CN109537051A - A kind of method of high-speed growth single-crystal diamond - Google Patents
A kind of method of high-speed growth single-crystal diamond Download PDFInfo
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- CN109537051A CN109537051A CN201811426915.3A CN201811426915A CN109537051A CN 109537051 A CN109537051 A CN 109537051A CN 201811426915 A CN201811426915 A CN 201811426915A CN 109537051 A CN109537051 A CN 109537051A
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- diamond
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- speed
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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
- C30B25/02—Epitaxial-layer 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 present invention relates to the technical fields of diamond growth, the speed of production of diamond can be improved within the unit time when producing Gem Grade single-crystal diamond more particularly to a kind of method of high-speed growth single-crystal diamond, shorten the growth cycle of diamond, improves production efficiency and economic benefit；The following steps are included: (1) selects substrate；(2) substrate tentatively cleans；(3) ultrasonic cleaning；(4) it is dried；(5) water route connects；(6) growth conditions is adjusted；(7) substrate pre-treatment；(8) gas mixing；(9) diamond growth；(10) it post-processes；(11) cooling.
Description
Technical field
The present invention relates to the technical fields of diamond growth, more particularly to a kind of side of high-speed growth single-crystal diamond
Method.
Background technique
It is well known that chemical vapor deposition (CVD) refers to the gas phase reaction under high temperature, for example, metal halide, You Jijin
The thermal decomposition of category, hydrocarbon etc., hydrogen reduction or the mixed gas for making it occur at high temperature chemical reaction with precipitating metal,
The method of the inorganic material such as oxide, carbide.This technology is initially the means as coating and develops, but is not only applied
In the coating of coctostable substance, and it is applied to purification, powder synthesis, the semiconductive thin film etc. of high purity metal, is one and has much
The technical field of feature is technically characterized in that high-melting-point substances can synthesize at low temperature；The form of substance is precipitated in list
Crystalline substance, polycrystalline, whisker, powder, film etc. are a variety of, can not only carry out coating on substrate, and can in powder surface coating,
High-melting-point substances such as single-crystal diamond can be especially synthesized at low temperature, be made that huge contribution in energy conservation invention.
Chemical vapor deposition (CVD) is a kind of important method for preparing monocrystalline diamond, uses CVD growth single crystal diamond
During stone, single-crystal diamond substrate is placed directly in chemical vapor depsotition equipment and is grown, usual CVD extension is raw
During long diamond, the process gas used is H2And CH4, growth rate only have it is several to more than ten microns per hour, growth speed
Rate is slow.And the single-crystal diamond of Gem Grade is produced, growth thickness usually requires to reach 3mm or more.This allows for growth cycle mistake
It is long, reduce production efficiency and economic benefit.
Therefore, the speed of production that diamond how is improved within the unit time, shortens the growth cycle of diamond, improves life
It produces efficiency and economic benefit is production gem grade diamond urgent problem.
Summary of the invention
In order to solve the above technical problems, the present invention provides one kind when producing Gem Grade single-crystal diamond, it can be in unit
The speed of production that diamond is improved in time, shortens the growth cycle of diamond, improves the high speed of production efficiency and economic benefit
The method of rate growth single-crystal diamond.
A kind of method of high-speed growth single-crystal diamond of the invention, comprising the following steps:
(1) it selects substrate: selecting the ultra thin single crystalline diamond of quality height, few surface defects as substrate；
(2) substrate tentatively cleans: diamond substrate being put into the cleaning container with 45 DEG C of acetone cleaning solution, is impregnated
10min；
(3) ultrasonic cleaning: will be put into ultrasonic cleaner immersed with the cleaning container of diamond substrate, to by preliminary clear
The diamond substrate washed carries out ultrasonic cleaning；
(4) it is dried: by the diamond substrate Jing Guo ultrasonic cleaning in drying in oven；
(5) water route connects: connecting inflow and outflow pipeline in growth chamber, and is passed through cooling water；
(6) it adjusts growth conditions: the diamond substrate after drying being put into growth chamber, and will be vacuumized in growth chamber,
The temperature for adjusting diamond substrate is 850 DEG C, pressure 35kPa；
(7) H that flow is 500sccm substrate pre-treatment: is passed through into growth chamber2The quarter of 35min is carried out to diamond substrate
Erosion；
(8) H gas mixing: is passed through into gas medium2、CH4、CO2And Ar, and be mixed uniformly, reaction gas is obtained,
Middle CH4Account for the 6-20% of reacting gas concentration；
(9) diamond growth: the temperature for adjusting diamond substrate is 1150 DEG C, and reaction gas is passed through into growth chamber,
Diamond substrate surface starts to grow；
(10) post-process: after completing growth, stopping is passed through reaction gas, and continue into reaction chamber to be passed through flow be
The H of 500sccm2The etching of 35min is carried out to the diamond after the completion of growth；
(11) cooling: to stop input H after the completion of post-processing2, and make post-processing after diamond be cooled to room temperature after, close power supply
And cooling water, and vent valve is opened, restore growth chamber room pressure to normal pressure, then the diamond grown is taken out.
A kind of method of high-speed growth single-crystal diamond of the invention, the temperature of the ultrasonic cleaning in the step (3)
Degree is 45 DEG C.
The temperature of a kind of method of high-speed growth single-crystal diamond of the invention, the drying in the step (4) is 65-
70℃。
A kind of method of high-speed growth single-crystal diamond of the invention, it is preferred that the CH in the step (8)4It accounts for anti-
Answer the 15% of gas concentration.
A kind of method of high-speed growth single-crystal diamond of the invention, the H in reaction gas in the step (8)2
Volume is CH42 times of volume.
A kind of method of high-speed growth single-crystal diamond of the invention, the CO in reaction gas in the step (8)2
It is respectively 7% and 20% with Ar concentration.
Compared with prior art the invention has the benefit that a kind of side of high-speed growth single-crystal diamond of the invention
Method can be passed through CO when producing Gem Grade single-crystal diamond in reaction gas2And Ar, it improves in plasma
The concentration of carbon group, and the temperature of plasmasphere is improved, and then promote the raising of growth efficiency, so as in unit
The interior speed of production for improving diamond, shortens the growth cycle of diamond, improves production efficiency and economic benefit.
Specific embodiment
With reference to embodiment, the embodiment of the present invention is furthur described in detail.Following embodiment is used for
Illustrate the present invention, but is not intended to limit the scope of the invention.
Embodiment 1
It selects the ultra thin single crystalline diamond of quality height, few surface defects as substrate, diamond substrate is put into 45 DEG C
In the cleaning container of acetone cleaning solution, 10min is impregnated, ultrasonic cleaner will be put into immersed with the cleaning container of diamond substrate
It is interior, ultrasonic cleaning is carried out to the diamond substrate by tentatively cleaning at 45 DEG C, by the diamond Jing Guo ultrasonic cleaning
Drying in oven of the substrate at 65-70 DEG C, connects inflow and outflow pipeline, and be passed through cooling water in growth chamber, will dry
Diamond substrate afterwards is put into growth chamber, and will be vacuumized in growth chamber, and the temperature for adjusting diamond substrate is 850
DEG C, pressure 35kPa is passed through the H that flow is 500sccm into growth chamber2The etching of 35min is carried out to diamond substrate,
After the completion of etching, H is passed through into gas medium2、CH4、CO2And Ar, and be mixed uniformly, reaction gas is obtained, wherein CH4
Account for the 15% of reacting gas concentration, and H2Volume is CH42 times of volume, CO2It is respectively 7% and 20% with Ar concentration, adjusts Buddha's warrior attendant
Stone substrate temperature is 1150 DEG C, and reaction gas is passed through into growth chamber, starts to grow on diamond substrate surface, when complete
After growth, stopping is passed through reaction gas, and continues to be passed through the H that flow is 500sccm into reaction chamber2After the completion of growth
Diamond carry out 35min etching, post-processing after the completion of stop input H2, and it is cooled to room temperature the diamond after post-processing
Afterwards, power supply and cooling water are closed, and opens vent valve, restores growth chamber room pressure to normal pressure, then the Buddha's warrior attendant that will be grown
Stone takes out.
Embodiment 2
It selects the ultra thin single crystalline diamond of quality height, few surface defects as substrate, diamond substrate is put into 45 DEG C
In the cleaning container of acetone cleaning solution, 10min is impregnated, ultrasonic cleaner will be put into immersed with the cleaning container of diamond substrate
It is interior, ultrasonic cleaning is carried out to the diamond substrate by tentatively cleaning at 45 DEG C, by the diamond Jing Guo ultrasonic cleaning
Drying in oven of the substrate at 65-70 DEG C, connects inflow and outflow pipeline, and be passed through cooling water in growth chamber, will dry
Diamond substrate afterwards is put into growth chamber, and will be vacuumized in growth chamber, and the temperature for adjusting diamond substrate is 850
DEG C, pressure 35kPa is passed through the H that flow is 500sccm into growth chamber2The etching of 35min is carried out to diamond substrate,
After the completion of etching, H is passed through into gas medium2、CH4、CO2And Ar, and be mixed uniformly, reaction gas is obtained, wherein CH4
Account for the 6% of reacting gas concentration, and H2Volume is CH42 times of volume, CO2It is respectively 7% and 20% with Ar concentration, adjusts Buddha's warrior attendant
Stone substrate temperature is 1150 DEG C, and reaction gas is passed through into growth chamber, starts to grow on diamond substrate surface, when complete
After growth, stopping is passed through reaction gas, and continues to be passed through the H that flow is 500sccm into reaction chamber2After the completion of growth
Diamond carry out 35min etching, post-processing after the completion of stop input H2, and it is cooled to room temperature the diamond after post-processing
Afterwards, power supply and cooling water are closed, and opens vent valve, restores growth chamber room pressure to normal pressure, then the Buddha's warrior attendant that will be grown
Stone takes out.
Embodiment 3
It selects the ultra thin single crystalline diamond of quality height, few surface defects as substrate, diamond substrate is put into 45 DEG C
In the cleaning container of acetone cleaning solution, 10min is impregnated, ultrasonic cleaner will be put into immersed with the cleaning container of diamond substrate
It is interior, ultrasonic cleaning is carried out to the diamond substrate by tentatively cleaning at 45 DEG C, by the diamond Jing Guo ultrasonic cleaning
Drying in oven of the substrate at 65-70 DEG C, connects inflow and outflow pipeline, and be passed through cooling water in growth chamber, will dry
Diamond substrate afterwards is put into growth chamber, and will be vacuumized in growth chamber, and the temperature for adjusting diamond substrate is 850
DEG C, pressure 35kPa is passed through the H that flow is 500sccm into growth chamber2The etching of 35min is carried out to diamond substrate,
After the completion of etching, H is passed through into gas medium2、CH4、CO2And Ar, and be mixed uniformly, reaction gas is obtained, wherein CH4
Account for the 20% of reacting gas concentration, and H2Volume is CH42 times of volume, CO2It is respectively 7% and 20% with Ar concentration, adjusts Buddha's warrior attendant
Stone substrate temperature is 1150 DEG C, and reaction gas is passed through into growth chamber, starts to grow on diamond substrate surface, when complete
After growth, stopping is passed through reaction gas, and continues to be passed through the H that flow is 500sccm into reaction chamber2After the completion of growth
Diamond carry out 35min etching, post-processing after the completion of stop input H2, and it is cooled to room temperature the diamond after post-processing
Afterwards, power supply and cooling water are closed, and opens vent valve, restores growth chamber room pressure to normal pressure, then the Buddha's warrior attendant that will be grown
Stone takes out.
What embodiment 1 to embodiment 3 was grown is respectively designated as sample 1, sample 2 and sample 3, and to sample 1 to 3 in life
Indices in growth process and after growth are detected, and result is as shown in the table:
| The speed of growth | Growth cycle | Growth quality | Diamond purity | |
| Sample 1 | 205μm/h | 52h | Well | 99.5% |
| Sample 2 | 189μm/h | 56h | Well | 99.5% |
| Sample 3 | 193μm/h | 55h | Well | 99.5% |
A kind of method of high-speed growth single-crystal diamond of the invention, when producing Gem Grade single-crystal diamond, Ke Yi
CO is passed through in reaction gas2And Ar, the concentration of the carbon group in plasma is improved, and improve the temperature of plasmasphere,
And then the raising of growth efficiency is promoted, so as to improve the speed of production of diamond within the unit time, shorten diamond
Growth cycle, improve production efficiency and economic benefit.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications, these improvements and modifications can also be made
Also it should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of method of high-speed growth single-crystal diamond, which comprises the following steps:
(1) it selects substrate: selecting the ultra thin single crystalline diamond of quality height, few surface defects as substrate；
(2) substrate tentatively cleans: diamond substrate being put into the cleaning container with 45 DEG C of acetone cleaning solution, is impregnated
10min；
(3) ultrasonic cleaning: will be put into ultrasonic cleaner immersed with the cleaning container of diamond substrate, to by preliminary clear
The diamond substrate washed carries out ultrasonic cleaning；
(4) it is dried: by the diamond substrate Jing Guo ultrasonic cleaning in drying in oven；
(5) water route connects: connecting inflow and outflow pipeline in growth chamber, and is passed through cooling water；
(6) it adjusts growth conditions: the diamond substrate after drying being put into growth chamber, and will be vacuumized in growth chamber,
The temperature for adjusting diamond substrate is 850 DEG C, pressure 35kPa；
(7) H that flow is 500sccm substrate pre-treatment: is passed through into growth chamber2The quarter of 35min is carried out to diamond substrate
Erosion；
(8) H gas mixing: is passed through into gas medium2、CH4、CO2And Ar, and be mixed uniformly, reaction gas is obtained,
Middle CH4Account for the 6-20% of reacting gas concentration；
(9) diamond growth: the temperature for adjusting diamond substrate is 1150 DEG C, and reaction gas is passed through into growth chamber,
Diamond substrate surface starts to grow；
(10) post-process: after completing growth, stopping is passed through reaction gas, and continue into reaction chamber to be passed through flow be
The H of 500sccm2The etching of 35min is carried out to the diamond after the completion of growth；
(11) cooling: to stop input H after the completion of post-processing2, and make post-processing after diamond be cooled to room temperature after, close power supply
And cooling water, and vent valve is opened, restore growth chamber room pressure to normal pressure, then the diamond grown is taken out.
2. a kind of method of high-speed growth single-crystal diamond as described in claim 1, which is characterized in that the step (3)
In ultrasonic cleaning temperature be 45 DEG C.
3. a kind of method of high-speed growth single-crystal diamond as described in claim 1, which is characterized in that the step (4)
In drying temperature be 65-70 DEG C.
4. a kind of method of high-speed growth single-crystal diamond as described in claim 1, which is characterized in that it is preferred, it is described
CH in step (8)4Account for the 15% of reacting gas concentration.
5. a kind of method of high-speed growth single-crystal diamond as described in claim 1, which is characterized in that the step (8)
In reaction gas in H2Volume is CH42 times of volume.
6. a kind of method of high-speed growth single-crystal diamond as described in claim 1, which is characterized in that the step (8)
In reaction gas in CO2It is respectively 7% and 20% with Ar concentration.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811426915.3A CN109537051A (en) | 2018-11-27 | 2018-11-27 | A kind of method of high-speed growth single-crystal diamond |
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| CN201811426915.3A CN109537051A (en) | 2018-11-27 | 2018-11-27 | A kind of method of high-speed growth single-crystal diamond |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63117996A (en) * | 1986-11-05 | 1988-05-21 | Kobe Steel Ltd | Device for synthesizing diamond in vapor phase |
| JPH0248494A (en) * | 1988-08-05 | 1990-02-19 | Semiconductor Energy Lab Co Ltd | Method for preparing carbon |
| TW208047B (en) * | 1992-01-28 | 1993-06-21 | Nat Science Committee | A method of synthesizing diamond by gas phase reaction |
| JPH069294A (en) * | 1991-03-27 | 1994-01-18 | Kafu Chin | Method for synthesis of diamond by means of cvd process |
| CN1132267A (en) * | 1995-12-12 | 1996-10-02 | 吉林大学 | Method of growing diamond film on large area of monocrystalline silicon |
| CN101024893A (en) * | 2007-01-11 | 2007-08-29 | 武汉理工大学 | Method for micro-wave plasma low-temperature synthesizing film |
| CN101696515A (en) * | 2009-11-10 | 2010-04-21 | 宋建华 | Method for homogeneous endotaxy repair and homogeneous epitaxial growth of diamond single crystal |
| CN104988578A (en) * | 2015-07-24 | 2015-10-21 | 哈尔滨工业大学 | Method for optimizing monocrystal diamond homoepitaxial growth by utilizing plasma baffle |
| CN105779967A (en) * | 2016-04-22 | 2016-07-20 | 武汉理工大学 | Method for preparing diamond film through MPCVD medium-frequency inducing auxiliary heating |
| CN107059120A (en) * | 2017-05-09 | 2017-08-18 | 中国电子科技集团公司第四十六研究所 | A kind of method that utilization square groove inserting collet suppresses polycrystalline diamond growth |
-
2018
- 2018-11-27 CN CN201811426915.3A patent/CN109537051A/en active Pending
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|---|---|---|---|---|
| JPS63117996A (en) * | 1986-11-05 | 1988-05-21 | Kobe Steel Ltd | Device for synthesizing diamond in vapor phase |
| JPH0248494A (en) * | 1988-08-05 | 1990-02-19 | Semiconductor Energy Lab Co Ltd | Method for preparing carbon |
| JPH069294A (en) * | 1991-03-27 | 1994-01-18 | Kafu Chin | Method for synthesis of diamond by means of cvd process |
| TW208047B (en) * | 1992-01-28 | 1993-06-21 | Nat Science Committee | A method of synthesizing diamond by gas phase reaction |
| CN1132267A (en) * | 1995-12-12 | 1996-10-02 | 吉林大学 | Method of growing diamond film on large area of monocrystalline silicon |
| CN101024893A (en) * | 2007-01-11 | 2007-08-29 | 武汉理工大学 | Method for micro-wave plasma low-temperature synthesizing film |
| CN101696515A (en) * | 2009-11-10 | 2010-04-21 | 宋建华 | Method for homogeneous endotaxy repair and homogeneous epitaxial growth of diamond single crystal |
| CN104988578A (en) * | 2015-07-24 | 2015-10-21 | 哈尔滨工业大学 | Method for optimizing monocrystal diamond homoepitaxial growth by utilizing plasma baffle |
| CN105779967A (en) * | 2016-04-22 | 2016-07-20 | 武汉理工大学 | Method for preparing diamond film through MPCVD medium-frequency inducing auxiliary heating |
| CN107059120A (en) * | 2017-05-09 | 2017-08-18 | 中国电子科技集团公司第四十六研究所 | A kind of method that utilization square groove inserting collet suppresses polycrystalline diamond growth |
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