CN113667961B - Preparation device and preparation method of chemical vapor deposition high-quality diamond - Google Patents

Preparation device and preparation method of chemical vapor deposition high-quality diamond Download PDF

Info

Publication number
CN113667961B
CN113667961B CN202110876413.6A CN202110876413A CN113667961B CN 113667961 B CN113667961 B CN 113667961B CN 202110876413 A CN202110876413 A CN 202110876413A CN 113667961 B CN113667961 B CN 113667961B
Authority
CN
China
Prior art keywords
temperature
low
diamond
gas
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110876413.6A
Other languages
Chinese (zh)
Other versions
CN113667961A (en
Inventor
于盛旺
郑可
高洁
马永
贾文茹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Guomai Jinjing Carbon Based Semiconductor Materials Industry Research Institute Co Ltd
Original Assignee
Shanxi Guomai Jinjing Carbon Based Semiconductor Materials Industry Research Institute Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi Guomai Jinjing Carbon Based Semiconductor Materials Industry Research Institute Co ltd filed Critical Shanxi Guomai Jinjing Carbon Based Semiconductor Materials Industry Research Institute Co ltd
Priority to CN202110876413.6A priority Critical patent/CN113667961B/en
Publication of CN113667961A publication Critical patent/CN113667961A/en
Application granted granted Critical
Publication of CN113667961B publication Critical patent/CN113667961B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/265—Drying gases or vapours by refrigeration (condensation)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D7/00—Sublimation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention relates to a preparation device and a preparation method of chemical vapor deposition high-quality diamond, wherein the device is composed of H 2 Container, hydrogen purification device and CO 2 Container, low-temperature dewatering device or drying device, low-temperature H removing device 2 S device, low-temperature dry ice preparation device, impurity removal vacuum pump, CH 4 The reaction device, the secondary water removal device and the CVD diamond synthesis device. During the preparation, the high-purity CO is prepared respectively 2 And H 2 Then react to form H 2 、H 2 O、CH 4 Mixing the gases, and then removing water for the second time to obtain H 2 、CH 4 And mixing the gases, and finally introducing the gases into a CVD diamond synthesis device to deposit diamond. The device and the method can effectively reduce the impurity elements N, S and the like in the raw material gas, thereby realizing the production of high-quality diamond.

Description

Preparation device and preparation method of chemical vapor deposition high-quality diamond
Technical Field
The invention relates to the technical field of chemical vapor deposition, in particular to a preparation device and a preparation method of high-quality diamond by chemical vapor deposition.
Background
The high-quality diamond has excellent physical and chemical properties and has wide application prospect in the fields of machinery, aerospace, semiconductors, ornaments and the like. Chemical Vapor Deposition (CVD) is a method commonly used for the synthesis of diamond, and is generally carried out by direct use of high purity H 2 And high purity CH 4 As a feed gas, diamond was synthesized under negative pressure with the aid of plasma. The purity of the reaction gas directly influences the quality of the diamond prepared by CVD. Due to H 2 The molecules are smaller, and the high-purity H can be generally obtained by separating the palladium metal from other gases through filtration or adsorption and other methods 2 Feed gas (> 99.9999%). However, conventional adsorption methods generally only allow for the conversion of CH 4 Purification to about 99.9% requires cryogenic rectification at very low temperatures to achieve higher purity. This is due to N 2 Boiling point of-195.8 ℃, CH 4 Has a boiling point of-161 ℃, and can convert CH only below-161 DEG C 4 Liquefying, N in the gaseous state 2 Separating and gasifying the obtained CH 4 The purity can reach 99.999 percent. This method is not only costly but also makes it difficult to obtain CH of higher purity 4 Therefore, the method becomes a difficult problem of preparing high-quality diamond by a CVD method, and the development of the industry is affected to a certain extent.
Disclosure of Invention
The invention aims at directly adopting high-purity H for synthesizing diamond by adopting a CVD device 2 And high purity CH 4 Is used as raw material gas for production, while the key raw material gas is high-purity CH 4 The purification is difficult, the purity is difficult to exceed 99.999%, and the impurity gas in the impurity gas reduces the quality of diamond in the diamond growth process, so that the preparation device and the preparation method of the chemical vapor deposition high-quality diamond are provided. The device and the method can effectively reduce the impurity elements N, S and the like in the raw material gas, thereby realizing the production of high-quality diamond.
The invention is realized by the following technical scheme:
a preparation device for chemical vapor deposition high-quality diamond comprises H 2 Container, hydrogen purification device and CO 2 Container, low-temperature dewatering device or drying device, low-temperature H removing device 2 S device, low-temperature dry ice preparation device, impurity removal vacuum pump, CH 4 A reaction device, a secondary water removal device and a CVD diamond synthesis device;
H 2 the container is connected with a hydrogen purification device which is connected with CH 4 The reaction device is connected;
CO 2 the container is connected with a low-temperature water removing device or a drying device, and the low-temperature water is removedThe device or the drying device is also used for removing H at low temperature 2 S device connection, low temperature H removal 2 The S device is connected with a low-temperature dry ice preparation device, the low-temperature dry ice preparation device is connected with a impurity removal vacuum pump, and the impurity removal vacuum pump is connected with CH 4 The reaction device is connected;
CH 4 the reaction device is connected with a secondary water removing device which is connected with the CVD diamond synthesizing device.
The preparation method of the chemical vapor deposition high-quality diamond based on the device specifically comprises the following steps:
1）CO 2 purifying: CO is processed by 2 The gas condenses the water vapor into ice and H under low temperature condition 2 S is condensed into liquid to lead CO 2 Condensing into dry ice, adding N 2 Removing impurity gases such as CO and the like, and heating and gasifying the dry ice to obtain high-purity CO 2 ；
2）CH 4 Preparation of the first stage: high purity CO obtained in step 1) 2 With an excessive amount of high purity H 2 Introducing CH 4 In the reaction apparatus, CO 2 Decomposition into C-O groups, H 2 Decomposing into H atoms; by reacting a portion of the H atoms with O in the C-O group to form H 2 O vapor, another part of H atoms react with C in the C-O group to generate CH 4 Gas, and finally obtain H 2 、H 2 O、CH 4 Mixing the gases;
3）CH 4 and (2) preparing a second stage: subjecting the mixed gas obtained in step 2) to H under low temperature conditions 2 The O gas is condensed into ice and separated, and finally H-containing gas is obtained 2 And CH (CH) 4 Mixing the gases;
4) Diamond deposition: and 3) conveying the mixed gas obtained in the step 3) to a chemical vapor deposition diamond device to prepare diamond.
The preparation steps are further described with respect to the preparation method:
CO as described in step 1) 2 The purification is specifically as follows: CO is processed by 2 CO in a container 2 The gas is condensed into ice by a low-temperature water removing device or a drying device to removeRemoving H therefrom 2 O impurity is removed by low temperature 2 S device removes H therein 2 S impurity, and then CO is prepared by a low-temperature dry ice preparation device 2 Condensing into dry ice, and then utilizing a vacuum pump for removing impurities to remove N in the dry ice 2 Removing impurity gases such as CO and the like, and finally heating and gasifying the dry ice to obtain high-purity CO 2 ；
CH described in step 2) 4 The first preparation stage comprises the following steps: high purity CO obtained in step 1) 2 Introducing CH 4 In the reaction device, H is simultaneously added 2 H in the container 2 The raw material gas is introduced into a hydrogen purification device for purification and then introduced into CH 4 In the reaction apparatus, in CH 4 High purity CO is produced in a reaction apparatus 2 Breaking down into C-O groups to give H 2 Is decomposed into H atoms, and H is generated by reacting part of H atoms with O in the C-O group 2 O vapor, another part of H atoms react with C in the C-O group to generate CH 4 Gas and finally form a main component H 2 、H 2 O、CH 4 Is a mixed gas of (a) and (b);
CH described in step 3) 4 The second stage of preparation is specifically as follows: the mixed gas obtained in the step 2) is passed through a secondary water removing device, and H is led under the condition of low temperature 2 The O gas is condensed into ice and separated, and finally H is obtained 2 And CH (CH) 4 Is a mixed gas of (a) and (b);
the diamond deposition in the step 4) is specifically as follows: and 3) conveying the mixed gas obtained in the step 3) into a CVD diamond synthesis device to prepare diamond.
Further, CO 2 The purification needs to control the temperature to be lower than CO 2 Boiling point of-78.5 ℃, N is added 2 Removing impurity gases such as CO and the like to obtain high-purity CO 2 。
Further, CH 4 In the first stage of preparation, high-purity H 2 The content is high purity CO 2 2-5 times of the content of CO to ensure high purity 2 And high purity H 2 Can fully react without CO 2 Or CO residue.
Further, in step 1), CO is used 2 The purity of the raw material gas is 9999% or more, the temperature of the low-temperature water removing device or the drying device is controlled to be 0 ℃ to-10 ℃, and H is removed at low temperature 2 The temperature of the S device is controlled to be minus 61 ℃ to minus 78 ℃, and the temperature of the low-temperature dry ice preparation device is controlled to be below minus 78.5 ℃.
Further, in step 2), H is used 2 The purity of the raw material gas is more than 99 percent.
Further, in step 3), the temperature is reduced to below 0 ℃ to allow H 2 The O gas is condensed into ice, and the residual gas is filtered by a filter device to obtain H 2 And CH (CH) 4 And (3) mixing the gases.
Further, during the diamond deposition in the step 4), H is introduced into the CVD diamond synthesis device 2 And CH (CH) 4 Can be controlled by regulating the ratio of the high-purity H in the step 2) 2 And high purity CO 2 Is regulated and controlled by the ratio of the components.
The invention aims at high purity CH 4 The purification is difficult, the purity is difficult to exceed 99.999 percent, and then the problem of difficult preparation of high-quality diamond is caused, a novel diamond preparation device is designed, and the device can adopt CO with lower purity 2 （>99.99%) and H 2 (>99%) as feed gas, CO in plant systems 2 CO is purified by a purifying part and a hydrogen purifying device 2 And H 2 Purifying into high-purity CO 2 And high purity H 2 Then utilize CH 4 The reaction device uses high-purity CO 2 And excessive amount of high purity H 2 Conversion to H 2 、H 2 O、CH 4 Is mixed with the gas mixture to remove H 2 O, H 2 、CH 4 The mixed gas is input into a CVD diamond synthesis device for synthesizing diamond, so that the preparation of high-quality diamond can be realized, and in particular, the N and S and the content in the diamond are reduced.
The innovation of the invention has the following beneficial effects: the device structure of the invention is different from the structure of the common CVD diamond synthesizing device, besides the CVD diamond synthesizing device, the device also comprises H 2 Container, hydrogen purification device and CO 2 Container, low-temperature dewatering device or drying device, low-temperature H removing device 2 S device, low-temperature dry ice preparation device, impurity removal vacuum pump, CH 4 Reaction unit, secondary water removal unit and other devices for raw gas purification and reaction gas preparation by CO removal 2 N-containing and S-containing impurities in the diamond synthesis apparatus, and reduce H in the final CVD diamond synthesis apparatus 2 、CH 4 The N and S contents of the mixed gas can realize the preparation of ultra-high purity diamond, and the N and S contents in the CVD diamond are reduced to be below 100 ppb.
The invention selects CO 2 And H 2 As a raw material gas, by CO 2 Purifying to solve CH 4 Cryogenic rectification requires equipment to achieve temperatures of-161 ℃, is relatively difficult, and still has the problem of impurity gases, and is relatively easy to achieve at temperatures below-78.5 ℃ in the purification step.
All the conventional diamond preparation devices adopt or finally adopt H 2 、CH 4 As a reaction gas source, the invention adopts CO 2 And H 2 As an initial raw material gas, CO is not directly adopted after purification 2 And H 2 As a source of reaction gas for diamond, but by using CH 4 The reaction device converts into H 2 、H 2 O、CH 4 Is mixed with the gas mixture to remove H 2 O, form H 2 、CH 4 Mixing the gases and using them as a gas source, unlike other methods, and controlling H by chromatography 2 、CH 4 The content ratio is such that it meets the deposition requirements of high quality diamond film.
The invention adopts CO 2 And H 2 As the initial raw material gas, the purity of the raw material gas is not high, the gas cost can be reduced by more than 5 times, and the production cost can be reduced in mass production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention.
FIG. 1 is a system block diagram and process flow diagram of the apparatus of the present invention.
In the figure: 1-H 2 Container, 2-hydrogen purification device and 3-CO 2 Container4-low temperature water removing device or drying device, 5-low temperature H removing device 2 S device, 6-low temperature dry ice preparation device, 7-edulcoration vacuum pump and 8-CH 4 A reaction device, a 9-secondary water removal device and a 10-CVD diamond synthesis device.
Detailed Description
For a better understanding of the present invention, reference will be made to the following description of the invention taken in conjunction with the accompanying drawings and examples. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
Example 1
An apparatus for preparing high-quality diamond by chemical vapor deposition, as shown in figure 1, comprises H 2 Vessel 1, hydrogen purification device 2, CO 2 Container 3, low temperature dewatering device or drying device 4, low temperature H removal 2 S device 5, low-temperature dry ice preparation device 6, impurity removal vacuum pump 7, CH 4 A reaction device 8, a secondary water removal device 9 and a CVD diamond synthesis device 10.
H 2 The container 1 is connected with a hydrogen purification device which is connected with CH 4 The reaction device is connected.
CO 2 The container is connected with a low-temperature water removing device or a drying device which is connected with a low-temperature H removing device 2 S device connection, low temperature H removal 2 The S device is connected with a low-temperature dry ice preparation device, the low-temperature dry ice preparation device is connected with a impurity removal vacuum pump, and the impurity removal vacuum pump is connected with CH 4 The reaction device is connected.
CH 4 The reaction device is connected with a secondary water removing device which is connected with the CVD diamond synthesizing device.
The preparation method for preparing the chemical vapor deposition high-quality diamond based on the device comprises the following steps as shown in fig. 1:
step 1), CO 2 Purifying: CO is processed by 2 CO with purity of 99.99% or more in container 3 2 The gas condenses the water vapor into ice by a low-temperature water removing device or a drying device 4 to remove H 2 O impurityThe temperature of the low-temperature water removing device or the drying device 4 is controlled at-10 ℃; then H is removed by low temperature 2 S device 5 removes H therein 2 S impurity, low temperature H removal 2 S, controlling the temperature of the device 5 at-70 ℃; CO is further processed by a low-temperature dry ice preparation device 6 2 Condensing into dry ice, and controlling the temperature of the low-temperature dry ice preparation device 6 below-78.5 ℃; and then N in the mixture is removed by utilizing a impurity removal vacuum pump 7 2 Removing impurity gases such as CO and the like, and finally heating and gasifying the dry ice to obtain high-purity CO 2 ；
Step 2), CH 4 Preparation of the first stage: high purity CO obtained in step 1) 2 Introducing CH 4 In the reaction device 8, H is simultaneously introduced into 2 H with purity of 99% or more in vessel 1 2 Introducing into a hydrogen purification device 2 for purification, and then introducing CH 4 In the reaction apparatus 8, high purity H 2 The content is high purity CO 2 5 times of the content; on CH 4 High purity CO is produced in the reaction apparatus 8 2 Breaking down into C-O groups to give H 2 Is decomposed into H atoms, and H is generated by reacting part of H atoms with O in the C-O group 2 O vapor, another part of H atoms react with C in the C-O group to generate CH 4 Gas and finally form a main component H 2 、H 2 O、CH 4 Is a mixed gas of (a) and (b);
step 3): CH (CH) 4 And (2) preparing a second stage: the mixed gas obtained in the step 2) passes through a secondary water removing device 9, the temperature of the secondary water removing device 9 is reduced to be lower than 0 ℃ so as to lead H 2 The O gas is condensed into ice and separated, and finally H is obtained 2 And CH (CH) 4 Is a mixed gas of (a) and (b);
step 4): diamond deposition: and 3) conveying the mixed gas obtained in the step 3) into a CVD diamond synthesis device 10 to prepare diamond.
Example 2
An apparatus for preparing high-quality diamond by chemical vapor deposition, as shown in figure 1, comprises H 2 Vessel 1, hydrogen purification device 2, CO 2 Container 3, low temperature dewatering device or drying device 4, low temperature H removal 2 S device 5, low-temperature dry ice preparation device 6, impurity removal vacuum pump 7, CH 4 A reaction device 8, a secondary water removal device 9 and a CVD diamond synthesis device 10.
H 2 The container 1 is connected with a hydrogen purification device which is connected with CH 4 The reaction device is connected.
CO 2 The container is connected with a low-temperature water removing device or a drying device which is connected with a low-temperature H removing device 2 S device connection, low temperature H removal 2 The S device is connected with a low-temperature dry ice preparation device, the low-temperature dry ice preparation device is connected with a impurity removal vacuum pump, and the impurity removal vacuum pump is connected with CH 4 The reaction device is connected.
CH 4 The reaction device is connected with a secondary water removing device which is connected with the CVD diamond synthesizing device.
The preparation method for preparing the chemical vapor deposition high-quality diamond based on the device comprises the following steps as shown in fig. 1:
step 1), CO 2 Purifying: CO is processed by 2 CO with purity of 99.99% or more in container 3 2 The gas condenses the water vapor into ice by a low-temperature water removing device or a drying device 4 to remove H 2 O impurity, the temperature of the low-temperature water removing device or the drying device 4 is controlled at-4 ℃; then H is removed by low temperature 2 S device 5 removes H therein 2 S impurity, low temperature H removal 2 S, controlling the temperature of the device 5 at-78 ℃; CO is further processed by a low-temperature dry ice preparation device 6 2 Condensing into dry ice, and controlling the temperature of the low-temperature dry ice preparation device 6 below-78.5 ℃; and then N in the mixture is removed by utilizing a impurity removal vacuum pump 7 2 Removing impurity gases such as CO and the like, and finally heating and gasifying the dry ice to obtain high-purity CO 2 ；
Step 2), CH 4 Preparation of the first stage: high purity CO obtained in step 1) 2 Introducing CH 4 In the reaction device 8, H is simultaneously introduced into 2 H with purity of 99% or more in vessel 1 2 Introducing into a hydrogen purification device 2 for purification, and then introducing CH 4 In the reaction apparatus 8, high purity H 2 The content is high purity CO 2 2 times of the content; on CH 4 High purity CO is produced in the reaction apparatus 8 2 Decomposition into C-O groupsGroup, make H 2 Is decomposed into H atoms, and H is generated by reacting part of H atoms with O in the C-O group 2 O vapor, another part of H atoms react with C in the C-O group to generate CH 4 Gas and finally form a main component H 2 、H 2 O、CH 4 Is a mixed gas of (a) and (b);
step 3): CH (CH) 4 And (2) preparing a second stage: the mixed gas obtained in the step 2) passes through a secondary water removing device 9, the temperature of the secondary water removing device 9 is reduced to be lower than 0 ℃ so as to lead H 2 The O gas is condensed into ice and separated, and finally H is obtained 2 And CH (CH) 4 Is a mixed gas of (a) and (b);
step 4): diamond deposition: and 3) conveying the mixed gas obtained in the step 3) into a CVD diamond synthesis device 10 to prepare diamond.
Example 3
An apparatus for preparing high-quality diamond by chemical vapor deposition, as shown in figure 1, comprises H 2 Vessel 1, hydrogen purification device 2, CO 2 Container 3, low temperature dewatering device or drying device 4, low temperature H removal 2 S device 5, low-temperature dry ice preparation device 6, impurity removal vacuum pump 7, CH 4 A reaction device 8, a secondary water removal device 9 and a CVD diamond synthesis device 10.
H 2 The container 1 is connected with a hydrogen purification device which is connected with CH 4 The reaction device is connected.
CO 2 The container is connected with a low-temperature water removing device or a drying device which is connected with a low-temperature H removing device 2 S device connection, low temperature H removal 2 The S device is connected with a low-temperature dry ice preparation device, the low-temperature dry ice preparation device is connected with a impurity removal vacuum pump, and the impurity removal vacuum pump is connected with CH 4 The reaction device is connected.
CH 4 The reaction device is connected with a secondary water removing device which is connected with the CVD diamond synthesizing device.
The preparation method for preparing the chemical vapor deposition high-quality diamond based on the device comprises the following steps as shown in fig. 1:
step 1), CO 2 Purifying: CO is processed by 2 CO with purity of 99.99% or more in container 3 2 The gas condenses the water vapor into ice by a low-temperature water removing device or a drying device 4 to remove H 2 O impurity, the temperature of the low-temperature water removing device or the drying device 4 is controlled at 0 ℃; then H is removed by low temperature 2 S device 5 removes H therein 2 S impurity, low temperature H removal 2 S, controlling the temperature of the device 5 at-61 ℃; CO is further processed by a low-temperature dry ice preparation device 6 2 Condensing into dry ice, and controlling the temperature of the low-temperature dry ice preparation device 6 below-78.5 ℃; and then N in the mixture is removed by utilizing a impurity removal vacuum pump 7 2 Removing impurity gases such as CO and the like, and finally heating and gasifying the dry ice to obtain high-purity CO 2 ；
Step 2), CH 4 Preparation of the first stage: high purity CO obtained in step 1) 2 Introducing CH 4 In the reaction device 8, H is simultaneously introduced into 2 H with purity of 99% or more in vessel 1 2 Introducing into a hydrogen purification device 2 for purification, and then introducing CH 4 In the reaction apparatus 8, high purity H 2 The content is high purity CO 2 4 times of the content; on CH 4 High purity CO is produced in the reaction apparatus 8 2 Breaking down into C-O groups to give H 2 Is decomposed into H atoms, and H is generated by reacting part of H atoms with O in the C-O group 2 O vapor, another part of H atoms react with C in the C-O group to generate CH 4 Gas and finally form a main component H 2 、H 2 O、CH 4 Is a mixed gas of (a) and (b);
step 3): CH (CH) 4 And (2) preparing a second stage: the mixed gas obtained in the step 2) passes through a secondary water removing device 9, the temperature of the secondary water removing device 9 is reduced to be lower than 0 ℃ so as to lead H 2 The O gas is condensed into ice and separated, and finally H is obtained 2 And CH (CH) 4 Is a mixed gas of (a) and (b);
step 4): diamond deposition: and 3) conveying the mixed gas obtained in the step 3) into a CVD diamond synthesis device 10 to prepare diamond.
Example 4
An apparatus for preparing high-quality diamond by chemical vapor deposition, as shown in figure 1, comprises H 2 Vessel 1, hydrogen purification device 2, CO 2 Container 3, low temperature dewatering device or drying device 4, low temperature H removal 2 S device 5, low-temperature dry ice preparation device 6, impurity removal vacuum pump 7, CH 4 A reaction device 8, a secondary water removal device 9 and a CVD diamond synthesis device 10.
H 2 The container 1 is connected with a hydrogen purification device which is connected with CH 4 The reaction device is connected.
CO 2 The container is connected with a low-temperature water removing device or a drying device which is connected with a low-temperature H removing device 2 S device connection, low temperature H removal 2 The S device is connected with a low-temperature dry ice preparation device, the low-temperature dry ice preparation device is connected with a impurity removal vacuum pump, and the impurity removal vacuum pump is connected with CH 4 The reaction device is connected.
CH 4 The reaction device is connected with a secondary water removing device which is connected with the CVD diamond synthesizing device.
The preparation method for preparing the chemical vapor deposition high-quality diamond based on the device comprises the following steps as shown in fig. 1:
step 1), CO 2 Purifying: CO is processed by 2 CO with purity of 99.99% or more in container 3 2 The gas condenses the water vapor into ice by a low-temperature water removing device or a drying device 4 to remove H 2 O impurity, the temperature of the low-temperature water removing device or the drying device 4 is controlled at-7 ℃; then H is removed by low temperature 2 S device 5 removes H therein 2 S impurity, low temperature H removal 2 S, controlling the temperature of the device 5 at-75 ℃; CO is further processed by a low-temperature dry ice preparation device 6 2 Condensing into dry ice, and controlling the temperature of the low-temperature dry ice preparation device 6 below-78.5 ℃; and then N in the mixture is removed by utilizing a impurity removal vacuum pump 7 2 Removing impurity gases such as CO and the like, and finally heating and gasifying the dry ice to obtain high-purity CO 2 ；
Step 2), CH 4 Preparation of the first stage: high purity CO obtained in step 1) 2 Introducing CH 4 In the reaction device 8, H is simultaneously introduced into 2 H with purity of 99% or more in vessel 1 2 Introducing hydrogen into the purifying device 2Purifying and then introducing CH 4 In the reaction apparatus 8, high purity H 2 The content is high purity CO 2 3 times of the content; on CH 4 High purity CO is produced in the reaction apparatus 8 2 Breaking down into C-O groups to give H 2 Is decomposed into H atoms, and H is generated by reacting part of H atoms with O in the C-O group 2 O vapor, another part of H atoms react with C in the C-O group to generate CH 4 Gas and finally form a main component H 2 、H 2 O、CH 4 Is a mixed gas of (a) and (b);
step 3): CH (CH) 4 And (2) preparing a second stage: the mixed gas obtained in the step 2) passes through a secondary water removing device 9, the temperature of the secondary water removing device 9 is reduced to be lower than 0 ℃ so as to lead H 2 The O gas is condensed into ice and separated, and finally H is obtained 2 And CH (CH) 4 Is a mixed gas of (a) and (b);
step 4): diamond deposition: and 3) conveying the mixed gas obtained in the step 3) into a CVD diamond synthesis device 10 to prepare diamond.
The foregoing has been a clear and complete description of the technical solutions of embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Claims (8)

1. The preparation device of the high-quality diamond by chemical vapor deposition is characterized in that: includes H 2 Container, hydrogen purification device and CO 2 Container, low-temperature dewatering device or drying device, low-temperature H removing device 2 S device, low-temperature dry ice preparation device, impurity removal vacuum pump, CH 4 A reaction device, a secondary water removal device and a CVD diamond synthesis device;
H 2 the container is connected with a hydrogen purification device which is connected with CH 4 The reaction device is connected;
CO 2 the container is connected with a low-temperature water removing device or a drying device, and the low-temperature water removing device or the drying device is connected with the containerRemoving H at low temperature 2 S device connection, low temperature H removal 2 The S device is connected with a low-temperature dry ice preparation device, the low-temperature dry ice preparation device is connected with a impurity removal vacuum pump, and the impurity removal vacuum pump is connected with CH 4 The reaction device is connected; wherein, the temperature of the low-temperature water removing device or the drying device is 0 ℃ to minus 10 ℃, and the low-temperature H removing device is arranged 2 The temperature of the S device is minus 61 ℃ to minus 78 ℃, and the temperature of the low-temperature dry ice preparation device is minus 78.5 ℃;
CH 4 the reaction device is connected with a secondary water removing device which is connected with the CVD diamond synthesizing device.
2. A method for preparing high quality diamond by chemical vapor deposition based on the apparatus of claim 1, comprising the steps of:
1）CO 2 purifying: CO is processed by 2 The gas condenses the water vapor into ice and H under low temperature condition 2 S is condensed into liquid to lead CO 2 Condensing into dry ice, adding N 2 After removing CO impurity gas, heating and gasifying dry ice to obtain high-purity CO 2 ；
2）CH 4 Preparation of the first stage: high purity CO obtained in step 1) 2 With an excessive amount of high purity H 2 Introducing CH 4 In the reaction apparatus, CO 2 Decomposition into C-O groups, H 2 Decomposing into H atoms; by reacting a portion of the H atoms with O in the C-O group to form H 2 O vapor, another part of H atoms react with C in the C-O group to generate CH 4 Gas, and finally obtain H 2 、H 2 O、CH 4 Mixing the gases;
3）CH 4 and (2) preparing a second stage: subjecting the mixed gas obtained in step 2) to H under low temperature conditions 2 The O gas is condensed into ice and separated, and finally H-containing gas is obtained 2 And CH (CH) 4 Mixing the gases;
4) Diamond deposition: and 3) conveying the mixed gas obtained in the step 3) to a chemical vapor deposition diamond device to prepare diamond.
3. The method for preparing high-quality diamond by chemical vapor deposition according to claim 2, wherein:
CO as described in step 1) 2 The purification is specifically as follows: CO is processed by 2 CO in a container 2 The gas condenses the water vapor into ice by a low-temperature water removing device or a drying device to remove H 2 O impurity is removed by low temperature 2 S device removes H therein 2 S impurity, and then CO is prepared by a low-temperature dry ice preparation device 2 Condensing into dry ice, and then utilizing a vacuum pump for removing impurities to remove N in the dry ice 2 Removing CO impurity gas, and finally heating and gasifying the dry ice to obtain high-purity CO 2 ；
CH described in step 2) 4 The first preparation stage comprises the following steps: high purity CO obtained in step 1) 2 Introducing CH 4 In the reaction device, H is simultaneously added 2 H in the container 2 The raw material gas is introduced into a hydrogen purification device for purification and then introduced into CH 4 In the reaction apparatus, in CH 4 High purity CO is produced in a reaction apparatus 2 Breaking down into C-O groups to give H 2 Is decomposed into H atoms, and H is generated by reacting part of H atoms with O in the C-O group 2 O vapor, another part of H atoms react with C in the C-O group to generate CH 4 Gas and finally form a main component H 2 、H 2 O、CH 4 Is a mixed gas of (a) and (b);
CH described in step 3) 4 The second stage of preparation is specifically as follows: the mixed gas obtained in the step 2) is passed through a secondary water removing device, and H is led under the condition of low temperature 2 The O gas is condensed into ice and separated, and finally H is obtained 2 And CH (CH) 4 Is a mixed gas of (a) and (b);
the diamond deposition in the step 4) is specifically as follows: and 3) conveying the mixed gas obtained in the step 3) into a CVD diamond synthesis device to prepare diamond.
4. A method of producing high quality diamond by chemical vapor deposition according to claim 3, wherein: CO 2 The purification needs to control the temperature to be lower than CO 2 The boiling point of the catalyst is-78.5 DEG CN 2 Removing CO impurity gas to obtain high-purity CO 2 。
5. A method of producing high quality diamond by chemical vapor deposition according to claim 3, wherein: CH (CH) 4 In the first stage of preparation, high-purity H 2 The content is high purity CO 2 2-5 times of the content of CO to ensure that the reaction process can be fully carried out 2 Or CO residue.
6. A method of producing high quality diamond by chemical vapor deposition according to claim 3, wherein: in step 1), CO used 2 The purity of the raw material gas is more than 99.99 percent, the temperature of the low-temperature water removing device or the drying device is controlled to be 0 ℃ to-10 ℃, and the H is removed at low temperature 2 The temperature of the S device is controlled to be minus 61 ℃ to minus 78 ℃, and the temperature of the low-temperature dry ice preparation device is controlled to be below minus 78.5 ℃.
7. A method of producing high quality diamond by chemical vapor deposition according to claim 3, wherein: in step 2), H is used 2 The purity of the raw material gas is more than 99 percent.
8. A method of producing high quality diamond by chemical vapor deposition according to claim 3, wherein: in step 3), the temperature is reduced to below 0 ℃ to lead H 2 The O gas is condensed into ice, and the residual gas is filtered by a filter device to obtain H 2 And CH (CH) 4 And (3) mixing the gases.
CN202110876413.6A 2021-07-31 2021-07-31 Preparation device and preparation method of chemical vapor deposition high-quality diamond Active CN113667961B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110876413.6A CN113667961B (en) 2021-07-31 2021-07-31 Preparation device and preparation method of chemical vapor deposition high-quality diamond

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110876413.6A CN113667961B (en) 2021-07-31 2021-07-31 Preparation device and preparation method of chemical vapor deposition high-quality diamond

Publications (2)

Publication Number Publication Date
CN113667961A CN113667961A (en) 2021-11-19
CN113667961B true CN113667961B (en) 2023-07-07

Family

ID=78540912

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110876413.6A Active CN113667961B (en) 2021-07-31 2021-07-31 Preparation device and preparation method of chemical vapor deposition high-quality diamond

Country Status (1)

Country Link
CN (1) CN113667961B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1126714C (en) * 2000-11-14 2003-11-05 湖南凯美特干冰有限公司 Dynamic vacuumizing process for purifying CO2
CN101607708A (en) * 2009-07-27 2009-12-23 申屠晶 The co-production of technical grade and food-class liquid CO 2 and device
CN204400624U (en) * 2015-01-19 2015-06-17 兰州裕隆气体有限责任公司 A kind of production system for the preparation of high purity liquid carbonic acid gas
GB2535152A (en) * 2015-02-06 2016-08-17 Ecotricity Group Ltd A method of producing a synthetic diamond
US10551120B2 (en) * 2017-02-06 2020-02-04 Hall Labs Llc Method for condensing a CO2 vapor stream beyond the frost point
CN108821290B (en) * 2018-09-19 2020-11-03 山东京博众诚清洁能源有限公司 Production device and method of carbon dioxide
CN108914088B (en) * 2018-09-29 2023-07-28 北京科技大学 Gas circulation system for preparing high-quality diamond and application method thereof
CN113135562B (en) * 2020-01-20 2024-02-23 山东大展纳米材料有限公司 Method and device for preparing carbon nano tube and hydrogen

Also Published As

Publication number Publication date
CN113667961A (en) 2021-11-19

Similar Documents

Publication Publication Date Title
JPH01283817A (en) Evaporation of semiconductor silicon by cvd
CA2719858C (en) Method and system for the production of pure silicon
KR101778068B1 (en) System and methods of producing trichlorosilane
US20110206842A1 (en) CVD-Siemens Reactor Process Hydrogen Recycle System
CN113797568B (en) Synthesis device and synthesis method of electronic grade tri (dimethylamino) silane
CN114752061B (en) Dimethyl dichlorosilane hydrolysis process with desorption function
CN113667961B (en) Preparation device and preparation method of chemical vapor deposition high-quality diamond
CN109368593B (en) Method for preparing electronic grade hydrogen chloride gas containing ppbv grade moisture impurities
CN110745830B (en) Method and system for controlling balance of dichlorosilane in polycrystalline silicon production
CN115403048B (en) Disilane purification method
KR100653541B1 (en) Method for preparation of hydrogen from coke oven gas
CN110683513B (en) Preparation method of high-purity chlorine
CN104388139A (en) Direct methanation method and system for raw coal gas
CN215743355U (en) Electronic grade tri (dimethylamino) silane synthesis device
CN112827319B (en) Chlorine-based SiC-CVD epitaxial tail gas full-temperature-range pressure swing adsorption hydrogen extraction and recycling method containing low-concentration silane and light hydrocarbons above carbon two
CN112723359B (en) Method and system for preparing disilane by reaction of multi-metal silicide and ammonium chloride
CN108586515B (en) Synthesis method of trisilylamine
CN112645976A (en) Method for preparing methyl chlorosilane organic silicon by using tail gas FTrPSA (fluorine-doped polysilicon-fluoride) in growth process of chlorine-based CVD (chemical vapor deposition) crystal film
CN114671405A (en) Process for preparing high-purity hydrogen chloride from by-product hydrochloric acid in methane chloride process
KR960014903B1 (en) Hydrogen, purification process
CN114956092A (en) Method for separating monomethyldichlorosilane impurities from trichlorosilane
JPH02196014A (en) Production of high purity dichlorosilane
CN112642259A (en) Method for recovering FTrPSA (fluorine substituted PSA) tail gas generated in epitaxial process of chlorine-based SiC-CVD (chemical vapor deposition) by alkane and silane reaction
CN103562125A (en) Method for producing gas products from syngas
CN115594183B (en) Electronic grade hexachlorodisilane and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20220816

Address after: 048026 No. 1060 Lanhua Road, Jincheng Economic and Technological Development Zone, Jincheng City, Shanxi Province (Room 501, Kanglian Trade Office Building)

Applicant after: Shanxi Guomai Jinjing Carbon-based Semiconductor Materials Industry Research Institute Co., Ltd.

Address before: 030024 No. 79 West Main Street, Taiyuan, Shanxi, Yingze

Applicant before: Taiyuan University of Technology

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant