of:
1) Providing a matrix material;
2) Depositing the single crystal diamond on the surface of the substrate material by using a direct current glow plasma chemical vapor deposition method;
wherein the deposition atmosphere of the deposition is as follows: a carbon source, hydrogen and argon;
The base material is type Ib single crystal diamond, and the base material comprises 20-60 single pieces of single crystal diamond having the following dimensions: 3.3-4.5mm in length, 3.3-4.5mm in width and 1-2.5mm in thickness;
The deposition atmosphere for the deposition is as follows: the flow rate of the carbon source is 25-40sccm, the flow rate of the hydrogen is 500-800sccm, and the flow rate of the argon is 6-15sccm;
the carbon source is methane;
the deposition is carried out at a deposition temperature of 960-1100 ℃;
The deposition time of the deposition is 30-60h;
the deposition pressure of the deposition is 20000-30000Pa;
The Raman peak full width at half maximum FWHM value of the single crystal diamond is 2.9-3.1cm -1;
the hardness of the single crystal diamond is 108-120GPa;
the infrared transmittance of the monocrystal diamond is more than or equal to 70%;
the single crystal diamond is of a single crystal structure;
The single crystal diamond is composed of single oriented (100) plane carbon crystals;
The length of the single crystal diamond is 50-80mm;
the width of the single crystal diamond is 50-80mm;
The thickness of the single crystal diamond is 2-2.5mm.
2. The method of claim 1, wherein the deposition atmosphere for the deposition is as follows: the flow rate of the carbon source is 30-35sccm, the flow rate of the hydrogen is 550-800sccm, and the flow rate of the argon is 6-12sccm.
3. The method of claim 1, wherein the deposition pressure of the deposition is 20000 to 25000Pa.
4. The method according to claim 1, characterized in that step 2) is followed by the optional further step of:
3) And cooling the product obtained in the step 2) to obtain the single crystal diamond.
5. The method of claim 1, wherein the single crystal diamond has a Raman peak full width at half maximum FWHM value of 3.0 to 3.1cm -1.
6. The method of claim 1, wherein the single crystal diamond has a hardness of 108-115GPa.
7. The method of claim 1, wherein the single crystal diamond has a length of 52 mm to 65mm.
8. The method of claim 1, wherein the single crystal diamond has a width of 52 mm to 65mm.
9. The method of claim 1, wherein the single crystal diamond has a length of 53-60mm.
10. The method of claim 1, wherein the single crystal diamond has a hardness of 108-110GPa.
11. The method of claim 1, wherein the single crystal diamond has a width of 53-60mm.
12. The method of claim 1, wherein the depositing is performed at a deposition temperature of 970-1000 ℃.
13. The method of claim 1, wherein the single crystal diamond has a length of 54-58mm;
the width of the single crystal diamond is 54-58mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010037077.1A CN113186597B (en) | 2020-01-14 | 2020-01-14 | Low-cost, large-size and high-quality single crystal diamond as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010037077.1A CN113186597B (en) | 2020-01-14 | 2020-01-14 | Low-cost, large-size and high-quality single crystal diamond as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113186597A CN113186597A (en) | 2021-07-30 |
| CN113186597B true CN113186597B (en) | 2024-04-30 |
Family
ID=76972480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010037077.1A Active CN113186597B (en) | 2020-01-14 | 2020-01-14 | Low-cost, large-size and high-quality single crystal diamond as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113186597B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01308896A (en) * | 1988-02-01 | 1989-12-13 | Sumitomo Electric Ind Ltd | Diamond and vapor synthesis thereof |
| CN105992835A (en) * | 2014-01-24 | 2016-10-05 | Ii-Vi有限公司 | Substrate including a diamond layer and a composite layer of diamond and silicon carbide, and, optionally, silicon |
| CN108291326A (en) * | 2015-09-23 | 2018-07-17 | 六号元素技术有限公司 | The method for manufacturing multiple single crystal CVD synthetic diamonds |
-
2020
- 2020-01-14 CN CN202010037077.1A patent/CN113186597B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01308896A (en) * | 1988-02-01 | 1989-12-13 | Sumitomo Electric Ind Ltd | Diamond and vapor synthesis thereof |
| CN105992835A (en) * | 2014-01-24 | 2016-10-05 | Ii-Vi有限公司 | Substrate including a diamond layer and a composite layer of diamond and silicon carbide, and, optionally, silicon |
| CN108291326A (en) * | 2015-09-23 | 2018-07-17 | 六号元素技术有限公司 | The method for manufacturing multiple single crystal CVD synthetic diamonds |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113186597A (en) | 2021-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ali et al. | Surface morphology, growth rate and quality of diamond films synthesized in hot filament CVD system under various methane concentrations | |
| Lee et al. | CVD diamond films: nucleation and growth | |
| Bühlmann et al. | Characterization of ballas diamond depositions | |
| Haque et al. | Large-area diamond thin film on Q-carbon coated crystalline sapphire by HFCVD | |
| JP2013542906A (en) | Method for producing white single crystal diamond | |
| Guo et al. | High-quality diamond film deposition on a titanium substrate using the hot-filament chemical vapor deposition method | |
| Zhang et al. | The effect of boron doping on the morphology and growth rate of micron diamond powders synthesized by HFCVD method | |
| Saito et al. | Growth rate anomaly in ultralow-pressure chemical vapor deposition of 3C-SiC on Si (001) using monomethylsilane | |
| CN106517165A (en) | Method for growing graphene by metal-assisted internal/external carbon sources combination mode on 6H/4H-SiC silicon surface | |
| Pu et al. | High-temperature oxidation behaviors of CVD diamond films | |
| Zhang et al. | The effect of deposition parameters on the morphology of micron diamond powders synthesized by HFCVD method | |
| Tiwari et al. | The synthesis of diamond films on adamantane-coated Si substrate at low temperature | |
| GB2575366A (en) | Method of manufacture of single crystal synthetic diamond material | |
| Cheng et al. | Homogeneous nanocrystalline cubic silicon carbide films prepared by inductively coupled plasma chemical vapor deposition | |
| Wang et al. | Heteroepitaxial diamond film deposition on KTaO3 substrates via single-crystal iridium buffer layers | |
| Liu et al. | Enhancement of nucleation of diamond films deposited on copper substrate by nickel modification layer | |
| CN113186597B (en) | Low-cost, large-size and high-quality single crystal diamond as well as preparation method and application thereof | |
| US6558742B1 (en) | Method of hot-filament chemical vapor deposition of diamond | |
| Beckmann et al. | Influence of gas phase parameters on the deposition kinetics and morphology of thin diamond films deposited by HFCVD and MWCVD technique | |
| Shang et al. | Intrinsic stress evolution in diamond films prepared in a CH4 H2 NH3 hot filament chemical vapor deposition system | |
| Zhang et al. | The deposition parameters in the synthesis of CVD microcrystalline diamond powders optimized by the orthogonal experiment | |
| Reinke et al. | Investigation of the nucleation mechanism in bias‐enhanced diamond deposition | |
| Nakamura et al. | High quality chemical vapor deposition diamond growth on iron and stainless steel substrates | |
| Eaton-Magaña et al. | Recent advances in CVD synthetic diamond quality | |
| Hei et al. | Effect of growth parameters on single crystal diamond deposition by dc arc plasma jet cvd |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |