CN111778556A - Method for improving epitaxial growth of monocrystalline diamond seed crystal by utilizing defects and impurities - Google Patents
Method for improving epitaxial growth of monocrystalline diamond seed crystal by utilizing defects and impurities Download PDFInfo
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- CN111778556A CN111778556A CN202010662250.7A CN202010662250A CN111778556A CN 111778556 A CN111778556 A CN 111778556A CN 202010662250 A CN202010662250 A CN 202010662250A CN 111778556 A CN111778556 A CN 111778556A
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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
- C30B25/18—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
Abstract
The invention discloses a method for improving the epitaxial growth of a single crystal diamond seed crystal by utilizing defects and impurities, which is suitable for the epitaxial growth of the single crystal diamond by a microwave plasma Chemical Vapor Deposition (CVD) method and comprises the following steps: step one, determining the impurity and defect concentration of the surface of the single crystal diamond. And step two, impurity and defect treatment is carried out. And step three, carrying out surface hydrogenation treatment. And fourthly, performing high-speed epitaxial growth. The method can improve the growth rate of the epitaxial diamond and improve the product quality by utilizing the defects of the quality of the single crystal diamond with high internal defects and impurity content.
Description
Technical Field
The invention relates to a method for improving epitaxial growth of monocrystalline diamond seed crystals by utilizing defects and impurities, and relates to preparation of monocrystalline diamond.
Background
The preparation technology of the single crystal diamond is gradually mature, generally, the microwave method epitaxial growth of the single crystal diamond needs a seed crystal with a clean and defect-free surface, but the growth cost is improved, and a plurality of single crystal diamonds with poor quality and low quality need to be abandoned, so that great waste is caused. Particularly, the quality and the performance uniformity of the diamond obtained by the CVD method are greatly improved. However, the improvement of the yield in the preparation process always has a great problem, and the samples with insufficient quality are mainly caused by the problems of growth defects and impurities, so that the waste of the seed crystals is caused.
The technical scheme provided by the invention utilizes the surface defects of the sample with insufficient quality to obtain better growth effect. And no report to the literature and patents is found at present.
Disclosure of Invention
The invention solves the problems: the defects of the prior art are overcome, the defect and the impurity are utilized to improve the epitaxial growth of the single crystal diamond seed crystal, the internal defect and the defect of high quality of the single crystal diamond are utilized, the growth rate of the epitaxial diamond is improved, and the product quality is improved.
The technical scheme of the invention is as follows:
a method for improving epitaxial growth of single crystal diamond seeds using defects and impurities, as shown in fig. 1, is achieved by: carrying out acid cleaning treatment on impurities and defects contained on a main surface (001) of a single crystal diamond sheet through boiled mixed solution of concentrated sulfuric acid and concentrated nitric acid, then carrying out etching treatment, carrying out deposition growth on the diamond subjected to the acid cleaning and etching treatment, and finally obtaining micro openings on the main surface (001) surface, thereby finishing the epitaxial growth of the single crystal diamond seed crystal.
The sample adopted by the invention is part of low-quality monocrystalline diamond obtained by a high-temperature high-pressure method, and the low-quality monocrystalline diamond is classified according to the surface defect area. Specifically, the area of the micro-openings on the main surface (001) plane accounts for about 5%, 15% and 25% of the total area of the main surface (001) plane. For the sample with more area occupied by the micro-open pores, when the open pore area exceeds 35%, the randomness of the growth direction is too high, polycrystalline diamond crystal nuclei are easily formed, and the finally grown sample is also polycrystalline diamond, so the invention does not cover the sample with the open pore area exceeding 35%.
Cleaning a sample by using concentrated sulfuric acid and concentrated nitric acid in an industry standard process, wherein the molar ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:1, and the boiling time is not less than 30 min.
The area of the microapertures on the major (001) plane accounts for about 5% of the total area of the major (001) plane.
The area of the microapertures on the major (001) plane accounts for about 15% of the total area of the major (001) plane.
The area of the microapertures on the major (001) plane accounts for about 25% of the total major (001) plane area.
The surface areas correspond to the surface defect classification of the high-temperature high-pressure low-quality sample.
The etching treatment adopts a microwave hydrogen plasma etching process, the etching temperature range is 770-800 ℃, the hydrogen flow range is 450-550 sccm, the growth pressure range is 90-110 torr, and the microwave power range is 1800-2600W. The technological process can make hydrogen plasma with high energy fully react with the surface of the diamond, so that high-energy carbon atoms at the defect positions form methane, and etching is realized.
And etching by adopting an industry standard process with microwave hydrogen plasma diamond, wherein the etching time in the microwave hydrogen plasma etching process is not less than 60 minutes.
And carrying out deposition growth on the diamond subjected to acid cleaning and etching treatment by adopting a plasma of a hydrogen and methane mixed gas to carry out vapor deposition growth.
The ratio of the mixed gas of hydrogen and methane is 20:1 to 10:1, the flow rate of hydrogen is 400 to 600sccm, the growth pressure is 180to 220torr, and the microwave power is 2500 to 4000W. According to the area proportion of the micro-openings on the surface, the hydrogen flow, the growth pressure, the microwave power and the methane content are sequentially improved along with the increase of the area proportion of the micro-openings occupying the main surface. The design is mainly because the contact area with the plasma is low when the area of the micro-opening is low, and the needed hydrogen flow, growth pressure, microwave power and methane content are also low; as the area of the micro-openings increases, the hydrogen flow, the growth pressure, the microwave power and the methane content are correspondingly increased. The process has the advantages that the exposed surface of the micro-open pore is fully utilized, the surface energy of carbon atoms on the exposed surface is higher, and the carbon atoms are more easily combined with carbon in plasma to realize higher-speed growth.
Compared with the prior art, the invention has the advantages that:
(1) the invention utilizes the defects and impurities on the surface of the single crystal diamond to form a growth surface with high specific surface area and containing nano pores, the growth rate of more than 10 mu m/h can be realized after surface hydrogenation treatment, and the growth mode of the diamond sheet after the treatment by the technology is a layered mode, which is a typical single crystal diamond growth mode.
(2) Generally, the microwave method for epitaxial growth of the single crystal diamond needs a seed crystal with a clean and defect-free surface, but the growth cost is increased, and some single crystal diamonds with poor quality and lower quality need to be abandoned. Resulting in greater waste. The acid washing and hydrogenation treatment modes adopted by the invention can fully utilize the impurities and defects of the single crystal diamond, can realize high-speed single crystal epitaxial growth, and the obtained sample has higher quality.
(3) The method is suitable for the epitaxial growth of the single crystal diamond containing defects and impurities as the seed crystal, in particular to the epitaxial growth of low-quality single crystal diamond with high content of the defects and the impurities. The invention can fully utilize the internal defects of the seed crystal and is greatly helpful for the development of the artificial diamond industry.
(4) The present invention can achieve the above advantages because amorphous carbon and high-energy carbon dots on the surface of low-quality diamond are cleaned by a specific pickling and etching process to form a sample with a porous surface. The porous surface has more contact surface area with plasma, and more efficient deposition is formed
Drawings
FIG. 1 shows a hollow shape of the surface of a (001) plane diamond according to the present invention;
FIG. 2 shows that the surface of the (001) diamond in the prior art is in a hollow shape.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The method of the invention is realized as follows: the method is suitable for epitaxial growth of the monocrystalline diamond by a microwave plasma Chemical Vapor Deposition (CVD) method and comprises the following steps: step one, determining the impurity and defect concentration of the surface of the single crystal diamond. And step two, impurity and defect treatment is carried out. And step three, carrying out surface hydrogenation treatment. And fourthly, performing high-speed epitaxial growth.
The method specifically comprises the following steps: the method comprises the steps of carrying out acid cleaning on a diamond sheet with certain impurity and defect proportion through a boiled mixed solution of concentrated sulfuric acid and concentrated nitric acid, sequentially cleaning the acid-cleaned diamond sheet by adopting acetone-alcohol-water, placing cleaned seed crystals in a seed crystal holder, placing the seed crystal holder in a microwave plasma vapor deposition cavity, carrying out etching treatment by adopting hydrogen plasma, and carrying out deposition growth by adopting hydrogen and methane plasma after the treatment. The diamond sheet treated by the process can realize the growth rate of more than 10 mu m/h, and can better realize the growth rate of more than 30 mu m/h depending on different equipment.
Example 1
And after the acid washing step, the diamond sheet with the micro-holes on the (001) surface accounting for about 5% of the total area of the main surface is etched at the temperature of 800 ℃, the hydrogen flow is 280-300 sccm, the microwave power is 1800W, and the hydrogen plasma etching time is not less than 10 minutes.
And then, carrying out vapor deposition growth on the processed diamond sheet, wherein the ratio of hydrogen to methane is 20:1, the hydrogen flow is 400sccm, the growth pressure is 160torr, the power is 2500W, and the growth temperature is 1000-1100 ℃. The growth rate can reach 15 mu m/h.
Example 2
After the acid washing step, the surface of the sample was as shown in fig. 1, and the micro-openings on the (001) plane as seen in fig. 1 occupied about 15% of the total area of the main surface, and the sample was a single crystal diamond wafer, and the surface had many openings due to the reason during the preparation process, and was a low quality sample. Through the process disclosed by the invention, the porous surface can be grown into a relatively flat single crystal surface. The growth process is that the surface is etched at 800 ℃, the hydrogen flow is 300-330 sccm, the microwave power is 2000W, and the hydrogen plasma etching time is not less than 15 minutes.
And then, carrying out vapor deposition growth on the processed diamond sheet, wherein the ratio of hydrogen to methane is 15:1, the hydrogen flow is 400sccm, the growth pressure is 160torr, the power is 2500W, and the growth temperature is 1000-1100 ℃. The growth rate can reach more than 20 mu m/h.
Example 3
And after the acid washing step, the diamond sheet with the micro-holes on the (001) surface accounting for about 15% of the total area of the main surface is etched at the temperature of 800 ℃, the hydrogen flow is 330-350 sccm, the microwave power is 2200W, and the hydrogen plasma etching time is not less than 20 minutes.
And then, carrying out vapor deposition growth on the processed diamond wafer, wherein the ratio of hydrogen to methane is 15:1, the hydrogen flow is 400sccm, the growth pressure is 180torr, the power is 2500W, and the growth temperature is 1000-1100 ℃. The growth rate can reach more than 25 mu m/h.
Example 4
And after the acid washing step, the diamond sheet with the micro-holes on the (001) surface accounting for about 15% of the total area of the main surface is etched at the temperature of 800 ℃, the hydrogen flow is 350-380 sccm, the microwave power is 2000W, and the hydrogen plasma etching time is not less than 30 minutes.
And then, carrying out vapor deposition growth on the processed diamond wafer, wherein the ratio of hydrogen to methane is 15:1, the hydrogen flow is 400sccm, the growth pressure is 180torr, the power is 2500W, and the growth temperature is 1000-1100 ℃. The growth rate can reach more than 25 mu m/h.
Example 5
And after the acid washing step, the diamond sheet with the micro-holes on the (001) surface accounting for about 25% of the total area of the main surface is etched at the temperature of 800 ℃, the hydrogen flow is 380-400 sccm, the microwave power is 2400W, and the hydrogen plasma etching time is not less than 20 minutes.
And then, carrying out vapor deposition growth on the processed diamond wafer, wherein the ratio of hydrogen to methane is 15:1, the hydrogen flow is 500sccm, the growth pressure is 200torr, the power is 3000W, and the growth temperature is between 1000 and 1100 ℃. The growth rate can reach more than 30 mu m/h.
When the micro-openings occupy about 25% of the total area of the main surface, the actual contact area of the surface with plasma is more than 2 times that of the (001) surface, so that the surface has a higher growth rate.
Example 6
And after the acid washing step, the diamond sheet with the micro-holes on the (001) surface accounting for about 25% of the total area of the main surface is etched at the temperature of 800 ℃, the hydrogen flow is 380-400 sccm, the microwave power is 4000W, and the hydrogen plasma etching time is not less than 60 minutes.
And then, carrying out vapor deposition growth on the processed diamond wafer, wherein the ratio of hydrogen to methane is 7:1, the hydrogen flow is 700sccm, the growth pressure is 220torr, the power is 4000W, and the growth temperature is between 1000 and 1100 ℃. The growth rate can reach more than 40 mu m/h.
Comparative example 1
The traditional single crystal diamond seed crystal has the hydrogen flow of 300sccm, the etching temperature of 800 ℃ and the power of 2400W, but the time is not less than 30 minutes.
And then, carrying out vapor deposition growth on the processed diamond wafer, wherein the ratio of hydrogen to methane is 15:1, the hydrogen flow is 500sccm, the growth pressure is 200torr, the power is 3000W, and the growth temperature is between 1000 and 1100 ℃. The growth rate is about 10 mu m/h.
Comparative example 2
The traditional monocrystal diamond seed crystal has hydrogen flow of 400sccm, etching temperature of 800 deg.c and power of 3500W, but the time is not less than 30 min.
And then, carrying out vapor deposition growth on the processed diamond wafer, wherein the ratio of hydrogen to methane is 7:1, the hydrogen flow is 700sccm, the growth pressure is 220torr, the power is 4000W, and the growth temperature is between 1000 and 1100 ℃. The growth rate is about 20 mu m/h.
The surface of the single crystal diamond seed mentioned in the above comparative example is a smooth surface without micro-openings, as shown in fig. 2.
The difference between the surface of the seed crystal used in the present invention and the conventional seed crystal is illustrated by comparing fig. 1 and fig. 2. To better illustrate the advantages of the present invention, the main data of the above examples and comparative examples are compared, and the details are shown in Table 1.
Table 1: comparison of the data in the examples with those in the comparative examples
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | |
| Area of micropores | 5％ | 15％ | 15％ | 15％ | 25％ | 25％ | 0 | 0 |
| H2:CH4 | 20:1 | 15:1 | 15:1 | 15:1 | 15:1 | 7:1 | 15:1 | 7:1 |
| Pressure of | 160torr | 160torr | 180torr | 180torr | 200torr | 220torr | 200torr | 220torr |
| Power of | 2500W | 2500W | 2500W | 2500W | 3000W | 4000W | 3000W | 4000W |
| Rate of speed | 15μm/h | 20μm/h | 25μm/h | 25μm/h | 30μm/h | 40μm/h | 10μm/h | 20μm/h |
As can be seen from the above table, the present invention can obtain higher growth rate by adjusting parameters such as hydrogen-methane ratio, reaction pressure and power to grow the seed crystals with different micropore areas. Specifically, in the presence of micro-openings, higher methane content, reaction pressure and power are required to achieve higher rates as the area of the openings increases. Compared with the prior art, the method fully utilizes the low-quality monocrystalline diamond seed crystal prepared by the high-temperature and high-pressure method, improves the growth rate, and is an improvement and supplement for preparing diamond by the microwave method.
The above examples are provided only for the purpose of describing the present invention, and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims. Various equivalent substitutions and modifications can be made without departing from the spirit and principles of the invention, and are intended to be within the scope of the invention.
Claims (9)
1. A method for improving the epitaxial growth of single crystal diamond seeds using defects and impurities, characterized by: carrying out acid cleaning treatment on impurities and defects contained on a main surface (001) of a single crystal diamond sheet and impurities and defects contained on the main surface (001) of the single crystal diamond sheet through boiled mixed solution of concentrated sulfuric acid and concentrated nitric acid, then carrying out etching treatment, carrying out deposition growth on the diamond subjected to acid cleaning and etching treatment, and finally obtaining micro openings on the main surface (001) surface, thereby completing the epitaxial growth of the improved single crystal diamond seed crystal.
2. The method of claim 1, wherein: the molar ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1:1, and the boiling time is not less than 30 min.
3. The method of claim 1, wherein: the area of the microapertures on the major (001) plane accounts for about 5% of the total area of the major (001) plane.
4. The method of claim 1, wherein: the area of the microapertures on the major (001) plane accounts for about 15% of the total area of the major (001) plane.
5. The method of claim 1, wherein: the area of the microapertures on the major (001) plane accounts for about 25% of the total major (001) plane area.
6. The method of claim 1, wherein: the etching treatment adopts a microwave hydrogen plasma etching process, the etching temperature range is 770-800 ℃, the hydrogen flow range is 450-550 sccm, the growth pressure range is 90-110 torr, and the microwave power range is 1800-2600W.
7. The method of claim 6, wherein: in the microwave hydrogen plasma etching process, the etching time is not less than 20 minutes.
8. The method of claim 7, wherein: and carrying out deposition growth on the diamond subjected to acid cleaning and etching treatment by adopting a plasma of a hydrogen and methane mixed gas to carry out vapor deposition growth.
9. The method of claim 8, wherein: the ratio of the mixed gas of hydrogen and methane is 20:1 to 10:1, the flow rate of hydrogen is 400 to 600sccm, the growth pressure is 180to 220torr, and the microwave power is 2500 to 4000W.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113145553A (en) * | 2021-02-07 | 2021-07-23 | 福建新峰二维材料科技有限公司 | Classifying method for cast monocrystalline silicon wafers |
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| CN101037793A (en) * | 2007-02-07 | 2007-09-19 | 吉林大学 | Device and method for high-speed rapid growth of diamond single-crystal |
| WO2018100023A1 (en) * | 2016-12-01 | 2018-06-07 | Element Six Technologies Limited | Single crystal synthetic diamond material via chemical vapour deposition |
| CN110281142A (en) * | 2019-06-20 | 2019-09-27 | 山东大学 | Diamond seed preparation method, diamond seed and monocrystalline |
| CN110938864A (en) * | 2019-11-08 | 2020-03-31 | 武汉大学 | Method for efficiently regulating and controlling dislocation density of CVD single crystal diamond local area |
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- 2020-07-10 CN CN202010662250.7A patent/CN111778556A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037793A (en) * | 2007-02-07 | 2007-09-19 | 吉林大学 | Device and method for high-speed rapid growth of diamond single-crystal |
| WO2018100023A1 (en) * | 2016-12-01 | 2018-06-07 | Element Six Technologies Limited | Single crystal synthetic diamond material via chemical vapour deposition |
| CN110281142A (en) * | 2019-06-20 | 2019-09-27 | 山东大学 | Diamond seed preparation method, diamond seed and monocrystalline |
| CN110938864A (en) * | 2019-11-08 | 2020-03-31 | 武汉大学 | Method for efficiently regulating and controlling dislocation density of CVD single crystal diamond local area |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113145553A (en) * | 2021-02-07 | 2021-07-23 | 福建新峰二维材料科技有限公司 | Classifying method for cast monocrystalline silicon wafers |
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