CN113249787A - Preparation method of static growth monocrystalline diamond - Google Patents
Preparation method of static growth monocrystalline diamond Download PDFInfo
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- CN113249787A CN113249787A CN202110322264.9A CN202110322264A CN113249787A CN 113249787 A CN113249787 A CN 113249787A CN 202110322264 A CN202110322264 A CN 202110322264A CN 113249787 A CN113249787 A CN 113249787A
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 43
- 239000010432 diamond Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000003068 static effect Effects 0.000 title claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 239000013589 supplement Substances 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to the technical field of diamond substrate preparation, in particular to a preparation method of a static growth monocrystalline diamond, which comprises the following steps of putting a seed crystal into a cavity, and introducing hydrogen into the cavity to fill the cavity to generate plasma; and introducing a carbon-containing gas source for diamond growth, wherein the carbon-containing gas source is discontinuously introduced in the diamond growth process to supplement, so that the cavity is ensured to maintain a certain pressure, the seed crystal grows, and the preparation is completed. The invention adopts hydrogen to fill the cavity integrally, namely the hydrogen is used as a catalyst for diamond reaction, the hydrogen is in a certain amount in the cavity, the methane is supplemented, and the utilization rate of the methane reaches 100 percent. The cost is saved, the synthesis quality is greatly improved, gas impurities can be mixed in the dynamic process in the past, the purity is not enough, and the introduction of the gas impurities can be completely avoided.
Description
Technical Field
The invention relates to the technical field of single crystal diamond preparation, in particular to a preparation method of statically grown single crystal diamond.
Background
Single crystal diamond has a number of excellent physicochemical properties and is widely used in a number of industrial fields. Microwave Plasma Chemical Vapor Deposition (MPCVD) is the most common method for preparing single crystal diamond at present and is the most mature method. The hydrogen and carbon-containing gas sources which are introduced into the reaction chamber are dissociated into atomic hydrogen and carbon-containing groups by using microwave energy, and the adsorption deposition of sp3 single crystal diamond phase carbon-containing groups on the single crystal diamond substrate can realize homoepitaxial growth of the single crystal diamond. CN201710960808.8 discloses a gradient single crystal diamond and a preparation method thereof, and a microwave plasma chemical vapor deposition device is used for continuously introducing high-purity air with gradient concentration in a hydrogen and methane mixed gas source to realize the alternate deposition of a nitrogen-free high-quality single crystal diamond layer and a nitrogen-containing diamond layer. However, in the prior art, the methane and the hydrogen are continuously introduced in a basically adopted mode, and are discharged while being introduced, and by adopting the continuous methane introduction mode, the plasma decomposition rate is only less than 1%, so that the utilization rate is less than 1%, other 99% of the plasma is wasted, and the methane and the hydrogen are discharged as waste gas, so that resources are wasted. Further optimization of the existing process is therefore required.
Disclosure of Invention
The invention aims to provide a preparation method of statically grown single crystal diamond.
The technical scheme of the invention is as follows:
a method of producing statically grown single crystal diamond, the method comprising the steps of:
s1: putting the seed crystal into a cavity, and introducing hydrogen into the cavity to fill the cavity to generate plasma;
s2: introducing a carbon-containing gas source for diamond growth, wherein the carbon-containing gas source is discontinuously introduced in the diamond growth process to supplement, so that the cavity is ensured to maintain a certain pressure, and the seed crystal grows;
and finishing the preparation of the static growth monocrystalline diamond.
Preferably, the method employs microwave, hot wire or direct current plasma chemical vapor deposition equipment.
Preferably, in step S2, the volume ratio of the hydrogen gas to the carbon-containing gas source is 1% to 20%.
Preferably, in step S2, the pressure of the chamber is maintained at 1kpa to 100kpa by intermittently feeding a carbon-containing gas source.
Preferably, in the step S2, the growth temperature of the diamond is 900-1000 ℃.
Preferably, in step S2, the carbon-containing gas source is intermittently introduced: supplementing carbon-containing gas of 1-1000sccm for 0.1-10min in stages to maintain a certain pressure in the cavity.
Further preferably, the carbon-containing gas source comprises methane, acetylene or acetone.
The invention has the beneficial effects that:
1. the invention adopts hydrogen to fill the cavity integrally, namely the hydrogen is used as a catalyst for diamond reaction, the hydrogen is in a certain amount in the cavity, the methane is supplemented, and the utilization rate of the methane reaches 100 percent.
2. The cost is saved, in the existing continuous introducing process, the introducing speed of the hydrogen is 100-. By adopting the technology of the invention, gas is intermittently introduced and supplemented, hydrogen is not increased, only a small amount of hydrogen is needed, and methane is supplemented to meet the production requirement. The volume of the hydrogen and carbon-containing gas source needed before is 2000-3000L, the carbon-containing gas source (methane, ethanol, carbon dioxide and the like) consumes 300-400L, the application only needs 2-3L of hydrogen, the carbon-containing gas source (methane, ethanol, carbon dioxide and the like) only needs 0.2L, the cost of the hydrogen is 1/1000, and the cost of the carbon-containing gas source (methane, ethanol, carbon dioxide and the like) is 1/100.
3. The synthesis quality is greatly improved, gas impurities can be mixed in the dynamic process in the past, the purity is insufficient, and the introduction of the gas impurities can be completely avoided.
Drawings
FIG. 1 is a schematic flow diagram of the gas feed in the process of the invention;
FIG. 2 is a schematic flow diagram of a conventional continuous gas feed;
FIG. 3 optical photograph of sample after growth by the method of the present invention: a, optically magnifying by 10 times, and optically magnifying by 100 times;
FIG. 4 shows the results of Raman spectroscopy measurements of samples grown by the method of the present invention;
FIG. 5 is a Raman diagram of diamond production with continuous carbon source gas introduction;
FIG. 6 is a surface topography and an enlarged view of a sample grown by a conventional method: a surface topography map, optical magnification 30 times, b optical magnification 30 times.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
A method of producing statically grown single crystal diamond, the method comprising the steps of:
s1: placing seed crystal into the cavity, and vacuumizing to 1 × 10-4Introducing hydrogen into the cavity to fill the cavity within Pa, inputting energy (including hot wires, microwaves, direct current and the like), generating discharge, and generating plasma;
s2: introducing a carbon-containing gas source for diamond growth, wherein the carbon-containing gas source is discontinuously introduced in the diamond growth process to supplement, so that the cavity is ensured to maintain a certain pressure, and the seed crystal grows;
and finishing the preparation of the static growth monocrystalline diamond.
Preferably, the method employs a microwave plasma chemical vapor deposition apparatus.
Preferably, in step S2, the volume ratio of the hydrogen gas to the carbon-containing gas source in the cavity is ensured to be 5%.
Preferably, in step S2, the pressure of the chamber is maintained at 15kpa by intermittently feeding a carbon-containing gas source.
Preferably, in the step S2, the growth temperature of the diamond is 950 ℃, and the growth is performed for 75 hours.
Preferably, in step S2, the carbon-containing gas source is intermittently introduced: and supplementing 500sccm of carbon-containing gas for 5min in a staged manner, so that the pressure in the cavity is 15 kpa.
Further preferably, the carbon-containing gas source is methane.
The results are shown in FIGS. 3-4, and FIG. 3 shows that the diamond surface prepared by the method of the present invention is relatively dense, the Raman spectrum test result of the growth sample is shown in FIG. 4, and the high intensity sharp is 1332.5cm-1The first-order Raman peak of the diamond shows that the prepared diamond sample has higher quality.
Comparative example 1
A method of preparing single crystal diamond, the method comprising the steps of:
1): placing seed crystal into the cavity, and vacuumizing to 1 × 10-4The method comprises the following steps of (1) introducing hydrogen into a cavity to fill the cavity to generate plasma within Pa, introducing 1-1000sccm hydrogen, maintaining balance of gas inlet and gas exhaust, keeping the gas pressure constant, keeping the pressure at 15kpa, and inputting energy (including hot wires, microwaves, direct current and the like) to generate discharge;
2) introducing carbon-containing gas source methane for diamond growth, ensuring that the volume ratio of hydrogen to the carbon-containing gas source is 5 percent in the cavity, growing seed crystals, controlling the temperature of the seed crystals to be 950 ℃, and controlling the growth time to be 75 hours;
the preparation of the single crystal diamond is completed.
Preferably, the method employs a microwave plasma chemical vapor deposition apparatus.
The pictures of the product are shown in figures 5-6. FIG. 5 is a Raman diagram of diamond produced by continuously introducing a carbon source gas, showing impurity peaks. FIG. 6 is a surface topography and an enlarged view of a sample grown by a conventional method, showing impurities with a relatively high surface roughness and pure black color.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (7)
1. A method of producing statically grown single crystal diamond, the method comprising the steps of: s1: putting the seed crystal into a cavity, and introducing hydrogen into the cavity to fill the cavity to generate plasma;
s2: introducing a carbon-containing gas source for diamond growth, wherein the carbon-containing gas source is discontinuously introduced in the diamond growth process to supplement, so that the cavity is ensured to maintain a certain pressure, and the seed crystal grows;
and finishing the preparation of the static growth monocrystalline diamond.
2. A method of gradient single crystal diamond according to claim 1, wherein: the method adopts microwave, hot wire or direct current plasma chemical vapor deposition equipment.
3. The method of claim 1, wherein: in the step S2, the volume ratio of the hydrogen gas to the carbon-containing gas source is 1% to 20%.
4. The method of claim 1, wherein: in the step S2, the pressure of the cavity is maintained at 1-100 kpa by intermittently introducing a carbon-containing gas source.
5. The method of claim 1, wherein: in the step S2, the growth temperature of diamond is 800-1300 ℃.
6. The method of claim 1, wherein: in the step S2, the carbon-containing gas source is intermittently introduced: supplementing carbon-containing gas of 1-1000sccm for 0.1-10min in stages to maintain a certain pressure in the cavity.
7. The method of claim 6, wherein: the carbon-containing gas source comprises methane, acetylene or acetone or others.
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| CN202110322264.9A CN113249787B (en) | 2021-03-25 | 2021-03-25 | Preparation method of statically grown single crystal diamond |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0826798A2 (en) * | 1996-08-27 | 1998-03-04 | Samsung Electronics Co., Ltd. | Heteroepitaxy cyclic texture growth method for diamond film |
| CN103710748A (en) * | 2013-12-12 | 2014-04-09 | 王宏兴 | Growth method of high-quality high-speed monocrystal diamond film |
| CN107740184A (en) * | 2017-09-30 | 2018-02-27 | 湖北碳六科技有限公司 | A kind of gradient single-crystal diamond and preparation method thereof |
| CN108588822A (en) * | 2018-04-08 | 2018-09-28 | 北京科技大学 | The method of uninterrupted dynamic in-situ synthetic single crystal and super nano-diamond composite |
| CN110820044A (en) * | 2019-12-02 | 2020-02-21 | 长沙新材料产业研究院有限公司 | High-quality diamond growth method and system |
-
2021
- 2021-03-25 CN CN202110322264.9A patent/CN113249787B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0826798A2 (en) * | 1996-08-27 | 1998-03-04 | Samsung Electronics Co., Ltd. | Heteroepitaxy cyclic texture growth method for diamond film |
| CN103710748A (en) * | 2013-12-12 | 2014-04-09 | 王宏兴 | Growth method of high-quality high-speed monocrystal diamond film |
| CN107740184A (en) * | 2017-09-30 | 2018-02-27 | 湖北碳六科技有限公司 | A kind of gradient single-crystal diamond and preparation method thereof |
| CN108588822A (en) * | 2018-04-08 | 2018-09-28 | 北京科技大学 | The method of uninterrupted dynamic in-situ synthetic single crystal and super nano-diamond composite |
| CN110820044A (en) * | 2019-12-02 | 2020-02-21 | 长沙新材料产业研究院有限公司 | High-quality diamond growth method and system |
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