CN110578124A - Method for preparing hard film on flexible substrate and related product - Google Patents
Method for preparing hard film on flexible substrate and related product Download PDFInfo
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- CN110578124A CN110578124A CN201911004499.2A CN201911004499A CN110578124A CN 110578124 A CN110578124 A CN 110578124A CN 201911004499 A CN201911004499 A CN 201911004499A CN 110578124 A CN110578124 A CN 110578124A
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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
- C23C14/0635—Carbides
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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
- C23C14/0641—Nitrides
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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
- C23C14/0664—Carbonitrides
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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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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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
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
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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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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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
- C23C14/3485—Sputtering using pulsed power to the target
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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
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Abstract
The invention relates to the technical field of film materials, and discloses a method for preparing a hard film on a flexible substrate and a related product, wherein the method for preparing the hard film on the flexible substrate comprises the following steps: after a flexible substrate is cleaned by utilizing a gas ion source, a metal film layer, an organic-metal heterojunction and a metal transition layer are sequentially prepared on the flexible substrate by deposition through a magnetic filtration technology, and then a gradient transition layer and a hard film are prepared through a high-power pulse magnetron sputtering technology, so that the preparation of the hard film on the flexible substrate is completed. The preparation method provided by the embodiment of the invention ensures that the structure of the prepared hard film is more stable, can greatly improve the bonding strength among coating interfaces in the hard film, and further improves the service performance of a workpiece using the hard film.
Description
Technical Field
The invention relates to the technical field of film materials, in particular to a method for preparing a hard film on a flexible substrate and a related product.
Background
The hard film is mainly applied to the field of traditional mechanical manufacturing and processing, and the application and popularization of the hard film can effectively improve the performance of a workpiece, improve the processing efficiency of the workpiece and prolong the service life of the workpiece.
with the development of science and technology, the application range of the hard film is gradually expanded to emerging industries, for example, the hard film is used in the forms of protective coatings or wear-resistant coatings in the fields of biomedicine, flexible electronic devices, flat panel displays, micro-electromechanical devices and the like. But in contrast to traditional industries, which are primarily metal or alloy surface applications, hard films are needed in emerging industries to protect a large number of non-rigid surfaces, such as polymer foils, thin sheets of glass, and textiles. And with the improvement of the surface performance requirements of parts in emerging industries, the application range of the hard film is expanded to the flexible surface at an accelerated speed. At present, the hard film manufacturing process generally adopts a pure metal transition layer between the surface of a flexible substrate and a hard coating to combine the flexible substrate and the hard coating.
However, the existing hard film with a three-layer structure of a flexible matrix, a metal transition layer and a hard coating layer has the problems of insufficient bonding strength and easy cracking and falling off in use. Particularly, after a workpiece needing to be bent in a working environment is subjected to multiple bending deformation cycles, the coating on the hard coating at the bending position cracks and falls off, so that the workpiece cannot be used continuously and fails prematurely. Therefore, the deposition of a hard coating on the surface of a flexible substrate requires further improvement in the bonding strength between the interfaces of the respective coatings in the hard film.
Disclosure of Invention
In view of the above, an object of the embodiments of the present invention is to provide a method for preparing a hard film on a flexible substrate and a related product, in which the hard film preparation process of the present invention makes the structure of the hard film more stable, and can greatly improve the bonding strength between the interfaces of the coatings in the hard film, thereby improving the performance of a workpiece using the hard film.
To achieve the above object, a first aspect of the present invention provides a method for preparing a hard film on a flexible substrate, comprising:
cleaning the substrate layer by using inert gas ions generated by a gas ion source;
Depositing a first metal element on the cleaned substrate layer by using a magnetic filtration cathodic arc deposition system, and forming a corresponding metal film layer by magnetic filtration cathodic arc deposition;
Injecting a second metal element on the metal film layer by using a metal vapor vacuum arc ion source to form an organic-metal heterojunction;
Depositing a third metal element on the surface of the organic-metal heterojunction by using a magnetic filtration cathodic arc deposition system to form a corresponding metal transition layer;
Depositing a fourth metal element on the metal transition layer by using high-power pulse magnetron sputtering equipment to form a corresponding gradient transition layer;
And depositing a metal compound on the gradient transition layer by using high-power pulse magnetron sputtering equipment to form a corresponding hard coating.
Optionally, in another embodiment of the first aspect of the present invention, the substrate layer is a polyimide polymer; the first metal element is Ti ions or Cr ions, and the thickness of the metal film layer is 3-10 nm; the second metal element is Ti ion or Cr ion; the third metal element is Ti ion or Cr ion, and the thickness of the metal transition layer is 100-300 nm.
Optionally, in another embodiment of the first aspect of the present invention, the fourth metal element is a simple metal or an alloy of two or more metals; the thickness of the gradient transition layer is 50-400 nm.
Optionally, in another embodiment of the first aspect of the present invention, the metal compound is one of a metal nitride, a metal carbide, and a metal carbonitride; the thickness of the hard coating is 0.8-4 mu m.
Optionally, in another embodiment of the first aspect of the present invention, the power of the gas ion source is set to 1 to 2.5kW, the frequency is set to 90 to 150KHz, the pulse width is set to 1.5 to 3 μ s, the voltage is set to-100 to-300V, and the cleaning time is set to 5 to 30 min.
Optionally, in another embodiment of the first aspect of the present invention, the arc flow of the magnetic filtration cathodic arc deposition system is set to 90-120A, and the bent-tube magnetic field current is set to 1-4A.
Optionally, in another embodiment of the first aspect of the present invention, the voltage of the metal vapor vacuum arc ion source is set to 10-15 kV, the beam intensity is set to 1-4 mA, and the implantation dose is set to 1 × 1015～5×1015/cm2The implantation depth is set to be 70-120 nm.
Optionally, in another embodiment of the first aspect of the present invention, the power of the high power pulse magnetron sputtering apparatus is set to 2 to 8kW, and the pulse width is set to 20 to 60 μ s.
The invention provides a hard film, which is prepared by the method for preparing the hard film on the flexible substrate.
the invention provides an integrated deposition device of a hard film, which comprises a gas ion source, a magnetic filtration cathodic arc deposition system, a metal vapor vacuum arc ion source, high-power pulse magnetron sputtering equipment, a rotatable substrate seat and a rotatable baffle plate, wherein the rotatable substrate seat is used for rotating a substrate layer and locking the position of the substrate layer; the rotatable baffle is used for rotating the baffle for observation; the gas ion source is used for generating inert gas ions to bombard the surface of the basic layer; the magnetic filtration cathode arc deposition system is used for depositing a first metal element on the cleaned substrate layer to form a corresponding metal film layer; the metal vapor vacuum arc ion source is used for forming an organic-metal heterojunction on the metal film layer; the high-power pulse magnetron sputtering equipment is used for forming a corresponding gradient transition layer on the metal transition layer and forming a corresponding hard coating on the gradient transition layer.
According to the technical scheme provided by the invention, after the flexible substrate is cleaned by utilizing a gas ion source, a metal film layer, an organic-metal heterojunction, a metal transition layer, a gradient transition layer and a hard film are sequentially formed on the flexible substrate in a magnetic filtration cathodic arc deposition mode, so that the preparation of the hard film on the flexible substrate is completed. The preparation method provided by the embodiment of the invention ensures that the structure of the prepared hard film is more stable, can greatly improve the bonding strength among coating interfaces in the hard film, and further improves the service performance of a workpiece using the hard film.
drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic flow chart of a method for preparing a hard film on a flexible substrate according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a hard film according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a substrate layer/organic-metal heterojunction/metal film layer in a hard film according to an embodiment of the invention;
FIG. 4 is a schematic diagram of an integrated deposition apparatus for a hard film according to an embodiment of the present invention.
Detailed Description
In order to make the technical field of the invention better understand the scheme of the invention, the embodiment of the invention will be described in conjunction with the attached drawings in the embodiment of the invention.
referring to fig. 1, a flow chart of a method for preparing a hard film on a flexible substrate according to an embodiment of the present invention is schematically shown, where the method for preparing a hard film on a flexible substrate includes:
101. and generating inert gas ions by using a gas ion source to clean the substrate layer.
specifically, the substrate layer is subjected to early-stage sputtering cleaning in the preparation process of the hard film, and inert gas ions are generated by a gas ion source to perform cleaning treatment on the substrate layer. The substrate layer may be polyimide polymer or other flexible substrate layer material, and the inert gas ions may be Ar ions. During specific implementation, for example, the substrate layer is a polyimide film, the inert gas ions are Ar ions, and the Ar ions have certain energy in the sputtering cleaning process, so that the Ar ions are sputtered to the polyimide film, and the impurities physically adsorbed or chemically adsorbed on the surface of the polyimide film can have certain sputtering effect, so that the surface of the polyimide film can be activated, and the cleanliness of the surface of the substrate layer is improved. The following description will be made by taking a polyimide film as a base layer of a hard film.
in addition, the polyimide film layer is sputtered by Ar ions in the early stage, so that organic groups on the surface of the polyimide film layer can be broken, the surface wettability of the polyimide film layer is enhanced, and a metal film layer deposited subsequently can be attached to the surface of the polyimide to the maximum extent.
Further, in specific implementation, the power of the gas ion source is preferably set to be 1-2.5 kW, the frequency is preferably set to be 90-150 KHz, the pulse width is preferably set to be 1.5-3 mus, the voltage is preferably set to be-100-300V, and the cleaning time is preferably set to be 5-30 min, so as to obtain better substrate layer cleaning effect.
102. And depositing a first metal element on the cleaned substrate layer by using a magnetic filtration cathodic arc deposition system, and forming a corresponding metal film layer by magnetic filtration cathodic arc deposition.
Specifically, the step is a preparation process of a metal film layer, a magnetic filtration cathodic arc deposition system is utilized to deposit a first metal element on a cleaned substrate layer, and a corresponding metal film layer is formed through magnetic filtration cathodic arc deposition, wherein the metal film layer is a layer of thin metal atoms and provides a material foundation for the preparation of an organic-metal heterojunction in the next step. In specific implementation, the first metal element can be Ti ions or Cr ions, and the thickness of the metal film layer is preferably 3-10 nm. Further, the arc flow of the magnetic filtration cathodic arc deposition system is preferably set to be 90-120A, the magnetic field current of the bent pipe is preferably set to be 1-4A, a 45-degree or 90-degree bent pipe is adopted, and the substrate bias voltage is preferably-100 to-400V.
103. And injecting a second metal element on the metal film layer by using a metal vapor vacuum arc ion source to form the organic-metal heterojunction.
Specifically, the step is a preparation process of the organic-metal heterojunction, and a second metal element is injected on the metal film layer by utilizing a metal vapor vacuum arc ion source to form the organic-metal heterojunction. In specific implementation, the second metal element may be Ti ion or Cr ion. And further, the voltage of the metal vapor vacuum arc ion source is preferably set to 10-15 kV, the beam intensity is preferably set to 1-4 mA, and the injection dosage is preferably set to 1 x 1015～5×1015/cm2The implantation depth is preferably set to 70 to 120 nm.
as shown in fig. 3, a schematic structural diagram of a substrate layer/organic-metal heterojunction/metal film layer in a hard film, a polyimide film substrate 200, a polyimide-metal heterojunction 210 and a metal film layer 220, according to the present invention, high energy metal ion implantation is adopted to enable the metal film layer deposited on the surface of the polyimide film to obtain recoil energy to enter the polyimide film, and an organic-metal heterojunction structure in which metal and polyimide are mixed at about 50nm can be formed, such that the binding force between the formed organic-metal heterojunction structure and the polyimide film substrate is very good, thereby improving the binding force of the structure of the substrate layer/organic-metal heterojunction/metal film layer in the hard film.
104. And depositing a third metal element on the surface of the organic-metal heterojunction by using a magnetic filtration cathodic arc deposition system to form a corresponding metal transition layer.
Specifically, the step is a preparation process of the metal transition layer, and a third metal element is deposited on the surface of the organic-metal heterojunction by using a magnetic filtration cathodic arc deposition system to form the corresponding metal transition layer. In the specific implementation, in the step, the metal in the metal transition layer is the same as the first metal element in the organic-metal heterojunction, so that the third metal element may be Ti ion or Cr ion, and the thickness of the metal transition layer is preferably 100 to 300 nm. By the steps, a metal transition layer is prepared on the surface of the organic-metal heterojunction, and the metal element used in the metal transition layer is consistent with the first metal element coating, so that the surface defects generated on the surface of the organic-metal heterojunction in the ion injection process can be densely filled, and the bonding strength of the organic-metal heterojunction and the adjacent coating can be enhanced.
105. And depositing a fourth metal element on the metal transition layer by using high-power pulse magnetron sputtering equipment to form a corresponding gradient transition layer.
Specifically, the step is a preparation process of the gradient transition layer, and a high-power pulse magnetron sputtering device is utilized to deposit a fourth metal element on the metal transition layer to form a corresponding gradient transition layer. In specific implementation, the fourth metal element is a simple metal or an alloy composed of two or more metals, such as Ti, Cr, TiAl, TiSi, or the like. The thickness of the gradient transition layer is 50-400 nm. The high-power pulse magnetron sputtering equipment is used for preparing gradient transition layers with different structural components by controlling the types or the flow of the introduced gas, and the gas introduction is set to be consistent with the deposition of the hard coating when the preparation of the gradient transition layers is finished.
Further, the voltage of the metal vapor vacuum arc ion source is preferably set to be 10-15 kV, the beam intensity is preferably set to be 1-4 mA, and the injection dose is preferably set to be 1 x 1015～5×1015/cm2the implantation depth is preferably set to 70 to 120 nm. As shown in FIG. 2, the structure of the hard film is schematically illustrated, wherein the structure of the hard film comprises a polyimide film substrate 100, an organic-metal heterojunction 110, and a gradient film in sequence from the bottom to the surfaceThe transition layer 120, the metal transition layer 130 and the hard coating 140, the gradient transition layer manufactured by the step of the invention is used for connecting the metal transition layer and the hard coating, so that no obvious interface exists in the structure, and the film falling caused by stress concentration at the interface and interface combination defects is avoided, thereby enhancing the combination strength between the coating interfaces of the hard film.
106. And depositing a metal compound on the gradient transition layer by using high-power pulse magnetron sputtering equipment to form a corresponding hard coating.
Specifically, the step is a preparation process of the hard coating, and a high-power pulse magnetron sputtering device is utilized to deposit a metal compound on the gradient transition layer to form the corresponding hard coating. In specific implementation, the metal compound is one of metal nitride, metal carbide and metal carbonitride, such as TiCN, TiAlN or TiSiCN, and the composition of the metal compound is approximately consistent with that of the gradient transition layer. The thickness of the hard coating is preferably 0.8-4 μm.
further, a high-power pulse magnetron sputtering device is used for preparing the hard coating on the basis of the gradient transition layer, the power of the high-power pulse magnetron sputtering device is set to be 2-8 kW, the pulse width is set to be 20-60 mu s, the substrate pulse negative bias is preferably-50V-150V, the duty ratio is preferably 70-90%, and the thickness of the deposited hard coating is preferably 0.8-4 mu m. The invention forms the corresponding hard coating by deposition, so that the structure of the hard film is more compact, and the bonding strength of the structure of the hard film is enhanced.
Therefore, in the embodiment of the invention, after the flexible substrate is cleaned by utilizing the gas ion source, the metal film layer, the organic-metal heterojunction, the metal transition layer, the gradient transition layer and the hard film are sequentially formed on the flexible substrate in a magnetic filtration cathodic arc deposition mode, so that the preparation of the hard film on the flexible substrate is completed. The preparation method provided by the embodiment of the invention ensures that the structure of the prepared hard film is more stable, can greatly improve the bonding strength among coating interfaces in the hard film, and further improves the service performance of a workpiece using the hard film.
Further, referring to fig. 4, a schematic diagram of an integrated hard film deposition apparatus according to an embodiment of the present invention includes a gas ion source 300, a magnetic filter cathode arc deposition system 310, a metal vapor vacuum arc ion source 320, a high power pulsed magnetron sputtering apparatus 330, a rotatable substrate holder 340, and a rotatable baffle 350. Wherein the rotatable base is used for rotating the base layer and locking the position of the base layer. The rotatable barrier is used to rotate the barrier for viewing. The gas ion source is used for generating inert gas ions to bombard the surface of the basic layer. The magnetic filtering cathode arc deposition system is used for depositing a first metal element on the cleaned substrate layer to form a corresponding metal film layer. The metal vapor vacuum arc ion source is used for forming an organic-metal heterojunction on the metal film layer. The high-power pulse magnetron sputtering equipment is used for forming a corresponding gradient transition layer on the metal transition layer and forming a corresponding hard coating on the gradient transition layer.
it should be noted that, for the device embodiment, since it is basically similar to the method embodiment, the description is relatively simple, and for the relevant points, reference may be made to part of the description of the method embodiment.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method of making a hard film on a flexible substrate, comprising:
Cleaning the substrate layer by using inert gas ions generated by a gas ion source;
Depositing a first metal element on the cleaned substrate layer by using a magnetic filtration cathodic arc deposition system, and forming a corresponding metal film layer by magnetic filtration cathodic arc deposition;
Injecting a second metal element on the metal film layer by using a metal vapor vacuum arc ion source to form an organic-metal heterojunction;
Depositing a third metal element on the surface of the organic-metal heterojunction by using a magnetic filtration cathodic arc deposition system to form a corresponding metal transition layer;
Depositing a fourth metal element on the metal transition layer by using high-power pulse magnetron sputtering equipment to form a corresponding gradient transition layer;
And depositing a metal compound on the gradient transition layer by using high-power pulse magnetron sputtering equipment to form a corresponding hard coating.
2. The method of claim 1, wherein the substrate layer is a polyimide polymer; the first metal element is Ti ions or Cr ions, and the thickness of the metal film layer is 3-10 nm; the second metal element is Ti ion or Cr ion; the third metal element is Ti ion or Cr ion, and the thickness of the metal transition layer is 100-300 nm.
3. The method for preparing a hard film on a flexible substrate according to claim 1, wherein the fourth metal element is a simple metal or an alloy of two or more metals; the thickness of the gradient transition layer is 50-400 nm.
4. The method of claim 1, wherein the metal compound is one of a metal nitride, a metal carbide, and a metal carbonitride; the thickness of the hard coating is 0.8-4 mu m.
5. The method for preparing a hard film on a flexible substrate according to claim 1, wherein the power of the gas ion source is set to 1 to 2.5kW, the frequency is set to 90 to 150KHz, the pulse width is set to 1.5 to 3 μ s, the voltage is set to-100 to-300V, and the cleaning time is set to 5 to 30 min.
6. the method for preparing the hard film on the flexible substrate according to claim 1, wherein the arc flow of the magnetic filtration cathodic arc deposition system is set to be 90-120A, and the magnetic field current of the bent pipe is set to be 1-4A.
7. The method for preparing a hard film on a flexible substrate according to claim 1, wherein the voltage of the metal vapor vacuum arc ion source is set to 10-15 kV, the beam intensity is set to 1-4 mA, and the implantation dose is set to 1 x 1015～5×1015/cm2the implantation depth is set to be 70-120 nm.
8. The method for preparing a hard film on a flexible substrate according to claim 1, wherein the high power pulse magnetron sputtering device is set to have a power of 2 to 8kW and a pulse width of 20 to 60 μ s.
9. A hard film produced by the method for producing a hard film on a flexible substrate according to any one of claims 1 to 8.
10. The integrated deposition device for the hard film is characterized by comprising a gas ion source, a magnetic filtration cathodic arc deposition system, a metal vapor vacuum arc ion source, high-power pulse magnetron sputtering equipment, a rotatable substrate seat and a rotatable baffle plate, wherein the rotatable substrate seat is used for rotating a substrate layer and locking the position of the substrate layer; the rotatable baffle is used for rotating the baffle for observation; the gas ion source is used for generating inert gas ions to bombard the surface of the basic layer; the magnetic filtration cathode arc deposition system is used for depositing a first metal element on the cleaned substrate layer to form a corresponding metal film layer; the metal vapor vacuum arc ion source is used for forming an organic-metal heterojunction on the metal film layer; the high-power pulse magnetron sputtering equipment is used for forming a corresponding gradient transition layer on the metal transition layer and forming a corresponding hard coating on the gradient transition layer.
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