CN116200825A - Preparation method of high-quality monocrystalline diamond for removing polycrystalline defects - Google Patents
Preparation method of high-quality monocrystalline diamond for removing polycrystalline defects Download PDFInfo
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- CN116200825A CN116200825A CN202310104712.7A CN202310104712A CN116200825A CN 116200825 A CN116200825 A CN 116200825A CN 202310104712 A CN202310104712 A CN 202310104712A CN 116200825 A CN116200825 A CN 116200825A
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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
- 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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- 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
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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
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/12—Etching in gas atmosphere or plasma
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the field of diamond preparation, and discloses a preparation method of high-quality monocrystalline diamond for removing polycrystalline defects. The method comprises the steps of realizing the directional etching of cerium oxide on a (100) surface around black point-shaped polycrystal by screen printing and plasma auxiliary etching, etching square grooves, covering the black point-shaped polycrystal with the slurry by screen printing, realizing the fixed point removal of the black point-shaped polycrystal by plasma auxiliary etching, and filling the etched grooves by a transverse growth process, so that growth defects can be well removed to grow monocrystalline diamond with better quality. The invention can greatly reduce the rejection rate of single crystal diamond products and improve the utilization rate of single crystal diamond. Is beneficial to saving the production cost and improving the benefit.
Description
Technical Field
The invention belongs to the field of diamond preparation, relates to a preparation method of monocrystalline diamond, and in particular relates to a preparation method of high-quality monocrystalline diamond for removing polycrystalline defects.
Background
Natural diamond reserves are rare and expensive, and are commonly used in the luxury consumption field of jewelry and the like; the diamond prepared by the high-temperature high-pressure method has more impurities, is difficult to dope and is mainly used in the field of abrasive dies, and the two are granular and difficult to meet the actual demands of single crystal diamond in the high and new technical field. The microwave chemical vapor deposition (MPCVD) method is the preferred scheme for preparing high-quality diamond by virtue of the advantages of high plasma density, no electrode pollution and the like.
In the growth process of the single crystal diamond, the problems of instability of spheres, untreated seed crystals, excessively high temperature of individual seed crystals in the growth process and the like exist, black-point polycrystalline is possibly generated in a single crystal area in the growth process, growth defects are generated, and accordingly the grown product is scrapped.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of high-quality monocrystalline diamond for removing polycrystalline defects.
In order to achieve the purpose of the invention, the specific technical scheme is as follows:
a method for preparing high quality single crystal diamond with polycrystalline defect removal, comprising the steps of:
(1) The preparation method comprises the following steps of mixing terpineol, butyl carbitol acetate, dibutyl phthalate and cerium oxide powder according to a mass ratio of 4-8: 1-3: 1-3: 3-5, preparing organic slurry; placing the cleaned monocrystalline diamond seed crystal under a screen plate, performing first screen printing on black point-shaped polycrystal of the monocrystalline diamond seed crystal aiming at the mesh openings, wherein the mesh openings are square in shape, the size of the mesh openings is larger than that of the black point-shaped polycrystal, and sequentially covering a layer of organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the organic slurry is 2-5 microns;
(2) Drying the monocrystalline diamond seed crystal subjected to the first silk-screen printing;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal to obtain a single crystal diamond seed crystal after the first etching;
(4) Cleaning the monocrystalline diamond seed crystal after the first etching, and drying;
(5) Terpineol, butyl carbitol acetate, dibutyl phthalate, ferric oxide or nickel oxide are mixed according to the mass ratio of 4-8: 1-3: 1-3: 3-5, preparing organic slurry; placing the single crystal diamond seed crystal processed in the step (4) under a screen plate, performing screen printing by aligning black dot-shaped polycrystal with mesh holes, wherein the size of the mesh holes is larger than that of the black dot-shaped polycrystal, the size of the mesh holes is smaller than that of the mesh holes subjected to the first screen printing, and sequentially covering a layer of organic slurry on the black dot-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing, wherein the thickness of the organic slurry is 2-5 microns;
(6) Drying the monocrystalline diamond seed crystal subjected to the second silk-screen printing;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal to obtain a single crystal diamond seed crystal after the second etching;
(8) Cleaning the monocrystalline diamond seed crystal after the second etching, and drying;
(9) Etching and growing the seed crystal treated in the step (8) in sequence;
(10) After the growth is completed, the temperature is increased by 100-150 ℃ on the basis of the growth temperature in the step (9), the temperature is kept for 1-2 hours, then the temperature is reduced to the room temperature, and the microwaves are turned off, so that the monocrystalline diamond is obtained.
Preferably, the step (3) specifically comprises:
s31, first oxygen etching: the atmosphere is at least one of oxygen, argon and air, the pressure is 5-10 KPa, the temperature is 200-500 ℃, and the etching time is 5-10 min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 5-8:3:2, the pressure is 8-15 KPa, the temperature is 500-900 ℃, and the etching time is 10-120 min;
s33, first plasma etching: the atmosphere is at least one of oxygen, argon, nitrogen, air and carbon monoxide, the pressure is 5-10 KPa, the temperature is 200-500 ℃, and the etching time is 5-40 min.
Preferably, the step (7) specifically comprises:
s71, performing second oxygen etching: the atmosphere is at least one of oxygen, argon and air, the pressure is 5-10 KPa, the temperature is 200-500 ℃, and the etching time is 5-10 min;
s72, carrying out active catalytic etching on the second plasma and metal: the atmosphere is at least one of hydrogen, carbon monoxide, argon and helium, the pressure is 8-15 KPa, the temperature is 500-900 ℃, and the etching time is 10-120 min;
S73, performing secondary plasma etching: the atmosphere is at least one of oxygen, argon, nitrogen, air and carbon monoxide, the pressure is 5-10 KPa, the temperature is 200-500 ℃, and the etching time is 5-40 min.
Preferably, the step (4) or (7) is specifically: putting the monocrystalline diamond seed crystal into aqua regia solution, and cleaning for 3-10 min; and then sequentially carrying out ultrasonic cleaning on the mixture by deionized water, acetone, absolute ethyl alcohol and deionized water for 5-10 min, and drying by nitrogen.
Preferably, in the step (2) or (6), the drying temperature is set to 80-100 ℃.
Preferably, the step (9) specifically comprises:
s91, placing the seed crystal cleaned in the step (8) into a substrate table, placing the substrate table into a deposition cavity, vacuumizing, starting to introduce hydrogen, starting microwaves, and etching for 0.5-2 hours at the temperature of 700-1000 ℃ and the pressure of 17-21 kPa;
and S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, and growing for 180-200 hours in an environment with the pressure of 20-24 kPa and the temperature of 900-1050 ℃.
Further preferably, step (10) is specifically: and (3) after the growth is finished, stopping introducing methane, carbon dioxide, argon and nitrogen, increasing the temperature by 100-150 ℃ on the basis of the growth temperature in the step (9), preserving heat for 1-2 hours, then cooling by taking 100-200 ℃ as a gradient, preserving heat for 1-2 hours at each gradient temperature, cooling to room temperature, closing microwaves, and stopping introducing hydrogen to obtain the single-crystal diamond.
Further preferably, in the step (9), the substrate table includes a substrate table main body having a cylindrical structure or a truncated cone structure, a circular groove is provided on an upper surface of the substrate table main body, and a plurality of grid grooves for accommodating seed crystals are provided at a bottom of the circular groove;
the width of the grid groove is 0.15-0.5 mm larger than that of the seed crystal, the depth of the grid groove is 0.05-0.15 mm smaller than the thickness of the seed crystal, and the width of a limit step between two grids is 0.9-1.5 mm; the diameter of the circular groove is 1-3 mm smaller than that of the upper surface of the substrate table, and the depth of the circular groove is 0.5-1 mm larger than the difference of the seed crystal thickness minus the depth of the grid groove.
Further preferably, the center of the circular groove coincides with the center of the surface of the substrate table main body.
Further preferably, the seed crystal is of a square columnar structure, and the grid groove is of a square columnar hollow structure.
Further preferably, the grid grooves are uniformly formed on the upper surface of the substrate table main body; the grid grooves are arranged on the upper surface of the substrate table main body in any one of a plurality of linear array arrangements, a plurality of layers of circumferential array arrangements and a plurality of layers of rectangular array arrangements.
Further preferably, the distance between adjacent grid grooves is 0.9-1.5 mm; adjacent grid grooves are communicated with each other.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the high-quality monocrystalline diamond for removing polycrystalline defects, disclosed by the invention, the directional etching of cerium oxide on the peripheral (100) surface of black-dot-shaped polycrystalline is realized through screen printing and plasma-assisted etching, square grooves are etched, then slurry of ferric oxide or nickel oxide is used for covering the black-dot-shaped polycrystalline by the slurry through screen printing, fixed-point removal of the black-dot-shaped polycrystalline is realized through plasma-assisted etching, and then the etched grooves are grown and filled through a transverse growth process, so that the growing defects can be well removed, and the monocrystalline diamond with better quality is grown.
(2) The invention can greatly reduce the rejection rate of single crystal diamond products and improve the utilization rate of single crystal diamond. Is beneficial to saving the production cost and improving the benefit.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a top view of a substrate table for single crystal diamond growth according to the present invention;
FIG. 3 is a cross-sectional view of a substrate table for single crystal diamond growth according to the present invention;
fig. 4 is a partially enlarged structural view of fig. 3.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
As shown in fig. 2-4, the embodiment provides a substrate table for growing single crystal diamond, the substrate table includes a substrate table main body 1 with a circular table structure, the substrate table main body 1 has a circular table structure with a top surface diameter of 53mm, wherein it is to be noted that the top surface and the side surface of the substrate table main body 1 are in arc transition, a circular groove 2 is arranged on the upper surface of the substrate table main body 1, the diameter of the circular groove 2 is 52mm, and the depth of the circular groove 2 is 0.65mm.
The circular grooves 2 are internally and uniformly provided with 23 grid grooves 3 with square columnar hollow structures, the grid grooves are used for accommodating and limiting seed crystals and are arranged in a layered linear array, the length, width and height parameters of the seed crystals to be accommodated are 5mm multiplied by 0.3mm, the width of each grid groove 3 is 5.2mm, and the depth of each grid groove 3 is 0.15mm;
in this embodiment, the distance between adjacent mesh grooves 3 is 0.9mm. And the adjacent grid grooves 3 are communicated with each other, which is shown in the embodiment that the adjacent grid grooves 3 are communicated with each other at the connection vertex angle, so that the temperature difference of each point of the whole substrate table and the temperature difference of each seed crystal are further reduced.
Example 2
The present embodiment provides a method for preparing high quality single crystal diamond for removing polycrystalline defect, as shown in fig. 1, comprising the steps of:
(1) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of cerium oxide powder into organic slurry, placing the cleaned monocrystalline diamond seed crystal under a screen plate, aligning black point-shaped polycrystal of the monocrystalline diamond seed crystal to mesh holes for first screen printing, wherein the mesh holes are square, the sizes of the mesh holes are larger than those of the black point-shaped polycrystal, and sequentially covering a layer of square organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the square organic slurry is 5 microns;
(2) Placing the single crystal diamond subjected to the first silk-screen printing into an oven, preserving heat at 80 ℃ for 60min, and drying;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal, wherein the method specifically comprises the following steps:
s31, first oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 5:3:2, the pressure is 8KPa, the temperature is 500 ℃, and the etching time is 120min;
s33, first plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(4) Cleaning: placing the single crystal diamond seed crystal etched in the step (3) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(5) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of ferric oxide powder into organic slurry, placing the single crystal diamond seed crystal cleaned in the step (4) under a screen plate, carrying out screen printing by aligning black point-shaped polycrystal with mesh openings, wherein the mesh openings are square, the size of the mesh openings is larger than that of the black point-shaped polycrystal, the size of the mesh openings is smaller than that of the mesh openings of the first screen printing, and covering a layer of square organic slurry on the black point-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing in sequence, wherein the thickness is 5 microns;
(6) Placing the monocrystalline diamond seed crystal subjected to the second screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal, wherein the second plasma etching specifically comprises the following steps:
s71, performing second oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s72, carrying out active catalytic etching on the second plasma and metal: 200sccm of hydrogen, 40sccm of argon, 8KPa of pressure, 500 ℃ of temperature and 120min of etching time;
s73, performing secondary plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(8) Cleaning: placing the single crystal diamond seed crystal etched in the step (8) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(9) And (3) growing:
s91, placing the seed crystal cleaned in the step (8) into a grid groove of a substrate table, placing the substrate table into a deposition cavity, pumping the cavity pressure to below 0.8Pa, opening a hydrogen valve, setting the hydrogen flow value to be 400sccm, starting microwaves after the pressure rises to 1kPa, setting the microwave power to be 600W, setting the heating speed to be 10 ℃/min, heating to 900 ℃, setting the pressure rise value to be 17KPa, and etching for 30min;
S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, setting a methane flow value to be 32sccm, setting a carbon dioxide flow value to be 2sccm, setting an argon flow value to be 10sccm, setting a nitrogen flow value to be 0.1sccm, setting the pressure to be 20kPa, keeping the temperature to be 950 ℃, and growing for 180 hours;
(10) And after the growth is completed, stopping introducing methane, carbon dioxide, argon and nitrogen, setting the heating rate to 5 ℃/min, heating to 1300 ℃, preserving heat for 1h, then cooling at the temperature of 200 ℃ with the gradient of 2 ℃/min, preserving heat for 1h at each gradient temperature, and stopping introducing hydrogen to obtain the monocrystalline diamond by closing microwaves.
Example 3
The present embodiment provides a method for preparing high quality single crystal diamond for removing polycrystalline defect, as shown in fig. 1, comprising the steps of:
(1) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 5g of cerium oxide powder into organic slurry, placing the cleaned monocrystalline diamond seed crystal under a screen plate, aligning black point-shaped polycrystal of the monocrystalline diamond seed crystal to mesh holes for first screen printing, wherein the mesh holes are square, the sizes of the mesh holes are larger than those of the black point-shaped polycrystal, and sequentially covering a layer of square organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the square organic slurry is 5 microns;
(2) Placing the single crystal diamond subjected to the first silk-screen printing into an oven, preserving heat at 80 ℃ for 60min, and drying;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal, wherein the method specifically comprises the following steps:
s31, first oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 5:3:2, the pressure is 8KPa, the temperature is 500 ℃, and the etching time is 120min;
s33, first plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(4) Cleaning: placing the single crystal diamond seed crystal etched in the step (3) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(5) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 5g of ferric oxide powder into organic slurry, placing the single crystal diamond seed crystal cleaned in the step (4) under a screen plate, carrying out screen printing by aligning black point-shaped polycrystal with mesh openings, wherein the mesh openings are square, the size of the mesh openings is larger than that of the black point-shaped polycrystal, the size of the mesh openings is smaller than that of the mesh openings of the first screen printing, and covering a layer of square organic slurry on the black point-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing in sequence, wherein the thickness is 5 microns;
(6) Placing the monocrystalline diamond seed crystal subjected to the second screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal, wherein the second plasma etching specifically comprises the following steps:
s71, performing second oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s72, carrying out active catalytic etching on the second plasma and metal: 200sccm of hydrogen and 40sccm of argon, wherein the pressure is 8KPa, the temperature is 500 ℃, and the etching time is 120min;
s73, performing secondary plasma etching: argon 197sccm, oxygen 3sccm, pressure 5KPa, temperature 200 ℃, etching time 5min;
(8) Cleaning: placing the single crystal diamond seed crystal etched in the step (8) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(9) And (3) growing:
s91, placing the seed crystal cleaned in the step (8) into a grid groove of a substrate table, placing the substrate table into a deposition cavity, pumping the cavity pressure to below 0.8Pa, opening a hydrogen valve, setting the hydrogen flow value to be 400sccm, starting microwaves after the pressure rises to 1kPa, setting the microwave power to be 600W, setting the heating speed to be 10 ℃/min, heating to 900 ℃, setting the pressure rise value to be 17KPa, and etching for 30min;
S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, setting a methane flow value to be 32sccm, setting a carbon dioxide flow value to be 2sccm, setting an argon flow value to be 10sccm, setting a nitrogen flow value to be 0.1sccm, setting the pressure to be 20kPa, keeping the temperature to be 950 ℃, and growing for 180 hours;
(10) And after the growth is completed, stopping introducing methane, carbon dioxide, argon and nitrogen, setting the heating rate to 5 ℃/min, heating to 1300 ℃, preserving heat for 1h, then cooling at the temperature of 200 ℃ with the gradient of 2 ℃/min, preserving heat for 1h at each gradient temperature, and stopping introducing hydrogen to obtain the monocrystalline diamond by closing microwaves.
Example 4
The present embodiment provides a method for preparing high quality single crystal diamond for removing polycrystalline defect, as shown in fig. 1, comprising the steps of:
(1) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of cerium oxide powder into organic slurry, placing the cleaned monocrystalline diamond seed crystal under a screen plate, aligning black point-shaped polycrystal of the monocrystalline diamond seed crystal to mesh holes for first screen printing, wherein the mesh holes are square, the sizes of the mesh holes are larger than those of the black point-shaped polycrystal, and sequentially covering a layer of square organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the square organic slurry is 5 microns;
(2) Placing the single crystal diamond subjected to the first silk-screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal, wherein the method specifically comprises the following steps:
s31, first oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 8:3:2, the pressure is 8KPa, the temperature is 500 ℃, and the etching time is 120min;
s33, first plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(4) Cleaning: placing the single crystal diamond seed crystal etched in the step (3) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(5) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of ferric oxide powder into organic slurry, placing the single crystal diamond seed crystal cleaned in the step (4) under a screen plate, carrying out screen printing by aligning black point-shaped polycrystal with mesh openings, wherein the mesh openings are square, the size of the mesh openings is larger than that of the black point-shaped polycrystal, the size of the mesh openings is smaller than that of the mesh openings of the first screen printing, and covering a layer of square organic slurry on the black point-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing in sequence, wherein the thickness is 5 microns;
(6) Placing the monocrystalline diamond seed crystal subjected to the second screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal, wherein the second plasma etching specifically comprises the following steps:
s71, performing second oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s72, carrying out active catalytic etching on the second plasma and metal: 200sccm of hydrogen, 40sccm of argon, 8KPa of pressure, 500 ℃ of temperature and 120min of etching time;
s73, performing secondary plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(8) Cleaning: placing the single crystal diamond seed crystal etched in the step (8) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(9) And (3) growing:
s91, placing the seed crystal cleaned in the step (8) into a grid groove of a substrate table, placing the substrate table into a deposition cavity, pumping the cavity pressure to below 0.8Pa, opening a hydrogen valve, setting the hydrogen flow value to be 400sccm, starting microwaves after the pressure rises to 1kPa, setting the microwave power to be 600W, setting the heating speed to be 10 ℃/min, heating to 900 ℃, setting the pressure rise value to be 17KPa, and etching for 30min;
S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, setting a methane flow value to be 32sccm, setting a carbon dioxide flow value to be 2sccm, setting an argon flow value to be 10sccm, setting a nitrogen flow value to be 0.1sccm, setting the pressure to be 20kPa, keeping the temperature to be 950 ℃, and growing for 180 hours;
(10) And after the growth is completed, stopping introducing methane, carbon dioxide, argon and nitrogen, setting the heating rate to 5 ℃/min, heating to 1300 ℃, preserving heat for 1h, then cooling at the temperature of 200 ℃ with the gradient of 2 ℃/min, preserving heat for 1h at each gradient temperature, and stopping introducing hydrogen to obtain the monocrystalline diamond by closing microwaves.
Example 5
The present embodiment provides a method for preparing high quality single crystal diamond for removing polycrystalline defect, as shown in fig. 1, comprising the steps of:
(1) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of cerium oxide powder into organic slurry, placing the cleaned monocrystalline diamond seed crystal under a screen plate, aligning black point-shaped polycrystal of the monocrystalline diamond seed crystal to mesh holes for first screen printing, wherein the mesh holes are square, the sizes of the mesh holes are larger than those of the black point-shaped polycrystal, and sequentially covering a layer of square organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the square organic slurry is 5 microns;
(2) Placing the single crystal diamond subjected to the first silk-screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal, wherein the method specifically comprises the following steps:
s31, first oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 5:3:2, the pressure is 15KPa, the temperature is 900 ℃, and the etching time is 120min;
s33, first plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(4) Cleaning: placing the single crystal diamond seed crystal etched in the step (3) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(5) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of ferric oxide powder into organic slurry, placing the single crystal diamond seed crystal cleaned in the step (4) under a screen plate, carrying out screen printing by aligning black point-shaped polycrystal with mesh openings, wherein the mesh openings are square, the size of the mesh openings is larger than that of the black point-shaped polycrystal, the size of the mesh openings is smaller than that of the mesh openings of the first screen printing, and covering a layer of square organic slurry on the black point-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing in sequence, wherein the thickness is 5 microns;
(6) Placing the monocrystalline diamond seed crystal subjected to the second screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal, wherein the second plasma etching specifically comprises the following steps:
s71, performing second oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s72, carrying out active catalytic etching on the second plasma and metal: 200sccm of hydrogen, 40sccm of argon, 15KPa of pressure, 900 ℃ of temperature and 120min of etching time;
s73, performing secondary plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(8) Cleaning: placing the single crystal diamond seed crystal etched in the step (8) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(9) And (3) growing:
s91, placing the seed crystal cleaned in the step (8) into a grid groove of a substrate table, placing the substrate table into a deposition cavity, pumping the cavity pressure to below 0.8Pa, opening a hydrogen valve, setting the hydrogen flow value to be 400sccm, starting microwaves after the pressure rises to 1kPa, setting the microwave power to be 600W, setting the heating speed to be 10 ℃/min, heating to 900 ℃, setting the pressure rise value to be 17KPa, and etching for 30min;
S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, setting a methane flow value to be 32sccm, setting a carbon dioxide flow value to be 2sccm, setting an argon flow value to be 10sccm, setting a nitrogen flow value to be 0.1sccm, setting the pressure to be 20kPa, keeping the temperature to be 950 ℃, and growing for 180 hours;
(10) And after the growth is completed, stopping introducing methane, carbon dioxide, argon and nitrogen, setting the heating rate to 5 ℃/min, heating to 1300 ℃, preserving heat for 1h, then cooling at the temperature of 200 ℃ with the gradient of 2 ℃/min, preserving heat for 1h at each gradient temperature, and stopping introducing hydrogen to obtain the monocrystalline diamond by closing microwaves.
Comparative example 1
The comparative example provides a method for preparing high quality single crystal diamond to remove polycrystalline defect, comprising the following steps:
(1) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 0.5g of cerium oxide powder into organic slurry, placing the cleaned monocrystalline diamond seed crystal under a screen plate, aligning black point-shaped polycrystal of the monocrystalline diamond seed crystal to mesh holes for first screen printing, wherein the mesh holes are square, the sizes of the mesh holes are larger than those of the black point-shaped polycrystal, and sequentially covering a layer of square organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the square organic slurry is 5 microns;
(2) Placing the single crystal diamond subjected to the first silk-screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal, wherein the method specifically comprises the following steps:
s31, first oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 10min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 5:3:2, the pressure is 8KPa, the temperature is 500 ℃, and the etching time is 120min;
s33, first plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(4) Cleaning: placing the single crystal diamond seed crystal etched in the step (3) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(5) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of ferric oxide powder into organic slurry, placing the single crystal diamond seed crystal cleaned in the step (4) under a screen plate, carrying out screen printing by aligning black point-shaped polycrystal with mesh openings, wherein the mesh openings are square, the size of the mesh openings is larger than that of the black point-shaped polycrystal, the size of the mesh openings is smaller than that of the mesh openings of the first screen printing, and covering a layer of square organic slurry on the black point-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing in sequence, wherein the thickness is 5 microns;
(6) Placing the monocrystalline diamond seed crystal subjected to the second screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal, wherein the second plasma etching specifically comprises the following steps:
s71, performing second oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s72, carrying out active catalytic etching on the second plasma and metal: 200sccm of hydrogen, 40sccm of argon, 8KPa of pressure, 500 ℃ of temperature and 120min of etching time;
s73, performing secondary plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(8) Cleaning: placing the single crystal diamond seed crystal etched in the step (8) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(9) And (3) growing:
s91, placing the seed crystal cleaned in the step (8) into a grid groove of a substrate table, placing the substrate table into a deposition cavity, pumping the cavity pressure to below 0.8Pa, opening a hydrogen valve, setting the hydrogen flow value to be 400sccm, starting microwaves after the pressure rises to 1kPa, setting the microwave power to be 600W, setting the heating speed to be 10 ℃/min, heating to 900 ℃, setting the pressure rise value to be 17KPa, and etching for 30min;
S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, setting a methane flow value to be 32sccm, setting a carbon dioxide flow value to be 2sccm, setting an argon flow value to be 10sccm, setting a nitrogen flow value to be 0.1sccm, setting the pressure to be 20kPa, keeping the temperature to be 950 ℃, and growing for 180 hours;
(10) And after the growth is completed, stopping introducing methane, carbon dioxide, argon and nitrogen, setting the heating rate to 5 ℃/min, heating to 1300 ℃, preserving heat for 1h, then cooling at the temperature of 200 ℃ with the gradient of 2 ℃/min, preserving heat for 1h at each gradient temperature, and stopping introducing hydrogen to obtain the monocrystalline diamond by closing microwaves.
Comparative example 2
The comparative example provides a method for preparing high quality single crystal diamond to remove polycrystalline defect, comprising the following steps:
(1) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of cerium oxide powder into organic slurry, placing the cleaned monocrystalline diamond seed crystal under a screen plate, aligning black point-shaped polycrystal of the monocrystalline diamond seed crystal to mesh holes for first screen printing, wherein the mesh holes are square, the sizes of the mesh holes are larger than those of the black point-shaped polycrystal, and sequentially covering a layer of square organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the square organic slurry is 5 microns;
(2) Placing the single crystal diamond subjected to the first silk-screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal, wherein the method specifically comprises the following steps:
s31, first oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 10:3:2, the pressure is 16KPa, the temperature is 1000 ℃, and the etching time is 120min;
s33, first plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(4) Cleaning: placing the single crystal diamond seed crystal etched in the step (3) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(5) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of ferric oxide powder into organic slurry, placing the single crystal diamond seed crystal cleaned in the step (4) under a screen plate, carrying out screen printing by aligning black point-shaped polycrystal with mesh openings, wherein the mesh openings are square, the size of the mesh openings is larger than that of the black point-shaped polycrystal, the size of the mesh openings is smaller than that of the mesh openings of the first screen printing, and covering a layer of square organic slurry on the black point-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing in sequence, wherein the thickness is 5 microns;
(6) Placing the monocrystalline diamond seed crystal subjected to the second screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal, wherein the second plasma etching specifically comprises the following steps:
s71, performing second oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s72, carrying out active catalytic etching on the second plasma and metal: 200sccm of hydrogen, 40sccm of argon, 8KPa of pressure, 500 ℃ of temperature and 120min of etching time;
s73, performing secondary plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(8) Cleaning: placing the single crystal diamond seed crystal etched in the step (8) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(9) And (3) growing:
s91, placing the seed crystal cleaned in the step (8) into a grid groove of a substrate table, placing the substrate table into a deposition cavity, pumping the cavity pressure to below 0.8Pa, opening a hydrogen valve, setting the hydrogen flow value to be 400sccm, starting microwaves after the pressure rises to 1kPa, setting the microwave power to be 600W, setting the heating speed to be 10 ℃/min, heating to 900 ℃, setting the pressure rise value to be 17KPa, and etching for 30min;
S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, setting a methane flow value to be 32sccm, setting a carbon dioxide flow value to be 2sccm, setting an argon flow value to be 10sccm, setting a nitrogen flow value to be 0.1sccm, setting the pressure to be 20kPa, keeping the temperature to be 950 ℃, and growing for 180 hours;
(10) And after the growth is completed, stopping introducing methane, carbon dioxide, argon and nitrogen, setting the heating rate to 5 ℃/min, heating to 1300 ℃, preserving heat for 1h, then cooling at the temperature of 200 ℃ with the gradient of 2 ℃/min, preserving heat for 1h at each gradient temperature, and stopping introducing hydrogen to obtain the monocrystalline diamond by closing microwaves.
Comparative example 3
The comparative example provides a method for preparing high quality single crystal diamond to remove polycrystalline defect, comprising the following steps:
(1) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of cerium oxide powder into organic slurry, placing the cleaned monocrystalline diamond seed crystal under a screen plate, aligning black point-shaped polycrystal of the monocrystalline diamond seed crystal to mesh holes for first screen printing, wherein the mesh holes are square, the sizes of the mesh holes are larger than those of the black point-shaped polycrystal, and sequentially covering a layer of square organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the square organic slurry is 5 microns;
(2) Placing the single crystal diamond subjected to the first silk-screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal, wherein the method specifically comprises the following steps:
s31, first oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 3:3:2, the pressure is 7KPa, the temperature is 400 ℃, and the etching time is 120min;
s33, first plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(4) Cleaning: placing the single crystal diamond seed crystal etched in the step (3) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(5) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of ferric oxide powder into organic slurry, placing the single crystal diamond seed crystal cleaned in the step (4) under a screen plate, carrying out screen printing by aligning black point-shaped polycrystal with mesh openings, wherein the mesh openings are square, the size of the mesh openings is larger than that of the black point-shaped polycrystal, the size of the mesh openings is smaller than that of the mesh openings of the first screen printing, and covering a layer of square organic slurry on the black point-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing in sequence, wherein the thickness is 5 microns;
(6) Placing the monocrystalline diamond seed crystal subjected to the second screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal, wherein the second plasma etching specifically comprises the following steps:
s71, performing second oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s72, carrying out active catalytic etching on the second plasma and metal: 200sccm of hydrogen, 40sccm of argon, 7KPa of pressure, 400 ℃ of temperature and 120min of etching time;
s73, performing secondary plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(8) Cleaning: placing the single crystal diamond seed crystal etched in the step (8) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(9) And (3) growing:
s91, placing the seed crystal cleaned in the step (8) into a grid groove of a substrate table, placing the substrate table into a deposition cavity, pumping the cavity pressure to below 0.8Pa, opening a hydrogen valve, setting the hydrogen flow value to be 400sccm, starting microwaves after the pressure rises to 1kPa, setting the microwave power to be 600W, setting the heating speed to be 10 ℃/min, heating to 900 ℃, setting the pressure rise value to be 17KPa, and etching for 30min;
S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, setting a methane flow value to be 32sccm, setting a carbon dioxide flow value to be 2sccm, setting an argon flow value to be 10sccm, setting a nitrogen flow value to be 0.1sccm, setting the pressure to be 20kPa, keeping the temperature to be 950 ℃, and growing for 180 hours;
(10) And after the growth is completed, stopping introducing methane, carbon dioxide, argon and nitrogen, setting the heating rate to 5 ℃/min, heating to 1300 ℃, preserving heat for 1h, then cooling at the temperature of 200 ℃ with the gradient of 2 ℃/min, preserving heat for 1h at each gradient temperature, and stopping introducing hydrogen to obtain the monocrystalline diamond by closing microwaves.
Comparative example 4
The comparative example provides a method for preparing high quality single crystal diamond to remove polycrystalline defect, comprising the following steps:
(1) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of cerium oxide powder into organic slurry, placing the cleaned monocrystalline diamond seed crystal under a screen plate, aligning black point-shaped polycrystal of the monocrystalline diamond seed crystal to mesh holes for first screen printing, wherein the mesh holes are square, the sizes of the mesh holes are larger than those of the black point-shaped polycrystal, and sequentially covering a layer of square organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the square organic slurry is 5 microns;
(2) Placing the single crystal diamond subjected to the first silk-screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal, wherein the method specifically comprises the following steps:
s31, first oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 5:3:2, the pressure is 8KPa, the temperature is 500 ℃, and the etching time is 120min;
s33, first plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(4) Cleaning: placing the single crystal diamond seed crystal etched in the step (3) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(5) Preparing 6g of terpineol, 2g of butyl carbitol acetate, 2g of dibutyl phthalate and 3g of ferric oxide powder into organic slurry, placing the single crystal diamond seed crystal cleaned in the step (4) under a screen plate, carrying out screen printing by aligning black point-shaped polycrystal with mesh openings, wherein the mesh openings are square, the size of the mesh openings is larger than that of the black point-shaped polycrystal, the size of the mesh openings is smaller than that of the mesh openings of the first screen printing, and covering a layer of square organic slurry on the black point-shaped polycrystal of the single crystal diamond seed crystal subjected to the first screen printing in sequence, wherein the thickness is 5 microns;
(6) Placing the monocrystalline diamond seed crystal subjected to the second screen printing into an oven, preserving heat at 100 ℃ for 60min, and drying;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal, wherein the second plasma etching specifically comprises the following steps:
s71, performing second oxygen etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
s72, carrying out active catalytic etching on the second plasma and metal: 200sccm of hydrogen, 40sccm of argon, 16KPa of pressure, 1100 ℃ of temperature and 120min of etching time;
s73, performing secondary plasma etching: 3sccm of oxygen and 197sccm of argon, wherein the pressure is 5KPa, the temperature is 200 ℃, and the etching time is 5min;
(8) Cleaning: placing the single crystal diamond seed crystal etched in the step (8) into aqua regia solution, cleaning for 10min, then sequentially ultrasonically cleaning with deionized water, acetone, absolute ethyl alcohol and deionized water for 10min, and drying with nitrogen;
(9) And (3) growing:
s91, placing the seed crystal cleaned in the step (8) into a grid groove of a substrate table, placing the substrate table into a deposition cavity, pumping the cavity pressure to below 0.8Pa, opening a hydrogen valve, setting the hydrogen flow value to be 400sccm, starting microwaves after the pressure rises to 1kPa, setting the microwave power to be 600W, setting the heating speed to be 10 ℃/min, heating to 900 ℃, setting the pressure rise value to be 17KPa, and etching for 30min;
S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, setting a methane flow value to be 32sccm, setting a carbon dioxide flow value to be 2sccm, setting an argon flow value to be 10sccm, setting a nitrogen flow value to be 0.1sccm, setting the pressure to be 20kPa, keeping the temperature to be 950 ℃, and growing for 180 hours;
(10) And after the growth is completed, stopping introducing methane, carbon dioxide, argon and nitrogen, setting the heating rate to 5 ℃/min, heating to 1300 ℃, preserving heat for 1h, then cooling at the temperature of 200 ℃ with the gradient of 2 ℃/min, preserving heat for 1h at each gradient temperature, and stopping introducing hydrogen to obtain the monocrystalline diamond by closing microwaves.
The growth process of the single crystal diamond of examples 3 to 5 and comparative examples 1 to 4 was examined, and the results are shown in table 1. As can be seen from the experimental data table, the method can well remove the growth defects, and grow the monocrystalline diamond with better quality.
TABLE 1
| Depth of groove | Residue of punctiform polycrystal | Thickness of growth | Whether the groove growth surface has polycrystal | |
| Example 2 | 0.12mm | Without any means for | 1.7mm | Without any means for |
| Example 3 | 0.15mm | Without any means for | 1.75mm | Without any means for |
| Example 4 | 0.16mm | Without any means for | 1.65mm | Without any means for |
| Example 5 | 0.18mm | Without any means for | 1.75mm | Without any means for |
| Comparative example 1 | 0.06mm | Has the following components | 1.72mm | No surface unevenness |
| Comparative example 2 | 0.23mm | Without any means for | 1.71mm | None but the grooves are not flat |
| Comparative example 3 | 0.03mm | Has the following components | 1.70mm | Has the following components |
| Comparative example 4 | 0.11mm | Without any means for | 1.71mm | None but the grooves are not flat |
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing high quality single crystal diamond with polycrystalline defect removal, comprising the steps of:
(1) The preparation method comprises the following steps of mixing terpineol, butyl carbitol acetate, dibutyl phthalate and cerium oxide powder according to a mass ratio of 4-8: 1-3: 1-3: 3-5, preparing organic slurry; placing the cleaned monocrystalline diamond seed crystal under a screen plate, performing first screen printing on black point-shaped polycrystal of the monocrystalline diamond seed crystal aiming at the mesh openings, wherein the mesh openings are square in shape, the size of the mesh openings is larger than that of the black point-shaped polycrystal, and sequentially covering a layer of organic slurry on the black point-shaped polycrystal of the monocrystalline diamond seed crystal, wherein the thickness of the organic slurry is 2-5 microns;
(2) Drying the monocrystalline diamond seed crystal subjected to the first silk-screen printing;
(3) Sequentially carrying out first oxygen etching, first plasma and metal active catalytic etching and first plasma etching on the dried single crystal diamond seed crystal to obtain a single crystal diamond seed crystal after the first etching;
(4) Cleaning the monocrystalline diamond seed crystal after the first etching, and drying;
(5) Terpineol, butyl carbitol acetate, dibutyl phthalate, ferric oxide or nickel oxide are mixed according to the mass ratio of 4-8: 1-3: 1-3: 3-5, preparing organic slurry; placing the monocrystalline diamond seed crystal processed in the step (4) under a screen plate, performing screen printing by aligning black dot-shaped polycrystal with mesh holes, wherein the size of the mesh holes is larger than that of the black dot-shaped polycrystal, the size of the mesh holes is smaller than that of the mesh holes subjected to the first screen printing, and sequentially covering a layer of organic slurry on the black dot-shaped polycrystal of the monocrystalline diamond seed crystal subjected to the first screen printing, wherein the thickness of the organic slurry is 2-5 microns;
(6) Drying the monocrystalline diamond seed crystal subjected to the second silk-screen printing;
(7) Sequentially carrying out second oxygen etching, second plasma and metal active catalytic etching and second plasma etching on the dried single crystal diamond seed crystal to obtain a single crystal diamond seed crystal after the second etching;
(8) Cleaning the monocrystalline diamond seed crystal after the second etching, and drying;
(9) Etching and growing the seed crystal treated in the step (8) in sequence;
(10) After the growth is completed, the temperature is increased by 100-150 ℃ on the basis of the growth temperature in the step (9), the temperature is kept for 1-2 hours, and then the temperature is reduced to the room temperature, so that the monocrystal diamond is obtained.
2. The preparation method according to claim 1, wherein the step (3) is specifically:
s31, first oxygen etching: the atmosphere is at least one of oxygen, argon and air, the pressure is 5-10 KPa, the temperature is 200-500 ℃, and the etching time is 5-10 min;
s32, carrying out active catalytic etching on the first plasma and metal: the atmosphere is a mixed atmosphere of hydrogen, nitrogen and argon, the volume ratio is 5-8:3:2, the pressure is 8-15 KPa, the temperature is 500-900 ℃, and the etching time is 10-120 min;
s33, first plasma etching: the atmosphere is at least one of oxygen, argon, nitrogen, air and carbon monoxide, the pressure is 5-10 KPa, the temperature is 200-500 ℃, and the etching time is 5-40 min.
3. The preparation method according to claim 1, wherein the step (7) is specifically:
s71, performing second oxygen etching: the atmosphere is at least one of oxygen, argon and air, the pressure is 5-10 KPa, the temperature is 200-500 ℃, and the etching time is 5-10 min;
s72, carrying out active catalytic etching on the second plasma and metal: the atmosphere is at least one of hydrogen, carbon monoxide, argon and helium, the pressure is 8-15 KPa, the temperature is 500-900 ℃, and the etching time is 10-120 min;
s73, performing secondary plasma etching: the atmosphere is at least one of oxygen, argon, nitrogen, air and carbon monoxide, the pressure is 5-10 KPa, the temperature is 200-500 ℃, and the etching time is 5-40 min.
4. The method of claim 1, wherein step (4) or (7) is specifically: putting the monocrystalline diamond seed crystal into aqua regia solution, and cleaning for 3-10 min; and then sequentially carrying out ultrasonic cleaning on the mixture by deionized water, acetone, absolute ethyl alcohol and deionized water for 5-10 min, and drying by nitrogen.
5. The preparation method according to claim 1, wherein the step (9) is specifically:
s91, placing the seed crystal cleaned in the step (8) into a substrate table, placing the substrate table into a deposition cavity, vacuumizing, starting to introduce hydrogen, starting microwaves, and etching for 0.5-2 hours at the temperature of 700-1000 ℃ and the pressure of 17-21 kPa;
and S92, after etching is finished, introducing methane, carbon dioxide, argon and nitrogen, and growing for 180-200 hours in an environment with the pressure of 20-24 kPa and the temperature of 900-1050 ℃.
6. The method of claim 5, wherein step (10) comprises: and (3) after the growth is finished, stopping introducing methane, carbon dioxide, argon and nitrogen, increasing the temperature by 100-150 ℃ on the basis of the growth temperature in the step (9), preserving heat for 1-2 hours, then cooling by taking 100-200 ℃ as a gradient, preserving heat for 1-2 hours at each gradient temperature, cooling to room temperature, closing microwaves, and stopping introducing hydrogen to obtain the single-crystal diamond.
7. The method according to claim 5, wherein in the step (9), the substrate table comprises a substrate table body having a cylindrical structure or a truncated cone-shaped structure, a circular groove is provided on an upper surface of the substrate table body, and a plurality of grid grooves for accommodating seed crystals are provided at a bottom of the circular groove;
the width of the grid groove is 0.15-0.5 mm larger than that of the seed crystal, the depth of the grid groove is 0.05-0.15 mm smaller than the thickness of the seed crystal, and the width of a limit step between two grids is 0.9-1.5 mm; the diameter of the circular groove is 1-3 mm smaller than that of the upper surface of the substrate table, and the depth of the circular groove is 0.5-1 mm larger than the difference of the seed crystal thickness minus the depth of the grid groove.
8. The method of manufacturing according to claim 7, wherein the center of the circular recess coincides with the center of the surface of the substrate table main body.
9. The method of claim 7, wherein the seed crystal has a square columnar structure and the grid grooves have a square columnar hollow structure.
10. The substrate table according to claim 7, wherein the mesh grooves are uniformly provided on the upper surface of the substrate table main body; the grid grooves are arranged on the upper surface of the substrate table main body in any one of a plurality of linear array arrangements, a plurality of layers of circumferential array arrangements and a plurality of layers of rectangular array arrangements; the distance between adjacent grid grooves is 0.9-1.5 mm; adjacent grid grooves are communicated with each other.
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