CN112281136B - Method for preparing ultra-nano diamond film - Google Patents

Method for preparing ultra-nano diamond film Download PDF

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CN112281136B
CN112281136B CN202011165540.7A CN202011165540A CN112281136B CN 112281136 B CN112281136 B CN 112281136B CN 202011165540 A CN202011165540 A CN 202011165540A CN 112281136 B CN112281136 B CN 112281136B
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substrate
preparing
reaction gas
diamond film
diamond
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CN112281136A (en
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曾一
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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
    • C23C16/274—Diamond only using microwave discharges
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching

Abstract

The application provides a method for preparing an ultra-nano diamond film, and relates to the field of diamond films. The preparation method of the ultra-nano diamond film comprises the following steps: substrate processing, substrate cleaning and film deposition. The whole method is simple in flow and high in preparation efficiency, and compared with the traditional preparation method, the temperature required by film deposition is reduced, so that the method is more convenient to apply in industry and is convenient to use.

Description

Method for preparing ultra-nano diamond film
Technical Field
The application relates to the technical field of diamond films, in particular to a method for preparing an ultra-nano diamond film.
Background
UNCD (ultra-nanodiamond) has been attracting attention for its excellent properties. The crystal grain is small and the proportion of grain boundary is high. In addition to inheriting the physical and chemical properties of diamond, it has a small size effect. Plays an important role in the fields of electrochemistry, microelectromechanical systems (MEMS), biomedical, acoustic, optical and others. The initial UNCD was C-fed under argon-excited plasma from Argonne national laboratory in the United states 60 Obtained as a carbon source at 800 ℃.
Currently, the method for preparing the UNCD generally adopts a microwave plasma device to prepare the UNCD at a temperature of more than 800 ℃, and the temperature of 800 ℃ is too high for some materials, so that the application of the UNCD is limited.
Disclosure of Invention
The application aims to provide a method for preparing a super-nanometer diamond film, which ensures the quality and the preparation efficiency of products and reduces the temperature required by preparing the super-nanometer diamond film compared with the prior method, thereby having wider application range.
The application solves the technical problems by adopting the following technical scheme:
first, the embodiment of the application provides a method for preparing a super-nanometer diamond film, which comprises the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder and ethanol, and performing ultrasonic cleaning to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning;
film deposition: placing the cleaned substrate on a base station, feeding the substrate into a vacuum cavity of MWPCVD equipment, operating the MWPCVD equipment, vacuumizing the equipment, and then injecting a reaction gas which comprises CH 4 、Ar、CO、H 2 After the inside of the vacuum cavity is stable, starting a microwave source to excite the plasma, continuously injecting the reaction gas to balance the air pressure, maintaining the temperature of the base station at 400-500 ℃ for deposition, maintaining the normal operation of the plasma until the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, backfilling air in the vacuum cavity after the sample is cooled, and taking out the sample to obtain the ultra-nano diamond film.
Further, in some embodiments of the present application, the diamond powder has a particle size of 5-8 μm and is ultrasonically cleaned for 8-15min during the substrate processing.
Further, in some embodiments of the present application, the ultrasonic cleaning is performed for 5-15min during the above substrate cleaning process.
Further, in some embodiments of the present application, in the thin film deposition process, the material of the base is Mo or Cu.
Further, in some embodiments of the present application, the MWPCVD apparatus is operated to evacuate the apparatus to background vacuum during the thin film deposition process described above.
Further, in some embodiments of the present application, during the film deposition process, the ratio of the parts by volume of each component CH in the reaction gas 4 :Ar:CO:H 2 1-2:65-99:7-20:0-25.
Further, in some embodiments of the present application, after the reaction gas is injected during the deposition process, the internal pressure of the vacuum chamber is maintained at 1-2torr, so as to stabilize the internal pressure.
Further, in some embodiments of the present application, during the deposition of the thin film, the microwave source is turned on after the inside of the vacuum chamber is stabilized, and the microwave frequency is 2.45GHz.
Further, in some embodiments of the present application, the microwave source is turned on during the deposition of the thin film, and then the gas pressure is adjusted to excite the plasma at 2-4 Torr.
Further, in some embodiments of the present application, the deposition is performed by continuously injecting the reactive gas at a flow rate of 100-150sccm, maintaining the gas pressure at 30-60torr, and maintaining the temperature of the susceptor in the chamber at 400-500 ℃.
Compared with the prior art, the embodiment of the application has at least the following advantages or beneficial effects:
the embodiment of the application provides a method for preparing a super-nanometer diamond film, which comprises the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder and ethanol, and performing ultrasonic cleaning to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning;
film deposition: placing the cleaned substrate on a base station, feeding the substrate into a vacuum cavity of MWPCVD equipment, operating the MWPCVD equipment, vacuumizing the equipment, and then injecting a reaction gas which comprises CH 4 、Ar、CO、H 2 After the inside of the vacuum cavity is stable, starting a microwave source to excite the plasma, continuously injecting the reaction gas to balance the air pressure, maintaining the temperature of the base station at 400-500 ℃ for deposition, maintaining the normal operation of the plasma until the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, backfilling air in the vacuum cavity after the sample is cooled, and taking out the sample to obtain the ultra-nano diamond film.
The method for preparing the ultra-nano diamond film comprises the steps of firstly carrying out the substrate treatment, carrying out scratch treatment on P-type Si (100) by diamond powder, promoting nucleation by scratching the substrate, improving the nucleation rate, further promoting the growth of diamond grains, improving the preparation efficiency of the film, carrying out preliminary cleaning on the substrate by using ethanol, taking away impurities such as slag generated by scratch, and the like, wherein the ethanol is easy to volatilize and remove, and cannot influence products; then through the substrate cleaning stepThe treated substrate is further cleaned by acetone, and impurities such as grease and the like attached to the substrate due to palm contact and the like are removed, so that the subsequent steps are ensured to be smoothly carried out, the product quality is ensured, and meanwhile, the acetone is easy to volatilize and cannot influence the product; after the cleaning is finished, the film deposition step is carried out, firstly, the cleaned substrate is put into a base station, and is sent into a vacuum cavity of MWPCVD equipment, the equipment is operated, and vacuum pumping is carried out, so that the original impurity gas in the cavity is removed, the impurity gas is prevented from influencing the follow-up step, and the quality of the prepared film is ensured; then injecting a reaction gas into which CH 4 Providing a carbon source with CO, and improving the deposition rate and the film quality by introducing CO so as to facilitate the deposition of the diamond film; ar can improve the plasma atmosphere and reduce the electron energy in the plasma, thereby playing the role of reducing the size of diamond; h 2 The quality of diamond grains can be controlled, so that the prepared film is controlled to be in the ultra-nanometer level; the mixed gas is used for preparing the ultra-nano diamond film, the preparation process is more stable, the preparation efficiency is higher, the deposition rate is faster, and the use is more convenient; after the interior of the vacuum cavity is stable, starting a microwave source to ensure that the cavity is filled with reaction gas and has no other impurities, thereby ensuring the proceeding of the subsequent steps and ensuring the quality of the prepared film; the plasma is excited, the reaction gas is continuously injected to balance the air pressure, the temperature of the substrate is maintained to be 400-500 ℃, the temperature required by film deposition is reduced, and experiments show that the film deposition is not greatly influenced in the temperature range. The method reduces the limitation of the deposition temperature on the substrate material, can adapt to more environments, solves the problem that the crystal grains cannot grow on the surface of some materials due to the temperature limitation, and is easier to apply to industry; and after the reaction is finished, the microwave source and the plasma are closed, the injection of the reaction gas is stopped, the sample is vacuumized and is cooled, and the sample is taken out after the cooling is finished, so that the ultra-nano diamond film can be obtained. The whole method has simple flow and high preparation efficiency, reduces the temperature required by film deposition compared with the traditional preparation method, and is more convenient for industrial applicationThe process is convenient to use, and through experimental detection, the deposition rate can be effectively improved to be more than 600nm/H, and the process can improve the content of H without affecting the diamond size, so that the quality of the ultra-nano diamond film is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram showing SEM analysis data in a test example of the present application;
FIG. 2 is a graph of data from Raman spectroscopy in a test example of the application;
FIG. 3 is a chart showing XRD analysis data in the test example of the present application;
FIG. 4 is a graph of OES analysis data in a test example of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to specific examples.
The embodiment of the application provides a method for preparing a super-nanometer diamond film, which comprises the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder and ethanol, and performing ultrasonic cleaning to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning;
film deposition: placing the cleaned substrate on a base station, feeding the substrate into a vacuum cavity of MWPCVD equipment, operating the MWPCVD equipment, vacuumizing the equipment, and then injecting a reaction gas which comprises CH 4 、Ar、CO、H 2 After the inside of the vacuum cavity is stable, starting a microwave source to excite the plasma, continuously injecting the reaction gas to balance the air pressure, maintaining the temperature in the cavity at 400-500 ℃ for deposition, maintaining the normal operation of the plasma until the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, backfilling air in the vacuum cavity after the sample is cooled, and taking out the sample to obtain the ultra-nano diamond film.
The method for preparing the ultra-nano diamond film comprises the steps of firstly carrying out the substrate treatment, carrying out scratch treatment on P-type Si (100) by diamond powder, promoting nucleation by scratching the substrate, improving the nucleation rate, further promoting the growth of diamond grains, improving the preparation efficiency of the film, carrying out preliminary cleaning on the substrate by using ethanol, taking away impurities such as slag generated by scratch, and the like, wherein the ethanol is easy to volatilize and remove, and cannot influence products; then, the processed substrate is further cleaned by acetone through the substrate cleaning step, and impurities such as grease and the like attached to the substrate due to palm contact and the like are removed, so that the subsequent steps are ensured to be carried out smoothly, the product quality is ensured, and meanwhile, the acetone is easy to volatilize and cannot influence the product; after the cleaning is finished, the film deposition step is carried out, firstly, the cleaned substrate is put into a base station, and is sent into a vacuum cavity of MWPCVD equipment, the equipment is operated, and vacuum pumping is carried out, so that the original impurity gas in the cavity is removed, the impurity gas is prevented from influencing the follow-up step, and the quality of the prepared film is ensured; then injecting a reaction gas into which CH 4 Providing a carbon source with CO, and improving the deposition rate and the film quality by introducing CO so as to facilitate the deposition of the diamond film; ar can improve the plasma atmosphere and reduce electrons in the plasmaEnergy, thereby playing a role in reducing the size of diamond; h 2 The quality of diamond grains can be controlled, so that the prepared film is controlled to be in the ultra-nanometer level; the mixed gas is used for preparing the ultra-nano diamond film, the preparation process is more stable, the preparation efficiency is higher, the deposition rate is faster, and the use is more convenient; after the interior of the vacuum cavity is stable, starting a microwave source to ensure that the cavity is filled with reaction gas and has no other impurities, thereby ensuring the proceeding of the subsequent steps and ensuring the quality of the prepared film; the plasma is excited, the reaction gas is continuously injected to balance the air pressure, the temperature of the substrate is maintained to be 400-500 ℃, the temperature required by film deposition is reduced, and experiments show that the film deposition is not greatly influenced in the temperature range. The method reduces the limitation of the deposition temperature on the substrate material, can adapt to more environments, solves the problem that the crystal grains cannot grow on the surface of some materials due to the temperature limitation, and is easier to apply to industry; and after the reaction is finished, the microwave source and the plasma are closed, the injection of the reaction gas is stopped, the sample is vacuumized and is cooled, and the sample is taken out after the cooling is finished, so that the ultra-nano diamond film can be obtained. The whole method has simple flow and high preparation efficiency, reduces the temperature required by film deposition compared with the traditional preparation method, is more convenient for industrial application, is convenient to use, can effectively improve the deposition rate to be more than 600nm/H through experimental detection, and can improve the content of H without affecting the diamond size, thereby improving the quality of the ultra-nano diamond film.
In some embodiments of the application, the diamond powder has a particle size of 5-8 μm and is ultrasonically cleaned for 8-15min during the substrate processing.
In the above embodiment, by controlling the particle size of the diamond powder and the time of ultrasonic cleaning, the substrate can be scratched more effectively, so as to improve the nucleation rate, promote the production of diamond grains, further improve the deposition efficiency and improve the quality of the product.
In some embodiments of the application, the ultrasonic cleaning is performed for 5-15min during the above substrate cleaning process.
In the above embodiment, by controlling the time of ultrasonic cleaning, the grease adhering to the substrate due to palm contact can be effectively cleaned without residue, so that the subsequent steps are ensured to be smoothly performed, and the quality of the prepared film is ensured.
In some embodiments of the application, in the thin film deposition process, the material of the base is Mo or Cu.
In the embodiment, the base made of Mo or Cu has stronger high temperature resistance and thermal conductivity, low cost and more convenient use.
In some embodiments of the present application, the MWPCVD apparatus is operated to evacuate the apparatus to background vacuum during the thin film deposition process described above.
In the above embodiment, the MWPCVD apparatus is vacuumized and brought to the background vacuum, so as to ensure that the residual gas in the chamber of the apparatus is completely discharged, and ensure that no other impurity gas is in the chamber, thereby ensuring the smooth proceeding of the subsequent steps, and simultaneously being helpful to improve the quality of the prepared film.
In some embodiments of the present application, the ratio of the parts by volume of each component CH in the reaction gas during the deposition of the thin film 4 :Ar:CO:H 2 1-2:65-99:7-20:0-25.
In the embodiment, by controlling the volume ratio of each component in the reaction gas, film deposition can be performed more stably, and diamond films with different quality and size can be prepared by controlling the concentration of the components according to the requirement, so that the method is beneficial to industrial application and is more convenient to use.
In some embodiments of the present application, after the reaction gas is injected during the deposition process, the internal pressure of the vacuum chamber is maintained at 1-2torr to stabilize the internal pressure.
In the above embodiment, after the reaction gas is injected, the internal air pressure of the vacuum chamber is kept at 1-2torr, so that the vacuum chamber is ensured to be filled with the reaction gas, and other impurity gases are not mixed, so that the normal operation of the subsequent process is ensured, and the quality of the prepared film is improved.
In some embodiments of the present application, in the film deposition process, the microwave source is turned on after the vacuum chamber is stabilized, and the microwave frequency is 2.45GHz.
In the embodiment, the deposition of the diamond film can be more effectively performed by controlling the microwave frequency to be 2.45GHz, which is beneficial to improving the quality of the prepared film and is more convenient to use.
In some embodiments of the present application, the microwave source is turned on during the deposition of the thin film, and then the gas pressure is adjusted to excite the plasma at 2-4 Torr.
In the embodiment, the pressure is controlled to be 2-4Torr, so that the plasma can be excited more conveniently, the normal operation of the plasma is ensured, and the quality of the prepared film is improved.
In some embodiments of the present application, the deposition is performed by continuously injecting the reactive gas at a flow rate of 100-150sccm, maintaining the pressure at 30-60torr, and maintaining the temperature of the chamber base at 400-500 ℃.
In the embodiment, the air flow is controlled to be 100-150sccm, the air pressure balance is kept at 30-60torr, the temperature of the base station in the cavity is 400-500 ℃, the environment in the cavity can be ensured to be stable, the deposition of the diamond film is facilitated, and the quality of the prepared diamond film can be improved; compared with the existing preparation method, the method reduces the required temperature, is beneficial to industrial application and is more convenient to use.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment provides a method for preparing a super-nanometer diamond film, which comprises the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder with the particle size of 5 mu m and ethanol, and carrying out ultrasonic cleaning for 8min to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning for 5min;
film deposition: placing the cleaned substrate on a base station made of Mo, feeding the base station into a vacuum cavity of MWPCVD equipment, operating the MWPCVD equipment, vacuumizing the equipment to reach background vacuum, injecting reaction gas, and adding the reaction gas into the reaction gas according to the volume ratio of each component CH 4 :Ar:CO:H 2 1:70:9:20; and after the internal stability of the vacuum cavity is maintained, starting a microwave source, the microwave frequency is 2.45GHz, the air pressure is adjusted to be 2Torr, exciting plasma, continuously injecting reaction gas, keeping the air pressure at 30Torr at 100sccm, keeping the temperature in the cavity at 420 ℃ for deposition, keeping the normal operation of the plasma until the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, backfilling air in the vacuum cavity after waiting for cooling of a sample, and taking out the sample to obtain the ultra-nano diamond film.
Example 2
The embodiment provides a method for preparing a super-nanometer diamond film, which comprises the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder with the particle size of 8 mu m and ethanol, and carrying out ultrasonic cleaning for 15min to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning for 15min;
film deposition: placing the cleaned substrate on a base station made of Cu, feeding the base station into a vacuum cavity of MWPCVD equipment, operating the MWPCVD equipment, vacuumizing the equipment to reach background vacuum, injecting reaction gas, and adding the reaction gas into the reaction gas according to the volume ratio of each component CH 4 :Ar:CO:H 2 1.6:82:12.3:4.1; after the internal stability of the vacuum cavity is maintained, starting a microwave source after the air pressure is kept at 2Torr, the microwave frequency is 2.45GHz, adjusting the air pressure to 4Torr, exciting the plasma, continuously injecting the reaction gas, keeping the air pressure at 60Torr at 150sccm, keeping the temperature in the cavity at 466 ℃ for deposition, keeping the normal working of the plasma until the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, and waiting for a sampleAnd (3) after cooling, backfilling air in the vacuum cavity, and taking out the sample to obtain the ultra-nano diamond film.
Example 3
The embodiment provides a method for preparing a super-nanometer diamond film, which comprises the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder with the particle size of 7 mu m and ethanol, and carrying out ultrasonic cleaning for 10min to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning for 10min;
film deposition: placing the cleaned substrate on a base station made of Mo, feeding the base station into a vacuum cavity of MWPCVD equipment, operating the MWPCVD equipment, vacuumizing the equipment to reach background vacuum, injecting reaction gas, and adding the reaction gas into the reaction gas according to the volume ratio of each component CH 4 :Ar:CO:H 2 1.5:73:11:14.5; and after the internal stability of the vacuum cavity is maintained, starting a microwave source, the microwave frequency is 2.45GHz, the air pressure is adjusted to be 3Torr, exciting plasma, continuously injecting reaction gas, keeping the air pressure at 40Torr at the gas flow of 125sccm, keeping the temperature in the cavity at 450 ℃ for deposition, keeping the normal operation of the plasma until the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, backfilling air in the vacuum cavity after waiting for cooling of a sample, and taking out the sample to obtain the ultra-nano diamond film.
Example 4
The embodiment provides a method for preparing a super-nanometer diamond film, which comprises the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder with the particle size of 6 mu m and ethanol, and carrying out ultrasonic cleaning for 12min to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning for 12min;
film deposition: placing the cleaned substrate on a base station made of Mo and feeding the substrate into a vacuum cavity of MWPCVD equipmentIn the process, MWPCVD equipment is operated, the equipment is vacuumized to reach background vacuum, then reaction gas is injected, and the volume ratio of each component CH in the reaction gas 4 :Ar:CO:H 2 Is 2:80:18:1; and after the internal stability of the vacuum cavity is maintained, starting a microwave source, the microwave frequency is 2.45GHz, the air pressure is adjusted to be 3Torr, exciting plasma, continuously injecting reaction gas, keeping the air pressure at 42Torr at 130sccm, keeping the temperature in the cavity at 420 ℃ for deposition, keeping the normal operation of the plasma until the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, backfilling air in the vacuum cavity after waiting for cooling of a sample, and taking out the sample to obtain the ultra-nano diamond film.
Example 5
The embodiment provides a method for preparing a super-nanometer diamond film, which comprises the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder with the particle size of 7.5 mu m and ethanol, and carrying out ultrasonic cleaning for 10min to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning for 10min;
film deposition: placing the cleaned substrate on a base station made of Mo, feeding the base station into a vacuum cavity of MWPCVD equipment, operating the MWPCVD equipment, vacuumizing the equipment to reach background vacuum, injecting reaction gas, and adding the reaction gas into the reaction gas according to the volume ratio of each component CH 4 :Ar:CO:H 2 1:75:9:15; and after the internal stability of the vacuum cavity is maintained, starting a microwave source, the microwave frequency is 2.45GHz, the air pressure is adjusted to be 3Torr, exciting plasma, continuously injecting reaction gas, keeping the air pressure at 40Torr at the air flow of 100sccm, keeping the temperature in the cavity at 450 ℃ for deposition, keeping the normal operation of the plasma until the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, backfilling air in the vacuum cavity after waiting for cooling of a sample, and taking out the sample to obtain the ultra-nano diamond film.
Test examples
The test and detection of the ultra-nano diamond film prepared by the method for preparing the ultra-nano diamond film provided in example 5:
the data obtained by cross-section SEM analysis are shown in fig. 1.
As can be seen from the data, the thickness of the prepared ultra-nano diamond film is 3.3 mu m, and the deposition rate of the method is 660nm/h through calculation.
Raman spectroscopy was performed and the data obtained is shown in fig. 2.
According to data fitting, the characteristic peaks of diamond appear in the middle 1332 of the map, two peaks at 1175 and 1470 are characteristic peaks of nano diamond, and the tail is characteristic peak of impurity graphite, so that the film prepared by the method can be judged to be the ultra-nano diamond film.
XRD analysis was performed and the data obtained is shown in FIG. 3.
As can be seen from the data, characteristic peaks of diamond at 43.92, 75.3 and 91.5 in the map, the size of the diamond is 8nm through half-width calculation.
OES analysis was performed and the data obtained is shown in figure 4.
From the data, there is C at 516 in the map 2 The characteristic peak of the group, which is the main group of the nano-diamond, is H at 656, which can be combined to prove that the reaction process is diamond deposition reaction.
According to the test result, compared with the traditional method, the method reduces the temperature required for preparing the ultra-nano diamond, is convenient for industrial application, does not influence the deposition rate due to the reduction of the temperature, ensures the preparation efficiency of the product, and can ensure that the product prepared by the method is an ultra-nano diamond film, and has the characteristics meeting the requirements, high product quality and good use performance.
In summary, an embodiment of the present application provides a method for preparing a super-nano diamond film, which includes performing the above substrate processing step, performing a scratch treatment on P-type Si (100) by diamond powder, and performing a scratch treatment on the substrateThe nucleation is promoted, the nucleation rate is improved, the growth of diamond grains is further promoted, the preparation efficiency of the film is improved, the substrate can be primarily cleaned by using ethanol, impurities such as slag generated by scratches are taken away, the ethanol is volatile and easy to remove, and the product cannot be influenced; then, the processed substrate is further cleaned by acetone through the substrate cleaning step, and impurities such as grease and the like attached to the substrate due to palm contact and the like are removed, so that the subsequent steps are ensured to be carried out smoothly, the product quality is ensured, and meanwhile, the acetone is easy to volatilize and cannot influence the product; after the cleaning is finished, the film deposition step is carried out, firstly, the cleaned substrate is put into a base station, and is sent into a vacuum cavity of MWPCVD equipment, the equipment is operated, and vacuum pumping is carried out, so that the original impurity gas in the cavity is removed, the impurity gas is prevented from influencing the follow-up step, and the quality of the prepared film is ensured; then injecting a reaction gas into which CH 4 Providing a carbon source with CO, and improving the deposition rate and the film quality by introducing CO so as to facilitate the deposition of the diamond film; ar can improve the plasma atmosphere and reduce the electron energy in the plasma, thereby playing the role of reducing the size of diamond; h 2 The quality of diamond grains can be controlled, so that the prepared film is controlled to be in the ultra-nanometer level; the mixed gas is used for preparing the ultra-nano diamond film, the preparation process is more stable, the preparation efficiency is higher, the deposition rate is faster, and the use is more convenient; after the interior of the vacuum cavity is stable, starting a microwave source to ensure that the cavity is filled with reaction gas and has no other impurities, thereby ensuring the proceeding of the subsequent steps and ensuring the quality of the prepared film; the plasma is excited, the reaction gas is continuously injected to balance the air pressure, the temperature of the substrate is maintained to be 400-500 ℃, the temperature required by film deposition is reduced, and experiments show that the film deposition is not greatly influenced in the temperature range. The method reduces the limitation of the deposition temperature on the substrate material, can adapt to more environments, solves the problem that the crystal grains cannot grow on the surface of some materials due to the temperature limitation, and is easier to apply to industry; after the reaction is finished, the microwave is turned offAnd (3) the source and the plasma, stopping injecting the reaction gas, vacuumizing, waiting for cooling the sample, filling air after cooling, and taking out the sample to obtain the ultra-nano diamond film. The whole method has simple flow and high preparation efficiency, reduces the temperature required by film deposition compared with the traditional preparation method, is more convenient for industrial application, is convenient to use, can effectively improve the deposition rate to be more than 600nm/H through experimental detection, and can improve the content of H without affecting the diamond size, thereby improving the quality of the ultra-nano diamond film. The embodiments described above are some, but not all embodiments of the application. The detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.

Claims (9)

1. A method for preparing a super-nanometer diamond film, which is characterized by comprising the following steps:
substrate processing: selecting single-sided polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder and ethanol, and performing ultrasonic cleaning to scratch the substrate;
and (3) cleaning a substrate: placing the processed substrate into an acetone solution for ultrasonic cleaning;
film deposition: placing the cleaned substrate on a base station, sending the cleaned substrate into a vacuum cavity of MWPCVD equipment, operating the MWPCVD equipment, vacuumizing the equipment, and then injecting reaction gas, wherein the reaction gas is mixed gas comprising CH4, ar, CO and H2, and the volume part ratio of each component in the mixed gas is CH 4to Ar to CO to H2 is 1-2:65-99:7-20:0-25; and after the inside of the vacuum cavity is stable, starting a microwave source, exciting plasma, continuously injecting reaction gas to balance the air pressure, maintaining the temperature of the base station at 400-500 ℃ for deposition, maintaining the normal operation of the plasma, closing the microwave source and the plasma until the reaction is finished, stopping injecting the reaction gas, vacuumizing, backfilling air in the vacuum cavity after the sample is cooled, and taking out the sample to obtain the ultra-nano diamond film.
2. The method for preparing a super nano-diamond film according to claim 1, wherein the diamond powder has a particle size of 5-8 μm and is ultrasonically cleaned for 8-15min during the substrate processing.
3. The method for preparing a super nano-diamond film according to claim 1, wherein the ultrasonic cleaning is performed for 5-15min during the substrate cleaning process.
4. The method for preparing a super nano-diamond film according to claim 1, wherein the material of the base is Mo or Cu during the film deposition process.
5. The method of claim 1, wherein the MWPCVD apparatus is operated to evacuate the apparatus to background vacuum during the film deposition process.
6. The method for preparing a super nano-diamond film according to claim 1, wherein the reaction gas is injected during the film deposition process, and the internal pressure of the vacuum chamber is maintained at 1-2torr to stabilize the vacuum chamber.
7. The method for preparing a super nano-diamond film according to claim 1, wherein in the film deposition process, a microwave source is started after the inside of the vacuum cavity is stabilized, and the microwave frequency is 2.45GHz.
8. The method for preparing a super nano-diamond film according to claim 1, wherein the plasma is excited at 2-4Torr by adjusting the gas pressure after turning on the microwave source during the film deposition.
9. The method for preparing a super nano-diamond film according to claim 1, wherein the reaction gas is continuously injected during the film deposition process, the gas flow is 100-150sccm, the gas pressure is kept balanced at 30-60torr, and the temperature of the base station in the cavity is maintained at 400-500 ℃ for deposition.
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