CN116905084A - Substrate table and method for growing single crystal diamond by microwave plasma chemical vapor deposition technology - Google Patents
Substrate table and method for growing single crystal diamond by microwave plasma chemical vapor deposition technology Download PDFInfo
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- CN116905084A CN116905084A CN202211322323.3A CN202211322323A CN116905084A CN 116905084 A CN116905084 A CN 116905084A CN 202211322323 A CN202211322323 A CN 202211322323A CN 116905084 A CN116905084 A CN 116905084A
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- 239000013078 crystal Substances 0.000 title claims abstract description 161
- 239000010432 diamond Substances 0.000 title claims abstract description 140
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 136
- 239000000758 substrate Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 23
- 238000005516 engineering process Methods 0.000 title abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000002401 inhibitory effect Effects 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 230000007547 defect Effects 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 230000002349 favourable effect Effects 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 229910001369 Brass Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010951 brass Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/12—Substrate holders or susceptors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
- C23C16/4582—Rigid and flat substrates, e.g. plates or discs
- C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
-
- 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
- C30B25/16—Controlling or regulating
- C30B25/165—Controlling or regulating the flow of the reactive gases
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/04—Diamond
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a substrate stage for growing single crystal diamond by microwave plasma chemical vapor deposition technology, which comprises the following steps: the substrate is arranged at the upper end of the base, and through holes are formed in the substrate at positions opposite to the conical grooves. The beneficial effects of the invention are as follows: the high-quality monocrystalline diamond can be grown in batches, the growth efficiency is improved, and in the growth process, the substrate of the substrate table needs to be replaced so as to keep the flat state of the growth surface of the monocrystalline diamond seed crystal, so that the impurity phases of the bottom and the side surface of the monocrystalline diamond can be remarkably reduced, and the phenomenon that the monocrystalline diamond is difficult to take out from the through hole is avoided.
Description
Technical Field
The invention relates to the field of crystal growth, in particular to a substrate table and a method for growing monocrystalline diamond by a microwave plasma chemical vapor deposition technology.
Background
The excellent physicochemical properties of single crystal diamond make it possess wide application prospects in numerous fields, reference: tallaire A, achard J, boussadi A, et al high quality thick CVD Diamond films homoepitaxially grown on (111) -oriented substrates [ J ]. Diamond & Related Materials,2014, 41 (1): 34-40, and Wu G, chen M H, liao j.the influence of recess depth and crystallographic orientation of seed sides on homoepitaxial growth of CVD single crystal diamonds [ J ]. Diamond & Related Materials,2016, 65:144-151, however, the number of high quality natural diamonds is so rare that it is difficult to meet the needs of the industrial application field, and thus has great significance to the development of the technology for artificially mass-producing high quality single crystal diamonds.
Among the numerous methods for synthesizing single crystal diamond, microwave plasma chemical vapor deposition (Microwave plasma chemical Vapor deposition, MPCVD) is considered as the preferred method for preparing high quality single crystal diamond due to its characteristics of electrodeless discharge, concentrated plasma energy, clean deposition environment, etc., reference is made to: willams B, tallaire a, achard j.optical study of defects in thick undoped CVD synthetic Diamond layers [ J ]. Diamond & Related Materials,2014, 41 (1): 25-33. The main idea of preparing high-quality monocrystalline diamond by MPCVD technology is to utilize high-energy density plasma balls formed around monocrystalline substrate, ionize carbon-containing working gas, and combine with proper substrate temperature to grow C atoms onto monocrystalline substrate in the form of sp3 hybridization to realize growth of monocrystalline diamond.
In batch growth of single crystal diamond using MPCVD techniques, substrate table design is critical, reference: mokuno Y, chayahara a, soda Y, et al synthesis single-crystal Diamond by repetition of high rate homoepitaxial growth by microwave plasma CVD [ J ]. Diamond & Related Materials,2005, 14 (11-12): 1743-1746.1. Substrate tables commonly used for epitaxial growth of single crystal diamond are divided into two types, namely open type and closed type, wherein the open type substrate table is relatively simple in design, but the defects of uneven surface, reduced size, difficult polishing and the like of the grown single crystal diamond are caused by increasing the growth difference between the middle area and the edge area of the single crystal diamond sheet. Compared with the prior art, the closed substrate table is difficult to process, but the surface flatness of the single crystal diamond can be effectively improved, the size of the single crystal diamond is ensured, and the later polishing difficulty is reduced. Therefore, the closed substrate table is fully and reasonably designed, and the batch growth of single crystal diamond is facilitated.
One of the problems encountered in the practical application process of the closed substrate table is that a large amount of impurity phases such as graphite, polycrystalline diamond and the like are easily deposited on the bottom surface of the monocrystalline substrate and the side surface contacted with the grooves in the growth process, so that the growth environment of monocrystalline diamond particles is changed, the quality of the monocrystalline diamond is reduced, and meanwhile, the phenomenon that the monocrystalline diamond grown for a long time is difficult to take out from the grooves can occur, so that the difficulty of post-treatment is increased.
Disclosure of Invention
The invention aims to provide a substrate table and a method for growing monocrystalline diamond by using a microwave plasma chemical vapor deposition technology, so as to overcome the defects in the prior art.
The technical scheme for solving the technical problems is as follows: a substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique, comprising:
the substrate is arranged at the upper end of the base, and through holes are formed in the substrate at positions opposite to the conical grooves.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the gap between the substrate and the base is less than 0.1mm.
Further, the diameter of the extraction opening at the bottom of the conical groove is more than or equal to 1mm; the diameter of the air inlet on the side wall of the conical groove is more than or equal to 1mm.
Further, the through hole is a square hole, and the conical groove is a square conical groove; the width of the through hole is 0-0.3 mm larger than that of the single crystal diamond seed crystal; the depth of the through hole is 0.1 mm-0.5 mm larger than the thickness of the single crystal diamond seed crystal; the maximum width of the conical groove is 0-0.3 mm smaller than the width of the single crystal diamond seed crystal, and the depth of the conical groove is more than or equal to 1/2 of the width of the through hole.
Further, the substrate is a molybdenum wafer with a smooth surface; the base is made of metal material.
Further, the material of the base is red copper, brass or stainless steel.
Further, the substrate and the base are combined by a locating pin, a locating groove or a threaded connection mode.
Based on the technical scheme, the invention also provides a method for growing single crystal diamond by using the microwave plasma chemical vapor deposition technology, which comprises the following steps:
s1, placing a substrate table in a reaction cavity of MPCVD, placing a single crystal diamond seed crystal in a through hole, and vacuumizing the reaction cavity of MPCVD;
s2, introducing hydrogen from an air inlet of the reaction cavity, starting microwaves, adjusting microwave power, exciting a plasma ball, adjusting the air pressure of the reaction cavity, and cleaning the monocrystalline diamond seed crystal;
s3, introducing oxygen from an air inlet of the reaction cavity, adjusting the air pressure of the reaction cavity, increasing microwave power, and etching the surface of the monocrystalline diamond seed crystal to remove the defect on the surface of the monocrystalline diamond seed crystal;
s4, stopping the oxygen, introducing hydrocarbon mixed gas from an air inlet of the reaction cavity, simultaneously introducing gas which is favorable for inhibiting the generation of impurity phases from an air inlet flow channel of the substrate table, and opening an air exhaust flow channel of the substrate table;
s5, adjusting microwave power and deposition air pressure, controlling the air inlet flow rate of an air inlet flow channel of the substrate table and the air exhaust rate of an air exhaust flow channel, and performing epitaxial growth of the single crystal diamond seed crystal while inhibiting generation of impurity phases at the bottom and side surfaces of the single crystal diamond seed crystal;
s6, stopping growing and replacing the substrate when the thickness of the single crystal diamond seed crystal is consistent with that of the through hole, wherein the width of the through hole of the replaced substrate is 0-0.3 mm larger than that of the single crystal diamond seed crystal, and the depth of the through hole is 0.1-0.5 mm larger than that of the single crystal diamond seed crystal;
and S7, repeating the steps, continuing epitaxial growth of the monocrystalline diamond seed crystal until the thickness meets the requirement, and stopping growth.
Further, the gas that is advantageous for suppressing the generation of the impurity phase is hydrogen, argon, or a mixed gas of hydrogen and argon.
Further, the hydrocarbon mixed gas is a mixed gas of hydrogen and methane.
The beneficial effects of the invention are as follows:
placing a single crystal diamond seed crystal in the through hole and keeping the growth surface of the single crystal diamond seed crystal flat;
the air inlet flow channel and the air exhaust flow channel are used for introducing gas for inhibiting the generation of impurity phases so as to reduce the generation of the impurity phases at the bottom and the side surfaces of the single crystal diamond seed crystal;
the substrate table and the method can be used for growing high-quality monocrystalline diamond in batches, the growth efficiency is improved, and in the growth process, the substrate of the substrate table is required to be replaced so as to keep the flat state of the growth surface of the monocrystalline diamond seed crystal, so that the impurity phases at the bottom and the side surface of the monocrystalline diamond can be remarkably reduced, and the phenomenon that the monocrystalline diamond is difficult to take out from a through hole is avoided.
Drawings
FIG. 1 is a schematic diagram of a substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique according to the present invention;
FIG. 2 is a schematic view showing a structure of a substrate table for mass-producing 40 single crystal diamond pieces of 3mm by 1mm in size in accordance with Experimental example 1;
FIG. 3 is a schematic view showing a substrate stage structure for mass-producing 16 single crystal diamond chips having a size of 4 mm. Times.4 mm. Times.1 mm and 24 single crystal diamond chips having a size of 3 mm. Times.3 mm. Times.1 mm in accordance with Experimental example 2.
In the figure, 1, a base, 110, a conical groove, 120, an air extraction runner, 130, an air inlet runner, 2, a substrate, 210 and a through hole.
Fig. 4 shows a sample of grown single crystal diamond, (a) single crystal diamond grown without using the substrate stage of the present invention, and (b) single crystal diamond grown with using the substrate stage of the present invention.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
As shown in fig. 1, a substrate stage for growing single crystal diamond by microwave plasma chemical vapor deposition technique, comprising: a base 1 and a substrate 2;
the upper end surface of the base 1 is provided with a plurality of conical grooves 110, and the conical grooves 110 on the base 1 are uniformly distributed from the center to the edge area in general;
the base 1 is internally provided with an air suction flow passage 120 communicated with the conical groove 110 through the bottom of the conical groove 110, the air suction flow passage 120 is generally provided with an air inlet port and a plurality of air outlet ports, and each air outlet port is respectively communicated with the plurality of conical grooves 110 in a one-to-one correspondence manner;
the inside of the base 1 is provided with an air inlet channel 130 communicated with the conical groove 110 through the side wall of the conical groove 110, the air inlet channel 130 is generally provided with an air inlet port and a plurality of air outlet ports, and each air outlet port is respectively communicated with the plurality of conical grooves 110 in a one-to-one correspondence manner;
the air extraction flow channel 120 and the air inlet flow channel 130 are used for forming proper atmosphere around the seed crystal and at the bottom so as to inhibit the generation of impurity phases;
a substrate 2 is arranged at the upper end of the base 1, and a through hole 210 is arranged on the substrate 2 at a position opposite to each conical groove 110;
the single crystal diamond seed crystal is placed in the through hole 210 for growth, and the atmosphere at the bottom and the side wall of the single crystal diamond seed crystal is controlled by adjusting the flow rate of the air inlet gas and the air pumping speed of air pumping in the growth process so as to fully inhibit the generation of impurity phases.
As a further improvement of the above-described technical solution, the gap between the substrate 2 and the base 1 is smaller than 0.1mm, by which it is ensured that no discharge occurs between the substrate 2 and the base 1.
As a further improvement of the above technical solution, the diameter of the air extraction opening at the bottom of the conical groove 110 is greater than or equal to 1mm; the diameter of the air inlet on the side wall of the conical groove 110 is larger than or equal to 1mm, and through the scheme, the bottom and the side surface of the single crystal diamond seed crystal are provided with the atmosphere which is suitable for inhibiting the generation of impurity phases.
As a further improvement of the above technical solution, the through hole 210 is a square hole, and the width of the through hole 210 is 0-0.3 mm larger than the width of the single crystal diamond seed crystal; the depth of the through hole 210 is 0.1 mm-0.5 mm greater than the thickness of the single crystal diamond seed crystal, and by the scheme, the single crystal diamond seed crystal can be placed in the through hole 210, and the edge of the single crystal diamond seed crystal does not generate edge discharge;
the conical groove 110 is a square conical groove 110; the maximum width of the conical groove 110 is 0-0.3 mm smaller than that of the single crystal diamond seed crystal, the depth of the conical groove 110 is 1/2 or more of the width of the through hole 210, and by adopting the scheme, the bottom and the side surface of the single crystal diamond seed crystal are immersed in the atmosphere which is favorable for inhibiting the generation of impurity phases
As a further improvement of the technical scheme, the substrate 2 is a molybdenum wafer with a smooth surface; the base 1 is a metal material.
As a further improvement of the above technical solution, the material of the base 1 is red copper, brass or stainless steel.
As a further improvement of the above technical solution, the substrate 2 and the base 1 are combined by a positioning pin, a positioning groove or a threaded connection.
A method for growing single crystal diamond by microwave plasma chemical vapor deposition technology, a substrate stage for growing single crystal diamond by the microwave plasma chemical vapor deposition technology, comprises the following steps:
s1, placing a substrate table in a reaction cavity of MPCVD, placing a single crystal diamond seed crystal in a through hole 210, and vacuumizing the reaction cavity of MPCVD;
s2, introducing hydrogen from an air inlet of the reaction cavity, starting microwaves, adjusting microwave power, exciting a plasma ball, adjusting the air pressure of the reaction cavity, and cleaning the monocrystalline diamond seed crystal;
s3, introducing oxygen from an air inlet of the reaction cavity, adjusting the air pressure of the reaction cavity, increasing microwave power, and etching the surface of the monocrystalline diamond seed crystal to remove the defect on the surface of the monocrystalline diamond seed crystal;
s4, stopping oxygen introduction, introducing hydrocarbon mixed gas from an air inlet of the reaction cavity, simultaneously introducing gas which is favorable for inhibiting generation of impurity phases from an air inlet flow channel 130 of the substrate table, and opening an air exhaust flow channel 120 of the substrate table;
s5, adjusting microwave power and deposition air pressure, controlling the air inlet flow of the substrate table air inlet flow channel 130 and the air exhaust speed of the air exhaust flow channel 120, and performing epitaxial growth of the single crystal diamond seed crystal while inhibiting the generation of impurities at the bottom and on the side surfaces of the single crystal diamond seed crystal;
s6, stopping growing and replacing the substrate 2 when the thickness of the single crystal diamond seed crystal is consistent with the thickness of the through hole 210, wherein the width of the through hole 210 of the replaced substrate 2 is 0-0.3 mm larger than that of the single crystal diamond seed crystal, and the depth of the through hole 210 is 0.1-0.5 mm larger than that of the single crystal diamond seed crystal;
and S7, repeating the steps, continuing epitaxial growth of the monocrystalline diamond seed crystal until the thickness meets the requirement, and stopping growth.
As a further improvement of the technical scheme, the gas which is favorable for inhibiting the generation of the impurity phase is hydrogen, argon or mixed gas of the hydrogen and the argon.
As a further improvement of the above technical scheme, the hydrocarbon mixed gas is a mixed gas of hydrogen and methane.
Experimental example 1
40 pieces of single crystal diamond with the thickness of 3mm multiplied by 1mm are grown in batches by using the substrate table of the invention;
s1: the substrate table designed in the implementation process consists of a base table 1 and a substrate 2, wherein two types of molybdenum wafers of type B1 and type B2 are designed for the substrate 2;
the molybdenum wafer of type B1 is uniformly distributed with square through holes 210 from the center to the edge, the surface is smooth, and the size of the through holes 210 is 3.1mm multiplied by 1.5mm;
the molybdenum wafer of type B2 is uniformly distributed with through holes 210 with the size of 3.1mm multiplied by 2.0mm from the center to the edge, and the surface of the molybdenum wafer is smooth;
the tapered grooves 110 of the submount 1 uniformly distributed from the center to the edge area are distributed in conformity with the distribution of the through holes 210 of the substrate 2 (type B1 and type B2);
the width of the conical groove 110 of the base 1 is 3.1mm and the depth is 2mm;
see fig. 2 for specific physical dimensions;
s2: coaxially installing the B1 type substrate 2 and the base station 1, and connecting and fixing the B1 type substrate 2 and the base station 1 by using screws to ensure that the gap between the substrate 2 and the base station 1 is 0.05mm;
s3: opening a reaction cavity of MPCVD, placing a substrate table obtained by coaxially connecting a B1 type substrate 2 with a base table 1 in the reaction cavity, sequentially placing 40 pieces of single crystal diamond seed crystals with the size of 3mm multiplied by 1mm in a through hole 210 of the substrate table, closing the reaction cavity of MPCVD, and vacuumizing the reaction cavity of MPCVD to 0.5Pa;
s4: introducing 500sccm hydrogen from an air inlet of the reaction cavity, adjusting the air pressure of the reaction cavity of MPCVD to 5kPa, increasing the microwave power to 1200W, and cleaning the surface of the monocrystalline diamond seed crystal for 60min to remove the defects on the surface of the monocrystalline diamond seed crystal;
s5: introducing 5sccm of oxygen from an air inlet of the reaction cavity, adjusting the air pressure of the reaction cavity of MPCVD to 7kPa, increasing the microwave power to 2000W, and etching the surface of the monocrystalline diamond seed crystal for 90 minutes to remove the defects on the surface of the monocrystalline diamond seed crystal;
s6: stopping introducing oxygen from the air inlet of the reaction cavity, introducing 20sccm of methane from the air inlet of the reaction cavity, simultaneously introducing 50sccm of hydrogen from the air inlet flow passage 130 of the substrate table, opening the air exhaust flow passage 120 of the substrate table, controlling the air exhaust speed of the air exhaust flow passage 120 to be 20sccm, adjusting the microwave power to 2500W, and performing epitaxial growth of single crystal diamond after the deposition air pressure is 12 kPa;
s7: stopping growing when the thickness of the single crystal diamond reaches 1.5mm, opening a reaction cavity of MPCVD, taking out the single crystal diamond, replacing the substrate 2 of the type B2 with the substrate 2 of the type B1, ensuring that the substrate 2 of the type B2 is connected with the base station 1 coaxially, connecting and fixing the substrate 2 of the type B2 with the base station 1 by using a screw, and ensuring that a gap between the substrate 2 of the type B2 and the base station 1 is within 0.1mm;
sequentially placing the obtained single crystal diamond seed crystals back into the through holes 210 of the substrate 2 of the type B2, closing the reaction cavity of MPCVD, and vacuumizing the reaction cavity of MPCVD to 0.5Pa;
s8: repeating the operation steps of S5-S6, continuing epitaxial growth of the single crystal diamond, stopping growth when the thickness of the single crystal diamond reaches 2.0mm, opening the reaction cavity of MPCVD, and taking out 40 epitaxially grown single crystal diamond sheets of 3mm multiplied by 2 mm.
Experimental example 2
A substrate table according to the present invention was used to grow 40 single crystal diamonds composed of 3mm by 1mm in size and 4mm by 1mm in size in batch
S1: the substrate table designed in the implementation process consists of a base table 1 and a substrate 2, wherein two types of molybdenum wafers of type B1 and type B2 are designed for the substrate 2;
the molybdenum wafer of type B1 has square through holes 210 uniformly distributed from the center to the edge and has a smooth surface, and the through holes 210 have dimensions of 3.15mm×3.15mm×1.5mm and 4.1mm×4.1mm×1.5mm;
the molybdenum wafer of type B2 is uniformly distributed with square through holes 210 from the center to the edge, the surface is smooth, and the sizes of the through holes 210 are 3.15mm multiplied by 1.7mm and 4.1mm multiplied by 1.7mm;
the tapered grooves 110 of the submount 1 uniformly distributed from the center to the edge area are distributed in conformity with the distribution of the through holes 210 of the substrate 2 (type B1 and type B2);
the conical groove 110 of the base station 1 has two types of 3.15mm and 4.1mm, the depth is 2mm, and the specific external dimension is shown in fig. 3;
s2: coaxially installing the B1 type substrate 2 and the base station 1, and connecting and fixing the B1 type substrate 2 and the base station 1 by using screws to ensure that the gap between the B1 type substrate 2 and the base station 1 is smaller than 0.1mm;
s3: opening a reaction cavity of MPCVD, placing a substrate table obtained by coaxially connecting a B1 type substrate 2 with a base table 1 in the cavity, sequentially placing 20 single crystal diamond seed crystals consisting of 3mm multiplied by 1mm and 4mm multiplied by 1mm in a through hole 210 of the substrate table, closing the reaction cavity of MPCVD, and vacuumizing the reaction cavity of MPCVD to 0.5Pa.
S4: introducing 500sccm hydrogen from an air inlet of the reaction cavity, adjusting the air pressure of the reaction cavity of MPCVD to 4kPa, increasing the microwave power to 1500W, and cleaning the surface of the monocrystalline diamond seed crystal for 60min to remove the defects on the surface of the monocrystalline diamond seed crystal;
s5: introducing 6sccm of oxygen from an air inlet of the reaction cavity, adjusting the air pressure of the reaction cavity of MPCVD to 8kPa, increasing the microwave power to 2100W, and etching the surface of the monocrystalline diamond seed crystal for 80 minutes to remove the defects on the surface of the monocrystalline diamond seed crystal;
s6: stopping introducing oxygen from the air inlet of the reaction cavity, introducing 30sccm of methane from the air inlet of the reaction cavity, simultaneously introducing 70sccm of hydrogen from the air inlet flow passage 130 of the substrate table, opening the air exhaust flow passage 120 of the substrate table, controlling the air exhaust speed of the air exhaust flow passage 120 to be 30sccm, adjusting the microwave power to 2700W, and performing epitaxial growth of single crystal diamond after the deposition air pressure is 11 kPa;
s7: stopping growing when the thickness of the single crystal diamond reaches 1.5mm, opening a reaction cavity of MPCVD, taking out the single crystal diamond, and replacing the substrate 2 of the type B2 with the substrate 2 of the type B1 to ensure that the substrate 2 of the type B2 is connected with the concentric shaft of the base station 1;
the substrate 2 of the type B2 is connected and fixed with the base station 1 by using screws, and the gap between the substrate 2 of the type B2 and the base station 1 is ensured to be within 0.1mm;
sequentially placing the obtained single crystal diamond seed crystals back into the through holes 210 of the substrate 2 of the type B2, closing the reaction cavity of MPCVD, and vacuumizing the reaction cavity of MPCVD to 0.5Pa;
s8: repeating the operation steps of S5-S6, and continuing epitaxial growth of the single crystal diamond. When the thickness of the single crystal diamond reaches 2.0mm, stopping growing, opening the reaction cavity of MPCVD, and taking out 20 epitaxially grown single crystal diamond sheets.
Fig. 4 shows single crystal diamond samples without (a) and with (b) the substrate stage designed by the invention, and experiments show that the substrate stage designed by the invention can meet the requirement of batch growth of single crystal diamond by microwave plasma chemical vapor deposition technology, so that the obtained single crystal diamond has a relatively flat surface, and simultaneously, the impurity phases of the bottom and the side surfaces of single crystal diamond particles are effectively reduced.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique, comprising: base station (1) and substrate (2), offer a plurality of toper recesses (110) on the up end of base station (1), inside suction runner (120) that are had through the tank bottom of toper recess (110) and toper recess (110) intercommunication of base station (1), inside intake runner (130) that are had through the lateral wall of toper recess (110) and toper recess (110) intercommunication of base station (1), substrate (2) are arranged in the upper end of base station (1), set up through-hole (210) in just to each toper recess (110) department on substrate (2).
2. A substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique according to claim 1, wherein: the gap between the substrate (2) and the base (1) is smaller than 0.1mm.
3. A substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique according to claim 1, wherein: the diameter of an extraction opening at the bottom of the conical groove (110) is more than or equal to 1mm; the diameter of an air inlet on the side wall of the conical groove (110) is more than or equal to 1mm.
4. A substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique according to claim 1, wherein: the through hole (210) is a square hole, and the conical groove (110) is a square conical groove (110); the width of the through hole (210) is 0-0.3 mm larger than the width of the single crystal diamond seed crystal; the depth of the through hole (210) is 0.1 mm-0.5 mm larger than the thickness of the single crystal diamond seed crystal; the maximum width of the conical groove (110) is 0-0.3 mm smaller than the width of the single crystal diamond seed crystal, and the depth of the conical groove (110) is more than or equal to 1/2 of the width of the through hole (210).
5. A substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique according to claim 1, wherein: the substrate (2) is a molybdenum wafer with a smooth surface; the base (1) is made of a metal material.
6. A substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique according to claim 1, wherein: the base (1) is made of copper, brass or stainless steel.
7. A substrate table for growing single crystal diamond by microwave plasma chemical vapor deposition technique according to claim 1, wherein: the substrate (2) and the base (1) are combined by a locating pin, a locating groove or a threaded connection mode.
8. A method of growing single crystal diamond by microwave plasma chemical vapour deposition technique, characterized in that a substrate stage for growing single crystal diamond by microwave plasma chemical vapour deposition technique according to any one of claims 1 to 7 is used, comprising the steps of:
s1, placing a substrate table in a reaction cavity of MPCVD, placing a single crystal diamond seed crystal in a through hole (210), and vacuumizing the reaction cavity of MPCVD;
s2, introducing hydrogen from an air inlet of the reaction cavity, starting microwaves, adjusting microwave power, exciting a plasma ball, adjusting the air pressure of the reaction cavity, and cleaning the monocrystalline diamond seed crystal;
s3, introducing oxygen from an air inlet of the reaction cavity, adjusting the air pressure of the reaction cavity, increasing microwave power, and etching the surface of the monocrystalline diamond seed crystal to remove the defect on the surface of the monocrystalline diamond seed crystal;
s4, stopping the oxygen, introducing hydrocarbon mixed gas from an air inlet of the reaction cavity, simultaneously introducing gas which is favorable for inhibiting the generation of impurity phases from an air inlet flow passage (130) of the substrate table, and opening an air exhaust flow passage (120) of the substrate table;
s5, adjusting microwave power and deposition air pressure, controlling air inlet flow of an air inlet flow channel (130) of the substrate table and air exhaust speed of an air exhaust flow channel (120), and carrying out epitaxial growth of the single crystal diamond seed crystal while inhibiting generation of impurities at the bottom and on the side surfaces of the single crystal diamond seed crystal;
s6, stopping growing when the thickness of the single crystal diamond seed crystal is consistent with the thickness of the through hole (210), replacing the substrate (2), wherein the width of the through hole (210) of the replaced substrate (2) is 0-0.3 mm larger than that of the single crystal diamond seed crystal, and the depth of the through hole (210) is 0.1-0.5 mm larger than that of the single crystal diamond seed crystal;
and S7, repeating the steps, continuing epitaxial growth of the monocrystalline diamond seed crystal until the thickness meets the requirement, and stopping growth.
9. A method of growing single crystal diamond by microwave plasma chemical vapor deposition technique according to claim 8, wherein: the gas favorable for inhibiting the generation of the impurity phase is hydrogen, argon or mixed gas of the hydrogen and the argon.
10. A method of growing single crystal diamond by microwave plasma chemical vapor deposition technique according to claim 8, wherein: the hydrocarbon mixed gas is a mixed gas of hydrogen and methane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117535791A (en) * | 2023-12-06 | 2024-02-09 | 广东省新兴激光等离子体技术研究院 | MPCVD-based substrate for growing single crystal diamond material and method thereof |
| CN117535789A (en) * | 2023-12-06 | 2024-02-09 | 广东省新兴激光等离子体技术研究院 | MPCVD deposition chamber for growing single crystal diamond material and method thereof |
| CN117535791B (en) * | 2023-12-06 | 2024-06-07 | 广东省新兴激光等离子体技术研究院 | MPCVD-based substrate for growing single crystal diamond material and method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117535791A (en) * | 2023-12-06 | 2024-02-09 | 广东省新兴激光等离子体技术研究院 | MPCVD-based substrate for growing single crystal diamond material and method thereof |
| CN117535789A (en) * | 2023-12-06 | 2024-02-09 | 广东省新兴激光等离子体技术研究院 | MPCVD deposition chamber for growing single crystal diamond material and method thereof |
| CN117535791B (en) * | 2023-12-06 | 2024-06-07 | 广东省新兴激光等离子体技术研究院 | MPCVD-based substrate for growing single crystal diamond material and method thereof |
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