CN114921753B - Carbon film deposition method based on mixed irradiation and carbon film - Google Patents
Carbon film deposition method based on mixed irradiation and carbon film Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 157
- 238000000151 deposition Methods 0.000 title claims abstract description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000000758 substrate Substances 0.000 claims abstract description 82
- 229910052786 argon Inorganic materials 0.000 claims abstract description 78
- 150000002500 ions Chemical class 0.000 claims abstract description 41
- -1 argon ions Chemical class 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000013077 target material Substances 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 9
- 230000005684 electric field Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 11
- 125000004429 atom Chemical group 0.000 abstract description 4
- 238000004299 exfoliation Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 21
- 229910021389 graphene Inorganic materials 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 238000001000 micrograph Methods 0.000 description 10
- 238000001237 Raman spectrum Methods 0.000 description 9
- 239000003574 free electron Substances 0.000 description 7
- 239000002159 nanocrystal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000001808 coupling effect Effects 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3471—Introduction of auxiliary energy into the plasma
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Abstract
The invention discloses a carbon film deposition method and a carbon film based on mixed irradiation, wherein the carbon film deposition method comprises the following steps: providing a substrate; placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, bombarding a carbon target material by utilizing argon ions, and simultaneously carrying out laser and electron mixed irradiation or laser and ion mixed irradiation, and depositing on the substrate to obtain the carbon film. According to the method, the carbon atoms in the carbon target are enabled to obtain energy by utilizing argon ions to bombard the carbon target, the energy is released into a vacuum chamber and deposited on a substrate by being separated from the constraint among atoms, in the process, the carbon film with the controllable nanocrystalline structure is prepared by introducing laser and electron mixed irradiation or laser and ion mixed irradiation under the condition that high irradiation energy or density is not needed, and the phenomena of exfoliation and roughness of the carbon film can be improved.
Description
Technical Field
The invention relates to the field of carbon material preparation, in particular to a carbon film deposition method based on mixed irradiation and a carbon film.
Background
The nano structure of the carbon film has decisive influence on the performance, and when the amorphous carbon film is embedded with graphene nano crystals, the quantum effect special for the graphene edge structure can obviously improve the performances of the carbon film in various aspects such as optics, electricity, magnetism, catalysis and the like. The existing sputtering deposition carbon film technology regulates and controls the nano structure of the carbon film mainly by changing parameters such as ion irradiation energy, ion irradiation density, electron irradiation energy, electron irradiation density, substrate temperature and the like. However, these single methods have the following drawbacks when the structure of graphene nanocrystals in carbon films is controlled: for example, when the graphene nanocrystalline growth is promoted by increasing the ion irradiation energy or density, the excessive internal stress of the carbon film is easily caused to peel off; when the electron irradiation energy or density is increased to promote the growth of graphene nanocrystalline, the carbon film is easily seriously roughened; when the substrate temperature is increased to promote the growth of graphene nanocrystals, the heat resistance of equipment and the substrate is required to be high, and meanwhile, the energy consumption in the carbon film deposition process is high and the production efficiency is low. Therefore, the single methods have limited structural control range for graphene nanocrystals, and have limitations in application.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a carbon film deposition method based on mixed irradiation and a carbon film, which aims to solve the problem that the existing single method is used for limiting the structure regulation range of graphene nanocrystals in the carbon film.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a carbon film deposition method based on mixed irradiation, comprising the steps of:
providing a substrate;
and placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, bombarding a carbon target material by utilizing argon ions, and simultaneously carrying out laser and electron mixed irradiation or laser and ion mixed irradiation, and depositing on the substrate to obtain the carbon film.
Optionally, the step of placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and bombarding a carbon target material with argon ions while performing laser and electron mixed irradiation or laser and ion mixed irradiation specifically includes:
placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and vacuumizing to a preset value;
argon is introduced, and the argon is ionized into argon plasma under the combined action of a magnetic field and an electric field;
and applying a direct current negative bias to the carbon target, so that the argon ions in the argon plasma bombard the carbon target, simultaneously turning on the laser and setting the substrate bias to be a positive bias for laser and electron mixed irradiation, or applying a direct current negative bias to the carbon target, so that the argon ions in the argon plasma bombard the carbon target, simultaneously turning on the laser and setting the substrate bias to be a negative bias for laser and ion mixed irradiation.
Optionally, in the step of vacuumizing to a preset value, the preset value is less than or equal to 8×10 -5 Pa。
Optionally, after argon is introduced, the pressure value in the vacuum chamber is 0.01-0.2 Pa.
Optionally, the time of the mixed irradiation is 15-30 min.
Optionally, the bias value of the direct current negative bias applied to the carbon target is-300 to-500V.
Optionally, the power of the laser is 2-50W, and the wavelength of the laser is 300-500 nm.
Optionally, in the step of setting the substrate bias to be a positive bias, the positive bias is 0 to 100V.
Optionally, in the step of setting the substrate bias to a negative bias, the negative bias is-100-0V.
In a second aspect of the present invention, there is provided a carbon film, wherein the carbon film is deposited using the hybrid irradiation-based carbon film deposition method of the present invention as described above.
The beneficial effects are that: according to the invention, the carbon target is bombarded by utilizing argon ions, so that carbon atoms in the carbon target obtain energy, and are released into a vacuum chamber to deposit on a substrate after being separated from the constraint among atoms, and in the process, the carbon film with the controllable nanocrystalline structure is prepared under the condition that high irradiation energy or density is not required by introducing laser and mixed irradiation of electrons or mixed irradiation of laser and ions. The method provided by the invention can regulate and control the nano structure in the carbon film, and remarkably expands the controllable range of the nano structure of the carbon film.
Drawings
Fig. 1 is a schematic structural diagram of an electron rotary irradiation system according to an embodiment of the present invention.
FIG. 2 is a Raman spectrum of a carbon film of a laser irradiation region and a non-laser irradiation region in a laser and ion mixed irradiation mode in example 1 of the present invention.
Fig. 3 (a) is a transmission electron microscope image of the carbon film of the laser irradiation region in the laser and ion mixed irradiation mode in example 1, and fig. 3 (b) is a transmission electron microscope image of the carbon film of the non-laser irradiation region in the laser and ion mixed irradiation mode in example 1.
FIG. 4 is a Raman spectrum of a carbon film of a laser irradiation region and a non-laser irradiation region in a laser irradiation mode in example 2 of the present invention.
Fig. 5 (a) is a transmission electron microscope image of a carbon film of a laser irradiation region in the laser irradiation mode in example 2 of the present invention, and fig. 5 (b) is a transmission electron microscope image of a carbon film of a non-laser irradiation region in the laser irradiation mode in example 2 of the present invention.
FIG. 6 is a Raman spectrum of a carbon film of a laser irradiation region and a non-laser irradiation region in a mixed irradiation mode of laser and electron in example 3 of the present invention.
Fig. 7 (a) is a transmission electron microscope image of the carbon film of the laser irradiation region in the laser and electron mixed irradiation mode in example 3 of the present invention, and fig. 7 (b) is a transmission electron microscope image of the carbon film of the non-laser irradiation region in the laser and electron mixed irradiation mode in example 3 of the present invention.
Detailed Description
The invention provides a carbon film deposition method based on mixed irradiation and a carbon film, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and are further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a carbon film deposition method based on mixed irradiation, which comprises the following steps:
providing a substrate;
and placing the substrate in a vacuum chamber of an electron cyclotron irradiation system (ECR), bombarding a carbon target material by utilizing argon ions, and simultaneously carrying out laser and electron mixed irradiation or laser and ion mixed irradiation, and depositing on the substrate to obtain the carbon film.
According to the embodiment of the invention, the carbon target is bombarded by utilizing the argon ions, so that carbon atoms in the carbon target obtain energy, and are released into the vacuum chamber to deposit on the substrate after being separated from the constraint among atoms, in the process, the carbon film with the controllable nanocrystalline structure is prepared by introducing laser and electron mixed irradiation or laser and ion mixed irradiation under the condition that high irradiation energy or density is not needed, and the carbon film peeling and roughness phenomena are reduced by the matched use of the laser and electron irradiation or the matched use of the laser and ion irradiation. The method provided by the invention realizes the regulation and control of the nano structure in the carbon film by utilizing the laser electron or the laser ion mixed irradiation or the laser electron and laser ion mixed irradiation switching, and simultaneously remarkably expands the controllable range of the nano structure in the carbon film.
The material of the substrate is not particularly limited, and the substrate can be selected according to actual needs. In addition, in the embodiment of the invention, the mixed irradiation of laser and electrons can be carried out in the process of bombarding the carbon target material by utilizing argon ions, so that the regulation and control of the nano structure in the carbon film can be realized; the mixed irradiation of laser and ions can be carried out in the process of bombarding the carbon target material by utilizing argon ions, so that the regulation and control of the nano structure in the carbon film can be realized; in the process of bombarding the carbon target material by utilizing argon ions, the mixed irradiation of laser and electrons is firstly carried out and then is switched into the mixed irradiation of laser and ions, so that the regulation and control of the nano structure in the carbon film are realized; in the process of bombarding the carbon target material by utilizing the argon ions, the mixed irradiation of laser and ions is firstly performed, and then the mixed irradiation of laser and electrons is switched to realize the regulation and control of the nano structure in the carbon film.
In one embodiment, the step of placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and performing laser and electron mixed irradiation or laser and ion mixed irradiation while bombarding a carbon target with argon ions specifically includes:
s11, placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and vacuumizing to a preset value;
s12, introducing argon, and ionizing the argon into argon plasma under the combined action of a magnetic field and an electric field;
s13, applying a direct current negative bias to the carbon target, so that the argon ions in the argon plasma bombard the carbon target, simultaneously, turning on the laser, setting the substrate bias to be a positive bias for laser and electron mixed irradiation, or applying a direct current negative bias to the carbon target, so that the argon ions in the argon plasma bombard the carbon target, simultaneously, turning on the laser, setting the substrate bias to be a negative bias for laser and ion mixed irradiation.
In the embodiment, the bias voltage of the substrate and the opening and closing of the laser are adjusted to form a laser electron or laser ion mixed irradiation carbon film preparation process, and the laser electron or laser ion mixed irradiation is introduced in the carbon film deposition process to avoid the problem that the existing single irradiation method is limited in the regulation and control range of the graphene nanocrystalline structure, so that the controllable range of the nanostructure in the carbon film is remarkably improved. Specifically, carbon film deposition is classified into two cases based on the bias applied to the substrate: unbiased, biased (positive or negative). When no bias is applied, the sputtered carbon atoms from the carbon target will fall on the substrate and randomly form an approximately amorphous structure, but as the laser is turned on, photons will strike the carbon structure and transfer energy to the valence electrons of the carbon, exciting the carbon structure to a higher excited energy state, and then the carbon structure will relax to a stable nanocrystalline structure. When a bias (positive bias or negative bias) is applied to the substrate, electrons (when a positive bias is applied) or argon ions (when a negative bias is applied) are attracted to the substrate, and the electrons or the argon ions can promote the growth of the nanocrystals. Further, under laser irradiation, on the one hand, the above-mentioned photon irradiation onto the carbon structure can promote its transformation into a nanocrystalline structure, and on the other hand, the photon-excited electrons (i.e. "secondary" electrons) will be accelerated by the applied bias, which can further excite the carbon structure and stimulate the growth of nanocrystalline.
In step S11, in one embodiment, in the step of evacuating to a preset value, the preset value is 8×10 or less -5 Pa。
In step S12, free electrons in the vacuum chamber of the electron cyclotron irradiation system generate electron cyclotron motion under the combined action of the magnetic field and the electric field, so that argon atoms in argon are ionized, and an argon plasma is generated.
In one embodiment, after the argon is introduced, the pressure value in the vacuum chamber is 0.01 to 0.2Pa.
In one embodiment, the electric field is generated by adjusting the positive and negative bias voltages of the substrate in the electron cyclotron illumination system.
In one embodiment, the magnetic field may be generated by a magnetic coil in an electron cyclotron irradiation system.
In one embodiment, microwaves generated by a microwave generator in the electron rotary irradiation system can give energy to free electrons in the vacuum chamber, and the free electrons with the energy can ionize argon in the vacuum chamber under the combined action of a magnetic field and an electric field to form argon plasma. The microwave current value of the microwave generator is set to be 100-350 mA.
In step S13, the specific implementation process of turning on the laser and setting the substrate bias to be the forward bias to perform the mixed irradiation of laser and electrons is as follows: turning on a laser to realize laser irradiation, setting a substrate bias voltage as a forward bias voltage to attract electrons in the argon plasma to realize electron irradiation; the specific implementation process of turning on the laser and setting the substrate bias as negative bias to perform laser and ion mixed irradiation comprises the following steps: the laser is turned on to effect laser irradiation and the substrate bias is set to a negative bias to attract argon ions in the argon plasma to effect ion irradiation.
In one embodiment, the DC negative bias voltage is applied to the carbon target material with a bias voltage value of-300 to-500V, and the bombardment of the argon ions to the carbon target material is realized under the negative bias voltage.
In one embodiment, the laser has a power of 2 to 50W and a wavelength of 300 to 500nm. The power and the wavelength are more beneficial to realizing the regulation and control of the carbon film nano structure, and simultaneously the energy consumption is reduced.
In one embodiment, in the step of setting the substrate bias voltage to be a positive bias voltage, the positive bias voltage is 0-100V to attract electrons in the argon plasma to realize electron irradiation. By way of example, the forward bias may be 5V, 10V, 20V, 30V, 40V, 50V, 60V, 70V, 80V, 90V, 100V, or the like. In the prior art, the carbon film is easily seriously roughened by improving the forward bias deposition, but after the laser irradiation is introduced while the electron irradiation is performed, the method can avoid the serious roughening of the carbon film under the condition of low electron irradiation energy and can obviously change the nano structure.
In one embodiment, in the step of setting the substrate bias to a negative bias, the negative bias is-100-0V to attract argon ions in the argon plasma to achieve ion irradiation. For example, the negative bias may be-5V, -10V, -20V, -30V, -40V, -50V, -60V, -70V, -80V, -90V, or-100V, etc. In the prior art, the negative bias deposition easily causes excessive internal stress of the carbon film to peel off, but after the laser irradiation is introduced while the ion irradiation is performed, the situation that the carbon film peels off is weakened under the condition of low ion irradiation energy, and the nano structure can be obviously changed.
In one embodiment, the time of the mixed irradiation is 15 to 30 minutes.
The method and principle of the carbon film are described in detail below with reference to fig. 1.
Placing the substrate 5 on a substrate frame 3 of a vacuum chamber of an electron cyclotron irradiation system, vacuumizing the vacuum chamber to a preset value, and then introducing argon gas to ensure that the vacuum degree of the vacuum chamber is increased and kept at 0.01-0.2 Pa.
A closed magnetic field is formed by setting the current value of the first magnetic coil 1 to 40A, the current value of the second magnetic coil 2 to 40A, and the current value of the third magnetic coil 4 to 48A. The microwave generator 8 is turned on, the microwave current value is set to 256mA, free electrons in the vacuum chamber generate electron cyclotron motion under the coupling action of a magnetic field and microwaves so as to ionize argon atoms in argon, and finally, closed argon plasma is generated.
After the argon plasma is stabilized, a DC negative bias is applied to the carbon target 7, and argon ions (Ar + ) The bombardment of the carbon target 7 is accelerated under the action of direct current negative bias, energy is transmitted to carbon atoms in the carbon target 7, the energy is obtained, the carbon atoms are separated from interatomic binding, and the energy is released into the vacuum chamber with certain kinetic energy.
When the substrate bias is set to be positive bias and the switch of the laser 6 is turned on at the same time, the substrate with the positive bias attracts electrons in the argon plasma, the electrons in the argon plasma move towards the direction of the substrate along with the carbon atoms with energy and are deposited on the surface of the substrate to form a carbon film during the process of carbon atom deposition, so that the mixed irradiation of the laser and the electrons is realized, namely, the carbon atoms are deposited on the substrate under the mixed irradiation of the laser and the electrons, and the carbon film with a nano structure is obtained; when the substrate bias is set to be negative bias and the switch of the laser 6 is turned on, the substrate with the negative bias attracts argon ions in the argon plasma, the argon ions in the argon plasma move towards the direction of the substrate along with carbon atoms which acquire energy and are deposited on the surface of the substrate to form a carbon film during laser and ion mixed irradiation in the carbon atom deposition process, namely, the carbon atoms are deposited on the substrate under the mixed irradiation effect of the laser and the ions, so that the carbon film with the nanostructure is obtained.
The embodiment of the invention also provides a carbon film, which is prepared by adopting the preparation method disclosed by the embodiment of the invention. The carbon film provided in this embodiment has a nano structure embedded therein, and further, the carbon film has a graphene nanocrystalline structure embedded therein.
The following is a detailed description of specific examples.
Example 1
As shown in FIG. 1, a silicon substrate 5 with a size of 20mm by 20mm is cleaned and then fixed on a substrate holder 3 of a vacuum chamber of an electron cyclotron irradiation system, the vacuum chamber is vacuumized, and when the vacuum degree reaches a preset value of 8 by 10 -5 Argon is introduced after Pa, so that the vacuum degree of the vacuum chamber is increased and kept at 0.1Pa. The current values of the first magnetic coil 1, the second magnetic coil 2 and the third magnetic coil 4 are respectively 40A, 40A and 48A to form a closed magnetic field, the microwave generator 8 is turned on, the microwave current value is adjusted to 256mA, free electrons in the vacuum chamber generate electron cyclotron motion under the coupling action of the magnetic field and microwaves to ionize argon atoms, and finally, closed argon plasma is generated. After the plasma is stabilized, negative-500V direct current bias is applied to the carbon target 7, argon ions in the argon plasma are accelerated to bombard the carbon target 7 under the negative-500V direct current bias, energy is transferred to carbon atoms in the target, the energy is obtained, the carbon atoms are separated from interatomic constraint, and the energy is released to a vacuum chamber by a certain kinetic energy. Setting the bias voltage of the substrate to-10V, simultaneously turning on the switch of the laser 6 (the laser power is 10W and the laser wavelength is 450 nm) and adjusting the position of the laser so that the laser beam irradiates the surface of the silicon substrate, enabling argon ions in the argon plasma along with carbon atoms which acquire energy to move towards the direction of the substrate and deposit on the surface of the silicon substrate to form a carbon film, and finally depositing the carbon atoms on the silicon substrate 5 under the action of mixed irradiation (the time is 15 min) of the laser and the ions.
FIG. 2 is a Raman spectrum of a carbon film of a laser irradiation region and a non-laser irradiation region in a mixed irradiation mode of laser and ion in example 1, and it can be seen that the laser irradiation can promote a significant change of the nanostructure of the carbon film, and the peak D, G in the Raman spectrum of the carbon film is more sharp. Fig. 3 (a) is a transmission electron microscope image of the carbon film of the laser irradiation region in the laser and ion mixed irradiation mode in example 1, and fig. 3 (b) is a transmission electron microscope image of the carbon film of the non-laser irradiation region in the laser and ion mixed irradiation mode in example 1, and it can be seen that the laser irradiation causes the increase in the nano-crystalline size of graphene in the carbon film. It is to be understood that the laser irradiation region refers to a region where laser irradiation and ion irradiation are present at the same time, and the non-laser irradiation region refers to a region where only ion irradiation is present.
Example 2
As shown in FIG. 1, a silicon substrate 5 with a size of 20mm by 20mm is cleaned and then fixed on a substrate holder 3 of a vacuum chamber of an electron cyclotron irradiation system, the vacuum chamber is vacuumized, and when the vacuum degree reaches a preset value of 8 by 10 -5 Argon is introduced after Pa, so that the vacuum degree of the vacuum chamber is increased and kept at 0.1Pa. The current values of the first magnetic coil 1, the second magnetic coil 2 and the third magnetic coil 4 are respectively 40A, 40A and 48A to form a closed magnetic field, the microwave generator 8 is turned on, the microwave current value is adjusted to 256mA, free electrons in the vacuum chamber generate electron cyclotron motion under the coupling action of the magnetic field and microwaves to ionize argon atoms, and finally, closed argon plasma is generated. After the plasma is stabilized, negative-500V direct current bias is applied to the carbon target 7, argon ions in the argon plasma are accelerated to bombard the carbon target 7 under the negative-500V direct current bias, energy is transferred to carbon atoms in the target, the energy is obtained, the carbon atoms are separated from interatomic constraint, and the energy is released to a vacuum chamber by a certain kinetic energy. Setting the bias voltage of the substrate to 0V, simultaneously turning on the switch of the laser 6 (the laser power is 10W and the laser wavelength is 450 nm) and adjusting the position of the laser so that the laser beam irradiates the surface of the silicon substrate, and enabling carbon atoms with energy to move towards the substrate and deposit on the surface of the silicon substrate to form a carbon film, wherein the carbon atoms are finally deposited on the silicon substrate 5 only under the action of laser irradiation (the time is 15 min).
FIG. 4 is a Raman spectrum of a carbon film of a laser irradiation region and a carbon film of a non-laser irradiation region in the laser irradiation mode in example 2, wherein the carbon film of the laser irradiation region is characterized in that a D, G peak in the Raman spectrum is more sharp, so that it can be explained that the carbon film structure can be promoted to change by the laser irradiation alone. Fig. 5 (a) is a transmission electron microscopic image of the carbon film of the laser irradiation region in the laser irradiation mode in example 2, and fig. 5 (b) is a transmission electron microscopic image of the carbon film of the non-laser irradiation region in the laser irradiation mode in example 2, and it can be seen that the laser irradiation causes the increase in the nano-crystalline size of graphene in the carbon film.
Example 3
As shown in FIG. 1, a silicon substrate 5 with a size of 20mm by 20mm is cleaned and then fixed on a substrate holder 3 of a vacuum chamber of an electron cyclotron irradiation system, the vacuum chamber is vacuumized, and when the vacuum degree reaches a preset value of 8 by 10 -5 Argon is introduced after Pa, so that the vacuum degree of the vacuum chamber is increased and kept at 0.1Pa. The current values of the first magnetic coil 1, the second magnetic coil 2 and the third magnetic coil 4 are respectively 40A, 40A and 48A to form a closed magnetic field, the microwave generator 8 is turned on, the microwave current value is adjusted to 256mA, free electrons in the vacuum chamber generate electron cyclotron motion under the coupling action of the magnetic field and microwaves to ionize argon atoms, and finally, closed argon plasma is generated. After the plasma is stabilized, negative-500V direct current bias is applied to the carbon target 7, argon ions in the argon plasma are accelerated to bombard the carbon target 7 under the negative-500V direct current bias, and energy is transferred to carbon atoms in the target. The carbon atoms which acquire energy are released from the constraint among the atoms and are released into the vacuum chamber with certain kinetic energy. Setting the bias voltage of the substrate to +80V, simultaneously turning on the switch of the laser 6 (the laser power is 10W and the laser wavelength is 450 nm) and adjusting the position of the laser so that the laser beam irradiates the surface of the silicon substrate, moving electrons in the argon plasma along with carbon atoms which acquire energy towards the direction of the substrate and depositing the electrons on the surface of the silicon substrate to form a carbon film, and finally depositing the carbon atoms on the silicon substrate 5 under the action of mixed irradiation (the time is 15 min) of the laser and the electrons.
FIG. 6 is a Raman spectrum of a carbon film of a laser irradiation region and a non-laser irradiation region in a mixed irradiation mode of laser and electron in example 3, and it can be seen that the laser irradiation can promote a significant change of the nanostructure of the carbon film, and the peak D, G in the Raman spectrum of the carbon film is more sharp. Fig. 7 (a) is a transmission electron microscope image of a carbon film of a laser irradiation region in a laser and electron mixed irradiation mode in example 3, and fig. 7 (b) is a transmission electron microscope image of a carbon film of a non-laser irradiation region in a laser and electron mixed irradiation mode in example 3, and it can be seen that the laser irradiation causes an increase in the size of graphene nanocrystals in the carbon film. It is to be understood that the laser irradiation region refers to a region where laser irradiation and electron irradiation are present at the same time, and the non-laser irradiation region refers to a region where only electron irradiation is present.
In summary, the invention provides a carbon film deposition method and a carbon film based on mixed irradiation, wherein argon ions are utilized to bombard a carbon target material, so that carbon atoms in the carbon target material obtain energy, and are released into a vacuum chamber to deposit on a substrate, and in the process, the carbon film with a controllable nanocrystalline structure is prepared under the condition that high irradiation energy or density is not needed by introducing laser and electron mixed irradiation or laser and ion mixed irradiation, and the phenomena of flaking and roughness of the carbon film are greatly improved. The method provided by the invention can regulate and control the nano structure in the carbon film, remarkably expands the controllable range of the nano structure of the carbon film, and can avoid the problems of excessive internal stress of the carbon film, peeling, serious roughening of the carbon film and high energy consumption of the carbon film by adopting a single method in the prior art.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (8)
1. A method for carbon film deposition based on mixed irradiation, comprising the steps of:
providing a substrate;
placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, bombarding a carbon target material by utilizing argon ions, and simultaneously carrying out laser and electron mixed irradiation or laser and ion mixed irradiation, and depositing on the substrate to obtain a carbon film;
the step of placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and performing laser and electron mixed irradiation or laser and ion mixed irradiation while bombarding a carbon target material by utilizing argon ions specifically comprises the following steps:
placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and vacuumizing to a preset value;
argon is introduced, and the argon is ionized into argon plasma under the combined action of a magnetic field and an electric field;
and applying a direct current negative bias to the carbon target, so that the argon ions in the argon plasma bombard the carbon target, simultaneously turning on the laser and setting the substrate bias to be a positive bias for laser and electron mixed irradiation, or applying a direct current negative bias to the carbon target, so that the argon ions in the argon plasma bombard the carbon target, simultaneously turning on the laser and setting the substrate bias to be a negative bias for laser and ion mixed irradiation.
2. The method for carbon film deposition based on mixed irradiation according to claim 1, wherein in the step of evacuating to a preset value, the preset value is 8×10 or less -5 Pa。
3. The method for carbon film deposition based on mixed irradiation according to claim 1, wherein the pressure value in the vacuum chamber after the argon gas is introduced is 0.01 to 0.2Pa.
4. The method for carbon film deposition based on mixed irradiation according to claim 1, wherein the time of the mixed irradiation is 15 to 30min.
5. The method for carbon film deposition based on mixed irradiation according to claim 1, wherein the bias value of applying a direct current negative bias to the carbon target is-300 to-500V.
6. The method for depositing a carbon film by mixed irradiation according to claim 1, wherein the power of the laser is 2 to 50W and the wavelength of the laser is 300 to 500nm.
7. The method for carbon film deposition based on mixed irradiation as claimed in claim 1, wherein in the step of setting the substrate bias voltage to a positive bias voltage, the positive bias voltage is 0 to 100V.
8. The method for carbon film deposition based on mixed irradiation as claimed in claim 1, wherein in said step of setting the substrate bias voltage to a negative bias voltage, the negative bias voltage is-100 to 0V.
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