CN113430490A - Variable magnetic field magnetron sputtering coating device and preparation method of high-conductivity carbon-based coating - Google Patents

Variable magnetic field magnetron sputtering coating device and preparation method of high-conductivity carbon-based coating Download PDF

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CN113430490A
CN113430490A CN202110701365.7A CN202110701365A CN113430490A CN 113430490 A CN113430490 A CN 113430490A CN 202110701365 A CN202110701365 A CN 202110701365A CN 113430490 A CN113430490 A CN 113430490A
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magnetic field
variable magnetic
cathode
target
substrate
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CN113430490B (en
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汪爱英
陈仁德
张栋
左潇
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The invention discloses a variable magnetic field magnetron sputtering coating device and a preparation method of a high-conductivity carbon-based coating. The variable magnetic field magnetron sputtering coating device comprises a vacuum cavity, a variable magnetic field magnetron cathode, a rotating mechanism and an auxiliary cathode, wherein a sputtering coating area is arranged in the vacuum cavity, the variable magnetic field magnetron cathode is used for sputtering a preset film material on a substrate arranged in the vacuum cavity, and the rotating mechanism is used for bearing the substrate and controlling the substrate to move relative to the variable magnetic field magnetron cathode; the auxiliary cathode is disposed in the sputter coating region. The variable magnetic field magnetron sputtering coating device provided by the invention has the advantages that the variable magnetic field magnetron cathode is an adjustable magnetic field, the magnetic field balance is regulated and controlled by regulating the angle of the magnetic column, the metal transition layer and the carbon-based coating are respectively prepared, and meanwhile, the auxiliary cathode is additionally arranged in the carbon target plasma region to form the compact high-conductivity corrosion-resistant carbon-based coating.

Description

Variable magnetic field magnetron sputtering coating device and preparation method of high-conductivity carbon-based coating
Technical Field
The invention belongs to the technical field of magnetron sputtering coating, and particularly relates to a variable magnetic field magnetron sputtering coating device and a preparation method of a high-conductivity carbon-based coating.
Background
Hydrogen energy and fuel cells are listed as the strategic emerging industries of the country, wherein Proton Exchange Membrane Fuel Cells (PEMFCs) account for 83% of the fuel cells, and become the key to the technical competition of the battery industry. However, under the high temperature and acidic working environment of PEMFCs, the high interfacial contact resistance and corrosion of the metal bipolar plate of the core component are key technical bottlenecks affecting the extreme development of battery life.
The surface coating technology can be adopted to improve the conductivity and corrosion resistance of the metal pole plate on the basis of keeping the excellent performance of the metal pole plate. The carbon-based coating has excellent chemical inertness and adjustable conductivity, and is considered to be an important means for breaking through the service limit of a polar plate material and improving the stability and the service life of the proton exchange membrane fuel cell. However, carbon-based coatings are a broad class consisting of sp2Bond, sp3According to the preparation technology, the coating preparation device and the core plasma discharge source, the structure of the coating can be cut in a large range, and the electric conduction performance and the corrosion resistance performance are opposite. The regulation and control means for the conductivity and the corrosion resistance of the carbon-based coating are mutually restricted, and the carbon-based coating with high conductivity and excellent corrosion resistance is difficult to obtain at the same time, so that novel equipment and a coating preparation method need to be developed for the preparation of the high-conductivity corrosion-resistant carbon-based coating.
Disclosure of Invention
The invention mainly aims to provide a variable magnetic field magnetron sputtering coating device and a preparation method of a high-conductivity carbon-based coating, so as to overcome the defects in the prior art.
In order to achieve the above object, the embodiment of the present invention adopts a technical solution comprising:
the embodiment of the invention provides a variable magnetic field magnetron sputtering coating device, which comprises:
the vacuum cavity is internally provided with a sputtering coating area;
the variable magnetic field magnetron cathode is used for sputtering a preset film material to a substrate arranged in the vacuum cavity; the variable magnetic field magnetic control cathode is internally provided with a permanent magnet, the outside of the variable magnetic field magnetic control cathode is provided with a permanent magnetic column, and the permanent magnetic column is arranged on the outer side surface of a connecting shaft of the variable magnetic field magnetic control cathode external flange;
the rotating mechanism is used for bearing the substrate and controlling the substrate to move relative to the variable magnetic field magnetic control cathode;
and the auxiliary cathode is arranged in the sputtering coating area.
Further, the variable magnetic field magnetron sputtering coating device comprises a first variable magnetic field magnetron cathode and a second variable magnetic field magnetron cathode, wherein a first target material is arranged on the first variable magnetic field magnetron cathode, the first target material comprises a chromium target, a second target material is arranged on the second variable magnetic field magnetron cathode, and the second target material comprises a carbon target.
Furthermore, the auxiliary cathode is arranged close to the second variable magnetic field magnetron cathode and is positioned in the carbon target plasma area.
Further, the substrate is disposed on a substrate support assembly, and the substrate support assembly is fixedly connected to the rotation mechanism.
Further, the variable magnetic field magnetron sputtering coating device further comprises: and the vacuum assembly is communicated with the vacuum cavity.
The embodiment of the invention also provides a preparation method of the high-conductivity carbon-based coating, the preparation method is mainly implemented based on the variable magnetic field magnetron sputtering coating device, and the preparation method comprises the following steps:
arranging a base material to be coated on a rotating mechanism in a vacuum cavity;
a chromium target is arranged on the first variable magnetic field magnetron cathode, and a carbon target is arranged on the second variable magnetic field magnetron cathode;
in a protective atmosphere, a chromium target is used as a sputtering target material, the angle of a permanent magnetic column outside the first variable magnetic field magnetron cathode is adjusted by rotating a connecting shaft, and high-energy pulse voltage is applied to the first variable magnetic field magnetron cathode; simultaneously applying negative electrode pulse voltage to the substrate so as to form a metal chromium transition layer on the substrate through sputtering deposition; and the number of the first and second groups,
in a protective atmosphere, a carbon target is used as a sputtering target material, the angle of a permanent magnetic column outside the second variable magnetic field magnetron cathode is adjusted by rotating the connecting shaft, and high-energy pulse voltage is applied to the second variable magnetic field magnetron cathode; and applying a direct-current negative voltage to the auxiliary cathode, and applying a positive pulse voltage to the substrate, so that the high-conductivity corrosion-resistant carbon-based coating is continuously deposited and formed on the metal transition layer.
Further, the preparation method also comprises the following steps: the method comprises the following steps of pretreating a base material to be coated, and then sputtering and depositing a metal transition layer, wherein the pretreatment preferably comprises ultrasonic treatment, drying and glow cleaning treatment.
The embodiment of the invention also provides the high-conductivity corrosion-resistant carbon-based coating prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a variable magnetic field magnetron sputtering coating device and a preparation method of a high-conductivity carbon-based coating, wherein for depositing a metal transition layer, a target surface magnetic field forms a non-equilibrium field by adjusting the angle of an external magnetic column of a magnetron cathode, and the non-equilibrium field is radiated to a sample holder, so that the coverage area of a plasma can be increased, and the compactness and the bonding force of the metal transition layer are improved.
(2) The invention relates to a variable magnetic field magnetron sputtering coating device and a preparation method of a high-conductivity carbon-based coating, wherein for depositing the high-conductivity corrosion-resistant carbon-based coating, a target surface magnetic field forms a balanced field by adjusting the angles of two magnetic columns outside a magnetron cathode, so that a plasma only covers the target surface, an auxiliary cathode applies negative voltage, and a sample holder applies positive bias voltage, thereby reducing the bombardment of carbon ions on the sample holder in the sputtering process, improving the compactness and the deposition efficiency of the coating by adjusting high-energy pulse power supply parameters and bias power supply parameters, and simultaneously increasing sp (sp) in the coating2High conductivity and excellent corrosion resistance.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a variable magnetic field magnetron sputtering coating apparatus according to an embodiment of the present application.
Fig. 2 is a schematic diagram of the specific structure of the variable magnetic field magnetron cathode in fig. 1.
Fig. 3 is a schematic view showing a detailed structure of the auxiliary cathode of fig. 1.
FIG. 4 is a schematic diagram showing the distribution of the magnetic field on the target surface when the permanent magnet pole is rotated inward by an angle of 60 ° in example 1 of the present invention.
FIG. 5 is a schematic diagram showing the distribution of the magnetic field on the target surface when the angle of the permanent magnet pole is rotated outward by 105 degrees in example 1 of the present invention.
Fig. 6 is a graph comparing the contact resistance of carbon-based coatings prepared in example 1, comparative example 1, and comparative example 2.
FIG. 7 is sp of carbon based coatings prepared in example 1 and comparative examples 1 and 22Bond content diagram.
FIG. 8 is a potentiodynamic polarization plot of carbon-based coatings prepared in example 1 and comparative examples 1 and 2.
Description of reference numerals: 1. the device comprises a vacuum cavity, 11, a vacuum component, 2, a sample holder, 21, a substrate, 22, a rotating frame, 3, a second variable magnetic field magnetron cathode, 31, a carbon target, 311, a target fixing frame, 32, an auxiliary cathode, 321, a vacuum flange, 322, insulating ceramics, 323, an electrode, 324, a metal cylinder, 33, a rectangular flange, 34, a permanent magnetic column, 35, a connecting shaft, 36, a permanent magnet, 361, a permanent magnet, 362, a permanent magnet, 38, a protective cover, 4, a first variable magnetic field magnetron cathode, 41 and a chromium target.
Detailed Description
The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
In view of the shortcomings of the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution of the present invention, and further explains the technical solution, the implementation process and the principle as follows.
One aspect of an embodiment of the present invention provides a variable magnetic field magnetron sputtering coating apparatus, including:
the vacuum cavity is internally provided with a sputtering coating area;
the variable magnetic field magnetron cathode is used for sputtering a preset film material to a substrate arranged in the vacuum cavity; the variable magnetic field magnetic control cathode is internally provided with a permanent magnet, the outside of the variable magnetic field magnetic control cathode is provided with a permanent magnetic column, and the permanent magnetic column is arranged on the outer side surface of a connecting shaft of the variable magnetic field magnetic control cathode external flange;
the rotating mechanism is used for bearing the substrate and controlling the substrate to move relative to the variable magnetic field magnetic control cathode;
and the auxiliary cathode is arranged in the sputtering coating area.
In some preferred embodiments, the variable magnetic field magnetron sputtering coating device includes a first variable magnetic field magnetron cathode on which a first target material is disposed, the first target material including a chromium target, and a second variable magnetic field magnetron cathode on which a second target material is disposed, the second target material including a carbon target.
In some preferred embodiments, the variable magnetic field magnetron cathode is further provided with a cooling pipeline inside.
In some preferred embodiments, the auxiliary cathode is disposed proximate to the second variable magnetic field magnetron cathode and in the carbon target plasma region.
In some preferred embodiments, the distance between the auxiliary cathode and the second target surface arranged on the second variable magnetic field magnetron cathode is 3-10 cm.
In some preferred embodiments, the auxiliary cathode comprises a metal cylinder disposed within the vacuum chamber via a vacuum flange.
In some more preferred embodiments, the metal cylinder has a diameter of 5mm to 40 mm.
In some preferred embodiments, the auxiliary cathode is provided insulated from the vacuum flange.
In some preferred embodiments, the permanent magnet is prepared from Ru FeB, and the magnetic field intensity distribution of the permanent magnet on the surface of the target material is 10 GS-80 GS.
In some preferred embodiments, the length of the permanent magnetic column is greater than or equal to the height of the target.
In some preferred embodiments, the permanent magnetic pole is made of Ru FeB, and the strength of the magnetic steel is 200-600 mT.
In some preferred embodiments, the substrate is disposed on a substrate support assembly, and the substrate support assembly is fixedly connected to a rotation mechanism, and in particular embodiments, the substrate support assembly is a sample holder and the rotation mechanism is a rotating holder, but not limited thereto.
In some preferred embodiments, the variable magnetic field magnetron sputtering coating apparatus further includes: and the vacuum assembly is communicated with the vacuum cavity.
Another aspect of the embodiments of the present invention provides a method for preparing a highly conductive carbon-based coating, the method is mainly implemented based on the variable magnetic field magnetron sputtering coating apparatus, and the method includes:
arranging a base material to be coated on a rotating mechanism in a vacuum cavity;
a chromium target is arranged on the first variable magnetic field magnetron cathode, and a carbon target is arranged on the second variable magnetic field magnetron cathode;
in a protective atmosphere, a chromium target is used as a sputtering target material, the angle of a permanent magnetic column outside the first variable magnetic field magnetron cathode is adjusted by rotating a connecting shaft, and high-energy pulse voltage is applied to the first variable magnetic field magnetron cathode; simultaneously applying negative electrode pulse voltage to the substrate so as to form a metal chromium transition layer on the substrate through sputtering deposition; and the number of the first and second groups,
in a protective atmosphere, a carbon target is used as a sputtering target material, the angle of a permanent magnetic column outside the second variable magnetic field magnetron cathode is adjusted by rotating the connecting shaft, and high-energy pulse voltage is applied to the second variable magnetic field magnetron cathode; and applying a direct-current negative voltage to the auxiliary cathode, and applying a positive pulse voltage to the substrate, so that the high-conductivity corrosion-resistant carbon-based coating is continuously deposited and formed on the metal transition layer.
In some preferred embodiments, in a protective atmosphere, adjusting the air pressure in the vacuum chamber to 2-4 mTorr, rotating a substrate supporting assembly where a substrate is located to be right in front of a first variable magnetic field magnetron cathode, starting autorotation, adjusting a permanent magnetic column outside the first variable magnetic field magnetron cathode to rotate outwards by 90-120 degrees through a rotating connecting shaft, applying high-energy pulse voltage to the first variable magnetic field magnetron cathode to be 800-1000V, applying pulse frequency to be 0.5-2 kHz, and applying a duty ratio to be 5-10%; meanwhile, applying a negative electrode pulse voltage of 50-200V to the base material, wherein the pulse frequency is 2-10 kHz, the duty ratio is 10-40%, and the sputtering time is 10-30 min, so that a metal chromium transition layer with the thickness of 200 nm-1 mu m is formed on the base material through sputtering deposition.
In some preferred embodiments, after the deposition of the metal transition layer is completed, keeping the air pressure unchanged, rotating a substrate supporting assembly where the substrate is located to the position right in front of the second variable magnetic field magnetron cathode, starting autorotation, adjusting a permanent magnetic column outside the second variable magnetic field magnetron cathode to rotate inwards by 40-80 degrees through a rotating connecting shaft, applying a high-energy pulse voltage of 500-800V to the second variable magnetic field magnetron cathode, applying a pulse frequency of 0.5-2 kHz and a duty ratio of 5-10%, and applying a direct-current negative voltage of 100-200V to the auxiliary cathode; meanwhile, 50-200V of positive electrode pulse voltage is applied to the base material, the pulse frequency is 2-10 kHz, the duty ratio is 10% -40%, and the sputtering time is 30-60 min, so that the high-conductivity corrosion-resistant carbon-based coating is obtained.
In some preferred embodiments, the preparation method further comprises: firstly, preprocessing a base material to be coated, then sputtering and depositing a metal transition layer, preferably, preprocessing comprises ultrasonic processing, drying and glow cleaning,
preferably, the process conditions of the glow cleaning treatment include:
the applied pulse negative bias is 400-650V, the pulse duty ratio is 20-40%, and the glow cleaning time is 20-40 min.
Another aspect of the embodiment of the invention also provides a highly conductive corrosion-resistant carbon-based coating prepared by the preparation method.
In some more specific embodiments, the method for preparing the conductive corrosion-resistant carbon-based coating by using the variable magnetic field magnetron sputtering coating device provided by the invention comprises the following steps:
(1) firstly, carrying out ultrasonic treatment and drying on a substrate to be coated, then pasting the substrate on a sample rack, placing the sample rack on a rotating rack in a vacuum cavity, wherein the target material for mounting the first variable magnetic field magnetic control cathode is a chromium target, the target material for mounting the second variable magnetic field magnetic control cathode is a carbon target, and starting a vacuum assembly for vacuumizing.
(2) When the vacuum degree meets the requirement, argon is introduced, the air pressure is adjusted to 20mTorr, 400-650V pulse negative bias is applied to the sample holder, the pulse duty ratio is 20-40%, and glow cleaning is carried out for 20-40 min.
(3) Introducing argon, adjusting the air pressure to 2-4 mTorr, rotating the sample frame to the position right in front of the first variable magnetic field magnetic control cathode, starting autorotation, adjusting an external permanent magnetic column of the first variable magnetic field magnetic control cathode to rotate outwards by 90-120 degrees through a rotating connecting shaft, and applying high-energy pulse voltage of 800-1000V, the pulse frequency of 0.5-2 kHz and the duty ratio of 5-10% to the first variable magnetic field magnetic control cathode; and applying 50-200V negative electrode pulse voltage to the sample holder, wherein the pulse frequency is 2-10 kHz, the duty ratio is 10-40%, and the sputtering time is 10-30 min, so as to prepare the metal chromium transition layer.
(4) Argon is introduced, the air pressure is adjusted to be 2-4 mTorr, the sample frame is rotated to the position right in front of the second variable magnetic field magnetron cathode, autorotation is started, the connecting shaft is rotated to adjust the outer permanent magnetic column of the second variable magnetic field magnetron cathode to rotate inwards by 40-80 degrees, high-energy pulse voltage of 500-800V, the pulse frequency of 0.5-2 kHz and the duty ratio of 5-10 percent are applied to the second variable magnetic field magnetron cathode, 100-200V direct-current negative voltage is applied to the auxiliary cathode, 50-200V positive pulse voltage is applied to the sample frame, the pulse frequency is 2-10 kHz, the duty ratio of 10-40 percent, and the sputtering time is 30-60 min, so that the conductive corrosion-resistant carbon-based coating is prepared.
Wherein, for the deposition of the metal transition layer, the mechanism is as follows: by adjusting the angle of the magnetic column outside the magnetic control cathode, the target surface magnetic field forms a non-equilibrium field which is radiated to the sample holder, the plasma covering area can be increased, and the compactness and the bonding force of the metal transition layer are improved.
Wherein, for the deposition of the high-conductivity corrosion-resistant carbon-based coating, the mechanism is as follows: through adjusting two magnetic column angles outside the magnetron cathode, the target surface magnetic field forms a balance field, so that the plasma only covers the target surface, the auxiliary cathode applies negative voltage and the sample holder applies positive bias voltage, thereby reducing the bombardment of carbon ions on the sample holder in the sputtering process, improving the coating compactness and the deposition efficiency by adjusting the high-energy pulse power supply parameter and the bias power supply parameter, and simultaneously increasing the sp in the coating2High conductivity and excellent corrosion resistance.
The variable magnetic field magnetron sputtering coating device and the preparation method of the high-conductivity carbon-based coating provided by the embodiment of the invention can be used for depositing the high-conductivity corrosion-resistant carbon-based coating by utilizing the equipment and the specific process, and the conductivity and corrosion resistance of the coating are obviously superior to those of conventional metal and nitride coatings.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
Referring to fig. 1, the embodiment of the invention provides a variable magnetic field magnetron sputtering coating device, which comprises a vacuum cavity 1, a variable magnetic field magnetron cathode, a rotating frame 22, an auxiliary cathode 32 and a vacuum component 11 communicated with the vacuum cavity 1, wherein a sputtering coating area is arranged in the vacuum cavity 1; the variable magnetic field magnetron cathode is used for sputtering a preset film material on a substrate 21 on a sample rack 2 arranged in the vacuum cavity 1.
The variable magnetic field magnetron cathode comprises a first variable magnetic field magnetron cathode 4 and a second variable magnetic field magnetron cathode 3, wherein a chromium target 41 is arranged on the first variable magnetic field magnetron cathode 4, and a carbon target 31 is arranged on the second variable magnetic field magnetron cathode 3; in this embodiment, the specific structures of the first variable magnetic field magnetron cathode 4 and the second variable magnetic field magnetron cathode 3 are the same, and the second variable magnetic field magnetron cathode 3 is used for detailed description, as shown in fig. 2, the carbon target 31 is fixed with the second variable magnetic field magnetron cathode 3 by the target fixing frame 311, and the second variable magnetic field magnetron cathode 3 is internally provided with a permanent magnet 36, a permanent magnet 361, a permanent magnet 362 and a cooling water channel for ensuring that the target is sufficiently cooled in the sputtering process; two permanent magnetic columns 34 are arranged outside, the permanent magnetic columns 34 are arranged on the outer side face of a connecting shaft 35 of a rectangular flange 33 outside the second variable magnetic field magnetron cathode 3, and a protective cover used for protecting the permanent magnetic columns 34 and the connecting shaft 35 is further arranged on the periphery of the connecting shaft 35; in the implementation process, the permanent magnet is prepared from Ru ferroboron, and the magnetic field intensity distribution of the permanent magnet on the surface of the target material is 10 GS-80 GS; the length of the permanent magnetic column 34 is larger than or equal to the height of the target, the permanent magnetic column 34 is made of Ru Fe B, and the strength of the magnetic steel is 200-600 mT.
In this embodiment, the rotating frame 22 is used for supporting the sample frame 2 and controlling the sample frame 2 to move relative to the variable magnetic field magnetron cathode; the auxiliary cathode 32 is arranged in the vacuum cavity 1, and the auxiliary cathode 32 is positioned in the sputtering coating area, is arranged close to the second variable magnetic field magnetron cathode 3 provided with the carbon target material 31, and is arranged 3-10cm away from the target surface of the variable magnetic field magnetron cathode; referring to fig. 3, the auxiliary cathode 32 includes a metal cylinder 324 having a diameter of 5mm-40mm disposed inside the vacuum chamber 1 through a vacuum flange 321, and an electrode 323 disposed outside the vacuum flange 321 through an insulating ceramic 322.
In this embodiment, based on the variable magnetic field magnetron sputtering coating apparatus of this embodiment, a conductive carbon film is prepared on a 316L stainless steel substrate, and the specific process is as follows:
(1) firstly, carrying out ultrasonic treatment and drying on a substrate 21 to be coated, then pasting the substrate on a sample rack 2, placing the sample rack on a rotating rack 22 in a vacuum cavity 1, wherein a target material mounted on a first variable magnetic field magnetic control cathode 4 is a chromium target, a target material mounted on a second variable magnetic field magnetic control cathode 3 is a carbon target, and starting a vacuum assembly 11 for vacuumizing.
(2) When the vacuum degree reaches the requirement, argon is introduced, the air pressure is adjusted to 20mTorr, 650V pulse negative bias is applied to the sample holder 2, the pulse duty ratio is 38%, and glow cleaning is carried out for 30 min.
(3) Introducing argon, adjusting the air pressure to 3mTorr, rotating the sample holder 2 to the position right in front of the first variable magnetic field magnetic control cathode 4, and starting autorotation, as shown in figure 5, adjusting an external permanent magnetic column 34 of the first variable magnetic field magnetic control cathode 4 to rotate outwards by 105 degrees by rotating a connecting shaft 35, and applying high-energy pulse voltage 900V, the pulse frequency 1kHz and the duty ratio 8% to the first variable magnetic field magnetic control cathode 4; and (3) applying 100V negative electrode pulse voltage to the sample holder 2, wherein the pulse frequency is 5kHz, the duty ratio is 25%, and the sputtering time is 20min, and preparing the metal chromium transition layer with the thickness of 600 nm.
(4) Introducing argon gas, adjusting the air pressure to 3mTorr, rotating the sample holder 2 to the position right in front of the second variable magnetic field magnetron cathode 3, and starting autorotation, as shown in FIG. 4, rotating the connecting shaft 35 to adjust the outer permanent magnetic column 34 of the magnetron cathode 3 to rotate inwards by 60 degrees, applying high-energy pulse voltage of 600V, pulse frequency of 1kHz and duty ratio of 8 percent to the second variable magnetic field magnetron cathode 3, applying 150V direct-current negative voltage to the auxiliary cathode 32, applying 150V positive pulse voltage to the sample holder 2, pulse frequency of 7kHz and duty ratio of 20 percent, and sputtering time of 50min, thereby preparing the high-conductivity anti-corrosion carbon-based coating.
Comparative example 1:
this example is a comparative example to example 1 above.
In this example, the base material 21 is completely the same as the base material 21 in example 1.
In this example, the preparation method was as follows:
(1) same as in step (1) in example 1;
(2) same as step (2) in example 1;
(3) same as step (3) in example 1;
(4) the same phase as in step (4) in example 1 was followed, except that no auxiliary cathode was provided before the target.
Comparative example 2:
this example is a comparative example to example 1 above.
In this example, the substrate was identical to that in example 1.
In this example, the preparation method was as follows:
(1) same as in step (1) in example 1;
(2) same as step (2) in example 1;
(3) substantially the same as the step (3) in the example 1, except that the connecting shaft is rotated to adjust the inward rotation of the outer magnetic column of the magnetron cathode by 70 degrees;
(4) the same as the step (4) in example 1, except that the connecting shaft was rotated to adjust the rotation of the outer magnetic pole of the magnetron cathode by 105 ° outward.
The contact resistance of the carbon-based coating prepared by the embodiment 1 and the comparative embodiments 1 and 2 is shown in fig. 6, and it can be seen that the high conductivity of the highly conductive and corrosion resistant carbon-based coating can be obtained by the technical solution of the embodiment of the present invention.
Sp of carbon-based coatings prepared by the above example 1 and comparative examples 1 and 22The bond content is shown in figure 7. Potentiodynamic polarization curves for the carbon-based coatings prepared via example 1 above and comparative examples 1 and 2 are shown in FIG. 8. It can be seen that after the magnetic field angle is adjusted, the content of carbon ions deposited in the sputtering process is reduced because the magnetic force lines are not radiated to the sample holder, and further the content of carbon ions in the filtering sputtering process is adjusted by adding the auxiliary cathode, so that more neutral particles, namely carbon atoms, bombard the base material to deposit and form a film, and the sp of the formed carbon-based coating is formed2The bond content and the conductivity are greatly changed, and simultaneously, the larger particle bombardment energy is kept, so that a relatively compact carbon-based coating is obtained, the internal stress defect caused by ion deposition is reduced, and a through corrosion passage is avoidedThereby obtaining excellent corrosion resistance of the final carbon-based coating.
Example 2:
in this embodiment, based on the variable magnetic field magnetron sputtering coating apparatus of embodiment 1, a conductive carbon film is prepared on a 316L stainless steel substrate, and the specific process is as follows:
in this embodiment, a conductive carbon film is prepared on a 316L stainless steel substrate by the following specific process:
(1) firstly, carrying out ultrasonic treatment and drying on a substrate 21 to be coated, then pasting the substrate on a sample rack 2, placing the sample rack on a rotating rack 22 in a vacuum cavity 1, wherein a target material mounted on a first variable magnetic field magnetic control cathode 4 is a chromium target, a target material mounted on a second variable magnetic field magnetic control cathode 3 is a carbon target, and starting a vacuum assembly 11 for vacuumizing.
(2) When the vacuum degree reaches the requirement, argon is introduced, the air pressure is adjusted to 20mTorr, 650V pulse negative bias is applied to the sample holder 2, the pulse duty ratio is 38%, and glow cleaning is carried out for 30 min.
(3) Argon is introduced, the air pressure is adjusted to be 2mTorr, the sample holder 2 is rotated to the position right in front of the first variable magnetic field magnetic control cathode 4, autorotation is started, the external permanent magnetic column 34 of the first variable magnetic field magnetic control cathode 4 is adjusted to rotate outwards by 90 degrees through the rotating connecting shaft 35, high-energy pulse voltage 800V, the pulse frequency is 0.5kHz, and the duty ratio is 5 percent, is applied to the first variable magnetic field magnetic control cathode 4; and applying 50V negative electrode pulse voltage to the sample holder, wherein the pulse frequency is 2kHz, the duty ratio is 10 percent, and the sputtering time is 10min, and preparing the metal chromium transition layer with the thickness of 200 nm.
(4) Argon is introduced, the air pressure is adjusted to be 2mTorr, the sample frame 2 is rotated to the position right in front of the second variable magnetic field magnetron cathode 3, autorotation is started, the rotating connecting shaft 35 adjusts the outer permanent magnetic column 34 of the magnetron cathode to rotate inwards by 40 degrees, high-energy pulse voltage of 500V, the pulse frequency of 0.5kHz and the duty ratio of 5 percent are applied to the second variable magnetic field magnetron cathode 3, 100V direct-current negative voltage is applied to the auxiliary cathode 32, 50V positive pulse voltage is applied to the sample frame 2, the pulse frequency is 2kHz, the duty ratio is 10 percent, the sputtering time is 30min, and the conductive corrosion-resistant carbon-based coating is prepared.
Example 3:
in this embodiment, based on the variable magnetic field magnetron sputtering coating apparatus of embodiment 1, a conductive carbon film is prepared on a 316L stainless steel substrate, and the specific process is as follows:
(1) firstly, carrying out ultrasonic treatment and drying on a substrate 21 to be coated, then pasting the substrate on a sample rack 2, placing the sample rack on a rotating rack 22 in a vacuum cavity 1, wherein a target material mounted on a first variable magnetic field magnetic control cathode 4 is a chromium target, a target material mounted on a second variable magnetic field magnetic control cathode 3 is a carbon target, and starting a vacuum assembly 11 for vacuumizing.
(2) When the vacuum degree reaches the requirement, argon is introduced, the air pressure is adjusted to 20mTorr, 650V pulse negative bias is applied to the sample holder 2, the pulse duty ratio is 38%, and glow cleaning is carried out for 30 min.
(3) Argon is introduced, the air pressure is adjusted to be 4mTorr, the sample holder 2 is rotated to the position right in front of the first variable magnetic field magnetic control cathode 4, autorotation is started, the external permanent magnetic column 34 of the first variable magnetic field magnetic control cathode 4 is adjusted to rotate outwards by 120 degrees through the rotating connecting shaft 35, high-energy pulse voltage 1000V, the pulse frequency is 2kHz, and the duty ratio is 10 percent is applied to the first variable magnetic field magnetic control cathode 4; and applying 200V negative electrode pulse voltage to the sample holder 2, wherein the pulse frequency is 10kHz, the duty ratio is 40 percent, and the sputtering time is 30min, and preparing the metal chromium transition layer with the thickness of 1 mu m.
(4) Argon is introduced, the air pressure is adjusted to be 4mTorr, the sample holder 2 is rotated to the position right in front of the second variable magnetic field magnetron cathode 3, autorotation is started, the connecting shaft 35 is rotated to adjust the outer permanent magnetic column 34 of the magnetron cathode 3 to rotate inwards by 80 degrees, high-energy pulse voltage of 800V, pulse frequency of 2kHz and duty ratio of 10 percent is applied to the second variable magnetic field magnetron cathode 3, 200V direct-current negative voltage is applied to the auxiliary cathode, 200V positive pulse voltage is applied to the sample holder, the pulse frequency of 10kHz and the duty ratio of 40 percent are applied, sputtering time is 60min, and the conductive corrosion-resistant carbon-based coating is prepared.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (10)

1. A variable magnetic field magnetron sputtering coating device is characterized by comprising:
the vacuum cavity is internally provided with a sputtering coating area;
the variable magnetic field magnetron cathode is used for sputtering a preset film material to a substrate arranged in the vacuum cavity; the variable magnetic field magnetic control cathode is internally provided with a permanent magnet, the outside of the variable magnetic field magnetic control cathode is provided with a permanent magnetic column, and the permanent magnetic column is arranged on the outer side surface of a connecting shaft of the variable magnetic field magnetic control cathode external flange;
the rotating mechanism is used for bearing the substrate and controlling the substrate to move relative to the variable magnetic field magnetic control cathode;
and the auxiliary cathode is arranged in the sputtering coating area.
2. The variable magnetic field magnetron sputtering coating device according to claim 1, characterized in that:
the variable magnetic field magnetron sputtering coating device comprises a first variable magnetic field magnetron cathode and a second variable magnetic field magnetron cathode, wherein a first target is arranged on the first variable magnetic field magnetron cathode and comprises a chromium target, a second target is arranged on the second variable magnetic field magnetron cathode and comprises a carbon target;
and/or a cooling pipeline is also arranged inside the variable magnetic field magnetron cathode.
3. The variable magnetic field magnetron sputtering coating device according to claim 2, characterized in that: the auxiliary cathode is arranged at the position close to the second variable magnetic field magnetic control cathode and is positioned in the carbon target plasma area;
and/or the distance between the auxiliary cathode and a second target surface arranged on the second variable magnetic field magnetron cathode is 3-10cm, and/or the auxiliary cathode comprises a metal cylinder arranged in the vacuum cavity through a vacuum flange; and/or the diameter of the metal cylinder is 5mm-40 mm; and/or the auxiliary cathode is arranged in an insulated way with the vacuum flange.
4. The variable magnetic field magnetron sputtering coating device according to claim 1, characterized in that: the permanent magnet is prepared from Ru ferroboron, and the magnetic field intensity distribution of the permanent magnet on the surface of the target material is 10 GS-80 GS; and/or the length of the permanent magnetic column is more than or equal to the height of the target, and/or the permanent magnetic column is prepared from Ru ferroboron, and the strength of the magnetic steel is 200-600 mT; and/or the substrate is arranged on the substrate supporting assembly, and the substrate supporting assembly is fixedly connected with the rotating mechanism.
5. The variable magnetic field magnetron sputtering coating device according to claim 1, further comprising: and the vacuum assembly is communicated with the vacuum cavity.
6. A method for preparing a high-conductivity carbon-based coating, characterized in that the method is mainly implemented based on the variable magnetic field magnetron sputtering coating device of any one of claims 1 to 5, and the method comprises:
arranging a base material to be coated on a rotating mechanism in a vacuum cavity;
a chromium target is arranged on the first variable magnetic field magnetron cathode, and a carbon target is arranged on the second variable magnetic field magnetron cathode;
in a protective atmosphere, a chromium target is used as a sputtering target material, the angle of a permanent magnetic column outside the first variable magnetic field magnetron cathode is adjusted by rotating a connecting shaft, and high-energy pulse voltage is applied to the first variable magnetic field magnetron cathode; simultaneously applying negative electrode pulse voltage to the substrate so as to form a metal chromium transition layer on the substrate through sputtering deposition; and the number of the first and second groups,
in a protective atmosphere, a carbon target is used as a sputtering target material, the angle of a permanent magnetic column outside the second variable magnetic field magnetron cathode is adjusted by rotating the connecting shaft, and high-energy pulse voltage is applied to the second variable magnetic field magnetron cathode; and applying a direct-current negative voltage to the auxiliary cathode, and applying a positive pulse voltage to the substrate, so that the high-conductivity corrosion-resistant carbon-based coating is continuously deposited and formed on the metal transition layer.
7. The method of claim 6, wherein: in a protective atmosphere, adjusting the air pressure in a vacuum cavity to 2-4 mTorr, rotating a substrate supporting assembly where a substrate is located to the front of a first variable magnetic field magnetic control cathode, starting autorotation, adjusting a permanent magnetic column outside the first variable magnetic field magnetic control cathode to rotate outwards by 90-120 degrees through a rotating connecting shaft, applying high-energy pulse voltage to the first variable magnetic field magnetic control cathode to be 800-1000V, applying pulse frequency to be 0.5-2 kHz, and applying the duty ratio to be 5-10%; meanwhile, applying a negative electrode pulse voltage of 50-200V to the base material, wherein the pulse frequency is 2-10 kHz, the duty ratio is 10-40%, and the sputtering time is 10-30 min, so that a metal chromium transition layer with the thickness of 200 nm-1 mu m is formed on the base material through sputtering deposition.
8. The method of claim 6, wherein: after the deposition of the metal transition layer is finished, keeping the air pressure unchanged, rotating a substrate supporting assembly where the substrate is located to the front of a second variable magnetic field magnetic control cathode, starting autorotation, adjusting a permanent magnetic column outside the second variable magnetic field magnetic control cathode to rotate inwards by 40-80 degrees through a rotating connecting shaft, applying high-energy pulse voltage to the second variable magnetic field magnetic control cathode to be 500-800V, applying pulse frequency to be 0.5-2 kHz, applying a duty ratio to be 5-10%, and applying a 100-200V direct-current negative voltage to an auxiliary cathode; meanwhile, 50-200V of positive electrode pulse voltage is applied to the base material, the pulse frequency is 2-10 kHz, the duty ratio is 10% -40%, and the sputtering time is 30-60 min, so that the high-conductivity corrosion-resistant carbon-based coating is obtained.
9. The method of claim 6, further comprising: firstly, preprocessing a base material to be coated, then sputtering and depositing a metal transition layer, preferably, preprocessing comprises ultrasonic processing, drying and glow cleaning,
preferably, the process conditions of the glow cleaning treatment include:
the applied pulse negative bias is 400-650V, the pulse duty ratio is 20-40%, and the glow cleaning time is 20-40 min.
10. A highly conductive corrosion-resistant carbon-based coating prepared by the preparation method of any one of claims 6 to 9.
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