CN117026356A - Preparation method of nitrogen-doped diamond monocrystal - Google Patents
Preparation method of nitrogen-doped diamond monocrystal Download PDFInfo
- Publication number
- CN117026356A CN117026356A CN202311063412.5A CN202311063412A CN117026356A CN 117026356 A CN117026356 A CN 117026356A CN 202311063412 A CN202311063412 A CN 202311063412A CN 117026356 A CN117026356 A CN 117026356A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped diamond
- diamond
- monocrystal
- carbon source
- 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.)
- Pending
Links
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 126
- 239000010432 diamond Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000013078 crystal Substances 0.000 claims abstract description 60
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 28
- 150000001721 carbon Chemical class 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- 229910005800 NiMnCo Inorganic materials 0.000 claims abstract description 9
- 238000010306 acid treatment Methods 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- -1 carbon nitrogen hydrogen oxygen organic compound Chemical class 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910002555 FeNi Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000005416 organic matter Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 238000001069 Raman spectroscopy Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 4
- 229910052903 pyrophyllite Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- UUXFWHMUNNXFHD-UHFFFAOYSA-N barium azide Chemical compound [Ba+2].[N-]=[N+]=[N-].[N-]=[N+]=[N-] UUXFWHMUNNXFHD-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 210000003000 inclusion body Anatomy 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/12—Single-crystal growth directly from the solid state by pressure treatment during the growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application belongs to the technical field of diamond preparation, and relates to a preparation method of a nitrogen-doped diamond monocrystal. After preparing a diamond monocrystal from a modified carbon source, a NiMnCo alloy catalyst, a crystal bed and a diamond seed crystal, carrying out acid treatment on the diamond monocrystal to obtain the high-quality nitrogen-doped diamond monocrystal, wherein the modified carbon source is obtained by modifying graphite powder by taking an organic matter containing carbon, nitrogen and oxygen as a nitrogen source, and other unnecessary impurity elements are not introduced, so that the poisoning effect on the catalyst is avoided, the preparation difficulty of the high-quality nitrogen-doped diamond monocrystal is reduced, the preparation cost is reduced, and the high-quality nitrogen-doped diamond monocrystal has repeatability. The method can effectively reduce the synthesis pressure and temperature for preparing the high-quality nitrogen-doped diamond monocrystal, and the nitrogen-doped diamond monocrystal prepared by the method has the advantages of high quality, fewer inclusion, perfect crystal form and high transparency.
Description
Technical Field
The application belongs to the technical field of diamond preparation, and particularly relates to a preparation method of a nitrogen-doped diamond monocrystal.
Background
Diamond is one of the special materials existing in nature, and has the highest hardness, low friction coefficient, high elastic modulus, high thermal conductivity, high insulation, wide energy gap, high acoustic propagation rate, good chemical stability and the like. Diamond has been widely used in high-end manufacturing industries such as precision tools, wear-resistant parts, optical element coatings, electronic product accessory processing, and the like, with its excellent physicochemical properties. Diamond has become a new material in the twentieth century of high-tech development, and technological development has further promoted the application of artificial diamond as a functional material in emerging industries. Natural diamond ore belongs to non-renewable resources, has the characteristics of rare mineral reserves, high exploitation cost, high ecological environment damage degree in the exploitation process and the like, and cannot be widely applied to the industrial field.
Thus, global industrial diamond is mainly synthetic diamond. The preparation of high-quality diamond monocrystal material is an important premise for promoting the application of diamond in the high-tech tip field. After other elements are doped in the diamond crystal, certain properties of the diamond material can be obviously improved, and even new functions can be endowed to the diamond.
Nitrogen is a common doping element in diamond. In the research of nitrogen-doped diamond preparation, a common nitrogen source is typically barium azide (Ba (N) 3 ) 2 ) Sodium azide (NaN) 3 ) Iron nitride (Fe) 3 N), and the like. The use of these nitrogen-containing substances inevitably introduces other impurity elements, changes the original catalyst properties, has toxic effect on the catalyst, increases the synthesis pressure and temperature of nitrogen-doped diamond monocrystal, increases the difficulty of synthesizing high-quality diamond, and increases the production cost.
Disclosure of Invention
In order to solve the technical problems, the application provides a preparation method of a nitrogen-doped diamond monocrystal. The graphite powder is modified by taking the organic matters containing only carbon, nitrogen and hydrogen as nitrogen sources, so that the synthesis pressure and temperature for preparing the high-quality nitrogen-doped diamond monocrystal can be effectively reduced, and the prepared nitrogen-doped diamond monocrystal has high quality, fewer inclusion, good crystal form and high transparency.
In order to achieve the above object, the present application provides a modified carbon source for preparing a nitrogen-doped diamond monocrystal, which is obtained by modifying graphite powder with carbon-nitrogen-oxygen organic compound powder; the molecular formula of the carbon nitrogen hydrogen oxygen organic compound powder is R 1 -(C＝O)-R 2 Wherein R is 1 、R 2 Consisting of nitrogen and hydrogen and/or carbon.
Further, the preparation method of the modified carbon source comprises the following steps: and weighing a nitrogen source according to the mass fraction of 0.1-1.0wt.% of the graphite powder, mixing the nitrogen source and the graphite powder in a vacuum environment for 4-6 hours to obtain graphite nitride powder, and then pressing and forming to obtain the modified carbon source.
Preferably, the vacuum environment has a vacuum degree of 1.0X10 -2 torr。
Further, the graphite powder is obtained by heating flake graphite powder to 1500-2000 ℃ for 1-10 h under inert gas atmosphere or vacuum condition.
Preferably, the inert gas atmosphere includes one of an argon atmosphere, a helium atmosphere, a neon atmosphere, a krypton atmosphere, a xenon atmosphere, and a nitrogen atmosphere.
Preferably, the vacuum degree of the vacuum is 1.0X10 -2 torr。
On the other hand, the application also provides a preparation method of the nitrogen-doped diamond monocrystal, which takes the modified carbon source for preparing the nitrogen-doped diamond monocrystal as a raw material, and forms a diamond synthesis block with a catalyst, a crystal bed and diamond seed crystals, and the nitrogen-doped diamond monocrystal is obtained through pressurized synthesis treatment.
Further, the catalyst is NiMnCo alloy or FeNi alloy.
Further, the pressure of the pressurizing synthesis treatment is 5.5-8.0 GPa, the temperature is 1300-1400 ℃, and the time is 1-200 h.
Further, the pressurizing synthesis treatment further comprises an acid treatment process.
Preferably, the acid treatment process comprises the following steps: and dissolving the catalyst in hot dilute nitric acid solution, and then finely boiling the sample in hot mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 9:1) for 2-6 hours.
More preferably, the concentration of the dilute nitric acid solution is not higher than 6mol/L; the concentration of the concentrated nitric acid is not lower than 8mol/L; the concentration of the concentrated sulfuric acid is not lower than 10mol/L.
On the other hand, the application also provides a nitrogen-doped diamond monocrystal prepared by the method.
On the other hand, the application also provides application of the nitrogen doped diamond monocrystal in the fields of aerospace and precision instruments.
On the other hand, the application also provides a method for improving the quality of the nitrogen-doped diamond monocrystal, which takes the modified carbon source for preparing the nitrogen-doped diamond monocrystal as a raw material, and a NiMnCo alloy catalyst, a crystal bed and a diamond seed crystal form a diamond synthetic block, and the nitrogen-doped diamond monocrystal is obtained through pressurized synthetic treatment.
Compared with the prior art, the technical scheme has the following beneficial effects:
1. the application uses the organic matter containing only carbon, nitrogen, oxygen and hydrogen as the nitrogen source, has simple structure and easy decomposition, the nitrogen in the organic matter is the main source of nitrogen atoms in the nitrogen doped diamond, and a small amount of oxygen in the organic matter is more beneficial to synthesizing high-quality diamond single crystals.
2. The nitrogen source used in the application does not introduce other unnecessary impurity elements when synthesizing the diamond monocrystal, thereby avoiding the poisoning effect of the unnecessary impurity elements on the catalyst and further reducing the synthesis pressure and temperature of the preparation of the nitrogen doped diamond monocrystal.
3. The nitrogen source used in the application is used as an additive to effectively inhibit precipitation of recrystallized graphite when synthesizing diamond monocrystal, and improves the preparation efficiency of high-quality diamond.
4. The preparation method is carried out in an inert gas atmosphere or under vacuum conditions in the process of preparing the modified carbon source, so that the exposure time of the original material in the air is reduced, and the pollution of the external temperature and humidity and the complex components of the air to the original material is greatly reduced.
5. The application uses the organic matter containing only carbon, nitrogen, hydrogen and oxygen as the nitrogen source, and the synthesized nitrogen doped diamond has high monocrystals, fewer inclusion bodies, perfect crystal form and high transparency.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
fig. 1 is a schematic diagram of a diamond synthesis block structure.
FIG. 2 is an optical photograph (a) and characterization spectra of infrared (b) and Raman (c) of high-quality nitrogen-doped diamond single crystals prepared in example 1.
FIG. 3 is an optical photograph (a) and characterization spectra of infrared (b) and Raman (c) of high-quality nitrogen-doped diamond single crystals prepared in example 2.
FIG. 4 is an optical photograph (a) and characterization spectra of infrared (b) and Raman (c) of high-quality nitrogen-doped diamond monocrystal prepared in comparative example 1.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
Preparation of nitrogen doped diamond single crystal:
s1, carrying out high-temperature purification treatment on the flake graphite powder at 2000 ℃ for 5 hours in an argon environment in an ultrahigh-temperature graphitization furnace to obtain purified graphite powder.
S2, weighing nitrogen source Carbohydrazide (CH) according to the mass fraction of 0.1wt.% of the purified graphite powder 6 N 4 O) adding the purified graphite powder and the nitrogen source carbohydrazide powder into a vacuum stirring tank, and stirring for 4 hours to obtain modified graphite powder; and pressing the modified graphite powder into a cylinder through powder pressing forming equipment to obtain a modified carbon source, and placing the modified carbon source in a constant-temperature vacuum box at 100 ℃ for later use.
S3, sequentially filling the modified carbon source, the NiMnCo alloy catalyst, the crystal bed and the diamond seed crystal into the pyrophyllite composite block to form a diamond composite block, and placing the diamond composite block in a constant temperature vacuum box at 110 ℃ for 4 hours.
S4,: and placing the diamond synthesis block into a hexahedral hydraulic press, setting the technological parameters of 5.5GPa synthesis pressure and 1300 ℃ synthesis temperature, and carrying out synthesis period for 13 hours to prepare the diamond monocrystal sample column without finding recrystallized graphite.
S5, dissolving the catalyst in a hot dilute nitric acid solution for the diamond monocrystal sample column, then finely boiling the diamond monocrystal sample column for 4 hours by using a hot mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 9:1) to remove residual catalyst and surface impurities on the surface of the crystal, and obtaining the nitrogen-doped diamond monocrystal after the acid treatment is completed.
Example 2
Preparation of nitrogen doped diamond single crystal:
s1, carrying out high-temperature purification treatment on the flake graphite powder at 2000 ℃ for 5 hours in an argon environment in an ultrahigh-temperature graphitization furnace to obtain purified graphite powder.
S2 purified graphite powder and 0.6wt.% (mass ratio to purified graphite powder) urea (CH 4 N 2 Adding the powder into a vacuum stirring tank, and stirring for 4 hours to obtain modified graphite powder; and pressing the modified graphite powder into a cylinder through powder pressing forming equipment to obtain a modified carbon source, and placing the modified carbon source in a constant-temperature vacuum box at 100 ℃ for later use.
S3, sequentially filling the modified carbon source, the NiMnCo alloy catalyst, the crystal bed and the diamond seed crystal into the pyrophyllite composite block to form a diamond composite block, and placing the diamond composite block in a constant temperature vacuum box at 110 ℃ for 4 hours.
S4,: and placing the diamond synthesis block into a hexahedral hydraulic press, setting the technological parameters of synthesis pressure of 5.5GPa, synthesis temperature of 1320 ℃, and synthesis period of 10 hours, and preparing the diamond single crystal sample column without finding recrystallized graphite.
S5, dissolving the catalyst in a hot dilute nitric acid solution for the diamond monocrystal sample column, then finely boiling the diamond monocrystal sample column for 4 hours by using a hot mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 9:1) to remove residual catalyst and surface impurities on the surface of the crystal, and obtaining the nitrogen-doped diamond monocrystal after the acid treatment is completed.
Comparative example 1
Preparation of nitrogen doped diamond single crystal:
s1 purified graphite powder and 0.4wt.% (mass ratio to purified graphite powder) sodium azide (NaN) 3 ) Adding the powder into a vacuum stirring tank, and stirring for 4 hours to obtain modified graphite powder; modified graphite powderAnd (5) pressing the mixture into a cylinder through powder pressing forming equipment to obtain a modified carbon source, and placing the modified carbon source in a constant-temperature vacuum box at 100 ℃ for later use.
S2, sequentially filling the modified carbon source, the NiMnCo alloy catalyst, the crystal bed and the diamond seed crystal into the pyrophyllite composite block to form a diamond composite block, and placing the diamond composite block in a constant temperature vacuum box at 110 ℃ for 4 hours.
S3,: and placing the diamond synthesis block into a hexahedral hydraulic press, setting the technological parameters of 5.8GPa synthesis pressure and 1350 ℃ synthesis temperature, and carrying out synthesis for 10 hours to prepare the diamond monocrystal sample column without finding recrystallized graphite.
S4, dissolving the catalyst in a hot dilute nitric acid solution for the diamond monocrystal sample column, then finely boiling the diamond monocrystal sample column for 4 hours by using a hot mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 9:1) to remove residual catalyst and surface impurities on the surface of the crystal, and obtaining the nitrogen-doped diamond monocrystal after the acid treatment is completed.
In the examples and comparative examples, the purpose of the inert gas atmosphere and the vacuum atmosphere is to reduce the influence of the external temperature and humidity and the complex components of air on the raw materials, so that the inert gas atmosphere or the vacuum condition defined by the present application in the technical scheme does not affect the final technical effect and can be replaced equally.
Fig. 1 is a schematic view of the diamond synthesis block structure in example 1. Comprising the following steps: 1-pyrophyllite composite block, 2-heating pipe, 3-outer layer heat-preservation pressure-transmitting material, 4-seed crystal, 5-conductive graphite sheet, 6-inner layer heat-preservation ceramic material, 7-modified carbon source, 8-NiMnCo alloy catalyst and 9-crystal bed.
Fig. 2 is an optical photograph and an infrared and raman characterization map of the high-quality nitrogen-doped diamond single crystal prepared in example 1. Fig. 2a is an optical photograph of a high-quality nitrogen-doped diamond monocrystal prepared in example 1, wherein the crystal is yellow-green in color, good in crystal quality, free of inclusion and good in transparency. Fig. 2b is an infrared spectrum of the high quality nitrogen doped diamond single crystal prepared in example 1. Infrared characterization of the prepared nitrogen doped diamond monocrystal with Fourier transform micro infrared spectrometer, as shown in figure 2b, the intrinsic peak of diamond is located in the binaural subregion in infrared spectrum1500-2680cm -1 Therein 2030cm -1 、2160cm -1 And 2350cm -1 Is an intrinsic peak of diamond, represents the vibration infrared absorption between C-C, and is a unique infrared absorption peak in the crystal structure of diamond. The characteristic absorption peak of nitrogen is concentrated at 800-1400cm of the first sound sub-zone -1 The region, infrared absorption peak 1130cm in FIG. 2b -1 And 1344cm -1 Indicating that the nitrogen atoms in diamond are distributed in the diamond lattice primarily in a monoatomic discrete state and that the nitrogen content is about 570ppm.
Fig. 2c is a raman spectrum of the high quality nitrogen doped diamond single crystal prepared in example 1. Raman characterization of the prepared diamond single crystal with a micro raman spectrometer as shown in fig. 2c, the prepared nitrogen doped diamond single crystal has a raman spectrum with only one main peak 1331.9cm which is narrow and strong -1 And the half-width is 4.3cm, which shows that the synthesized nitrogen doped diamond monocrystal has higher crystallinity and better crystal quality.
FIG. 3 is an optical photograph and an infrared and Raman characterization map of the high-quality nitrogen-doped diamond monocrystal prepared in example 2. Fig. 3a is an optical photograph of a high-quality nitrogen-doped diamond monocrystal prepared in example 2, wherein the crystal color is dark green, the crystal quality is good, and no inclusion exists. Fig. 3b is an infrared spectrum of the high quality nitrogen doped diamond single crystal prepared in example 2. The infrared absorption peak in FIG. 3b is at 1130cm -1 And 1344cm -1 Has a strong infrared absorption peak and a nitrogen content of about 1000ppm. Fig. 3c is a raman spectrum of the high quality nitrogen doped diamond single crystal prepared in example 2. As shown in FIG. 3c, the prepared nitrogen-doped diamond single crystal has a Raman spectrum with only one narrow and strong main peak 1329.9cm -1 And the half-width is 3.8cm, which shows that the synthesized nitrogen doped diamond monocrystal has higher crystallinity and better crystal quality.
Fig. 4 is an optical photograph and an infrared and raman characterization map of the high-quality nitrogen-doped diamond single crystal prepared in comparative example 1. Fig. 4a is an optical photograph of a high-quality nitrogen-doped diamond single crystal prepared in comparative example 1, the crystal color is dark green, and there is a small amount of burrs inside the crystal, and no inclusion. The presence of burrs can seriously affect the quality of the crystalThe application value diagram of the nitrogen doped diamond monocrystal is greatly reduced. Fig. 4b is an infrared spectrum of the high-quality nitrogen-doped diamond single crystal prepared in comparative example 1. The infrared absorption peak in FIG. 4b is at 1130cm -1 And 1344cm -1 Has a strong infrared absorption peak and a nitrogen content of about 1200ppm. Fig. 4c is a raman spectrum of the high quality nitrogen-doped diamond single crystal prepared in comparative example 1. As shown in FIG. 4c, the prepared nitrogen-doped diamond single crystal has a Raman spectrum with only one narrow and strong main peak 1330.1cm -1 And the half-width is 4.7cm, which shows that the synthesized nitrogen-doped diamond monocrystal has higher crystallinity.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A modified carbon source for preparing nitrogen-doped diamond monocrystal is characterized in that graphite powder is modified by carbon-nitrogen-oxygen-hydrogen organic compound powder; the molecular formula of the carbon nitrogen hydrogen oxygen organic compound powder is R 1 -(C＝O)-R 2 Wherein R is 1 、R 2 Consisting of nitrogen and hydrogen and/or carbon.
2. The modified carbon source for producing a nitrogen-doped diamond single crystal according to claim 1, wherein the production method of the modified carbon source comprises: and weighing a nitrogen source according to the mass fraction of 0.1-1.0wt.% of the graphite powder, mixing the nitrogen source and the graphite powder in a vacuum environment for 4-6 hours to obtain graphite nitride powder, and then pressing and forming to obtain the modified carbon source.
3. The modified carbon source for producing a nitrogen-doped diamond monocrystal according to claim 2, wherein the graphite powder is a flake graphite powder obtained by heating to 1500 to 2000 ℃ under an inert gas atmosphere or vacuum condition for 1 to 10 hours.
4. A method for preparing a nitrogen-doped diamond single crystal, which is characterized in that the nitrogen-doped diamond single crystal is prepared by taking the modified carbon source for preparing the nitrogen-doped diamond single crystal as a raw material, forming a diamond synthesis block with a catalyst, a crystal bed and a diamond seed crystal, and performing pressurized synthesis treatment.
5. The method according to claim 4, wherein the catalyst is NiMnCo alloy or FeNi alloy; the pressure of the pressurizing synthesis treatment is 5.5-8.0 GPa, the temperature is 1300-1400 ℃ and the time is 1-200 h.
6. The method according to claim 4, wherein the pressurized synthesis treatment is followed by an acid treatment step.
7. The method according to claim 6, wherein the acid treatment step comprises: and (3) placing the sample after the pressurized synthesis in a dilute nitric acid solution to dissolve a catalyst, and then finely boiling the sample for 2 to 6 hours by using a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 9:1.
8. A nitrogen doped diamond single crystal produced by the method of any one of claims 4 to 7.
9. Use of a nitrogen-doped diamond single crystal according to claim 8 in the field of aerospace and precision instruments.
10. A method for improving the quality of nitrogen-doped diamond monocrystal, which is characterized in that the nitrogen-doped diamond monocrystal is obtained by taking the modified carbon source for preparing the nitrogen-doped diamond monocrystal as a raw material, forming a diamond synthetic block with NiMnCo alloy catalyst, a crystal bed and diamond seed crystal and performing pressurized synthesis treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311063412.5A CN117026356A (en) | 2023-08-23 | 2023-08-23 | Preparation method of nitrogen-doped diamond monocrystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311063412.5A CN117026356A (en) | 2023-08-23 | 2023-08-23 | Preparation method of nitrogen-doped diamond monocrystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117026356A true CN117026356A (en) | 2023-11-10 |
Family
ID=88624314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311063412.5A Pending CN117026356A (en) | 2023-08-23 | 2023-08-23 | Preparation method of nitrogen-doped diamond monocrystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117026356A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2640788C1 (en) * | 2016-12-27 | 2018-01-11 | Федеральное государственное бюджетное научное учреждение "Технологический институт сверхтвердых и новых углеродных материалов" (ФГБНУ ТИСНУМ) | Method for obtaining doped diamond monocrystal |
| CN112481698A (en) * | 2020-10-22 | 2021-03-12 | 河南工业大学 | Novel method for improving nitrogen content of high-temperature high-pressure synthesized gem-grade diamond |
| CN115400691A (en) * | 2022-08-24 | 2022-11-29 | 内蒙古唐合科技有限公司 | Preparation method of artificial diamond |
| CN116116326A (en) * | 2022-12-09 | 2023-05-16 | 浙江大学 | Semiconductor modification process for diamond cutter material |
-
2023
- 2023-08-23 CN CN202311063412.5A patent/CN117026356A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2640788C1 (en) * | 2016-12-27 | 2018-01-11 | Федеральное государственное бюджетное научное учреждение "Технологический институт сверхтвердых и новых углеродных материалов" (ФГБНУ ТИСНУМ) | Method for obtaining doped diamond monocrystal |
| CN112481698A (en) * | 2020-10-22 | 2021-03-12 | 河南工业大学 | Novel method for improving nitrogen content of high-temperature high-pressure synthesized gem-grade diamond |
| CN115400691A (en) * | 2022-08-24 | 2022-11-29 | 内蒙古唐合科技有限公司 | Preparation method of artificial diamond |
| CN116116326A (en) * | 2022-12-09 | 2023-05-16 | 浙江大学 | Semiconductor modification process for diamond cutter material |
Non-Patent Citations (1)
| Title |
|---|
| 郭龙锁: "肼类有机物掺杂金刚石大单晶的高温高压合成及退火研究", 《中国博士学位论文全文数据库 工程科技I辑》, pages 37 - 38 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102596802A (en) | System and method for manufacturing silicon carbide pulverulent body | |
| KR101637567B1 (en) | High purity silicon carbide manufacturing method and system | |
| CN114180969B (en) | Preparation method and application of nitrogen-containing high-entropy MAX phase material and two-dimensional material | |
| US20020151428A1 (en) | Silicon/silicon carbide composite and process for manufacturing the same | |
| CA1151836A (en) | Process for producing metallic carbonitride | |
| US4040848A (en) | Polycrystalline silicon articles containing boron by sintering | |
| CN109663543B (en) | Preparation method for synthesizing polycrystalline diamond with boron-skin-nitrogen core through direct conversion | |
| CN117026356A (en) | Preparation method of nitrogen-doped diamond monocrystal | |
| KR101549477B1 (en) | Manufacturing Method of High Purity SiC Powder | |
| JP2721678B2 (en) | β-silicon carbide molded body and method for producing the same | |
| KR20100115993A (en) | A method for manufacturing sic micro-powder with high purity at low temperature | |
| KR20110027915A (en) | Silicon carbide powder derived from mesoporous silica and its synthesis method | |
| JP2002018267A (en) | Graphite material for synthesizing semiconductor diamond and semiconductor diamond manufactured using the same | |
| RU2393112C1 (en) | Method of producing silicon carbide nanofibre | |
| JPS616110A (en) | Manufacture of silicon carbide | |
| CN112110731A (en) | Sc2SC (metal-ceramic) laminated material and preparation method thereof | |
| JP3997596B2 (en) | Silicon nitride powder | |
| CN114164492B (en) | Large-size mesoporous/microporous tungsten nitride single crystal material and preparation method and application thereof | |
| CN114790107B (en) | SiO preparation at low temperature by using polycrystalline silicon cutting waste 2 -Si 3 N 4 Method for compounding ceramic | |
| JP2620294B2 (en) | Silicon carbide-graphite composite material and method for producing the same | |
| CN116747852A (en) | Boron doped diamond, preparation method and application | |
| JPH0227318B2 (en) | ||
| JP2000044223A (en) | Production of silicon carbide | |
| JPH0733447A (en) | Production of nitrogen doped glass | |
| CN116730334A (en) | Method for converting vertical graphene into diamond |
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 |