CN110724930A - Preparation method of diamond film - Google Patents
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- CN110724930A CN110724930A CN201911076437.2A CN201911076437A CN110724930A CN 110724930 A CN110724930 A CN 110724930A CN 201911076437 A CN201911076437 A CN 201911076437A CN 110724930 A CN110724930 A CN 110724930A
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- 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
- C23C16/271—Diamond only using hot filaments
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- 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
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
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- 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
- C23C16/56—After-treatment
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Abstract
The invention discloses a preparation method of a diamond film, and belongs to the technical field of diamond preparation. The preparation method comprises the following steps: placing the pretreated porous metal substrate in a reaction chamber of a hot wire chemical vapor deposition device, and filling reaction gas into the reaction chamber to enable the reaction gas to grow on the surface of the porous metal substrate to form a diamond/silicon carbide/metal composite film; corroding the obtained diamond/silicon carbide/metal composite film, and removing a metal phase and a silicon carbide phase in the diamond/silicon carbide/metal composite film to obtain a diamond film; and calcining the diamond film in an oxygen-containing atmosphere to obtain the finished diamond film with the hierarchical pore structure. The method can prepare the diamond film with the hierarchical pore structure.
Description
Technical Field
The invention belongs to the technical field of diamond preparation, and particularly relates to a preparation method of a diamond film.
Background
The porous material can be divided into three types of micropores (the aperture is less than 2 nm), mesopores (the aperture is between 2 ~ 50 nm) and macropores (the aperture is more than 50 nm) according to the aperture size.
Diamond has high chemical stability and good mechanical strength, and has the advantages that other materials do not have, but the preparation of the porous diamond material is difficult. Chinese patent CN104178745B discloses a "method for preparing a porous diamond or porous cubic silicon carbide self-supporting film", which prepares a porous diamond self-supporting film by a method of etching a diamond/cubic silicon carbide composite film with a mixed etching solution. However, the porous diamond self-supporting membrane has single pore size distribution and low porosity.
Disclosure of Invention
In order to solve the problems of single pore size distribution, low porosity and the like of porous diamond in the prior art, the invention provides a preparation method of a diamond film.
The technical scheme adopted by the invention is as follows: a preparation method of a diamond film comprises the following steps:
(1) placing the pretreated porous metal substrate in a reaction chamber of a hot wire chemical vapor deposition device, and filling reaction gas into the reaction chamber to enable the reaction gas to grow on the surface of the porous metal substrate to form a diamond/silicon carbide/metal composite film;
the porous metal substrate is through-hole foam copper or through-hole foam nickel, the volume of the reaction gas comprises 100 parts of hydrogen, 1 ~ 4 parts of methane, 0.01 ~ 0.2.2 parts of monosilane and 0.05 ~ 0.2.2 parts of nitrogen, and the nitrogen is added mainly for improving the growth rate of the film;
in the growth process, the flow rate of the reaction gas is 300 ~ 800ml/min, the air pressure of the reaction chamber is 1 ~ 3kPa, when the flow rate and the air pressure of the reaction gas are too low, the growth rate of the film is slow, and when the flow rate and the air pressure of the reaction gas are too high, the film is easy to generate defects;
the temperature of the hot wire is 1600 ~ 2000 ℃, the temperature of the matrix is 600 ~ 800 ℃, when the temperature of the matrix is too low, the film can not grow, and when the temperature of the matrix is too high, the contact part of the diamond phase and the metal phase is easy to generate the phenomenon of graphitization, thereby generating defects;
(2) corroding the diamond/silicon carbide/metal composite film obtained in the step (1) by using dilute acid, and removing a metal phase in the diamond/silicon carbide/metal composite film to obtain a diamond/silicon carbide composite film;
(3) corroding the diamond/silicon carbide composite film obtained in the step (2) by using acid liquor, and removing a silicon carbide phase in the diamond/silicon carbide composite film to obtain a diamond film;
(4) after cleaning and drying the diamond film obtained in the step (3), calcining the diamond film in an oxygen-containing atmosphere to obtain a finished diamond film with a hierarchical pore structure;
the method comprises the following steps of (1) obtaining a diamond film, wherein the oxygen volume content of the oxygen-containing atmosphere is 10 ~ 25%, when the oxygen volume content in the oxygen-containing atmosphere is too low, the calcination is longer, and when the oxygen volume content is too high, the graphitization speed of the diamond is too high, so that the film is easily damaged;
the calcination temperature is 500 ~ 600 ℃, when the calcination temperature is too low, the diamond cannot be graphitized, and when the calcination temperature is too high, the graphitization speed of the diamond is too high, and the film is easy to damage.
The open porosity of the porous metal matrix is more than or equal to 70 percent. When the porosity of the open pores of the porous metal matrix is too small, the film is easy to generate more defects.
The thickness of the porous metal matrix is less than 0.5 mm. When the porous metal substrate is too thick, a good deposition effect cannot be obtained.
The pretreatment comprises the specific steps of putting the porous metal matrix into a suspension containing diamond and acetone, performing ultrasonic treatment for 10 ~ 30min, cleaning the porous metal matrix with ethanol, and drying.
The dilute acid is selected from one or more of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid.
The acid solution comprises 1 part of concentrated nitric acid and 1 ~ 5 parts of concentrated hydrofluoric acid by volume, and the temperature of the acid solution is not lower than 50 ℃.
The calcination time in the step (4) is 30-60 min. When the calcination time is too short, the diamond cannot be graphitized; when the calcination time is too long, the graphitization degree of the diamond is too large, and the film is easily damaged.
The invention has the beneficial effects that the porous metal matrix can provide macropores with the aperture larger than 1000nm for the film, the silicon carbide phase can provide macropores with the aperture between 50 ~ 1000nm and 1000nm for the film, and the porous metal matrix can provide micropores and mesopores for the film after being calcined in oxygen-containing atmosphere.
The proportion of the pores with different apertures in the diamond film can be controlled by changing the porosity of the porous metal matrix, the numerical value of monosilane to methane in reaction gas, the temperature during calcination, the oxygen content in oxygen-containing atmosphere and other parameters, thereby preparing the required diamond film with the hierarchical pore structure.
Detailed Description
The present invention will be described in further detail with reference to specific examples. In order to highlight the focus of the present invention, some conventional operations and devices, apparatuses, components are omitted or only briefly described. Hereinafter, the diamond particle size of the diamond-acetone suspension was 5nm and the mass concentration was 0.1%.
Example 1
Through-hole copper foam with the thickness of 0.2mm and the open porosity of 70% is selected and put into diamond-acetone suspension for ultrasonic treatment for 10min to obtain higher nucleation density. And then washing the copper foam with ethanol and drying to obtain the pretreated through-hole copper foam.
And placing the pretreated through-hole foamy copper in a reaction chamber of a hot wire chemical gas phase device. Specifically, it is placed on a sample support table in the reaction chamber. Preferably, the sample support table is rotated and water cooled to improve the uniformity of the film. Vacuumizing, and introducing hydrogen to make the air pressure in the reaction chamber reach 1kPa after the air pressure in the reaction chamber is less than 100 Pa. At the same time, the hot wire temperature was raised to 1600 ℃ and the open-cell copper foam was heated to 600 ℃. And introducing reaction gas into the reaction chamber at a flow rate of 300ml/min for deposition. Wherein, the volume composition of the reaction gas is as follows: 100 parts of hydrogen, 1 part of methane, 0.01 part of monosilane and 0.05 part of nitrogen. After 8h of deposition, a 0.2mm thick diamond/silicon carbide/metal composite film was obtained.
Putting the obtained diamond/silicon carbide/metal composite film into dilute hydrochloric acid to corrode and remove the through-hole copper foam, and then putting the film into acid liquor at 50 ℃ to corrode and remove the silicon carbide phase to obtain the diamond film. Wherein, the volume composition of acidizing fluid is: 1 part nitric acid and 1 part hydrofluoric acid.
The obtained diamond film was washed and dried, and then placed in a muffle furnace. Vacuumizing, and introducing mixed gas of argon and oxygen for heating after the air pressure in the muffle furnace is less than 100 Pa. Wherein the volume content of the oxygen is 10 percent. The diamond film was calcined at 500 ℃ for 30min at a temperature rise rate of 10 ℃/min to obtain sample S1.
Example 2
Through-hole foamed nickel with the thickness of 0.5mm and the open porosity of 95% is selected and firstly placed in diamond-acetone suspension for ultrasonic treatment for 30min to obtain higher nucleation density. And then washing the nickel powder by using ethanol and drying to obtain the pretreated through-hole foamed nickel.
And placing the pretreated through-hole foamed nickel in a reaction chamber of a hot wire chemical gas phase device. Specifically, it is placed on a sample support table in the reaction chamber. Preferably, the sample support table is rotated and water cooled to improve the uniformity of the film. Vacuumizing, and introducing hydrogen to make the air pressure in the reaction chamber reach 3kPa after the air pressure in the reaction chamber is less than 100 Pa. At the same time, the hot wire temperature was raised to 2000 ℃ and the open-cell nickel foam was heated to 800 ℃. And introducing reaction gas into the reaction chamber at a flow rate of 800ml/min for deposition. Wherein, the volume composition of the reaction gas is as follows: 100 parts of hydrogen, 4 parts of methane, 0.2 part of monosilane and 0.2 part of nitrogen. After 10h of deposition, a 0.5mm thick diamond/silicon carbide/metal composite film was obtained.
Putting the obtained diamond/silicon carbide/metal composite film into dilute sulfuric acid to corrode and remove the through-hole foamed nickel, and then putting the film into acid liquor at 70 ℃ to corrode and remove the silicon carbide phase to obtain the diamond film. Wherein, the volume composition of acidizing fluid is: 1 part nitric acid and 5 parts hydrofluoric acid.
The obtained diamond film was washed and dried, and then placed in a muffle furnace. Vacuumizing, and introducing mixed gas of argon and oxygen for heating after the air pressure in the muffle furnace is less than 100 Pa. Wherein the volume content of oxygen is 25%. The diamond film was calcined at 600 ℃ for 60min at a temperature rise rate of 10 ℃/min to obtain sample S2.
Example 3
Through-hole copper foam with the thickness of 0.3mm and the open porosity of 90% is selected and put into diamond-acetone suspension for ultrasonic treatment for 15min to obtain higher nucleation density. And then washing the copper foam with ethanol and drying to obtain the pretreated through-hole copper foam.
And placing the pretreated through-hole foamy copper in a reaction chamber of a hot wire chemical gas phase device. Specifically, it is placed on a sample support table in the reaction chamber. Preferably, the sample support table is rotated and water cooled to improve the uniformity of the film. Vacuumizing to ensure that the air pressure in the reaction chamber is less than 100Pa, and introducing hydrogen to ensure that the air pressure in the reaction chamber reaches 1.5 kPa. At the same time, the hot wire temperature was raised to 1700 ℃, and the through-hole copper foam was heated to 650 ℃. And introducing reaction gas into the reaction chamber at a flow rate of 500ml/min for deposition. Wherein, the volume composition of the reaction gas is as follows: 100 parts of hydrogen, 3 parts of methane, 0.1 part of monosilane and 0.1 part of nitrogen. After 7h of deposition, a 0.3mm thick diamond/silicon carbide/metal composite film was obtained.
And putting the obtained diamond/silicon carbide/metal composite film into dilute nitric acid to corrode and remove the through-hole foamy copper, and then putting the film into acid liquor at 60 ℃ to corrode and remove the silicon carbide phase to obtain the diamond film. Wherein, the volume composition of acidizing fluid is: 1 part nitric acid and 3 parts hydrofluoric acid.
The obtained diamond film was washed and dried, and then placed in a muffle furnace. After the furnace was evacuated to a pressure of less than 100Pa, air (about 21% by volume of oxygen) was introduced and the furnace was heated. The diamond film was calcined at 500 ℃ for 30min at a temperature rise rate of 10 ℃/min to obtain sample S3.
Comparative example 1
Selecting a silicon wafer with the thickness of 0.3mm, and putting the silicon wafer into the diamond-acetone suspension for ultrasonic treatment for 15min to obtain higher nucleation density. And then washing the silicon wafer with ethanol and drying to obtain a pretreated silicon wafer.
And placing the pretreated silicon wafer in a reaction chamber of a hot wire chemical vapor device. Specifically, it is placed on a sample support table in the reaction chamber. Preferably, the sample support table is rotated and water cooled to improve the uniformity of the film. Vacuumizing to ensure that the air pressure in the reaction chamber is less than 100Pa, and introducing hydrogen to ensure that the air pressure in the reaction chamber reaches 1.5 kPa. At the same time, the hot wire temperature was raised to 1700 ℃ and the silicon wafer was heated to 650 ℃. And introducing reaction gas into the reaction chamber at a flow rate of 500ml/min for deposition. Wherein, the volume composition of the reaction gas is as follows: 100 parts of hydrogen, 3 parts of methane, 0.1 part of monosilane and 0.1 part of nitrogen. After 21h of deposition, a 0.3mm thick diamond/silicon carbide composite film was obtained.
Putting the obtained diamond/silicon carbide composite film into acid liquor at 60 ℃ for corrosion, and removing silicon carbide in the film to obtain the diamond film. Wherein, the volume composition of acidizing fluid is: 1 part nitric acid and 3 parts hydrofluoric acid.
The obtained diamond film was washed and dried to obtain sample a 1.
Comparative example 2
Sample A2 was prepared identically to sample S3 of example 3, except that no nitrogen was added. The required deposition time was 27 h.
Testing
The porosity of samples S1-S3 and samples A1-A2 were measured, respectively, using a BET specific surface area tester to measure the small pores and the medium pores of the samples, and a mercury porosimeter to measure the large pores of the samples, and the pore data obtained by combining the results of the two measurements are shown in Table 1, wherein "small pore ratio (< 2 nm)" is the volume ratio of small pores having a pore diameter of less than 2nm to all pores, "medium pore ratio (2 ~ 50 nm)" is the volume ratio of medium pores having a pore diameter of 2 ~ 50nm to all pores, "large pore ratio (50 ~ 100 nm)" is the volume ratio of large pores having a pore diameter of 50 ~ 100nm to all pores, "large pore ratio (> 100 ~ 1000 nm)" is the volume ratio of large pores having a pore diameter of 100 ~ 1000nm to all pores, and "large pore ratio (> 1000 nm)" is the volume ratio of large pores having a pore diameter of more than 1000nm to all pores.
TABLE 1
As can be seen from Table 1, S1-S3 and A2 both have a hierarchical pore structure. Whereas a1 has substantially only large pores.
The main cause of the small holes and the mesopores in the film is that the film is calcined in an oxygen-containing atmosphere to graphitize, the main cause of the macropores with the pore diameter of 50 ~ 1000nm in the film is that a silicon carbide phase in the film is corroded, and the main cause of the macropores with the pore diameter of more than 1000nm in the film is that a metal phase and a silicon carbide phase in the film are corroded.
When the porosity of the porous metal matrix is low, more pores are generated by corroding the metal phase in the film; when the porosity of the porous metal matrix is higher, the pores generated by corrosion of the metal phase in the film are less.
The pore diameter of the pores generated by the corrosion of the silicon carbide phase in the film is mainly between 50 ~ 100nm when the value of monosilane to methane in the reaction gas is low, and the pore diameter of the pores generated by the corrosion of the silicon carbide phase in the film is mostly larger than 100nm when the value of monosilane to methane in the reaction gas is high.
Under the conditions of higher calcination temperature, higher oxygen volume content in oxygen-containing atmosphere and longer calcination time, the calcined film hardly generates pores; on the other hand, when the calcination temperature is low, the oxygen volume content in the oxygen-containing atmosphere is low, and the calcination time is short, the proportion of the pores in the pores generated by calcining the film is increased.
Nitrogen has little effect on the pore structure in the film.
7 hours were required to obtain sample S3 of 0.3mm in example 3, and 21 hours were required to obtain sample A1 of 0.3mm in comparative example 1. This is because the through-hole copper foam has a larger specific surface area and a larger contact area with the reaction gas than the silicon wafer, resulting in a higher deposition rate. Sample a2, which took 27 hours to obtain 0.3mm in comparative example 2, illustrates that the addition of nitrogen had a significant effect on the increase in deposition rate.
Therefore, the required diamond with the hierarchical pore structure can be prepared by controlling the proportion of pores with different pore diameters in the diamond film by changing parameters such as the porosity of the porous metal matrix, the numerical value of silane to methane in reaction gas, the temperature during calcination, the oxygen content in oxygen-containing atmosphere and the like.
It is to be understood that: although the present invention has been described in considerable detail with reference to certain embodiments thereof, it is not intended to be limited to the details shown, since various changes in form and detail can be made therein without departing from the scope of the invention encompassed by the appended claims.
Claims (7)
1. A method for preparing a diamond film, comprising the steps of:
(1) placing the pretreated porous metal substrate in a reaction chamber of a hot wire chemical vapor deposition device, and filling reaction gas into the reaction chamber to enable the reaction gas to grow on the surface of the porous metal substrate to form a diamond/silicon carbide/metal composite film;
the porous metal matrix is through-hole foam copper or through-hole foam nickel, the volume of the reaction gas comprises 100 parts of hydrogen, 1 ~ 4 parts of methane, 0.01 ~ 0.2.2 parts of monosilane and 0.05 ~ 0.2.2 parts of nitrogen, and in the growth process, the flow rate of the reaction gas is 300 ~ 800ml/min, the air pressure of a reaction chamber is 1 ~ 3kPa, the temperature of a hot wire is 1600 ~ 2000 ℃, and the temperature of the matrix is 600 ~ 800 ℃;
(2) corroding the diamond/silicon carbide/metal composite film obtained in the step (1) by using dilute acid, and removing a metal phase in the diamond/silicon carbide/metal composite film to obtain a diamond/silicon carbide composite film;
(3) corroding the diamond/silicon carbide composite film obtained in the step (2) by using acid liquor, and removing a silicon carbide phase in the diamond/silicon carbide composite film to obtain a diamond film;
(4) after cleaning and drying the diamond film obtained in the step (3), calcining the diamond film in an oxygen-containing atmosphere to obtain a finished diamond film with a hierarchical pore structure;
wherein the oxygen-containing atmosphere has an oxygen volume content of 10 ~ 25% and a calcination temperature of 500 ~ 600 ℃.
2. The method for preparing a diamond film according to claim 1, wherein the porosity of the open pores of the porous metal substrate is not less than 70%.
3. The method for producing a diamond film according to claim 1, wherein the porous metal substrate has a thickness of less than 0.5 mm.
4. The method for preparing a diamond film according to claim 1, wherein the pretreatment comprises the steps of putting the porous metal substrate into a suspension containing diamond-acetone, performing ultrasonic treatment for 10 ~ 30min, washing the porous metal substrate with ethanol, and drying.
5. The method for preparing a diamond film according to claim 1, wherein the dilute acid is one or more selected from the group consisting of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid.
6. The method for preparing a diamond film according to claim 1, wherein the acid solution comprises 1 part by volume of concentrated nitric acid and 1 ~ 5 parts by volume of concentrated hydrofluoric acid, and the temperature of the acid solution is not lower than 50 ℃.
7. The method for producing a diamond film according to claim 1, wherein the calcination time in the step (4) is 30 to 60 min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178745A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院金属研究所 | Method for manufacturing porous diamond or porous cubic silicon carbide self-supporting film |
| CN104498894A (en) * | 2014-12-04 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Preparation method of porous diamond film |
| CN104759272A (en) * | 2014-12-09 | 2015-07-08 | 上海维埃姆环保科技有限公司 | Membrane electrode of membrane electrode low-voltage electrolysis type ozone generator and manufacturing method for positive and negative electrodes of membrane electrode low-voltage electrolysis type ozone generator |
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2019
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|---|---|---|---|---|
| CN104178745A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院金属研究所 | Method for manufacturing porous diamond or porous cubic silicon carbide self-supporting film |
| CN104498894A (en) * | 2014-12-04 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Preparation method of porous diamond film |
| CN104759272A (en) * | 2014-12-09 | 2015-07-08 | 上海维埃姆环保科技有限公司 | Membrane electrode of membrane electrode low-voltage electrolysis type ozone generator and manufacturing method for positive and negative electrodes of membrane electrode low-voltage electrolysis type ozone generator |
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| 余家国等: ""人造金刚石在空气中的热稳定性研究"", 《无机材料学报》 * |
| 王强: ""超疏水碳材料的制备及其性能研究"", 《中国博士学位论文全文数据库 工程科技II辑》 * |
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