A Cr-based hydrogen barrier composite coating, a Cr-based hydrogen barrier plate and a preparation method thereof

Abstract

The application provides a Cr-based hydrogen barrier composite coating, which is composed of a Cr metal transition layer, a CrAlSiN nano coating combined with the surface of the Cr metal transition layer, and a Cr2O3 layer combined with the surface of the CrAlSiN nano coating. The application also provides a Cr-based hydrogen barrier plate and a preparation method thereof. The Cr metal transition layer, the CrAlSiN nano coating and the Cr2O3 layer are deposited by a high-power magnetron sputtering method. The Cr-based hydrogen barrier composite coating provided by the application utilizes the huge difference in hydrogen permeability between the hydrogen barrier coating material and the substrate material, and a nano composite coating is prepared on the hydrogen surface of the metal substrate to inhibit and slow down the diffusion of hydrogen and its isotopes, so as to avoid the premature failure of the equipment, and the Cr-based hydrogen barrier composite coating has hydrogen barrier performance and mechanical performance at the same time.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of composite coatings, in particular to a Cr-based hydrogen-blocking composite coating, a Cr-based hydrogen-blocking plate and a preparation method thereof. BACKGROUND

[0002] Hydrogen fuel cell engines are used in hydrogen-rich or pure hydrogen environments. Hydrogen can penetrate into the metal materials in the components, causing serious hydrogen embrittlement, which may lead to component failure and accidents. Therefore, researchers propose to use hydrogen-blocking coatings to prevent hydrogen penetration, thereby effectively controlling the hydrogen embrittlement damage of hydrogen fuel engine components, improving the service life of the components and avoiding accidents.

[0003] Common hydrogen-blocking coatings can be divided into three categories: oxide coatings, non-oxide coatings and composite coatings. Coatings prepared by traditional coating preparation methods are difficult to avoid the generation of nanoscale micropores or cracks in the coatings during deposition. These defects, which are usually caused by dust particles or any other random events during film growth, are very easy to develop into hydrogen penetration channels along the growth direction of the coating, resulting in a decrease in the hydrogen-blocking performance of the coating. Moreover, the hydrogen-blocking coatings in the prior art have poor mechanical properties and low hardness, and are easy to scratch and fall off under external load. Therefore, a hydrogen-blocking coating that simultaneously considers hydrogen-blocking performance and mechanical properties is of great significance. SUMMARY

[0004] The technical problem solved by the application is to provide a preparation method of a Cr-based hydrogen-blocking composite coating and a Cr-based hydrogen-blocking composite plate. The Cr-based hydrogen-blocking composite coating provided by the application simultaneously has hydrogen-blocking performance and mechanical properties.

[0005] Therefore, the application further provides a Cr-based hydrogen-blocking composite coating, which is composed of a Cr metal transition layer, a CrAlSiN nano-coating complexed on the surface of the Cr metal transition layer and a Cr2O3 layer complexed on the surface of the CrAlSiN nano-coating.

[0006] Preferably, the content of N elements increases in the direction from the Cr metal transition layer to the CrAlSiN nano-coating, and the content of N elements decreases and the content of O elements increases in the direction from the CrAlSiN nano-coating to the Cr2O3 layer.

[0007] Preferably, the thickness of the Cr metal transition layer is 0.1-0.5 microns, the thickness of the CrAlSiN nano-coating is 0.5-20 microns, and the thickness of the Cr2O3 layer is 0.5-2 microns.

[0008] The application also provides a Cr-based hydrogen barrier plate, comprising a substrate and a Cr-based hydrogen barrier composite coating.

[0009] The application also provides a preparation method of the Cr-based hydrogen barrier plate, comprising the following steps:

[0010] A) sequentially performing pre-cleaning and ion cleaning on the substrate;

[0011] B) depositing a Cr metal transition layer on the surface of the substrate obtained in step A) by using a high-power magnetron sputtering technology;

[0012] C) depositing a CrAlSiN layer on the surface of the substrate obtained in step B) by using a high-power magnetron sputtering technology;

[0013] D) depositing a Cr2O3 layer on the surface of the substrate obtained in step C) by using a high-power magnetron sputtering technology.

[0014] Preferably, the step of ion cleaning is specifically as follows:

[0015] The pre-cleaned substrate is placed in a vacuum chamber, the Cr target and the CrAlSi target are cleaned, the vacuum chamber is closed, and after vacuumizing, argon is introduced, the working gas pressure is 0.3-2.0 Pa, the micro-pulse width of the HiPIMS target is 10-80 μs, the average power is 4-10 kW, the bias voltage is 0-200 V, and the cleaning time is 5-30 minutes.

[0016] Preferably, the step of depositing the Cr metal transition layer is specifically as follows:

[0017] A pure Cr target is used, argon gas with a flow rate of 80-200 sccm is introduced into the vacuum chamber of the high-power magnetron sputtering device, the working gas pressure is adjusted to 0.3-2.0 Pa, the micro-pulse width is adjusted to 10-80 μm, the average power is 4-10 kW, and the bias voltage is 0-100 V to deposit on the surface of the ion-cleaned substrate.

[0018] Preferably, the step of depositing the CrAlSiN layer is specifically as follows:

[0019] A CrAlSi target is used, the micro-pulse width of the high-power magnetron sputtering device in the vacuum chamber is set to 10-80 μs, the average power is 4-10 kW, the bias voltage is 0-200 V, the argon flow rate is 80-150 sccm, the nitrogen flow rate in the vacuum chamber is linearly increased to 30-50 sccm within 5 min, and the gas pressure of the mixed gas in the vacuum chamber is 0.5-3.0 Pa.

[0020] Preferably, the step of depositing the Cr2O3 layer is specifically as follows:

[0021] The CrAlSi target is closed, the Cr target is started, the average power of the target is 4-10 kW, the nitrogen flow rate is reduced to 0 sccm within 3 min, the oxygen flow rate is linearly increased to 20 sccm within 2 min at the 2nd min after the nitrogen flow rate is reduced to 0 sccm, and at this time, the mixed gas pressure in the vacuum chamber is 0.5-3.2 Pa.

[0022] Preferably, the atomic ratio of Cr, Al and Si in the CrAlSi target is 6:3:1.

[0023] The application provides a Cr-based hydrogen barrier composite coating, which is composed of a Cr metal transition layer, a CrAlSiN nano coating combined with the surface of the Cr metal transition layer, and a Cr2O3 layer combined with the surface of the CrAlSiN nano coating. The Cr-based hydrogen barrier composite coating provided by the application has the hydrogen barrier performance and mechanical performance by the arrangement of the three layers. The Cr metal transition layer can enhance the adhesion of the coating, the CrAlSiN nano coating has excellent mechanical performance and hydrogen barrier performance, and the dense Cr2O3 layer on the surface can significantly improve the durability and corrosion resistance of the coating.

[0024] Further, the application also provides a preparation method of the Cr-based hydrogen barrier composite plate, which uses the high-power pulsed magnetron sputtering technology to prepare each layer, avoids the micro-particle defects which are difficult to suppress in the conventional PVD deposition process, and simultaneously, the high-density ion beam bombardment can significantly improve the density of the coating, reduce the micro-defects in the coating, has a uniform and dense microstructure with low defects, can effectively suppress the diffusion of hydrogen along the micro-defects, and the dangling bonds at the nanocrystal and amorphous interfaces in the nano-composite coating can effectively adsorb free hydrogen atoms to form hydrogen traps, further improve the hydrogen barrier performance of the coating, and is particularly suitable for application in the hydrogen-containing parts under acidic working conditions in the hydrogen fuel cell engine and presents excellent hydrogen barrier performance. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 FIG. 1 is a structural schematic diagram of the Cr-based composite plate of the application;

[0026] Figure 2 FIG. 4 is a structural schematic diagram of the high-power pulsed magnetron sputtering equipment of the application. DETAILED DESCRIPTION

[0027] In order to further understand the application, the preferred embodiments of the application are described below in combination with examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the application, and are not a limitation on the claims of the application.

[0028] In view of the poor mechanical properties and low hardness of the hydrogen barrier coating in the prior art, the hydrogen barrier coating is easy to be scratched and peeled off under external load, the application provides a Cr-based hydrogen barrier composite coating, which utilizes the great difference in hydrogen permeation performance between the hydrogen barrier coating material and the substrate, and a nano-composite coating is prepared on the hydrogen surface of the substrate by high-power pulse magnetron sputtering technology to inhibit and slow down the diffusion of hydrogen-based isotopes, so that the hydrogen barrier composite coating has good hydrogen barrier performance and mechanical properties. Specifically, the application discloses a Cr-based hydrogen barrier composite coating, which comprises a Cr metal transition layer, a CrAlSiN nano-coating combined on the surface of the Cr metal transition layer, and a Cr2O3 layer combined on the surface of the CrAlSiN nano-coating.

[0029] In the Cr-based hydrogen barrier composite coating provided in the application, the content of N element increases in the direction from the Cr metal transition layer to the CrAlSiN nano-coating, and the content of N element decreases and the content of O element increases in the direction from the CrAlSiN nano-coating to the Cr2O3 layer.

[0030] In the application, the thickness of the Cr metal transition layer is 0.1-0.5 μm, the thickness of the CrAlSiN nano-coating is 0.5-20 μm, and the thickness of the Cr2O3 layer is 0.5-2 μm.

[0031] Further, the application provides a Cr-based hydrogen barrier plate, which comprises a substrate and a Cr-based hydrogen barrier composite coating, and the Cr-based hydrogen barrier composite coating is the Cr-based hydrogen barrier composite coating described in the above scheme.

[0032] In the Cr-based hydrogen barrier plate, the substrate is well known to those skilled in the art, and the application has no particular limitation thereon, for example, the substrate can be selected from stainless steel.

[0033] The application also provides a preparation method of the Cr-based hydrogen barrier plate, which comprises the following steps:

[0034] A) sequentially performing pre-cleaning and ion cleaning on the substrate;

[0035] B) depositing a Cr metal transition layer on the surface of the substrate obtained in step A) by using high-power magnetron sputtering technology;

[0036] C) depositing a CrAlSiN layer on the surface of the substrate obtained in step B) by using high-power magnetron sputtering technology;

[0037] D) depositing a Cr2O3 layer on the surface of the substrate obtained in step C) by using high-power magnetron sputtering technology.

[0038] In the preparation of the Cr-based hydrogen barrier plate, the substrate is first pre-cleaned, which can be ultrasonically cleaned with alcohol, acetone and deionized water in sequence to remove impurities or dirt on the surface of the substrate.

[0039] Then the substrate is ion cleaned, specifically by placing the substrate in a vacuum chamber, cleaning the Cr target and CrAlSi target, closing the vacuum chamber, introducing argon after vacuumizing, and cleaning at a working gas pressure of 0.3-2.0 Pa, a micro-pulse width of 10-80 μs, an average power of 4-10 kW, and a bias voltage of 0-200 V. The cleaning time is 5-30 minutes. The Cr target and the CrAlSi target are used for subsequent deposition of the coating. The cleaning time is 5-30 min.

[0040] After the above preparation is completed, a Cr metal transition layer is then deposited on the surface of the substrate, specifically by using a pure Cr target, introducing argon into the vacuum chamber of the high-power magnetron sputtering device at a flow rate of 80-200 sccm, adjusting the working gas pressure to 0.3-2.0 Pa, adjusting the micro-pulse width to 10-80 μm, and depositing on the surface of the ion-cleaned substrate at an average power of 4-10 kW and a bias voltage of 0-100 V. The above process realizes the deposition of the Cr transition layer.

[0041] After the Cr transition layer is prepared, a CrAlSiN layer is deposited, specifically by:

[0042] Using a CrAlSi target, setting the adjusted micro-pulse width in the vacuum chamber of the high-power magnetron sputtering device to 10-80 μs, the average power to 4-10 kW, the bias voltage to 0-200 V, the argon flow rate to 80-150 sccm, and linearly increasing the nitrogen flow rate in the vacuum chamber to 30-50 sccm within 5 min, so that the gas pressure of the mixed gas in the vacuum chamber is 0.5-3.0 Pa.

[0043] The deposition time of the CrAlSiN layer is 20-50 min, and the atomic ratio of Cr, Al and Si in the CrAlSi target is 6:3:1. During the above deposition process, the nitrogen flow rate is gradually increased, and therefore the N content in the Cr transition layer to the CrAlSiN layer is gradually increased.

[0044] Finally, the deposition of the Cr2O3 layer is performed, specifically by closing the CrAlSi target, starting the Cr target, setting the target average power to 4-10 kW, reducing the nitrogen flow rate to 0 sccm within 3 min, and linearly increasing the oxygen flow rate to 20 sccm within 2 min after the nitrogen flow rate is reduced to 0 sccm. At this time, the gas pressure of the mixed gas in the vacuum chamber is 0.5-3.2 Pa.

[0045] During the deposition of the Cr2O3 layer, the content of N element gradually decreases and the content of O element gradually increases in the direction from the CrAlSiN layer to the Cr2O3 layer.

[0046] The structural schematic diagram of the high-power magnetron sputtering device is specifically shown in the figure. Figure 2

[0047] During the preparation process, the greater the negative bias voltage, the larger the nanocrystal size, so the negative bias voltage needs to be controlled, and the target power and target composition will affect the composition of the coating and further affect the hydrogen barrier property.

[0048] The high-power magnetron sputtering technology is adopted to prepare the hydrogen barrier composite coating, and a uniform, dense and low-defect microstructure can be obtained, and the combination of the coating composition and the preparation method is conducive to forming a nanocrystal / amorphous composite structure, and the dangling bond energy of the composite structure can effectively adsorb free hydrogen atoms, thereby further improving the hydrogen barrier property.

[0049] In order to further understand the present application, the Cr-based hydrogen barrier composite coating, the Cr-based composite plate and the preparation method thereof provided by the present application will be described in detail below in combination with examples, and the protection scope of the present application is not limited by the following examples.

[0050] Example 1

[0051] 1) Pre-cleaning: ultrasonic cleaning of 316L stainless steel substrate with alcohol, acetone and deionized water in sequence to remove impurities or dirt on the surface of the substrate;

[0052] 2) Ion cleaning: placing the substrate into a vacuum chamber and installing it on a sample table, cleaning the surfaces of the sputtering targets Cr and CrAlSi (Cr:Al:Si atomic ratio = 6:3:1), closing the vacuum chamber, evacuating the air in the vacuum chamber to 4x10 -3 Pa, introducing argon gas with a flow rate of 100sccm, working gas pressure 1.5Pa, adjusting the micro-pulse width of the HiPIMS target to 60us, average power 6kW, bias voltage 100V, and cleaning time 20 minutes;

[0053] 3) Depositing Cr metal transition layer: using a pure Cr target, introducing argon gas with a flow rate of 100sccm into the vacuum chamber, working gas pressure 1.5Pa, adjusting the micro-pulse width to 50us, average power 6kW, bias voltage 60V, depositing a Ti transition layer on the surface of the substrate, and the thickness is 0.3um;

[0054] ​4) Depositing CrAlSiN coating: after the metal transition layer is deposited, depositing CrAlSiN coating on the metal transition layer, the specific steps are as follows: using CrAlSi target, setting the adjusting micro-pulse width in the vacuum chamber to 60 μs, the average power to 5 kW, the bias voltage to 120 V, the argon flow to 120 sccm, linearly increasing the nitrogen flow in the vacuum chamber to 40 sccm within 5 min, so that the mixed gas pressure in the vacuum chamber is 2.0 Pa, and the deposition time is 40 min;

[0055] 5) Depositing Cr2O3 coating: after the CrAlSiN coating is deposited, the CrAlSi target is closed, the Cr target is started, the target average power is 6 kW, and the nitrogen flow is reduced to 0 sccm within 3 min; 2 min after the nitrogen flow is reduced to 0 sccm, the oxygen flow is linearly increased (from 0 sccm to 20 sccm) within 2 min, at this time, the mixed gas pressure in the vacuum chamber is 2.5 Pa, and the deposition time is 10 min.

[0056] In this embodiment, the structure of the composite coating is as follows: the pure Cr transition layer is closest to the substrate, then the CrAlSiN nanocomposite coating, and the Cr2O3 coating is farthest;

[0057] In the direction from the Cr metal transition layer to the CrAlSiN nanocoating, the content of N element increases, in the direction from the CrAlSiN nanocoating to the Cr2O3 layer, the content of N element decreases, and the content of O element increases.

[0058] In this embodiment, CrAlSiN and Cr2O3 nanocomposite hydrogen barrier coatings are prepared on 316L stainless steel, the total thickness of the coating is about 5.8 μm, the structure diagram is as shown in Figure 1 The hydrogen barrier performance of the CrAlSiN and Cr2O3 nanocomposite coating with Cr transition layer is about 650 times that of the 316L austenitic stainless steel substrate at a permeation temperature of 600 ℃, the CrAlSiN and Cr2O3 nanocomposite coating with Cr transition layer has good hydrogen barrier performance, and the coating hardness is about 22 GPa.

[0059] Example 2

[0060] 1) Pre-cleaning: using alcohol, acetone and deionized water to ultrasonically clean the 316L stainless steel substrate in sequence, removing impurities or dirt on the surface of the substrate;

[0061] 2) Ion cleaning: placing the substrate into the vacuum chamber and installing it on the sample table, cleaning the surfaces of the sputtering targets Cr and CrAlSi target (Cr:Al:Si atomic ratio = 6:3:1), closing the vacuum chamber, and evacuating the air in the vacuum chamber to 4×10 -3Pa, the argon flow rate is 80 sccm, the working gas pressure is 0.6 Pa, the bias voltage is -800 V, and the cleaning time is 30 min;

[0062] 3) Depositing a Cr metal transition layer: pure Cr target is used, argon with a flow rate of 80 sccm is introduced into the vacuum chamber, the working gas pressure is 0.6 Pa, the micro-pulse width is adjusted to 50 μs, the average power is 5 kW, the bias voltage is 0-100 V, a Cr transition layer with a thickness of 0.3 μm is deposited on the surface of the substrate;

[0063] 4) Depositing a CrAlSiN coating layer: after the metal transition layer is deposited, a CrAlSiN coating layer is deposited on the metal transition layer, and the specific steps are as follows: a CrAlSi target is used, the micro-pulse width is adjusted to 50 μs, the average power is 5 kW, the bias voltage is -100 V, the argon flow rate is 100 sccm, the nitrogen flow rate in the vacuum chamber is linearly increased to 30 sccm within 5 min, the mixed gas pressure in the vacuum chamber is 1.4 Pa, and the deposition time is 50 min;

[0064] 5) Depositing a Cr2O3 coating layer: after the CrAlSiN coating layer is deposited, the CrAlSi target is closed, the Cr target is started, the target average power is 4 kW, and the nitrogen flow rate is reduced to 0 sccm within 3 min; 2 min after the nitrogen flow rate is reduced to 0 sccm, the oxygen flow rate is linearly increased (from 0 sccm to 20 sccm) within 2 min, at this time, the mixed gas pressure in the vacuum chamber is 0.7 Pa, and the deposition time is 10 min.

[0065] In this embodiment, the structure of the composite coating is as shown in Figure 1 The closest to the substrate is a pure Cr transition layer, followed by a CrAlSiN nanocomposite coating layer, and the farthest is a Cr2O3 coating layer. In the direction from the Cr metal transition layer to the CrAlSiN nanocoating layer, the content of N element increases, in the direction from the CrAlSiN nanocoating layer to the Cr2O3 layer, the content of N element decreases, and the content of O element increases.

[0066] A CrAlSiN and Cr2O3 nanocomposite hydrogen barrier coating layer is prepared on a 316L stainless steel substrate through this embodiment, the total thickness of the coating layer is about 6.4 μm, the structure diagram is as shown in Figure 1 , and the hydrogen barrier performance is tested. At a permeation temperature of 400 ℃, the hydrogen barrier performance of the CrAlSiN and Cr2O3 nanocomposite coating layer with a Cr transition layer is about 480 times that of the 316L austenitic stainless steel substrate. The CrAlSiN and Cr2O3 nanocomposite coating layer with a Cr transition layer has good hydrogen barrier performance, and the coating layer hardness is about 18 GPa.

[0067] Comparative Example 1 is a comparative example without a Cr2O3 coating layer.

[0068] 1) Pre-cleaning: 316L stainless steel substrate was cleaned by ultrasonic cleaning with alcohol, acetone and deionized water in sequence to remove impurities or dirt on the surface of the substrate;

[0069] 2) Ion cleaning: The substrate was placed in a vacuum chamber and installed on a sample table, and the surfaces of the sputtering target Cr and CrAlSi target (Cr:Al:Si atomic ratio = 6:3:1) were cleaned. The vacuum chamber was closed, and the air in the vacuum chamber was pumped to 4x10 -3 Pa, argon gas was introduced at a flow rate of 100sccm, the working gas pressure was 1.5Pa, the micro-pulse width of the HiPIMS target was adjusted to 60μs, the average power was 6kW, the bias voltage was 100V, and the cleaning time was 20 minutes;

[0070] 3) Depositing Cr metal transition layer: pure Cr target was used, argon gas was introduced into the vacuum chamber at a flow rate of 100sccm, the working gas pressure was 1.5Pa, the micro-pulse width was adjusted to 50μs, the average power was 6kW, the bias voltage was 60V, and the Ti transition layer was deposited on the surface of the substrate with a thickness of 0.3μm;

[0071] 4) Depositing CrAlSiN coating: After depositing the metal transition layer, CrAlSiN coating was deposited on the metal transition layer. The specific steps are as follows: CrAlSi target was used, the micro-pulse width in the vacuum chamber was adjusted to 60μs, the average power was 5kW, the bias voltage was 120V, the argon gas flow rate was 120sccm, the nitrogen gas flow rate in the vacuum chamber was linearly increased to 40sccm within 5min, the gas pressure of the mixed gas in the vacuum chamber was 2.0Pa, and the deposition time was 40min.

[0072] In this embodiment, the structure of the composite coating is as follows: the nearest to the substrate is the pure Cr transition layer, followed by the CrAlSiN nanocomposite coating; the content of N element increases in the direction from the Cr metal transition layer to the CrAlSiN nanocoating.

[0073] In this embodiment, the CrAlSiN coating and the Cr metal transition layer were prepared on the 316L stainless steel, and the total thickness of the coating was about 4.5μm. The hydrogen barrier performance of the composite coating was tested, and the hydrogen barrier performance of the composite coating was about 460 times that of the 316L austenitic stainless steel substrate at a permeation temperature of 600℃.

[0074] The above embodiments are only used to help understand the method of the present application and its core idea. It should be noted that for those skilled in the art, without departing from the principles of the present application, the present application can be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present application.

[0075] The foregoing description of the disclosed embodiments enables a person skilled in the art to make or use the application. Modifications of these embodiments will occur to persons of skill in the art, and that the appended claims are intended to cover all such modifications that do not depart from the true spirit and scope of the application. Therefore, the application is not limited to the embodiments shown but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A Cr-based hydrogen barrier composite coating, comprising a Cr metal transition layer, a CrAlSiN nano-coating layer deposited on the surface of the Cr metal transition layer, and a Cr 2 O 3 layer deposited on the surface of the CrAlSiN nano-coating layer. The content of N element increases from the Cr metal transition layer to the CrAlSiN nano-coating layer, and the content of O element increases from the CrAlSiN nano-coating layer to the Cr 2 O 3 layer.

2. The Cr-based hydrogen barrier composite coating according to claim 1, characterized in that, The thickness of the Cr metal transition layer is 0.1-0.5 μm, the thickness of the CrAlSiN nano-coating layer is 0.5-20 μm, and the thickness of the Cr 2 O 3 layer is 0.5-2 μm. 3.A Cr-based hydrogen barrier plate, comprising a substrate and a Cr-based hydrogen barrier composite coating, wherein the Cr-based hydrogen barrier composite coating is the Cr-based hydrogen barrier composite coating according to any one of claims 1-2. 4.A method for preparing the Cr-based hydrogen barrier plate according to claim 3, comprising the following steps: A) sequentially performing pre-cleaning and ion cleaning on the substrate; B) depositing a Cr metal transition layer on the surface of the substrate obtained in step A) by using high-power magnetron sputtering technology; C) depositing a CrAlSiN layer on the surface of the substrate obtained in step B) by using high-power magnetron sputtering technology; D) depositing a Cr 2 O 3 layer on the surface of the substrate obtained in step C) by using high-power magnetron sputtering technology.

5. The production method according to claim 4, characterized by, The ion cleaning step is specifically as follows: placing the pre-cleaned substrate in a vacuum chamber, cleaning the Cr target and the CrAlSi target, closing the vacuum chamber, introducing argon after vacuumizing, performing cleaning at a working gas pressure of 0.3-2.0 Pa, a micro-pulse width of 10-80 μs, an average power of 4-10 kW, and a bias voltage of 0-200 V, and the cleaning time is 5-30 minutes.

6. The preparation method according to claim 4, characterized in that, The step of depositing the Cr metal transition layer is specifically as follows: using a pure Cr target, introducing argon into the vacuum chamber of the high-power magnetron sputtering device at a flow rate of 80-200 sccm, adjusting the working gas pressure to 0.3-2.0 Pa, adjusting the micro-pulse width to 10-80 μm, and depositing on the surface of the ion-cleaned substrate at an average power of 4-10 kW and a bias voltage of 0-100 V.

7. The preparation method according to claim 4, characterized in that, The step of depositing the CrAlSiN layer is specifically as follows: using a CrAlSi target, setting the micro-pulse width to 10-80 μs, the average power to 4-10 kW, the bias voltage to 0-200 V, the argon flow rate to 80-150 sccm, and the nitrogen flow rate to 30-50 sccm within 5 minutes, linearly increasing the nitrogen flow rate in the vacuum chamber, and adjusting the mixed gas pressure in the vacuum chamber to 0.5-3.0 Pa.

8. The preparation method according to claim 4, characterized in that, The step of depositing the Cr 2 O 3 layer is specifically as follows: closing the CrAlSi target, starting the Cr target, setting the average power to 4-10 kW, reducing the nitrogen flow rate to 0 sccm within 3 minutes, increasing the oxygen flow rate to 20 sccm within 2 minutes after the nitrogen flow rate is reduced to 0 sccm, and adjusting the mixed gas pressure in the vacuum chamber to 0.5-3.2 Pa.

9. The preparation method according to claim 7, characterized in that, The CrAlSi target has an atomic ratio of Cr, Al and Si of 6:3:

1. The CrAlSi target has an atomic ratio of Cr, Al and Si of 6:3:1.

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