CN115058770B - Single crystal diamond manufacturing method for improving growth quantity of CVD single crystal diamond - Google Patents
Single crystal diamond manufacturing method for improving growth quantity of CVD single crystal diamond Download PDFInfo
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- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
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- 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
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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- 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
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- 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
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Abstract
The invention belongs to the technical field of single crystal diamond preparation processes, and particularly relates to a single crystal diamond manufacturing method for improving the growth quantity of CVD single crystal diamond. Aiming at the defects existing in the prior art, the invention provides a single crystal diamond manufacturing method for improving the growth quantity of CVD single crystal diamond, which is characterized in that a plasma ball is controlled to be contacted with a seed crystal, the temperature difference between a center seed crystal and an edge seed crystal is controlled, ar is added to improve the concentration of the plasma ball, the single growth quantity of the seed crystal is improved, and the higher yield can be ensured. The method for manufacturing the single-crystal diamond for improving the growth quantity of the CVD single-crystal diamond greatly improves the production efficiency by controlling the growth process, solves the problems of small single-time growth quantity and low efficiency of the CVD single-crystal wafer, provides stable guarantee for industrial production of the single-crystal diamond, and has higher development prospect and economic value.
Description
Technical Field
The invention belongs to the technical field of single crystal diamond preparation processes, and particularly relates to a single crystal diamond manufacturing method for improving the growth quantity of CVD single crystal diamond.
Background
Diamond is a special material that integrates many excellent properties and is widely used in the fields of cutting tools, protective coatings, optical windows, acoustic sensors, semiconductors, electronic devices, and the like. The single crystal diamond has excellent physical and chemical properties and good optical properties, and is widely applied to various fields of industry, science and technology, national defense, medical treatment and health and the like. The natural diamond has small reserves and high price, and along with the increase of the use amount of the diamond, how to improve the yield of the high-quality diamond material is an urgent problem to be solved.
Chemical Vapor Deposition (CVD) is currently the primary method of synthesizing large-sized single crystal diamond. Conventionally, the size of a diamond single crystal synthesized by a CVD method depends on the size of a seed crystal, and generally the size of the synthesized single crystal is equal to or smaller than the seed crystal. Therefore, there is a need for an improved technique for producing large-sized diamond single crystals. Among the CVD methods, MPCVD (microwave plasma chemical vapor deposition) is the most suitable method for single crystal diamond growth, and has the advantages of high synthesis efficiency, high plasma density, stable temperature field, and the like, and the produced single crystal diamond has good uniformity and high quality.
In the prior art, equipment for synthesizing CVD single crystal diamond by adopting an MPCVD method often has the problems of uneven plasma distribution, uneven cooling of a water cooling heat dissipation base station, difference between a seed crystal and a sample station, and the like, so that the growth state of the seed crystal is greatly different, and the single-time growth single crystal diamond is different in quality.
Chinese patent publication No. CN108251892a discloses a laser-enhanced plasma CVD apparatus for preparing single crystal diamond and a method thereof, the apparatus including a plasma CVD device and a laser device; the method utilizes low-cost high-energy laser to improve the energy and gas dissociation rate of plasma in the diamond synthesis process, thereby improving the synthesis rate of the diamond.
In the MPCVD single crystal diamond growth process, the single growth quantity and the yield are improved, the production efficiency can be greatly improved, the seed crystal preparation period is shortened, and the method is a foundation and a guarantee for realizing the industrial production of single crystal diamond. Based on this, the inventors have made a change in the growth rate and the number of single seed crystals by contacting a plasma ball on an MPCVD apparatus with the seed crystals and adding Ar, in order to improve the synthesis efficiency of CVD single crystal diamond.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a single crystal diamond manufacturing method for improving the growth quantity of CVD single crystal diamond, which is characterized in that the plasma ball is controlled to be contacted with the seed crystal, the temperature difference between the center seed crystal and the edge seed crystal is controlled, ar is added to improve the concentration of the plasma ball, the single growth quantity of the seed crystal is improved, and the higher yield can be ensured.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a single crystal diamond manufacturing method for increasing the number of CVD single crystal diamond grown, comprising the steps of:
(1) Seed crystal screening:
using 25-27 CVD single crystal wafers with the crystallographic orientation of (100) as seed crystals, wherein the surface is required to be defect-free and the edge quality is required to be good;
(2) Pretreatment of seed crystal:
soaking the seed crystal in an organic solvent, and then cleaning;
(3) Single wafer growth using MPCVD apparatus:
a. placing the seed crystal in the step (2) in a molybdenum sample base station, placing the seed crystal on MPCVD equipment, and vacuumizing to 1X 10 - 3 Pa or below, then simultaneously introducing H 2 、N 2 Ar, forming a plasma ball in MPCVD equipment and contacting with a seed crystal to promote the growth of the seed crystal, setting the microwave power to be 2-3kw and the air pressure to be 100-120mbar, keeping the temperature to be 700-800 ℃ and keeping for 1-2h, so as to reduce the difference between the growth states of the center and the edge seed crystal, and ensuring the stability of the energy required by the growth of the seed crystal by keeping the temperature at a moderate temperature for a long time;
b. adjusting microwave power to 2.5-3.5kw and air pressure to 120-140mbarThe temperature is gradually increased when the microwave power and the air pressure are increased, and CH is introduced when the temperature reaches 850-900 DEG C 4 Keeping for 10-15min, adjusting microwave power to 2.8-3.8kw, adjusting air pressure to 140-160mbar, and keeping stable growth at 1000-1050 ℃ for 40-45h to obtain the product;
in the step, the volume of the plasma ball is increased mainly through the cooperation of high microwave power and low air pressure, the coverage area of a sample table is increased, and the uniformity of a temperature field in a cavity is ensured; by a higher proportion of CH 4 Promote the growth speed of the crystal orientation of (100), and properly adjust the microwave power and the air pressure to keep stable growth.
Preferably, the CVD single wafer size selected in step (1) is 8mm by 0.3mm.
Preferably, in the step (2), the seed crystal is sequentially soaked in acetone and alcohol, and then ultrasonically cleaned, wherein the soaking time in each cleaning medium is 20-30min, and the ultrasonic cleaning time is 2-3min.
Preferably, in the step (3), the molybdenum sample base is of an upper and lower double-layer combined structure, the upper layer is a wafer with the dimension phi 60mm multiplied by 10mm, the lower layer is a molybdenum support with the dimension phi 50mm multiplied by 5mm and provided with a bottom bulge structure, the seed crystal is placed between the upper and lower double layers of the molybdenum sample base, and the placing distance between two adjacent seed crystals is 0.5-1 mm.
Preferably, H in step (3) 2 、N 2 Ar flow is 900-1000sccm, 2-3sccm, 10-20sccm, N 2 The concentration is 20-35ppm.
Preferably, H is introduced in step (3) 2 、N 2 After Ar, an E-H tuner on MPCVD equipment is adjusted (the E-H tuner can ensure the maximum transmission power to enter a plasma source and change the shape of a plasma cluster by adjusting microwave impedance matching), so that a plasma ball is in an oblate spheroid shape, and the temperature difference between a seed crystal at the center and the edge is adjusted to be not more than 80 ℃.
Preferably, in step (3), CH 4 The flow rate of (2) is 80-90sccm.
Preferably, CH is closed at intervals of 12-18h during the growth process 4 、N 2 Using H-plasma during shut-downPerforming plasma etching with microwave power of 3.5-3.8kw and air pressure of 140-150mbar for about 1-2min, and introducing CH again after etching 4 、N 2 And the microwave power and the air pressure are regulated in the process of growth recovery, the temperature fluctuation is kept to be no more than 30 ℃, the growth environment in the reaction cavity is favorably purified by adopting an interval etching mode, the quality of the growth surface is improved, and the growth time is obviously promoted.
Specifically, H as described in step (4) 2 、N 2 The purity of (C) is greater than 99.999%, CH 4 The purity of (2) is more than 99.995%.
Further, the invention also provides the CVD single crystal diamond prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a device for improving the growth quantity of CVD single crystal diamond and a manufacturing method of single crystal diamond, which adopt a uniquely designed molybdenum sample base structure, have good heat dissipation performance, improve the energy of a plasma ball by adding Ar, simultaneously control the volume of the plasma ball and the coverage area of a seed crystal, improve the uniformity of the temperature field of a reaction cavity, greatly improve the single growth quantity of single crystal diamond by matching with proper technological parameters, and ensure higher yield.
2. The method for manufacturing the single-crystal diamond for improving the growth quantity of the CVD single-crystal diamond greatly improves the production efficiency by controlling the growth process, solves the problems of small single-time growth quantity and low efficiency of the CVD single-crystal wafer, provides stable guarantee for industrial production of the single-crystal diamond, and has higher development prospect and economic value.
Drawings
FIG. 1 is a photograph of single crystal diamond in a grown state in step (3) of example 1;
FIG. 2 is a schematic diagram of a molybdenum sample base;
FIG. 3 is a photograph of single crystal diamond after the end of the growth of example 1;
FIG. 4 is a photograph of a single crystal diamond on a molybdenum sample base after the end of the growth of example 1, the dimension being 60mm;
FIG. 5 is a photograph of single crystal diamond in a grown state in step (3) of comparative example 1;
fig. 6 is a photograph of single crystal diamond obtained after the end of the growth of comparative example 1.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention more clear and distinct. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The MPCVD apparatus used in the embodiment of the present invention is a CYRANNUS system of Germany, and the operating parameter is 6kw-2.45GHz.
Example 1
A single crystal diamond manufacturing method for increasing the growth amount of CVD single crystal diamond, comprising the steps of:
(1) Seed crystal screening:
using 27 pieces of CVD single crystal wafers with the dimensions of about 8mm x 0.3mm, crystallographic orientation of (100) and surface polishing (to nano-scale roughness) as seed crystals, the surface is required to be defect-free and the edge quality is good;
(2) Pretreatment of seed crystal:
soaking seed crystal in acetone and alcohol in turn for 20min, and then ultrasonically cleaning in alcohol for 3min;
(3) Single crystal growth:
a. selecting one surface with good edge quality and no visible defect on the surface as a growth surface, uniformly placing the surface into a molybdenum sample base (shown in figure 2), wherein the molybdenum sample base is of an upper-lower double-layer combined structure, the upper layer is a wafer with the size phi 60mm multiplied by 10mm, the lower layer is a molybdenum support with the size phi 50mm multiplied by 5mm and provided with a bottom bulge structure, placing seed crystals between the upper and lower double layers of the molybdenum sample base, placing two adjacent seed crystals at a distance of about 1mm on an MPCVD device, opening the MPCVD device, and vacuumizing to 1 multiplied by 10 -3 Then simultaneously introducing H 2 、N 2 Ar, the flow rates are 1000sccm, 3sccm and 15sccm respectively,N 2 forming a plasma sphere in an MPCVD apparatus and contacting the plasma sphere with a seed crystal to promote seed crystal growth at a concentration of 20ppm, and setting a microwave power of 3kw and a gas pressure of 110mbar; E-H tuner on MPCVD equipment is adjusted (the E-H tuner can ensure that the maximum transmission power enters a plasma source and change the form of a plasma cluster by adjusting microwave impedance matching) so that the plasma sphere is in an oblate spheroid shape, and the temperature is kept at 700-800 ℃ for 1H;
b. the microwave power is regulated to 3.5kw, the air pressure is regulated to 130mbar, at the moment, the temperature is gradually increased due to the increase of the microwave power and the air pressure, and when the temperature reaches 850-900 ℃, CH is introduced 4 The flow is 90sccm, the temperature is kept for 15min, the microwave power is adjusted to be 3.5-3.8kw, the air pressure is adjusted to be 150-160mbar, and the temperature is kept at 1000-1050 ℃ for stable growth for 40h; the growth state photo of the single crystal diamond is shown in figure 1, and as can be seen from figure 1, the whole temperature field of the single crystal wafer is uniform in the growth process, and the uniformity of the growth state is good;
during the growth process, the CH is closed at intervals of 12h 4 、N 2 During closing, H plasma is utilized to carry out plasma etching on the growth surface, the edge polycrystal and the inner wall of the reaction cavity, the microwave power used by etching is 3.5-3.8kw, the air pressure is 140-150mbar, the etching time is about 2min, and CH is introduced again after etching is finished 4 、N 2 And the microwave power and the air pressure are regulated in the process of growth recovery, the temperature fluctuation is kept to be no more than 30 ℃, the growth environment in the reaction cavity is favorably purified by adopting an interval etching mode, the quality of the growth surface is improved, and the growth time is obviously promoted.
H described in step (3) 2 、N 2 The purity of (C) is greater than 99.999%, CH 4 The purity of (2) is more than 99.995%.
The method of this embodiment realizes the increase of the single growth number of the seed crystal by controlling the contact of the plasma sphere with the seed crystal and controlling the temperature difference between the center seed crystal and the edge seed crystal and simultaneously adding Ar to increase the concentration of the plasma sphere, and the obtained results are shown in fig. 3 and fig. 4, wherein fig. 3 is a photograph of single crystal diamond obtained after the growth is completed, and fig. 4 is a photograph of single crystal diamond on a molybdenum sample base after the growth is completed.
In the prior art, a common CVD method is adopted to grow single crystal diamond, the size of a sample stage in common MPCVD equipment is basically phi 50mm, and because of the limitation of the equipment, the risk of system breakdown exists when the size of a plasma ball is forcibly increased, the equipment damage is easily caused by ablation of a quartz window, and therefore, the single growth quantity cannot be further improved.
Compared with the prior art, the invention has the advantages that on the premise of ensuring safety, the molybdenum sample base with the upper and lower double-layer combined structure is adopted to extrude the plasma ball to be adsorbed on the surface of the sample base, meanwhile, the plasma intensity is improved by adding a certain Ar, and the special design of the molybdenum sample base structure is adopted to have good heat dissipation performance, so that the uniform and stable temperature field of the growth surface of the CVD single crystal is achieved, and the growth efficiency is further improved on the basis of ensuring the yield not to be lower than 80 percent.
As can be seen from FIG. 3, the single crystals are better in color, good in crystallization quality and higher in yield, except for the individual single crystals which are yellowish in color.
Example 2
A single crystal diamond manufacturing method for increasing the growth amount of CVD single crystal diamond, comprising the steps of:
(1) Seed crystal screening:
using 27 pieces of CVD single crystal wafers with the dimensions of about 8mm x 0.3mm, crystallographic orientation of (100) and surface polishing (to nano-scale roughness) as seed crystals, the surface is required to be defect-free and the edge quality is good;
(2) Pretreatment of seed crystal:
soaking seed crystal in acetone and alcohol sequentially for 30min, and then ultrasonically cleaning in alcohol for 2min;
(3) Single crystal growth:
a. selecting one surface with good edge quality and no visible defect as a growth surface, uniformly placing the surface into a molybdenum sample base, wherein the molybdenum sample base is of an upper-lower double-layer combined structure, the upper layer is a circular sheet with phi 60mm multiplied by 10mm, the lower layer is a molybdenum support with phi 50mm multiplied by 5mm and provided with a bottom bulge structure, and placing a seed crystal into the molybdenum sample baseBetween the upper and lower layers of the table, two adjacent seed crystals are placed at a distance of about 0.5mm and placed on MPCVD equipment, the MPCVD equipment is opened and vacuumized to 1X 10 -3 Pa or below, and then simultaneously introducing H 2 、N 2 Ar, flow rate was 900sccm, 2.5sccm, 10sccm, N 2 Forming a plasma sphere in an MPCVD apparatus and contacting the plasma sphere with a seed crystal to promote seed crystal growth at a concentration of 30ppm, and setting a microwave power of 2.5kw and a gas pressure of 100mbar; E-H tuner on MPCVD equipment is adjusted (the E-H tuner can ensure that the maximum transmission power enters a plasma source and change the shape of a plasma cluster by adjusting microwave impedance matching) so that the plasma sphere is in an oblate spheroid shape, and the temperature is kept at 700-750 ℃ for 1.5H;
b. adjusting the microwave power to 3.5kw and the air pressure to 120mbar, gradually increasing the temperature due to the increase of the microwave power and the air pressure, and introducing CH when the temperature reaches 850-900 DEG C 4 The flow is 80sccm, the temperature is kept for 10min, the microwave power is adjusted to be 3.3-3.7kw, the air pressure is adjusted to be 145-155mbar, and the temperature is kept at 1000-1050 ℃ for stable growth for 45h;
during the growth process, the CH is closed at intervals of 12h 4 、N 2 During closing, H plasma is utilized to carry out plasma etching on the growth surface, the edge polycrystal and the inner wall of the reaction cavity, the microwave power used by etching is 3.6-3.8kw, the air pressure is 145-150mbar, the etching time is about 2min, and CH is introduced again after etching is finished 4 、N 2 And the microwave power and the air pressure are regulated in the process of growth recovery, the temperature fluctuation is kept to be no more than 30 ℃, the growth environment in the reaction cavity is favorably purified by adopting an interval etching mode, the quality of the growth surface is improved, and the growth time is obviously promoted.
H described in step (3) 2 、N 2 The purity of (C) is greater than 99.999%, CH 4 The purity of (2) is more than 99.995%.
The method of the embodiment controls the contact of the plasma ball and the seed crystal, controls the temperature difference between the center seed crystal and the edge seed crystal, and simultaneously adds Ar to improve the concentration of the plasma ball, thereby realizing the improvement of the single growth quantity of the seed crystal and ensuring the yield not to be lower than 80 percent.
Comparative example 1
Comparative example 1 a conventional CVD single crystal diamond manufacturing method was improved and compared with examples 1, 2, specifically comprising the steps of:
(1) Seed crystal screening:
using 27 pieces of CVD single crystal wafers with the dimensions of about 8mm x 0.3mm, crystallographic orientation of (100) and surface polishing (to nano-scale roughness) as seed crystals, the surface is required to be defect-free and the edge quality is good;
(2) Pretreatment of seed crystal:
soaking seed crystal in acetone and alcohol in turn for 20min, and then ultrasonically cleaning in alcohol for 3min;
(3) Single crystal growth:
a. selecting one surface with good edge quality and no visible defect on the surface as a growth surface, uniformly placing the surface into a molybdenum sample base station, wherein the molybdenum sample base station is of an upper-lower double-layer combined structure, the upper layer is a wafer with the size phi 60mm multiplied by 10mm, the lower layer is a molybdenum support with the size phi 60mm multiplied by 5mm, placing seed crystals between the upper-lower double layers of the molybdenum sample base station, placing adjacent two seed crystals at a distance of about 0.5mm, placing the seed crystals on MPCVD equipment, opening the MPCVD equipment, and vacuumizing to 1 multiplied by 10 -3 Pa or below, and then simultaneously introducing H 2 、N 2 The flow rates are respectively 1000sccm, 2.5sccm and N 2 The concentration is 30ppm, and the microwave power is set to be 3kw and the air pressure is set to be 140mbar; properly adjusting the height of the sample table, keeping the temperature at 700-750 ℃ for 1.5h;
b. the microwave power is adjusted to 3.5kw, the air pressure is adjusted to 160mbar, at the moment, the temperature is gradually increased due to the increase of the microwave power and the air pressure, and when the temperature reaches 850-900 ℃, CH is introduced 4 The flow is 90sccm, the temperature is kept for 10min, the microwave power is adjusted to be 3.4-3.9kw, the air pressure is adjusted to be 170-190mbar, and the temperature is kept to be 1000-1050 ℃ for stable growth for 40h;
during the growth process, the CH is closed at intervals of 12h 4 、N 2 During closing, H plasma is used to etch the growth surface, edge polycrystal and the inner wall of the reaction cavity, the microwave power used for etching is 3.6-3.9kw, and the air pressure is 180-190mbarEtching for about 3min, and re-introducing CH after etching 4 、N 2 And (5) recovering growth, and regulating microwave power and air pressure in the etching process, wherein the temperature fluctuation is kept at not more than 30 ℃.
H described in step (3) 2 、N 2 The purity of (C) is greater than 99.999%, CH 4 The purity of (2) is more than 99.995%.
In comparative example 1, the molybdenum sample base with heat dissipation function is not used, the state of the plasma ball is not changed by the depth of the E-H tuner, and meanwhile, the strength of the plasma ball is not improved by using Ar, so that the plasma activity is improved by using higher power and pressure, and the temperature of single crystal wafers at the center and the edge of the sample base is increased due to the further improvement of the pressure, which is not beneficial to ensuring the stability of the growth state. Comparative example 1 the growth state of single crystal diamond in step (3) is shown in fig. 5, and the result is shown in fig. 6.
As can be seen from fig. 5, the temperature difference between the center and the edge cannot be ensured in the growth process, the single crystal wafer is easy to overheat due to the too high strength of the plasma ball at the center, and the energy is insufficient due to the too low temperature at the edge. As can be seen from FIG. 6, the single crystals in the central region have a good color, but are prone to high temperature polycrystalline defects, and the single crystals in the edge region have a brown yellow color, and are prone to severe penetrating impurities and cracks.
While specific embodiments of the invention have been described above, it should be understood that the invention is not limited to the particular embodiments described above. Various changes or modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (6)
1. A single crystal diamond manufacturing method for increasing the number of CVD single crystal diamond grown, comprising the steps of:
(1) Seed crystal screening:
using a CVD single wafer with crystallographic orientation (100) as seed, it is desirable that the surface be defect free;
(2) Pretreatment of seed crystal:
soaking the seed crystal in an organic solvent, and then cleaning;
(3) Single wafer growth using MPCVD apparatus:
a. placing the seed crystal in the step (2) in a molybdenum sample base station, placing the seed crystal on MPCVD equipment, and vacuumizing to 1X 10 -3 Pa or below, then simultaneously introducing H 2 、N 2 Ar, forming a plasma ball in MPCVD equipment and contacting with a seed crystal to promote the growth of the seed crystal, setting the microwave power to be 2-3kw and the air pressure to be 100-120mbar, and keeping the temperature at 700-800 ℃ for 1-2h;
b. adjusting the microwave power to 2.5-3.5kw and the air pressure to 120-140mbar, gradually increasing the temperature due to the increase of the microwave power and the air pressure, and introducing CH when the temperature reaches 850-900 DEG C 4 Keeping for 10-15min, adjusting microwave power to 2.8-3.8kw, adjusting air pressure to 140-160mbar, and keeping stable growth at 1000-1050 ℃ for 40-45h to obtain the product;
in the step (3), the molybdenum sample base is of an upper-lower double-layer combined structure, the seed crystal is arranged between the upper and lower double layers of the molybdenum sample base, and the arrangement interval between two adjacent seed crystals is 0.5-1 mm;
h is introduced into the step (3) 2 、N 2 After Ar, adjusting an E-H tuner on MPCVD equipment, and adjusting the temperature difference between the seed crystals at the center and the edge to be not more than 80 ℃;
in the growth process of the step (3), closing CH at intervals of 12-18h 4 、N 2 During the closing period, H plasma is utilized to carry out plasma etching, the microwave power used for etching is 3.5-3.8kw, the air pressure is 140-150mbar, the etching time is 1-2min, and CH is introduced again after etching is finished 4 、N 2 And (5) recovering growth, and regulating microwave power and air pressure in the etching process, wherein the temperature fluctuation is kept at not more than 30 ℃.
2. The method of claim 1, wherein the CVD single-wafer dimensions selected in step (1) are 8mm x 0.3mm.
3. The method according to claim 1, wherein the step (2) of washing comprises immersing the seed crystal in acetone and alcohol in sequence, and then ultrasonic washing for 20-30min in each washing medium for 2-3min.
4. The method of claim 1, wherein H in step (3) 2 、N 2 Ar flow is 900-1000sccm, 2-3sccm, 10-20sccm, N 2 The concentration is 20-35ppm.
5. The method according to claim 1, wherein in the step (3), CH 4 The flow rate of (2) is 80-90sccm.
6. The method according to claim 1, wherein H is H in the step (4) 2 、N 2 The purity of (C) is greater than 99.999%, CH 4 The purity of (2) is more than 99.995%.
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