CN114232091B - Large-size single crystal diamond and preparation method thereof - Google Patents
Large-size single crystal diamond and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000012010 growth Effects 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000005520 cutting process Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000001020 plasma etching Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 230000002093 peripheral effect Effects 0.000 claims abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 238000005530 etching Methods 0.000 claims description 2
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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
- C30B25/02—Epitaxial-layer growth
- C30B25/025—Continuous 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
- 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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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/20—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer
- C30B25/205—Epitaxial-layer growth characterised by the substrate the substrate being of the same materials as the epitaxial layer the substrate being of insulating material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a large-size single crystal diamond and a preparation method thereof. The preparation method comprises the following steps: cutting the peripheral edge of the first diamond single crystal wafer along the thickness direction of the first diamond single crystal wafer to enable the formed cutting surface to be perpendicular to the upper surface and the lower surface of the first diamond single crystal wafer, then sequentially carrying out grinding, cleaning and plasma etching treatment, and then growing a diamond single crystal layer by taking the first diamond single crystal wafer as a growth substrate; and then separating the diamond monocrystal layer to obtain a second diamond monocrystal sheet with radial size larger than that of the first diamond monocrystal sheet, taking the second diamond monocrystal sheet as a new growth substrate, and circulating the above operation until the required large-size monocrystal diamond is obtained. The invention effectively solves the problem that small-size single crystal diamond can not be directly epitaxially grown into large-size single crystal diamond and is easy to generate polycrystal in the epitaxial process; the prepared large-size single crystal diamond has high crystal uniformity and strong integrity.
Description
Technical Field
The invention relates to the technical field of diamond preparation, in particular to a large-size monocrystalline diamond and a preparation method thereof.
Background
Precious diamond, also known as diamond, is brilliant, sparkling and crystal clear, known as the "king of precious stones", is expensive, and is the world-accepted first commodity, and its occupancy level and consumption level are often regarded as a sign for measuring the economic abundance of individuals and countries. Diamond (industrial diamond) which can not reach precious stone grade is widely used in the industrial fields of electromechanics, optics, construction, traffic, metallurgy, land exploration, national defense and the like and the modern high and new technical fields by the ultra-hard property.
Diamond can be classified into type ia diamond and type IIa diamond according to microelements contained therein. The ia-type diamond is mostly common diamond. IIa type diamond is rare, and accounts for 1% -2% of the total amount of diamond. IIa type diamond is widely used in space technology and tip industry because of its excellent thermal conductivity, cleavage and semiconducting properties.
The diamond has excellent physical and chemical properties and has wide application prospect in a plurality of fields of industry and civil use. Currently, methods for artificially synthesizing diamond include a high temperature high pressure method (HTHP), a direct current arc plasma spray method (DCAPJ), a hot wire chemical vapor deposition method (HFCVD), and a microwave plasma chemical vapor deposition Method (MPCVD), wherein the MPCVD method is a preferred method for preparing high quality diamond. This is due to the advantages of good controllability of microwave excited plasma, high plasma density, no electrode pollution, etc.
In the prior art, the MPCVD method is generally a splicing method, and the small-size single-crystal diamond directly epitaxially grows the large-size single-crystal diamond, and the edge of the small-size single-crystal diamond is easy to generate polycrystal in the growth process so as to limit the epitaxy of the single crystal, thus the large-size single-crystal diamond cannot be directly epitaxially grown.
For example, patent CN112899774a discloses a method for homoepitaxial growth of single crystal diamond by cutting, cleaning and plasma etching pretreatment of natural diamond, then carrying out epitaxial growth to obtain a single crystal diamond film, then carrying out oblique cutting on a growth surface into two parts to form two right-angled triangles, again processing the cutting surface, bonding the two obtained natural diamond sheets on the same substrate surface, and then carrying out splice growth on the two natural diamond sheets under the microwave plasma condition to finally obtain the large-size single crystal diamond.
However, the splicing growth process flow is complex, and has the defect of poor splicing of the splicing seams, so that the application range of the large-size single crystal diamond is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a large-size single crystal diamond and a preparation method thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
In a first aspect, the present invention provides a method of preparing large-sized single crystal diamond, comprising:
s1, providing a first diamond single crystal wafer serving as a growth substrate, and cutting the peripheral edge of the first diamond single crystal wafer along the axial direction, so that the formed cutting surface is perpendicular to a first surface and a second surface of the first diamond single crystal wafer, and the first surface and the second surface are oppositely arranged along the axial direction;
S2, grinding the cutting surface, the first surface and the second surface;
S3, cleaning the first diamond monocrystal wafer processed in the step S2;
s4, carrying out plasma etching treatment on the surface of the first diamond single crystal wafer treated in the step S3;
S5, growing a diamond monocrystal layer on the first diamond monocrystal wafer treated in the step S4;
S6, separating and obtaining a second diamond single crystal plate from the diamond single crystal layer, wherein the radial dimension of the second diamond single crystal plate is larger than that of the first diamond single crystal plate;
S7, taking the second diamond single crystal wafer as a new growth substrate, and circularly repeating the steps S1-S6 for more than one time until the required large-size single crystal diamond is obtained.
In a second aspect, the invention also provides a large-size single crystal diamond prepared by the method.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
According to the preparation method of the large-size single crystal diamond, the pretreated first diamond single crystal wafer is taken as a substrate to carry out repeated cyclic growth to obtain the large-size single crystal diamond, splicing growth is not needed, and the problems that the small-size single crystal diamond cannot be directly grown into the large-size single crystal diamond and polycrystal is easy to generate in the growth process are effectively solved; the prepared large-size single crystal diamond has no splicing influence, high crystal uniformity and strong integrity.
The above description is only an overview of the technical solutions of the present application, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present application may be implemented according to the content of the specification, and the following description is given of the preferred embodiments of the present application with reference to the detailed drawings.
Drawings
FIG. 1 is a process flow diagram of a method for preparing large-size single crystal diamond according to an exemplary embodiment of the present invention;
fig. 2 is a schematic diagram showing a part of a growth process of a method for preparing large-sized single crystal diamond according to an exemplary embodiment of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has long-term research and a great deal of practice, and has proposed the technical scheme of the present invention, mainly to invent a method for specially processing a single crystal diamond substrate sheet and improving the growth process, which is suitable for chemical vapor deposition (MPCVD) epitaxy to grow large-size single crystal diamond. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Referring to fig. 1 and 2, an embodiment of the present invention provides a method for preparing large-sized single crystal diamond, including the steps of:
Step S1: providing a first diamond single crystal wafer serving as a growth substrate, and cutting a peripheral edge part of the first diamond single crystal wafer along an axial direction, so that a formed cutting surface is perpendicular to a first surface and a second surface of the first diamond single crystal wafer, wherein the first surface and the second surface are oppositely arranged along the axial direction.
Step S2: and grinding the cutting surface, the first surface and the second surface.
Step S3: and (2) cleaning the first diamond monocrystal wafer after the treatment in the step (S2).
Step S4: and (3) performing plasma etching treatment on the surface of the first diamond single crystal wafer processed in the step (S3).
Step S5: and (3) growing a diamond monocrystal layer on the first diamond monocrystal wafer treated in the step (S4).
Step S6: and separating and obtaining a second diamond single crystal plate from the diamond single crystal layer, wherein the radial dimension of the second diamond single crystal plate is larger than that of the first diamond single crystal plate.
Step S7: and taking the second diamond single crystal wafer as a new growth substrate, and circularly repeating the steps S1-S6 for more than one time until the required large-size single crystal diamond is obtained.
According to the technical scheme, the cutting surface is perpendicular to the first surface and the second surface of the diamond monocrystal piece, so that the orientation of crystal lattices exposed by the edge angle part of the first diamond monocrystal piece is more neat, the growth direction of crystal lattices of the orderly diamond monocrystal layer is further provided, meanwhile, the polycrystal generated by the edge angle part of the first diamond monocrystal piece is eliminated by matching with plasma etching treatment, the interference of the polycrystal on the crystal lattice orientation during the growth of the diamond monocrystal layer is avoided, the diamond monocrystal layer grows strictly according to the original crystal lattice orientation of the first diamond monocrystal piece, and therefore the large-size monocrystal diamond with high uniformity and high integrity is obtained.
The diamond single crystal wafer may be, for example, a diamond single crystal wafer obtained by growth by MPCVD, a natural diamond single crystal wafer, or a diamond single crystal wafer obtained by growth at high temperature and high pressure; the growth in step S5 may be performed by MPCVD, or may be performed by a high-temperature high-pressure method.
In some embodiments, the axial direction in step S1 may be a thickness direction of the first diamond microchip, and the first diamond microchip may have a length and/or width greater than the thickness.
In some embodiments, the first diamond monocrystal sheet processed in the step S2 may be rectangular.
In some embodiments, step S2 may include: and grinding the first surface and the second surface of the first diamond single crystal plate to the parallelism of less than 10 mu m.
In some embodiments, step S2 may include: and grinding two opposite cutting surfaces of the first diamond single crystal wafer to have parallelism within 10 mu m, and grinding verticality between the cutting surfaces and the first surface and the second surface to have parallelism within 10 mu m.
In some embodiments, the diamond single-crystal wafer may be cut and then each surface of the diamond single-crystal wafer may be polished.
In some embodiments, the diamond monocrystal wafer after grinding treatment may be cleaned with a mixture of concentrated sulfuric acid and peroxide.
In some embodiments, the diamond monocrystal wafer subjected to the grinding treatment may be sequentially washed with a mixture of concentrated sulfuric acid and peroxide, water and/or an organic solvent.
In some embodiments, the peroxide may include hydrogen peroxide.
In some embodiments, the mixture may comprise water, concentrated sulfuric acid, and hydrogen peroxide in a volume ratio of 0.9-1.1:4.5-5.5:0.9-1.1, and the temperature of the mixture may be 100-140 ℃.
In some embodiments, the first diamond single crystal wafer may be washed with the mixture for 10-15 minutes, then with water for 5-10 minutes, then with acetone for 10-15 minutes, and finally with isopropanol for 10-15 minutes.
In some embodiments, the process parameters of the plasma etching process in step S3 may include: the temperature is 800-1000 ℃, the pressure is 100-160torr, the plasma power is 2000-5000w, the hydrogen flow is 200-500sccm, the carbon dioxide flow is 5-20sccm, and the etching time is not less than 1 hour.
In some embodiments, step S5 may include: growing a diamond single crystal layer on the first diamond single crystal wafer by adopting a chemical vapor deposition method, wherein the chemical vapor deposition method comprises the following steps: the growth temperature is controlled to be 850-950 ℃, the microwave plasma epitaxial growth is carried out for 100-200h under the pressure of 130-160torr in the atmosphere of hydrogen and carbon-containing gas, and the microwave plasma power is 3000-5500W.
In some embodiments, the carbon-containing gas may include methane and carbon dioxide.
In some embodiments, the epitaxial growth may be performed by introducing hydrogen gas at a flow rate of 300-500sccm, methane at a flow rate of 25-30sccm, carbon dioxide at a flow rate of 1-5sccm, and a mixture of hydrogen gas and nitrogen gas at a flow rate of 1-5 sccm.
In some embodiments, step S5 may include: and arranging the plurality of first diamond single crystal plates in parallel on the same plane and mutually spacing, and respectively growing on the plurality of first diamond single crystal plates to form a diamond single crystal layer.
In some embodiments, the arrangement interval of the plurality of the first diamond single crystal plates may be 4 to 6mm.
Based on the embodiment, the embodiment of the invention can also effectively solve the problem of uniformity of the large-size single crystal diamond chips grown simultaneously, and the uniformity of the large-size single crystal diamond chips grown simultaneously is improved by controlling the interval, the gas flow and the plasma power of the diamond single crystal chips.
In some embodiments, the large-sized single crystal diamond may include a growth substrate and a diamond single crystal layer grown on the growth substrate.
With continued reference to fig. 1, in an exemplary embodiment, the method for preparing large-size single crystal diamond specifically includes:
and 1, performing four-side cutting on the first diamond single crystal wafer by using a laser cutting machine.
And 2, grinding the first surface, the second surface and the cutting surface edges of the diamond single crystal wafer by using a grinding fixture.
And step 3, cleaning the ground first diamond monocrystal wafer, cleaning oil stains and organic matters on the surface of the monocrystal wafer by concentrated sulfuric acid, acetone and isopropanol, then placing the monocrystal wafer into plasma etching treatment equipment, and introducing hydrogen and carbon dioxide for plasma etching treatment.
And 4, placing the treated diamond monocrystal wafer into an MPCVD furnace chamber for epitaxial growth.
And 5, performing laser cutting stripping on the single crystal obtained by growth, and separating from the grown diamond single crystal layer to obtain a second diamond single crystal plate.
And 6, taking the stripped second diamond single crystal wafer as a new substrate, and repeating the processing treatment according to the steps 2 and 3.
And 7, putting the treated second diamond single crystal into an MPCVD furnace chamber again for epitaxial growth, and repeating the process for 2-4 times. And finally, epitaxially growing finished single crystal diamond with the size of 10-20 mm.
The embodiment of the invention also provides the large-size monocrystalline diamond obtained by the preparation method.
In some embodiments, the large-size single crystal diamond has a size of 10-20mm.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
A method for preparing large-size single crystal diamond, comprising the following steps:
Step 1: providing a first diamond monocrystal wafer grown by MPCVD as a growth substrate, and cutting the first diamond monocrystal wafer into rectangular bodies with the thickness of 0.3 mm;
Step 2: grinding the first diamond single crystal wafer to make the parallelism of the upper surface and the lower surface of the first diamond single crystal wafer 5 mu m, the parallelism of the opposite cutting surface 8 mu m, and the perpendicularity of the cutting surface and the upper surface and the lower surface 5 mu m;
step 3: washing the first diamond single crystal wafer for 10min by using a cleaning solution consisting of water, concentrated sulfuric acid and hydrogen peroxide at the volume ratio of 1:5:1 at 130 ℃, and then washing the first diamond single crystal wafer by deionized water for 5min, washing the first diamond single crystal wafer by acetone for 15min and washing the first diamond single crystal wafer by isopropanol for 15min;
step 4: performing plasma etching on the first diamond single crystal wafer for 1 hour under the conditions of 900 ℃, 100torr pressure, 2000w plasma power, 200sccm hydrogen flow and 20sccm carbon dioxide flow;
step 5: carrying out microwave plasma epitaxial growth on 5 first diamond single crystal wafers in the same furnace, controlling the growth temperature to 850 ℃, controlling the pressure to 130torr, controlling the microwave plasma power to 3000W, controlling the hydrogen flow to 500sccm, controlling the methane flow to 30sccm, controlling the carbon dioxide flow to 1sccm, and controlling the volume ratio to 1:5, the flow of the mixed gas of hydrogen and nitrogen is 1sccm, the growth time is 200h, and the distance between adjacent first diamond single crystal wafers is 6mm;
Step 6: after the epitaxial growth is finished, a single crystal with the upper side length of 10.2mm and the lower side length of 7.5mm and the thickness of 2mm is obtained, the single crystal comprises an original first diamond single crystal sheet and a grown diamond single crystal layer, then the single crystal is cut along a plane vertical to the thickness direction of the single crystal layer, and a second diamond single crystal sheet with the upper side length of 10.2mm, the lower side length of 9.2mm and the thickness of 0.5mm is obtained by stripping from the diamond single crystal layer;
step 7: and (3) taking the second diamond single crystal wafer as a new growth substrate, and repeating the steps 1-6, wherein the total cycle number of the steps is 2, so as to prepare the large-size single crystal diamond.
Example 2
A method for preparing large-size single crystal diamond, comprising the following steps:
Step 1: providing a first diamond monocrystal wafer grown by a high-temperature high-pressure method as a growth substrate, and cutting the first diamond monocrystal wafer into cubes of 0.2 mm;
Step 2: grinding the first diamond single crystal wafer to make the parallelism of the upper surface and the lower surface of the first diamond single crystal wafer be 10 mu m, the parallelism of the opposite cutting surface be 10 mu m, and the perpendicularity of the cutting surface and the upper surface and the lower surface be 10 mu m;
Step 3: washing the first diamond single crystal wafer for 15min by using a cleaning solution consisting of water, concentrated sulfuric acid and hydrogen peroxide at the volume ratio of 1:5:1 at 130 ℃, and washing the first diamond single crystal wafer by deionized water for 5min, washing the first diamond single crystal wafer by acetone for 15min and washing the first diamond single crystal wafer by isopropanol for 15min;
Step 4: plasma etching the first diamond single crystal wafer for 3 hours under the conditions of 1000 ℃ and 100torr pressure, 3300w plasma power, 500sccm hydrogen flow and 5sccm carbon dioxide flow;
Step 5: carrying out microwave plasma epitaxial growth on 10 first diamond single crystal wafers in the same furnace, controlling the growth temperature to 950 ℃, controlling the pressure to 160torr, controlling the microwave plasma power to 5500W, controlling the hydrogen flow to 300sccm, controlling the methane flow to 25sccm, controlling the carbon dioxide flow to 3sccm, and controlling the volume ratio to 1:1, the flow of the mixed gas of hydrogen and nitrogen is 5sccm, the growth time is 150h, and the distance between adjacent first diamond single crystal wafers is 5mm;
Step 6: after the epitaxial growth is finished, obtaining a single crystal with the thickness of 2.3mm, wherein the single crystal comprises an original first diamond single crystal plate and a grown diamond single crystal layer, then cutting along a plane perpendicular to the thickness direction of the single crystal layer, and stripping the single crystal layer from the diamond single crystal layer to obtain a second diamond single crystal plate with the thickness of 0.4 mm;
Step 7: and (3) taking the second diamond single crystal wafer as a new growth substrate, and repeating the steps 1-6, wherein the total cycle number of the steps is 4, so as to prepare the large-size single crystal diamond.
Example 3
A method for preparing large-size single crystal diamond, comprising the following steps:
Step 1: providing a first diamond monocrystal wafer grown by MPCVD as a growth substrate, and cutting the first diamond monocrystal wafer into cubes with the thickness of 0.3 mm;
step 2: grinding the first diamond single crystal wafer to make the parallelism of the upper surface and the lower surface of the first diamond single crystal wafer be 2 mu m, the parallelism of the opposite cutting surface be 2 mu m, and the perpendicularity of the cutting surface and the upper surface and the lower surface be 2 mu m;
step 3: washing the first diamond single crystal wafer for 10min by using a cleaning solution consisting of water, concentrated sulfuric acid and hydrogen peroxide at the volume ratio of 1:5:1 at 130 ℃, and then washing the first diamond single crystal wafer by deionized water for 5min, washing the first diamond single crystal wafer by acetone for 15min and washing the first diamond single crystal wafer by isopropanol for 15min;
Step 4: performing plasma etching on the first diamond single crystal wafer for 5 hours under the conditions of 800 ℃, 160torr pressure, 5000w plasma power, 300sccm hydrogen flow and 15sccm carbon dioxide flow;
Step 5: carrying out microwave plasma epitaxial growth on 10 first diamond single crystal wafers in the same furnace, controlling the growth temperature to 900 ℃, controlling the pressure to 140torr, controlling the microwave plasma power to 4500W, controlling the hydrogen flow to 400sccm, controlling the methane flow to 28sccm, controlling the carbon dioxide flow to 5sccm, and controlling the volume ratio to 5:1, the flow of the mixed gas of hydrogen and nitrogen is 3sccm, the growth time is 100h, and the distance between adjacent first diamond single crystal wafers is 4mm;
Step 6: after the epitaxial growth is finished, obtaining a monocrystal with the thickness of 3mm, wherein the monocrystal comprises an original first diamond monocrystal and a grown diamond monocrystal layer, cutting along a plane perpendicular to the thickness direction of the monocrystal, and stripping the monocrystal from the diamond monocrystal layer to obtain a second diamond monocrystal with the thickness of 0.7 mm;
Step 7: and (3) taking the second diamond single crystal wafer as a new growth substrate, and repeating the steps 1-6, wherein the total cycle number of the steps is 3, so as to obtain the large-size single crystal diamond.
Comparative example 1
A method for producing single crystal diamond, the steps and parameters of which are substantially the same as those of example 1, except that:
The first diamond single crystal wafer was polished so that the parallelism of the upper and lower surfaces of the first diamond single crystal wafer was 15. Mu.m, the parallelism of the opposed cut surfaces was 15. Mu.m, and the perpendicularity of the cut surfaces to the upper and lower surfaces was 15. Mu.m.
Comparative example 2
A method for producing single crystal diamond, the steps and parameters of which are substantially the same as those of example 1, except that:
And (3) pickling the first diamond single-crystal wafer substrate by using heated aqua regia instead of using a cleaning solution consisting of water, concentrated sulfuric acid and hydrogen peroxide.
Comparative example 3
A method for producing single crystal diamond, the steps and parameters of which are substantially the same as those of example 1, except that:
During microwave plasma epitaxial growth, the distance between adjacent diamond single crystal wafers is 1mm.
Detection method
1. Crystal morphology observation was performed on the single crystal diamond grown in each example and comparative example;
2. the single crystal diamond grown in each of the examples and comparative examples was subjected to a size uniformity (four-sided length) test.
Analysis of results
The properties of the single crystal diamond in each example and comparative example are shown in Table 1 below
TABLE 1
Based on the detection results, it can be clear that the preparation method of the large-size single crystal diamond provided by the invention can successfully obtain the large-size single crystal diamond by directly growing on a diamond single crystal wafer serving as a substrate through MPCVD, does not need splice growth, avoids the generation of polycrystal, and simultaneously solves the problem of non-uniformity of a plurality of large-size single crystal diamonds grown simultaneously.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (7)
1. A method for preparing large-size single crystal diamond, comprising:
S1, providing a first diamond single crystal wafer serving as a growth substrate, and cutting the peripheral edge of the first diamond single crystal wafer along the axial direction, so that the formed cutting surface is perpendicular to a first surface and a second surface of the first diamond single crystal wafer, and the first surface and the second surface are oppositely arranged along the axial direction; the axial direction is the thickness direction of the first diamond single crystal wafer, the length and the width of the first diamond single crystal wafer are larger than the thickness, and the processed first diamond single crystal wafer is rectangular;
S2, grinding the cutting surface, the first surface and the second surface, wherein the grinding process specifically comprises the following steps: grinding the first face and the second face of the first diamond single crystal wafer to a parallelism within 10 mu m, grinding the two opposite cutting faces of the first diamond single crystal wafer to a parallelism within 10 mu m, and grinding the verticality of the cutting faces with the first face and the second face to a parallelism within 10 mu m;
S3, cleaning the first diamond monocrystal wafer processed in the step S2;
s4, carrying out plasma etching treatment on the surface of the first diamond single crystal wafer treated in the step S3;
S5, growing a diamond monocrystal layer on the first diamond monocrystal wafer treated in the step S4;
S6, cutting a plane perpendicular to the thickness direction, and separating from the diamond monocrystal layer to obtain a second diamond monocrystal piece, wherein the radial dimension of the second diamond monocrystal piece is larger than that of the first diamond monocrystal piece;
S7, taking the second diamond single crystal wafer as a new growth substrate, and circularly repeating the steps S1-S6 for more than one time until the required large-size single crystal diamond is obtained;
The step S3 specifically includes: and cleaning the diamond monocrystal wafer subjected to grinding treatment sequentially by using a mixture of concentrated sulfuric acid and peroxide, water and/or an organic solvent, wherein the mixture comprises water, concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 0.9-1.1:4.5-5.5:0.9-1.1, and the temperature of the mixture is 100-140 ℃.
2. The method of claim 1, wherein the first diamond single crystal wafer is washed with the mixture for 10 to 15 minutes, then with water for 5 to 10 minutes, then with acetone for 10 to 15 minutes, and finally with isopropanol for 10 to 15 minutes.
3. The method according to claim 1, wherein the process parameters of the plasma etching process in step S3 include:
The temperature is 800-1000 ℃, the pressure is 100-160torr, the plasma power is 2000-5000w, the hydrogen flow is 200-500sccm, the carbon dioxide flow is 5-20sccm, and the etching time is not less than 1 hour.
4. The method of claim 1, wherein step S5 comprises: growing a diamond single crystal layer on the first diamond single crystal wafer by adopting a chemical vapor deposition method, wherein the chemical vapor deposition method comprises the following steps:
the growth temperature is controlled to be 850-950 ℃, the microwave plasma epitaxial growth is carried out for 100-200h under the pressure of 130-160torr in the atmosphere of hydrogen and carbon-containing gas, and the microwave plasma power is 3000-5500W.
5. The method of claim 4, wherein the carbon-containing gas comprises methane and carbon dioxide;
And introducing hydrogen with the flow rate of 300-500sccm, methane with the flow rate of 25-30sccm, carbon dioxide with the flow rate of 1-5sccm and mixed gas of hydrogen and nitrogen with the flow rate of 1-5sccm during epitaxial growth.
6. The method of claim 1, wherein step S5 comprises: arranging a plurality of first diamond single crystal plates in parallel on the same plane at intervals, and respectively growing on the plurality of first diamond single crystal plates to form a diamond single crystal layer;
The arrangement interval of the plurality of first diamond single crystal plates is 4-6mm.
7. The method of manufacturing according to claim 1, wherein the large-sized single crystal diamond comprises a growth substrate and a diamond single crystal layer grown on the growth substrate.
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| US6096129A (en) * | 1997-04-18 | 2000-08-01 | Sumitomo Electric Industries, Ltd. | Method of and apparatus for producing single-crystalline diamond of large size |
| CN111690981A (en) * | 2020-07-23 | 2020-09-22 | 太原理工大学 | Method for enlarging size and number of single crystal diamond seed crystals |
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| US6096129A (en) * | 1997-04-18 | 2000-08-01 | Sumitomo Electric Industries, Ltd. | Method of and apparatus for producing single-crystalline diamond of large size |
| CN111690981A (en) * | 2020-07-23 | 2020-09-22 | 太原理工大学 | Method for enlarging size and number of single crystal diamond seed crystals |
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