CN112281136A - Method for preparing ultra-nano diamond film - Google Patents
Method for preparing ultra-nano diamond film Download PDFInfo
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- CN112281136A CN112281136A CN202011165540.7A CN202011165540A CN112281136A CN 112281136 A CN112281136 A CN 112281136A CN 202011165540 A CN202011165540 A CN 202011165540A CN 112281136 A CN112281136 A CN 112281136A
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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
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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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
Abstract
The invention provides a method for preparing an ultra-nano diamond film, and relates to the field of diamond films. A preparation method of an ultra-nano diamond film comprises the following steps: substrate processing, substrate cleaning and film deposition. The method for preparing the ultra-nano diamond film has the advantages of simple whole method flow and high preparation efficiency, and reduces the temperature required by film deposition compared with the traditional preparation method, so that the method is more convenient to apply in industry and use.
Description
Technical Field
The invention relates to the technical field of diamond films, in particular to a method for preparing an ultra-nano diamond film.
Background
UNCD (ultra nano diamond) is of great interest because of its excellent properties. Small crystal grains and high grain boundary proportion. In addition to inheriting the physical and chemical properties of diamond, it also has a small size effect. Plays an important role in electrochemistry, micro-electro-mechanical systems (MEMS), biomedicine, acoustics, optics and other fields. The first UNCD was introduced by C under argon-excited plasma in Argonne national laboratory in the United states60Obtained as a carbon source at 800 ℃.
The method for preparing the UNCD generally adopts a microwave plasma device to prepare the UNCD at the temperature of over 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 invention aims to provide a method for preparing an ultra-nano diamond film, which reduces the temperature required by preparing the ultra-nano diamond film while ensuring the product quality and the preparation efficiency compared with the prior method, thereby widening the application range of the method.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
first, an embodiment of the present invention provides a method for preparing an ultra-nano diamond film, which includes the following steps:
substrate processing: selecting single-side polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder and ethanol, and carrying out scratch treatment on the substrate through ultrasonic cleaning;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning;
and (3) thin film deposition: placing the cleaned substrate on a base table, feeding the substrate into a vacuum chamber of an MWPCVD device, operating the MWPCVD device, vacuumizing the device, and injecting a reaction gas comprising CH4、Ar、CO、H2After the interior of the vacuum cavity is stabilized, starting a microwave source, exciting a 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 work of the plasma until the microwave source and the plasma are closed after the reaction is finished, stopping injecting the reaction gas, vacuumizing, refilling air in the vacuum cavity after the sample is cooled, and then taking out the sample to obtain the ultra-nano diamond film.
Further, in some embodiments of the present invention, during the substrate processing, the diamond powder has a particle size of 5-8 μm, and is ultrasonically cleaned for 8-15 min.
Further, in some embodiments of the present invention, the substrate cleaning process is performed by ultrasonic cleaning for 5-15 min.
Further, in some embodiments of the present invention, in the film deposition process, a material of the base is Mo or Cu.
Further, in some embodiments of the present invention, during the thin film deposition process, the MWPCVD device is operated to evacuate the device to a background vacuum.
Go toIn some embodiments of the invention, the volume fraction ratio of each component in the reaction gas CH is CH during the deposition of the thin film4:Ar:CO:H2Is 1-2:65-99:7-20: 0-25.
Further, in some embodiments of the present invention, during the thin film deposition, after the reaction gas is injected, the pressure inside the vacuum chamber is maintained at 1-2torr to stabilize the reaction gas.
Further, in some embodiments of the present invention, during the film deposition process, after the interior of the vacuum chamber is stabilized, the microwave source is turned on, and the microwave frequency is 2.45 GHz.
Further, in some embodiments of the present invention, during the film deposition process, after the microwave source is turned on, the pressure is adjusted to ignite plasma at 2-4 Torr.
Further, in some embodiments of the present invention, during the deposition of the thin film, the reaction gas is continuously injected with a flow rate of 100-.
Compared with the prior art, the embodiment of the invention has at least the following advantages or beneficial effects:
the embodiment of the invention provides a method for preparing an ultra-nano diamond film, which comprises the following steps:
substrate processing: selecting single-side polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder and ethanol, and carrying out scratch treatment on the substrate through ultrasonic cleaning;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning;
and (3) thin film deposition: placing the cleaned substrate on a base table, feeding the substrate into a vacuum chamber of an MWPCVD device, operating the MWPCVD device, vacuumizing the device, and injecting a reaction gas comprising CH4、Ar、CO、H2After the interior of the vacuum cavity is stabilized, starting a microwave source to excite the plasma, continuously injecting reaction gas to balance the gas pressure, maintaining the temperature of the base station at 400-And after the reaction is finished, closing the microwave source and the plasma, stopping injecting the reaction gas, vacuumizing, refilling air in the vacuum cavity after the sample is cooled, and then taking out the sample to obtain the ultra-nano diamond film.
The method for preparing the ultra-nano diamond film comprises the following steps of firstly carrying out the substrate treatment step, carrying out scratch treatment on P-type Si (100) through diamond powder, promoting nucleation through scratching the substrate, improving the nucleation rate, further promoting the growth of diamond grains and improving the preparation efficiency of the film, preliminarily cleaning the substrate through using ethanol, taking away impurities such as crushed slag and the like generated by scratch, and easily volatilizing and removing the ethanol without influencing the product; then, the substrate after treatment is further cleaned by acetone in the substrate cleaning step, and impurities such as grease and the like attached to the substrate due to factors such as palm contact and the like are removed, so that the subsequent steps are smoothly carried out, the product quality is ensured, and meanwhile, the acetone is volatile and cannot affect the product; after cleaning, the film deposition step is carried out, the cleaned substrate is firstly placed into a base station and sent into a vacuum chamber of MWPCVD equipment, the equipment is operated and vacuumized so as to remove original impurity gas in the chamber and avoid the impurity gas from influencing the subsequent steps, thereby ensuring the quality of the prepared film; then injecting a reaction gas containing CH4Carbon source is provided with CO, and the deposition rate is improved and the film quality is improved by introducing CO, so that the deposition of the diamond film is facilitated; ar can improve the plasma atmosphere and reduce the electron energy in the plasma, thereby achieving the effect of reducing the size of the diamond; h2The quality of diamond grains can be controlled, so that the prepared film is controlled to be in an 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 higher, and the use is more convenient; after the interior of the vacuum cavity is stabilized, the microwave source is started to ensure that the cavity is filled with reaction gas and has no other impurities, so that the subsequent steps are ensured, and the quality of the prepared film is ensured; exciting plasma, and continuously injecting reaction gas to make pressure of the gasThe balance is carried out, the temperature of the substrate is maintained at 400-500 ℃, the temperature required by the film deposition is reduced, and experiments show that the film deposition cannot be greatly influenced in the temperature range. The method reduces the limitation on the substrate material due to high deposition temperature, can adapt to more environments, solves the problem that crystal grains cannot grow on the surfaces of some materials due to temperature limitation, and is easier to apply to the industry; and (3) closing the microwave source and the plasma after the reaction is finished, stopping injecting the reaction gas, vacuumizing to wait for the sample to be cooled, filling air after the cooling is finished, and taking out the sample to obtain the ultra-nano diamond film. The whole method is simple in flow and high in preparation efficiency, reduces the temperature required by film deposition compared with the traditional preparation method, enables the film deposition to be 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 influencing the size of diamond, thereby improving the quality of the ultra-nano diamond film.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a SEM analysis data chart in the experimental example of the present invention;
FIG. 2 is a Raman spectroscopy data spectrum in an experimental example of the present invention;
FIG. 3 is a data pattern of XRD analysis in an experimental example of the present invention;
FIG. 4 is a graph of OES analysis data in the experimental examples of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to specific examples.
The embodiment of the invention provides a method for preparing an ultra-nano diamond film, which comprises the following steps:
substrate processing: selecting single-side polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder and ethanol, and carrying out scratch treatment on the substrate through ultrasonic cleaning;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning;
and (3) thin film deposition: placing the cleaned substrate on a base table, feeding the substrate into a vacuum chamber of an MWPCVD device, operating the MWPCVD device, vacuumizing the device, and injecting a reaction gas comprising CH4、Ar、CO、H2After the interior of the vacuum cavity is stabilized, starting a microwave source, exciting a plasma, balancing the air pressure when continuously injecting the reaction gas, maintaining the temperature in the cavity at 400-500 ℃ for deposition, maintaining the normal work of the plasma until the microwave source and the plasma are closed after the reaction is finished, stopping injecting the reaction gas, vacuumizing, refilling air in the vacuum cavity after the sample is cooled, and then taking out the sample to obtain the ultra-nano diamond film.
The method for preparing the ultra-nano diamond film comprises the following steps of firstly carrying out the substrate treatment step, carrying out scratch treatment on P-type Si (100) through diamond powder, promoting nucleation through scratching the substrate, improving the nucleation rate, further promoting the growth of diamond grains and improving the preparation efficiency of the film, preliminarily cleaning the substrate through using ethanol, taking away impurities such as crushed slag and the like generated by scratch, and easily volatilizing and removing the ethanol without influencing the product; then, the substrate after treatment was further cleaned with acetone by the above-mentioned substrate cleaning step to remove the causeThe factors such as palm contact and the like are attached to impurities such as grease and the like on the substrate, so that the smooth proceeding of the subsequent steps is ensured, the product quality is ensured, and meanwhile, the acetone is volatile and cannot influence the product; after cleaning, the film deposition step is carried out, the cleaned substrate is firstly placed into a base station and sent into a vacuum chamber of MWPCVD equipment, the equipment is operated and vacuumized so as to remove original impurity gas in the chamber and avoid the impurity gas from influencing the subsequent steps, thereby ensuring the quality of the prepared film; then injecting a reaction gas containing CH4Carbon source is provided with CO, and the deposition rate is improved and the film quality is improved by introducing CO, so that the deposition of the diamond film is facilitated; ar can improve the plasma atmosphere and reduce the electron energy in the plasma, thereby achieving the effect of reducing the size of the diamond; h2The quality of diamond grains can be controlled, so that the prepared film is controlled to be in an 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 higher, and the use is more convenient; after the interior of the vacuum cavity is stabilized, the microwave source is started to ensure that the cavity is filled with reaction gas and has no other impurities, so that the subsequent steps are ensured, and the quality of the prepared film is ensured; the plasma is excited, the reaction gas is continuously injected to balance the gas pressure, the temperature of the substrate is maintained at 400-500 ℃, the temperature required by the film deposition is reduced, and experiments show that the film deposition cannot be greatly influenced in the temperature range. The method reduces the limitation on the substrate material due to high deposition temperature, can adapt to more environments, solves the problem that crystal grains cannot grow on the surfaces of some materials due to temperature limitation, and is easier to apply to the industry; and (3) closing the microwave source and the plasma after the reaction is finished, stopping injecting the reaction gas, vacuumizing to wait for the sample to be cooled, filling air after the cooling is finished, 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 to apply in industry, is convenient to use, and can effectively carry out the process through experimental detectionThe deposition rate is increased to be more than 600nm/H, and the process can increase the content of H without influencing the size of diamond, thereby improving the quality of the ultra-nano diamond film.
In some embodiments of the present invention, during the substrate processing, the diamond powder has a particle size of 5-8 μm and is ultrasonically cleaned for 8-15 min.
In the embodiment, the substrate can be scratched more effectively by controlling the grain size of the diamond powder and the ultrasonic cleaning time, so that the nucleation rate is improved, the production of diamond grains is promoted, the deposition efficiency is improved, and the product quality is improved.
In some embodiments of the present invention, the substrate cleaning process is performed by ultrasonic cleaning for 5-15 min.
In the embodiment, by controlling the ultrasonic cleaning time, grease attached to the substrate due to palm contact can be effectively cleaned without residue, so that the subsequent steps are ensured to be smoothly carried out, and the quality of the prepared film is ensured.
In some embodiments of the present invention, in the thin film deposition process, the material of the base is Mo or Cu.
In the above embodiments, the Mo or Cu base has higher heat resistance and thermal conductivity, and is low in cost and more convenient to use.
In some embodiments of the present invention, during the thin film deposition process, the MWPCVD device is operated to evacuate the device to a background vacuum.
In the embodiment, the MWPCVD equipment is vacuumized and reaches the background vacuum, so that residual gas in the cavity of the equipment is completely discharged, other impurity gases are not in the cavity, the subsequent steps are smoothly carried out, and the quality of the prepared film is improved.
In some embodiments of the present invention, the volume fraction ratio of each component in the reaction gas CH during the thin film deposition process4:Ar:CO:H2Is 1-2:65-99:7-20: 0-25.
In the embodiment, the volume ratio of each component in the reaction gas is controlled, so that the film deposition can be carried out more stably, and the diamond films with different qualities and sizes can be prepared by controlling the component concentration according to requirements, thereby being beneficial to industrial application and being more convenient to use.
In some embodiments of the present invention, during the thin film deposition process, after the reaction gas is injected, the pressure inside the vacuum chamber is maintained at 1-2torr to stabilize the reaction gas.
In the above embodiment, after the reaction gas is injected, the pressure inside the vacuum chamber is kept at 1-2torr, so that the vacuum chamber is stable, thereby ensuring that the vacuum chamber is filled with the reaction gas without mixing other impurity gases, further ensuring the normal operation of the subsequent process, and being beneficial to improving the quality of the prepared film.
In some embodiments of the present invention, 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 2.45 GHz.
In the embodiment, the deposition of the diamond film can be more effectively carried out by controlling the microwave frequency to be 2.45GHz, so that the quality of the prepared film is improved, and the use is more convenient.
In some embodiments of the present invention, the plasma is excited at 2-4Torr by adjusting the gas pressure after the microwave source is turned on during the film deposition process.
In the embodiment, the pressure is controlled to be 2-4Torr, which is more favorable for exciting the plasma, ensures the normal work of the plasma and is favorable for improving the quality of the prepared film.
In some embodiments of the present invention, during the deposition of the thin film, the reaction gas is continuously injected with a gas flow rate of 100-.
In the embodiment, the gas flow is controlled to be 100-; 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 properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a method for preparing an ultra-nano diamond film, which comprises the following steps:
substrate processing: selecting single-side 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;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning for 5 min;
and (3) thin film deposition: placing the cleaned substrate on a Mo base station, feeding the substrate into a vacuum chamber of an MWPCVD device, operating the MWPCVD device, vacuumizing the device to make the device reach background vacuum, and injecting reaction gas with the volume ratio of each component of CH in the reaction gas4:Ar:CO:H21:70:9: 20; and after the interior of the vacuum cavity is stable, keeping the air pressure at 1Torr, starting the microwave source, adjusting the microwave frequency to 2.45GHz, adjusting the air pressure to 2Torr, exciting the plasma, continuously injecting the reaction gas, keeping the air pressure at 30Torr in balance by using the gas flow of 100sccm, maintaining the temperature in the cavity at 420 ℃ for deposition, maintaining the normal work of the plasma until the microwave source and the plasma are closed after the reaction is finished, stopping injecting the reaction gas, vacuumizing, refilling air in the vacuum cavity after the sample is cooled, and then taking out the sample to obtain the ultra-nano diamond film.
Example 2
The embodiment provides a method for preparing an ultra-nano diamond film, which comprises the following steps:
substrate processing: selecting single-side 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;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning for 15 min;
and (3) thin film deposition: placing the cleaned substrate on a Cu base table, feeding the substrate into a vacuum chamber of an MWPCVD device, operating the MWPCVD device, vacuumizing the device to reach background vacuum, and injecting reaction gas with the volume ratio of each component being CH4:Ar:CO:H21.6:82:12.3: 4.1; and after the interior of the vacuum cavity is stable, keeping the air pressure at 2Torr, starting the microwave source, adjusting the microwave frequency to 2.45GHz, adjusting the air pressure to 4Torr, exciting the plasma, continuously injecting the reaction gas, keeping the air pressure at 60Torr in balance by using the gas flow of 150sccm, keeping the temperature in the cavity at 466 ℃ for deposition, keeping the plasma to normally work until the microwave source and the plasma are closed after the reaction is finished, stopping injecting the reaction gas, vacuumizing, refilling air in the vacuum cavity after the sample is cooled, and then taking out the sample to obtain the ultra-nano diamond film.
Example 3
The embodiment provides a method for preparing an ultra-nano diamond film, which comprises the following steps:
substrate processing: selecting single-side 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;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning for 10 min;
and (3) thin film deposition: placing the cleaned substrate on a Mo base station, feeding the substrate into a vacuum chamber of an MWPCVD device, operating the MWPCVD device, vacuumizing the device to make the device reach background vacuum, and injecting reaction gas with the volume ratio of each component of CH in the reaction gas4:Ar:CO:H21.5:73:11: 14.5; starting the microwave source after the inside of the vacuum cavity is stable and the gas pressure is kept at 1.5Torr, adjusting the microwave frequency to 2.45GHz and the gas pressure to 3Torr, exciting the plasma, continuously injecting the reaction gas, keeping the gas pressure balanced at 40Torr with the gas flow of 125sccm, maintaining the temperature in the cavity at 450 ℃ for deposition, maintaining the normal work of the plasma until the microwave source and the plasma are closed after the reaction is finished, stopping injecting the reaction gas, vacuumizing, waiting for the sample to be sampled, stopping injecting the reaction gas, and stopping vacuumizingAnd after cooling, backfilling air in the vacuum cavity, and then taking out the sample to obtain the ultra-nano diamond film.
Example 4
The embodiment provides a method for preparing an ultra-nano diamond film, which comprises the following steps:
substrate processing: selecting single-side 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;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning for 12 min;
and (3) thin film deposition: placing the cleaned substrate on a Mo base station, feeding the substrate into a vacuum chamber of an MWPCVD device, operating the MWPCVD device, vacuumizing the device to make the device reach background vacuum, and injecting reaction gas with the volume ratio of each component of CH in the reaction gas4:Ar:CO:H2Is 2:80:18: 1; and after the interior of the vacuum cavity is stable, keeping the air pressure at 1Torr, starting the microwave source, adjusting the microwave frequency to 2.45GHz, adjusting the air pressure to 3Torr, exciting the plasma, continuously injecting the reaction gas, keeping the air pressure at 42Torr balanced by the gas flow of 130sccm, keeping the temperature in the cavity at 420 ℃ for deposition, keeping the plasma to normally work until the microwave source and the plasma are closed after the reaction is finished, stopping injecting the reaction gas, vacuumizing, refilling air in the vacuum cavity after the sample is cooled, and then taking out the sample to obtain the ultra-nano diamond film.
Example 5
The embodiment provides a method for preparing an ultra-nano diamond film, which comprises the following steps:
substrate processing: selecting single-side polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder with the grain diameter of 7.5 mu m and ethanol, and carrying out ultrasonic cleaning for 10min to scratch the substrate;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning for 10 min;
and (3) thin film deposition: the cleaned substrate is placed on a Mo base table and sent into a vacuum chamber of an MWPCVD deviceRunning MWPCVD equipment, vacuumizing the equipment to make it reach background vacuum, then injecting reaction gas in which the volume ratio of all the components is CH4:Ar:CO:H21:75:9: 15; and after the interior of the vacuum cavity is stable, keeping the air pressure at 2Torr, starting the microwave source, adjusting the microwave frequency to 2.45GHz, adjusting the air pressure to 3Torr, exciting the plasma, continuously injecting the reaction gas, keeping the air pressure at 40Torr in balance by using the gas flow of 100sccm, keeping the temperature in the cavity at 450 ℃ for deposition, keeping the plasma to normally work until the microwave source and the plasma are closed after the reaction is finished, stopping injecting the reaction gas, vacuumizing, refilling air in the vacuum cavity after the sample is cooled, and then taking out the sample to obtain the ultra-nano diamond film.
Test examples
Experimental examination was performed on the ultra-nano diamond film prepared by the method for preparing an ultra-nano diamond film provided in example 5:
the data obtained by SEM analysis of the cross section are shown in FIG. 1.
As can be seen from the data, the thickness of the prepared ultra-nano diamond film is 3.3 μm, and the deposition rate of the method is 660nm/h by calculation.
Raman spectroscopy was performed and the data obtained are shown in fig. 2.
Through data fitting, the characteristic peak of diamond appears at the middle 1332 of the map, two peaks at 1175 and 1470 are the characteristic peaks of nano-diamond, and the tail is the 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.
The data show that the characteristic peaks of diamond are at 43.92, 75.3 and 91.5 in the map, and the size of diamond is 8nm calculated by the half-peak width.
OES analysis was performed and the data obtained are shown in FIG. 4.
As can be seen from the data, C is present at 516 in the map2Characteristic peak of group, the group is main group of nano diamond,at 656 is the characteristic peak of H, which together can demonstrate that the reaction process is a diamond deposition reaction.
According to the test results, compared with the traditional method, the method reduces the temperature required by preparing the ultra-nano diamond, is convenient for industrial application, does not influence the deposition rate due to temperature reduction, ensures the preparation efficiency of the product, and simultaneously can ensure that the product prepared by the method is the ultra-nano diamond film, the characteristics of which meet the requirements, the product quality is high, and the service performance is good.
To sum up, the embodiment of the invention provides a method for preparing an ultra-nano diamond film, which 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 primary cleaning on the substrate by using ethanol, taking away impurities such as broken slag and the like generated by scratch, and easily removing the ethanol which is volatile and does not influence the product; then, the substrate after treatment is further cleaned by acetone in the substrate cleaning step, and impurities such as grease and the like attached to the substrate due to factors such as palm contact and the like are removed, so that the subsequent steps are smoothly carried out, the product quality is ensured, and meanwhile, the acetone is volatile and cannot affect the product; after cleaning, the film deposition step is carried out, the cleaned substrate is firstly placed into a base station and sent into a vacuum chamber of MWPCVD equipment, the equipment is operated and vacuumized so as to remove original impurity gas in the chamber and avoid the impurity gas from influencing the subsequent steps, thereby ensuring the quality of the prepared film; then injecting a reaction gas containing CH4Carbon source is provided with CO, and the deposition rate is improved and the film quality is improved by introducing CO, so that the deposition of the diamond film is facilitated; ar can improve the plasma atmosphere and reduce the electron energy in the plasma, thereby achieving the effect of reducing the size of the diamond; h2The quality of diamond grains can be controlled, so that the prepared film is controlled to be in an ultra-nanometer level; such mixed gas is used for preparing ultra-nano diamond filmThe process is more stable, the preparation efficiency is higher, the deposition rate is higher, and the use is more convenient; after the interior of the vacuum cavity is stabilized, the microwave source is started to ensure that the cavity is filled with reaction gas and has no other impurities, so that the subsequent steps are ensured, and the quality of the prepared film is ensured; the plasma is excited, the reaction gas is continuously injected to balance the gas pressure, the temperature of the substrate is maintained at 400-500 ℃, the temperature required by the film deposition is reduced, and experiments show that the film deposition cannot be greatly influenced in the temperature range. The method reduces the limitation on the substrate material due to high deposition temperature, can adapt to more environments, solves the problem that crystal grains cannot grow on the surfaces of some materials due to temperature limitation, and is easier to apply to the industry; and (3) closing the microwave source and the plasma after the reaction is finished, stopping injecting the reaction gas, vacuumizing to wait for the sample to be cooled, filling air after the cooling is finished, and taking out the sample to obtain the ultra-nano diamond film. The whole method is simple in flow and high in preparation efficiency, reduces the temperature required by film deposition compared with the traditional preparation method, enables the film deposition to be 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 influencing the size of diamond, thereby improving the quality of the ultra-nano diamond film. The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A method for preparing an ultra-nano diamond film is characterized by comprising the following steps:
substrate processing: selecting single-side polished P-type Si (100) as a substrate, placing the substrate in a mixed solution of diamond powder and ethanol, and carrying out scratch treatment on the substrate through ultrasonic cleaning;
cleaning a substrate: putting the treated substrate into an acetone solution for ultrasonic cleaning;
and (3) thin film deposition: placing the cleaned substrate on a base table, feeding the substrate into a vacuum chamber of an MWPCVD device, operating the MWPCVD device, vacuumizing the device, and injecting a reaction gas comprising CH4、Ar、CO、H2After the interior of the vacuum cavity is stabilized, starting a microwave source, exciting a 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 work of the plasma until the microwave source and the plasma are closed after the reaction is finished, stopping injecting the reaction gas, vacuumizing, refilling air in the vacuum cavity after the sample is cooled, and then taking out the sample to obtain the ultra-nano diamond film.
2. The method for preparing an ultra-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 treatment process.
3. The method for preparing an ultra-nano diamond film according to claim 1, wherein the substrate cleaning process is carried out for 5-15min by ultrasonic cleaning.
4. The method for preparing an ultra-nano diamond film according to claim 1, wherein the base is made of Mo or Cu during the film deposition process.
5. The method for preparing an ultra-nano diamond film according to claim 1, wherein during the film deposition, an MWPCVD apparatus is operated, and the apparatus is vacuumed to reach a background vacuum.
6. The method for preparing an ultra-nano diamond film according to claim 5, wherein the volume fraction ratio of each component in the reaction gas CH in the film deposition process4:Ar:CO:H2Is 1-2:65-99:7-20:0-25。
7. The method for preparing an ultra-nano diamond film according to claim 1, wherein the pressure inside the vacuum chamber is maintained at 1-2torr after the reaction gas is injected during the film deposition process, so that the film is stabilized.
8. The method for preparing an ultra-nano diamond film according to claim 1, wherein the microwave source is turned on after the inside of the vacuum chamber is stabilized during the film deposition process, and the microwave frequency is 2.45 GHz.
9. The method for preparing an ultra-nano diamond film according to claim 1, wherein during the film deposition, after the microwave source is turned on, the gas pressure is adjusted to excite the plasma at 2-4 Torr.
10. The method as claimed in claim 1, wherein the deposition is performed by injecting the reaction gas with a flow rate of 100-.
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