CN114921753A - 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 169
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 153
- 238000000151 deposition Methods 0.000 title claims abstract description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000000758 substrate Substances 0.000 claims abstract description 80
- 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 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000013077 target material Substances 0.000 claims abstract description 26
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 10
- 125000004429 atom Chemical group 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 description 21
- 239000002159 nanocrystal Substances 0.000 description 15
- 229910021389 graphene Inorganic materials 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 238000003917 TEM image Methods 0.000 description 10
- 238000001237 Raman spectrum Methods 0.000 description 9
- 239000003574 free electron Substances 0.000 description 7
- 230000033228 biological regulation Effects 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 230000033001 locomotion Effects 0.000 description 5
- 230000001808 coupling effect Effects 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- 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
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- 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 based on mixed irradiation and a carbon film, wherein the carbon film deposition method comprises the following steps: providing a substrate; and placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, bombarding the carbon target material by using argon ions, and simultaneously performing mixed irradiation of laser and electrons or mixed irradiation of laser and ions to obtain the carbon film by deposition on the substrate. In the invention, the carbon target is bombarded by argon ions, so that the carbon atoms in the carbon target acquire energy, are further separated from the constraint among the atoms, are released into a vacuum chamber and are deposited on a substrate, and in the process, the carbon film with a controllable nanocrystalline structure is prepared by introducing laser and electron mixed irradiation or laser and ion mixed irradiation under the condition of not needing very high irradiation energy or density, and the phenomena of peeling 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 a decisive influence on the performance of the carbon film, and when the amorphous carbon film is embedded with graphene nanocrystals, the specific quantum effect of the graphene edge structure can obviously improve the optical, electrical, magnetic and catalytic performances of the carbon film. The existing technology for sputtering and depositing the carbon film mainly adjusts and controls the nano structure of the carbon film 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 disadvantages when controlling the structure of graphene nanocrystals in the carbon film: for example, when the growth of graphene nanocrystals is promoted by increasing ion irradiation energy or density, the carbon film is easy to peel off due to excessive internal stress; when the electron irradiation energy or density is increased to promote the growth of the graphene nanocrystals, the carbon film is easily seriously roughened; when the substrate temperature is increased to promote the growth of the graphene nanocrystals, higher requirements are imposed on the heat resistance of equipment and the substrate, and meanwhile, the energy consumption is high and the production efficiency is low in the carbon film deposition process. Therefore, the single methods have a limited structural regulation range on the graphene nanocrystals, and have limitations in application.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a carbon film deposition method based on hybrid irradiation and a carbon film, and aims to solve the problem that the structure control range of graphene nanocrystals in the carbon film is limited by using a single method.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, a method for depositing a carbon film based on mixed irradiation is provided, wherein the method comprises the steps of:
providing a substrate;
and placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, bombarding the carbon target material by using argon ions, and simultaneously performing laser and electron mixed irradiation or laser and ion mixed irradiation to obtain the carbon film by deposition on the substrate.
Optionally, the step of placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and performing laser/electron hybrid irradiation or laser/ion hybrid irradiation while bombarding the carbon target with argon ions specifically includes:
placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and vacuumizing to a preset value;
introducing argon, and ionizing the argon into argon plasma under the combined action of a magnetic field and an electric field;
and applying direct current negative bias to the carbon target material to enable the argon ions in the argon plasma to bombard the carbon target material and simultaneously turn on the laser and set the substrate bias to be positive bias to perform mixed irradiation of laser and electrons, or applying direct current negative bias to the carbon target material to enable the argon ions in the argon plasma to bombard the carbon target material and simultaneously turn on the laser and set the substrate bias to be negative bias to perform mixed irradiation of laser and ions.
Optionally, in the step of evacuating to a preset value, the preset value is less than or equal to 8 × 10 -5 Pa。
Optionally, after the argon gas 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 for applying the direct current negative bias to the carbon target material 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 voltage to a positive bias voltage, the positive bias voltage is 0-100V.
Optionally, in the step of setting the substrate bias voltage to a negative bias voltage, the negative bias voltage is-100 to 0V.
In a second aspect of the invention, a carbon film is provided, wherein the carbon film is deposited by the mixed irradiation-based carbon film deposition method of the invention.
Has the advantages that: in the invention, the carbon target is bombarded by argon ions, so that carbon atoms in the carbon target obtain energy, are separated from the constraint among the atoms, are released into a vacuum chamber and are deposited on a substrate, and in the process, the carbon film with the controllable nano-crystal structure is prepared by introducing laser and electron mixed irradiation or laser and ion mixed irradiation under the condition of not needing high irradiation energy or density. The method provided by the invention can regulate and control the nano structure in the carbon film, and obviously expands the controllable range of the nano structure of the carbon film.
Drawings
FIG. 1 is a schematic structural diagram of an electron flood irradiation system according to an embodiment of the present invention.
FIG. 2 is a Raman spectrum of a carbon film in a laser irradiation region and a non-laser irradiation region in a mixed irradiation mode of laser and ion in example 1 of the present invention.
Fig. 3 (a) is a transmission electron micrograph of a laser irradiation region carbon film in the laser and ion mixed irradiation mode in example 1, and fig. 3 (b) is a transmission electron micrograph of a non-laser irradiation region carbon film in the laser and ion mixed irradiation mode in example 1.
FIG. 4 is a Raman spectrum of the carbon film with laser irradiation region and non-laser irradiation region in the laser irradiation mode in example 2 of the present invention.
Fig. 5 (a) is a tem image of a carbon film in a laser-irradiated area in the laser irradiation mode in example 2 of the present invention, and fig. 5 (b) is a tem image of a carbon film in a non-laser-irradiated area in the laser irradiation mode in example 2 of the present invention.
FIG. 6 is a Raman spectrum of a carbon film with laser irradiation regions and non-laser irradiation regions in the laser and electron mixed irradiation mode in example 3 of the present invention.
Fig. 7 (a) is a transmission electron micrograph of a laser irradiation region carbon film in a laser and electron mixed irradiation mode in example 3 of the present invention, and fig. 7 (b) is a transmission electron micrograph of a non-laser irradiation region carbon film in a laser and electron mixed irradiation mode in example 3 of the present invention.
Detailed Description
The present invention provides a method for depositing a carbon film based on hybrid irradiation and a carbon film, and the present invention will be described in further detail below in order to make the objects, technical solutions, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit 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 Emission (ECR), bombarding a carbon target by using argon ions, and simultaneously performing laser and electron mixed irradiation or laser and ion mixed irradiation to obtain a carbon film by deposition on the substrate.
In the embodiment of the invention, the carbon target is bombarded by argon ions, so that the carbon atoms in the carbon target obtain energy, are separated from the constraint among the atoms, are released into a vacuum chamber and are deposited on a substrate, and in the process, the carbon film with a controllable nano-crystal structure is prepared by introducing laser and electron mixed irradiation or laser and ion mixed irradiation under the condition of not needing high irradiation energy or density, and the occurrence of carbon film peeling and roughness is reduced by the matched use of laser and electron irradiation or the matched use of laser and ion irradiation. The method provided by the invention realizes the regulation and control of the nano structure in the carbon film and simultaneously obviously expands the controllable range of the nano structure in the carbon film by utilizing the laser electron or the mixed irradiation of the laser ions or the switching of the mixed irradiation of the laser electron and the laser ions.
The material of the substrate is not particularly limited in the embodiment of the invention, and can be selected according to actual needs. In addition, in the embodiment of the invention, laser and electron mixed irradiation can be carried out in the process of bombarding the carbon target material by using argon ions, so that the nano structure in the carbon film can be regulated and controlled; 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 as to realize the regulation and control of the nano structure in the carbon film; in the process of bombarding the carbon target material by using argon ions, mixed irradiation of laser and electrons is performed first, and then the mixed irradiation of the laser and ions is switched, so that the nano structure in the carbon film is regulated and controlled; and in the process of bombarding the carbon target by using argon ions, the mixed irradiation of laser and ions is firstly carried out, and then the mixed irradiation of laser and electrons is switched, so that the nano structure in the carbon film is regulated and controlled.
In one embodiment, the step of placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and performing laser and electron hybrid irradiation or laser and ion hybrid irradiation while bombarding a carbon target material 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;
and S13, applying direct current negative bias to the carbon target material to enable the argon ions in the argon plasma to bombard the carbon target material and simultaneously turn on the laser and set the substrate bias to be positive bias to perform laser and electron mixed irradiation, or applying direct current negative bias to the carbon target material to enable the argon ions in the argon plasma to bombard the carbon target material and simultaneously turn on the laser and set the substrate bias to be negative bias to perform laser and ion mixed irradiation.
In the embodiment, the bias voltage of the substrate and the on-off 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 regulation and control range of the graphene nanocrystalline structure is limited by adopting a single irradiation method in the prior art, so that the controllable range of the nanostructure in the carbon film is remarkably improved. Specifically, carbon film deposition is divided into two cases based on the bias applied to the substrate: unbiased, biased (positive or negative). When no bias is applied, carbon atoms sputtered from the carbon target will fall on the substrate and randomly form a nearly amorphous structure, but with the laser 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 voltage (positive or negative) is applied to the substrate, electrons (when a positive bias voltage is applied) or argon ions (when a negative bias voltage is applied) are attracted to the substrate, which can promote the growth of nanocrystals. Further, under laser irradiation, on the one hand, photon irradiation onto the carbon structure as described above can promote its conversion into a nanocrystalline structure, and on the other hand, photon-excited electrons (i.e., "secondary" electrons) will be accelerated by the applied bias, and these "secondary" electrons can further excite the carbon structure and stimulate the growth of nanocrystals.
In step S11, in an embodiment, in the step of evacuating to a preset value, the preset value is less than or equal to 8 × 10 -5 Pa。
In step S12, the 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 the argon atoms in the argon gas are ionized to generate argon plasma.
In one embodiment, after the argon gas is introduced, the pressure value in the vacuum chamber is 0.01-0.2 Pa.
In one embodiment, the electric field is generated by modulating the substrate positive and negative bias in an 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, the microwaves generated by the microwave generator in the electron-rotating 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 the magnetic field and the 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 a positive bias for performing the hybrid irradiation of the laser and the electrons is as follows: turning on a laser to realize laser irradiation, and setting a substrate bias voltage as a positive 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 to negative bias for laser and ion mixed irradiation is as follows: the laser was turned on to achieve laser irradiation and the substrate bias was set to a negative bias to attract argon ions in the argon plasma to achieve ion irradiation.
In one embodiment, the bias voltage value of the direct current negative bias voltage applied to the carbon target material is-300V to-500V, and the bombardment of the carbon target material by the argon ions is realized under the negative bias voltage.
In one embodiment, the power of the laser is 2 to 50W, and the wavelength of the laser is 300 to 500 nm. The power and the wavelength are more favorable for 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 a positive bias voltage, the positive bias voltage is 0 to 100V to attract electrons in the argon plasma to achieve electron irradiation. By way of example, the positive bias voltage may be 5V, 10V, 20V, 30V, 40V, 50V, 60V, 70V, 80V, 90V, 100V, or the like. In the prior art, the carbon film is easy to be seriously roughened by improving the positive bias deposition, but after laser irradiation is introduced while electron irradiation is performed, the serious roughening of the carbon film is avoided under the condition of low electron irradiation energy, and the nano structure can be obviously changed.
In one embodiment, in the step of setting the substrate bias voltage to a negative bias voltage, the negative bias voltage is-100 to 0V, so as to attract argon ions in the argon plasma to realize the ion irradiation. By way of example, the negative bias voltage can be-5V, -10V, -20V, -30V, -40V, -50V, -60V, -70V, -80V, -90V, or-100V, and the like. In the prior art, negative bias deposition easily causes overlarge internal stress of the carbon film to peel off, but after laser irradiation is introduced while ion irradiation is performed, the peeling off of the carbon film 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 min.
The method and principle of the carbon film will be described in detail with reference to fig. 1.
The substrate 5 is placed on a substrate frame 3 of a vacuum chamber of an electron cyclotron irradiation system, the vacuum chamber is vacuumized to a preset value, then argon is introduced, and the vacuum degree of the vacuum chamber is increased and kept at 0.01-0.2 Pa.
The first magnetic coil 1 was set to a current value of 40A, the second magnetic coil 2 was set to a current value of 40A, and the third magnetic coil 4 was set to a current value of 48A, thereby forming a closed magnetic field. And (3) opening the microwave generator 8, setting the microwave current value to be 256mA, and enabling free electrons in the vacuum chamber to generate electron cyclotron motion under the coupling action of the magnetic field and the microwaves so as to ionize argon atoms in the argon gas and finally generate closed argon plasma.
After the argon plasma is stabilized, a direct current negative bias is applied to the carbon target 7, and argon ions (Ar) in the argon plasma + ) The carbon target material 7 is accelerated and bombarded under the action of direct current negative bias, energy is transferred to carbon atoms in the carbon target material 7, the carbon atoms with the energy are separated from the restraint among the atoms, and the carbon atoms are released into the vacuum chamber with certain kinetic energy.
When the substrate bias voltage is set to be the positive bias voltage and the switch of the laser 6 is turned on simultaneously, the substrate with the positive bias voltage attracts electrons in the argon plasma, the electrons in the argon plasma and carbon atoms obtaining energy move towards the substrate direction and are deposited on the surface of the substrate to form a carbon film while laser irradiation is carried out, mixed irradiation of the laser and the electrons is carried out 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 electrons, and the carbon film with the nano structure is obtained; when the substrate bias voltage is set to be negative bias voltage and the switch of the laser 6 is turned on simultaneously, the substrate with the negative bias voltage attracts argon ions in the argon plasma, the argon ions in the argon plasma and carbon atoms with obtained energy move towards the substrate direction and are deposited on the surface of the substrate to form a carbon film during laser irradiation, mixed irradiation of the laser and the ions is realized during 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, and the carbon film with the nano structure is obtained.
The embodiment of the invention also provides a carbon film, wherein the carbon film is prepared by the preparation method provided by the embodiment of the invention. The carbon film provided by the embodiment is embedded with a nano structure, and further, the carbon film is embedded with a graphene nano crystal structure.
The details are described below by way of specific examples.
Example 1
As shown in FIG. 1, a silicon substrate 5 having a size of 20mm × 20mm is cleaned and fixed on a substrate holder 3 of a vacuum chamber of an electron cyclotron irradiation system, the vacuum chamber is evacuated, and when the degree of vacuum reaches a predetermined value of 8 × 10 -5 After Pa, argon gas was introduced so that the vacuum degree of the vacuum chamber was increased and maintained at 0.1 Pa. Setting the current values of the first magnetic coil 1, the second magnetic coil 2 and the third magnetic coil 4 as 40A, 40A and 48A respectively to form a closed magnetic field, opening the microwave generator 8, adjusting the current value of the microwave to be 256mA, and generating electron cyclotron motion to ionize argon atoms by free electrons in the vacuum chamber under the coupling action of the magnetic field and the microwave to finally generate closed argon plasma. After the plasma is stabilized, a-500V direct current negative bias is applied to the carbon target 7, argon ions in the argon plasma bombard the carbon target 7 at an accelerated speed under the action of the-500V direct current negative bias, energy is transferred to carbon atoms in the target, the carbon atoms with the energy are separated from the restraint among the atoms, and the carbon atoms are released to the vacuum chamber with certain kinetic energy. Setting a substrate bias voltage to-10V, simultaneously opening a switch of a laser 6 (the laser power is 10W, the laser wavelength is 450nm) and adjusting the position of the laser to enable the laser beam to irradiate the surface of the silicon substrate, enabling argon ions in the argon plasma and carbon atoms with obtained energy to move towards the substrate direction 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 of the laser and the ions (the time is 15 min).
Fig. 2 is a raman spectrum of the carbon film in the laser irradiation region and the non-laser irradiation region in the mixed irradiation mode of laser and ion in example 1, and it can be seen that the laser irradiation can cause the carbon film nanostructure to be significantly changed, which is specifically shown in that the D, G peak in the raman spectrum of the carbon film is sharper. Fig. 3 (a) is a transmission electron micrograph of the laser-irradiated area carbon film in the laser and ion mixed irradiation mode in example 1, and fig. 3 (b) is a transmission electron micrograph of the non-laser-irradiated area carbon film in the laser and ion mixed irradiation mode in example 1, and it can be seen that laser irradiation causes the size of graphene nanocrystals in the carbon film to increase. Here, it is understood that the laser irradiation region refers to a region where both laser irradiation and ion irradiation exist, and the non-laser irradiation region refers to a region where only ion irradiation exists.
Example 2
As shown in FIG. 1, a silicon substrate 5 having a size of 20mm × 20mm is cleaned and fixed on a substrate holder 3 of a vacuum chamber of an electron cyclotron irradiation system, the vacuum chamber is evacuated, and when the degree of vacuum reaches a predetermined value of 8 × 10 -5 After Pa, argon gas was introduced so that the vacuum degree of the vacuum chamber was increased and maintained at 0.1 Pa. Setting the current values of the first magnetic coil 1, the second magnetic coil 2 and the third magnetic coil 4 as 40A, 40A and 48A respectively to form a closed magnetic field, opening the microwave generator 8, adjusting the current value of the microwave to be 256mA, and generating electron cyclotron motion to ionize argon atoms by free electrons in the vacuum chamber under the coupling action of the magnetic field and the microwave to finally generate closed argon plasma. After the plasma is stabilized, a-500V direct current negative bias is applied to the carbon target 7, argon ions in the argon plasma bombard the carbon target 7 at an accelerated speed under the action of the-500V direct current negative bias, energy is transferred to carbon atoms in the target, the carbon atoms with the energy are separated from the restraint among the atoms, and the carbon atoms are released to the vacuum chamber with certain kinetic energy. Setting the substrate bias voltage to 0V, simultaneously turning on a switch of a laser 6 (the laser power is 10W, the laser wavelength is 450nm) and adjusting the position of the laser to enable the laser beam to irradiate the surface of the silicon substrate, so that carbon atoms with acquired energy move towards the substrate direction and are deposited on the surface of the silicon substrate to form a carbon film, and finally the carbon atoms are 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 with laser irradiation region and non-laser irradiation region in the laser irradiation mode of example 2, and the carbon film with laser irradiation region is characterized by a sharp D, G peak in Raman spectrum, so that it can be shown that the carbon film structure can be changed by laser irradiation alone. Fig. 5 (a) is a transmission electron micrograph of the laser-irradiated domain carbon film in the laser irradiation mode of example 2, and fig. 5 (b) is a transmission electron micrograph of the non-laser-irradiated domain carbon film in the laser irradiation mode of example 2, and it can be seen that the laser irradiation causes the size of the graphene nanocrystals in the carbon film to increase.
Example 3
As shown in FIG. 1, a silicon substrate 5 with a size of 20mm × 20mm is cleaned and 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 × 10 -5 After Pa, argon gas was introduced so that the vacuum degree of the vacuum chamber was increased and maintained at 0.1 Pa. Setting the current values of the first magnetic coil 1, the second magnetic coil 2 and the third magnetic coil 4 as 40A, 40A and 48A respectively to form a closed magnetic field, opening the microwave generator 8, adjusting the current value of the microwave to be 256mA, and generating electron cyclotron motion to ionize argon atoms by free electrons in the vacuum chamber under the coupling action of the magnetic field and the microwave to finally generate closed argon plasma. After the plasma is stabilized, a-500V direct current negative bias is applied to the carbon target 7, argon ions in the argon plasma bombard the carbon target 7 at an accelerated speed under the action of the-500V direct current negative bias, and energy is transferred to carbon atoms in the target. The energetic carbon atoms are released from the atomic bonds with a certain kinetic energy into the vacuum chamber. Setting a substrate bias voltage to +80V, simultaneously opening a switch of a laser 6 (the laser power is 10W, the laser wavelength is 450nm) and adjusting the position of the laser to enable the laser beam to irradiate the surface of the silicon substrate, enabling electrons in the argon plasma and carbon atoms with obtained energy to move towards the substrate direction 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 of the laser and the electrons (the time is 15 min).
FIG. 6 is a Raman spectrum of the carbon film in the laser irradiation region and the non-laser irradiation region in the mixed irradiation mode of laser and electron in example 3, and it can be seen that the laser irradiation can cause the carbon film nanostructure to be significantly changed, which is particularly shown in that the D, G peak in the Raman spectrum of the carbon film is sharper. Fig. 7 (a) is a transmission electron micrograph of the carbon film in the laser irradiation region in the laser and electron mixed irradiation mode in example 3, and fig. 7 (b) is a transmission electron micrograph of the carbon film in the non-laser irradiation region in the laser and electron mixed irradiation mode in example 3, and it can be seen that the laser irradiation causes the size of the graphene nanocrystals in the carbon film to increase. Here, it is understood that the laser irradiation region refers to a region where both laser irradiation and electron irradiation exist, and the non-laser irradiation region refers to a region where only electron irradiation exists.
In summary, the present invention provides a carbon film deposition method based on mixed irradiation and a carbon film, wherein argon ions are used to bombard a carbon target material, so that carbon atoms in the carbon target material obtain energy, and then are released into a vacuum chamber to be deposited on a substrate, and in the process, laser and electron mixed irradiation or laser and ion mixed irradiation is introduced, so that the carbon film with a controllable nanocrystalline structure is prepared without high irradiation energy or density, and the phenomena of peeling 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, obviously expand the controllable range of the carbon film nano structure, and can avoid the problems of peeling of the carbon film due to overlarge internal stress, serious roughening of the carbon film and high energy consumption in the prior art by adopting a single method.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for carbon film deposition based on hybrid irradiation, comprising the steps of:
providing a substrate;
and placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, bombarding the carbon target material by using argon ions, and simultaneously performing laser and electron mixed irradiation or laser and ion mixed irradiation to obtain a carbon film by deposition on the substrate.
2. The method of claim 1, wherein the step of performing the laser/electron hybrid irradiation or the laser/ion hybrid irradiation while bombarding the carbon target with argon ions comprises:
placing the substrate in a vacuum chamber of an electron cyclotron irradiation system, and vacuumizing to a preset value;
introducing argon, and ionizing the argon into argon plasma under the combined action of a magnetic field and an electric field;
and applying direct current negative bias to the carbon target material to enable argon ions in the argon plasma to bombard the carbon target material and simultaneously open the laser and set the substrate bias to be positive bias to perform laser and electron mixed irradiation, or applying direct current negative bias to the carbon target material to enable the argon ions in the argon plasma to bombard the carbon target material and simultaneously open the laser and set the substrate bias to be negative bias to perform laser and ion mixed irradiation.
3. The method of claim 2, wherein the step of evacuating to a predetermined value, the predetermined value being less than or equal to 8 x 10 -5 Pa。
4. The mixed irradiation-based carbon film deposition method according to claim 2, wherein the pressure in the vacuum chamber is 0.01 to 0.2Pa after the argon gas is introduced.
5. The method of claim 2, wherein the time of the hybrid irradiation is 15-30 min.
6. The method of claim 2, wherein the bias value for applying the negative DC bias to the carbon target is-300V to-500V.
7. The method of claim 2, wherein the laser has a power of 2 to 50W and a wavelength of 300 to 500 nm.
8. The method of claim 2, wherein the step of setting the substrate bias voltage to a positive bias voltage, the positive bias voltage is 0-100V.
9. The method of claim 2, wherein the step of setting the substrate bias voltage to a negative bias voltage, the negative bias voltage is-100 to 0V.
10. A carbon film deposited by the method of mixed irradiation-based carbon film deposition according to any one of claims 1 to 9.
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