Three-target composite co-sputtering high-entropy alloy coating method

Abstract

The invention belongs to the technical field of material surface modification, and particularly relates to a three-target composite co-sputtering high-entropy alloy coating method. In order to solve the problems that a multi-target direct-current co-sputtering high-entropy alloy coating is low in ionization rate, phase composition and a microstructure are difficult to regulate and control, the deposition rate of multi-target high-power pulse magnetron co-sputtering is low, and the glow discharge stability is poor, the phase relation of high-power pulse magnetron sputtering and modulation pulse magnetron sputtering three-target composite co-deposition is designed and controlled; and different parameters are adjusted, so that effective regulation and control on the components, the phase composition and the microstructure of the high-entropy alloy coating are realized.

Description

Technical Field

[0001] This invention belongs to the field of material surface modification technology, specifically relating to a three-target composite co-sputtering method for high-entropy alloy coating. Background Technology

[0002] High-entropy alloys are multi-principal element alloys containing at least five elements, with each element having an atomic percentage between 5% and 35%. Due to the combined effects of high-entropy, slow diffusion, lattice distortion, and the cocktail effect, high-entropy alloys exhibit superior mechanical properties and chemical stability compared to traditional alloys.

[0003] Among them, magnetron sputtering technology can prepare coatings on substrates of any material, and the grain size, microstructure, and properties of the coating can be controlled by changing process parameters without post-processing. It has become the most commonly used method for preparing high-entropy alloy coatings, and is particularly suitable for preparing high-entropy alloy nitride coatings by reactive sputtering. According to the power discharge mode, magnetron sputtering can be divided into DC magnetron sputtering (DCMS), radio frequency magnetron sputtering (RFMS), high-power pulsed magnetron sputtering (HiPIMS), and modulated pulsed magnetron sputtering (MPPMS), etc.; according to the number of targets, magnetron sputtering can be divided into single-target sputtering and multi-target co-sputtering.

[0004] Compared to single-target sputtering, multi-target co-sputtering can improve the deposition rate and eliminates the need to prepare high-entropy alloy targets with different elemental ratios. The elemental content of the target material in the coating can be effectively controlled by adjusting parameters such as the sputtering power and pulse width of each target. Since the sputtering target voltage in DC magnetron sputtering is constant and pulse-free, if multiple sputtering targets are present, each target only needs to be connected to a DC power supply to achieve multi-target DC co-sputtering. Currently, some researchers have used dual-target DC co-sputtering to prepare high-entropy alloy coatings and studied the influence of elemental composition on the coating's microstructure and properties. Other researchers have used three-target DC co-sputtering to prepare high-entropy alloy coatings to further improve the deposition rate and have achieved control over the coating's microstructure, mechanical properties, and corrosion resistance by adjusting the nitrogen flow rate. However, due to limitations in the cooling capacity of the sputtering targets, the ionization rate and ion energy of traditional DC sputtering are relatively low, making it difficult for multi-target DC co-sputtering to effectively control the phase composition and microstructure of high-entropy alloy coatings.

[0005] HiPIMS features a low duty cycle and high peak power at the target surface, enabling highly ionized sputtered materials at relatively low average power. By bombarding the substrate with a high-energy ion beam, the microstructure of the coating, including phase composition, crystal orientation, density, lattice constant, grain size, and crystallinity, can be effectively controlled. It can even achieve the low-temperature preparation of dense, high-entropy alloy coatings. Therefore, compared with other multi-target co-sputtering methods, multi-target high-power pulsed magnetron co-sputtering offers better control over the microstructure of high-entropy alloy coatings. However, HiPIMS has drawbacks, including low deposition rate and poor stability under low-frequency, long-pulse-width discharge.

[0006] Therefore, it is necessary to invent a co-sputtering method that can improve the deposition rate and pulse discharge stability while also enabling effective control of the coating microstructure. Summary of the Invention

[0007] To address the challenges of low ionization rate, difficulty in controlling phase composition and microstructure in multi-target DC co-sputtering of high-entropy alloy thin films, low deposition rate in multi-target high-power pulsed magnetron co-sputtering, and poor glow discharge stability, this invention designs and controls the phase relationship of three-target composite co-deposition using high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering. This not only improves the deposition rate, broadens the process window, and enhances glow discharge stability, but also combines the plasma and pulsed discharge characteristics of high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering to achieve effective control over the composition, phase composition, and microstructure of high-entropy alloy coatings.

[0008] To achieve the above objectives, the present invention employs the following technical solution: This embodiment of a three-target composite co-sputtering high-entropy alloy coating method includes the following steps: Step 1: Install sputtering target 1, sputtering target 2, and sputtering target 3. Sputtering target 1 and sputtering target 2 are connected to the main circuit of the dual-target high-power pulsed magnetron co-sputtering power supply, and sputtering target 3 is connected to the main circuit of the modulated pulsed magnetron sputtering power supply. The main circuits of the dual-target high-power pulsed magnetron co-sputtering power supply and the modulated pulsed magnetron sputtering power supply are both connected to a DC power supply. Sputtering target 1, sputtering target 2, and sputtering target 3 are subjected to high-power pulsed magnetron sputtering, high-power pulsed magnetron sputtering, and modulated pulsed magnetron sputtering, respectively. Step 2: Install the ultrasonically cleaned and dried sample onto the sample stage, and connect the sample stage to a bias DC power supply. Step 3: Close the vacuum chamber, turn on the circulating water, and evacuate the vacuum chamber until the background vacuum level is below 1×10⁻⁶. - 3 Pa, then argon gas is introduced into the vacuum chamber at a flow rate of 5 Sccm to 100 Sccm to make the pressure in the vacuum chamber 0.05 to 10 Pa; Step 4: Set the sputtering frequency of the dual-target high-power pulsed magnetron co-sputtering power supply to 1KHz~5KHz, the period to 200ms~1000ms, the pulse width of both the first and second sputtering targets to 10ms~100ms, and the duty cycle to 1%~10%. Set the pulse interval between the first and second sputtering targets to promote the low-voltage ignition of the second sputtering target. Set the sputtering frequency of the modulated pulse magnetron sputtering power supply to 20Hz~200Hz, with a period more than 20 times the period of the first or second sputtering target. Set the auxiliary sputtering pulse width and the main sputtering pulse width to make the duty cycle 1%~10%, and the total pulse width (the sum of the auxiliary sputtering pulse width and the main sputtering pulse width) ≤ the period of the dual-target high-power pulse magnetron co-sputtering power supply. Step 5: Set the DC power supply voltage to 300V~2000V and the sputtering pressure to 0.05Pa~5Pa. Turn on the glow discharge sequentially in the order of sputtering target No. 1, sputtering target No. 2 and sputtering target No. 3 to perform pre-sputtering. Step 6: After pre-sputtering, introduce working gas and adjust the sputtering pressure to 0.1Pa~5Pa. Set the input voltage of the DC power supply to 300V~3000V. The sputtering power of sputtering target 1, sputtering target 2, and sputtering target 3 is 10W~1000W. Turn on glow discharge sequentially in the order of sputtering target 1, sputtering target 2, and sputtering target 3 to perform three-target composite co-sputtering and complete the coating deposition. Set the voltage of the DC bias power supply to 0V~500V, the deposition time to 0h~10h, and the flow rate of the working gas to 5Sccm~100Sccm.

[0009] Furthermore, the target materials of the No. 1 sputtering target, the No. 2 sputtering target, and the No. 3 sputtering target are homogeneous or heterogeneous target materials.

[0010] Furthermore, the target material is an alloy or an element, and contains ≥5 types of elements.

[0011] Furthermore, the first sputtering target is a permanent magnet target, and the second and third sputtering targets are permanent magnet targets or strong magnetic targets.

[0012] Furthermore, the pre-sputtering time is 0 min to 30 min.

[0013] Furthermore, the working gas is nitrogen, oxygen, or acetylene.

[0014] Compared with the prior art, the present invention has the following advantages: 1. By designing and controlling the phase relationship between the three sputtering targets, this invention can improve the deposition rate, broaden the process window, enhance the stability of high peak power co-sputtering glow discharge, and ensure the uniformity of the composition and structure of the obtained coating and the repeatability and consistency of the test results.

[0015] 2. This invention can use heterogeneous targets and achieve continuous systematic control of the composition of high-entropy alloy coatings by adjusting parameters such as sputtering target power and nitrogen-argon flow ratio, thus avoiding the problem of relatively fixed coating composition when using a single high-entropy alloy target.

[0016] 3. This invention employs a low duty cycle and high peak power, which can better combine the plasma and pulse discharge properties of high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering. By bombarding the substrate with high-density, high-energy ions, more effective control over the phase composition and microstructure of high-entropy alloy coatings can be achieved.

[0017] 4. Compared with three-target high-power pulsed magnetron co-sputtering, the three-target high-power pulsed magnetron co-sputtering and modulated pulsed magnetron sputtering composite co-sputtering of the present invention have a higher deposition rate and more stable glow discharge. Furthermore, the discharge characteristics of HiPIMS and MPPMS can be combined to regulate the coating microstructure and properties. It is a brand-new co-sputtering method with great potential for industrial application.

[0018] 5. This invention provides a phase-tunable dual-target high-power pulsed magnetron co-sputtering power supply and a modulated pulsed magnetron sputtering power supply, enabling two sputtering targets to undergo high-power pulsed magnetron sputtering, while one sputtering target undergoes modulated pulsed magnetron sputtering. To further broaden the process window and enhance glow discharge stability, high-power pulsed magnetron sputtering should employ a high frequency (≥1000Hz) and short pulse width (≤100ms), and the sputtering frequencies of the two sputtering targets must be identical. The pulse interval should be less than the plasma annihilation time to promote low-voltage ignition of the subsequent sputtering target and enhance its discharge stability. Furthermore, the pulse width of modulated pulsed magnetron sputtering must be ≥200ms to achieve effective voltage pulse control. Simultaneously, to achieve effective control over the coating microstructure, its duty cycle should be less than 10%. Therefore, it is difficult for modulated pulsed magnetron sputtering to be synchronized with high-power pulsed magnetron sputtering. To this end, the modulation pulse sputtering period was increased to more than 20 times that of the dual-target high-power pulse magnetron sputtering period, and the total pulse width of MPPMS was kept ≤ HiPIMS period, in order to further improve the glow discharge stability and ensure the uniformity of the coating composition and structure and the consistency and repeatability of the test results. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of a three-target co-sputtering apparatus, where 1 is the vacuum chamber, 2 is the first sputtering target, 3 is the second sputtering target, 4 is the third sputtering target, 5 is the sample stage, 6 is the dual-target high-power pulsed magnetron sputtering power supply, 7 is the first high-power pulsed magnetron sputtering main circuit, 8 is the second high-power pulsed magnetron sputtering main circuit, 9 is the modulated pulsed magnetron sputtering power supply, 10 is the modulated pulsed magnetron sputtering main circuit, and 11 is the DC bias power supply.

[0020] Figure 2The timing diagram shows the gate drive signals for the three sputtering target IGBTs.

[0021] Figure 3 The voltage and current waveforms of the three sputtering targets are shown when the Mo target power is 80W. Among them, (a) is the HiPIMS discharge characteristic curve of the Mo target and AlCr target; (b) is the MPPMS discharge characteristic curve of the TiSi target.

[0022] Figure 4 The voltage and current waveforms of the three sputtering targets are shown when the Mo target power is 90W. Among them, (a) is the HiPIMS discharge characteristic curve of the Mo target and AlCr target; (b) is the MPPMS discharge characteristic curve of the TiSi target.

[0023] Figure 5 The voltage and current waveforms of the three sputtering targets are shown without nitrogen gas. Among them, (a) is the HiPIMS discharge characteristic curve of the Mo target and the AlCr target; (b) is the MPPMS discharge characteristic curve of the TiSi target.

[0024] Figure 6 SEM images of high-entropy alloy coatings obtained with different parameters are shown. (a) shows an argon flow rate of 10 Sccm, a nitrogen flow rate of 20 Sccm, a Mo target voltage of 80 W, an AlCr target voltage of 80 W, and a TiSi target voltage of 110 W; (b) shows an argon flow rate of 10 Sccm, a nitrogen flow rate of 20 Sccm, a Mo target voltage of 90 W, an AlCr target voltage of 80 W, and a TiSi target voltage of 110 W; and (c) shows an argon flow rate of 30 Sccm, a nitrogen flow rate of 0 Sccm, a Mo target voltage of 90 W, an AlCr target voltage of 80 W, and a TiSi target voltage of 110 W.

[0025] Figure 7 GIXRD patterns of high-entropy alloy coatings obtained with different parameters.

[0026] Figure 8 Polarization curves of high-entropy alloy coatings obtained with different parameters. Detailed Implementation

[0027] To further illustrate the technical solution of the present invention, the present invention will be further described below through embodiments.

[0028] like Figure 1 As shown, the three-target composite co-sputtering device of the present invention includes a vacuum chamber 1, a first sputtering target 2, a second sputtering target 3, a third sputtering target 4, a sample stage 5, a dual-target high-power pulsed magnetron sputtering power supply 6, a first high-power pulsed magnetron sputtering main circuit 7, a second high-power pulsed magnetron sputtering main circuit 8, a modulated pulsed magnetron sputtering power supply 9, a modulated pulsed magnetron sputtering main circuit 10, and a DC bias power supply 11.

[0029] Sputtering target 1 (2), sputtering target 2 (3), sputtering target 3 (4), and sample stage 5 are located inside vacuum chamber 1.

[0030] The cathode of sputtering target 2 is connected to the cathode output terminal of high-power pulsed magnetron sputtering main circuit 7. The anode of sputtering target 2 is connected to the anode output terminal of high-power pulsed magnetron sputtering main circuit 7 and grounded. The anode input terminal of high-power pulsed magnetron sputtering main circuit 7 is connected to the anode of DC power supply and grounded. The cathode input terminal of high-power pulsed magnetron sputtering main circuit 7 is connected to the cathode output terminal of DC power supply.

[0031] The cathode of the second sputtering target 3 is connected to the cathode output terminal of the second high-power pulsed magnetron sputtering main circuit 8. The anode of the second sputtering target 3 is connected to the anode output terminal of the second high-power pulsed magnetron sputtering main circuit 8 and grounded. The anode input terminal of the second high-power pulsed magnetron sputtering main circuit 8 is connected to the anode of the DC power supply and grounded. The cathode input terminal of the second high-power pulsed magnetron sputtering main circuit 8 is connected to the cathode output terminal of the DC power supply.

[0032] The cathode of sputtering target 4 is connected to the cathode output terminal of the modulated pulse magnetron sputtering main circuit 10. The anode of sputtering target 4 is connected to the anode output terminal of the modulated pulse magnetron sputtering main circuit 10 and grounded. The anode input terminal of the modulated pulse magnetron sputtering main circuit 10 is connected to the anode of the DC power supply and grounded. The cathode input terminal of the modulated pulse magnetron sputtering main circuit 10 is connected to the cathode of the DC power supply.

[0033] The sample stage 5 is connected to the cathode output terminal of the bias DC power supply 11, and the anode of the bias circuit is connected to the anode of the bias DC power supply 11 and grounded.

[0034] The present invention provides a method for three-target composite co-sputtering high-entropy alloy coating, comprising the following steps: Step 1: Install sputtering target 2, sputtering target 3, and sputtering target 4. Sputtering target 2, sputtering target 3, and sputtering target 4 are respectively subjected to high-power pulsed magnetron sputtering, high-power pulsed magnetron sputtering, and modulated pulsed magnetron sputtering. Among them, the target materials of sputtering target 2, sputtering target 3 and sputtering target 4 are homogeneous or heterogeneous, the target materials are alloys or single substances, and the types of elements contained are ≥5. Sputtering target 1 is a permanent magnet target, and sputtering target 2 and sputtering target 3 are permanent magnet targets or strong magnetic targets.

[0035] Step 2: Install the ultrasonically cleaned and dried sample onto the sample stage 5.

[0036] Step 3: Close vacuum chamber 1, turn on circulating water, and evacuate vacuum chamber 1 to a background vacuum level below 1×10⁻⁶. -3Pa, then argon gas is introduced into vacuum chamber 1 at a flow rate of 5 Sccm to 100 Sccm, so that the pressure inside vacuum chamber 1 is 0.05 to 10 Pa.

[0037] Step 4: Control the PLC via the human-machine interface to set the sputtering frequency of the dual-target high-power pulsed magnetron co-sputtering power supply 6 to 1KHz~5KHz, and the cycle time... T 1= T 2. The pulse width of sputtering target 2 is 200ms~1000ms. t Pulse width of sputtering targets 1 and 2 t Both are set to 10ms~100ms, with a duty cycle of 1%~10%, to control the pulse interval between sputtering target 2 and sputtering target 3. D 12 The setting is based on promoting low-pressure ignition of the No. 2 sputtering target, and can generally be 0ms~200ms; The sputtering frequency of the modulated pulse magnetron sputtering power supply 9 is set to 20Hz~200Hz via the human-machine interface of the modulated pulse power supply, and the period is... T 3 is more than 20 times the period of either the first sputtering target 2 or the second sputtering target 3. T 3≥20 T 1) Assisted sputtering pulse width t 31 The main sputtering pulse width is set to 0μs~500μs. t 32 Set the pulse duration to 0μs~3000μs, making the duty cycle 1%~10%, and ensuring the total pulse width is less than or equal to the period of the dual-target high-power pulsed magnetron co-sputtering power supply 6. t 31 + t 32 )≤ T 1) The timing sequence of the gate drive signals for the three sputtering target IGBTs is as follows: Figure 2 As shown.

[0038] Step 5: Set the DC power supply voltage to 300V~2000V and the sputtering pressure to 0.05Pa~5Pa. Turn on the glow discharge sequentially in the order of sputtering target 2, sputtering target 3 and sputtering target 4 to perform pre-sputtering. The sputtering time is 0min~30min. Step 6: After pre-sputtering, introduce the working gas and adjust the sputtering pressure to 0.1Pa~5Pa. Set the input voltage of the DC power supply to 300V~3000V and the sputtering power to 10W~1000W. Turn on the glow discharge sequentially in the order of sputtering target 2, sputtering target 3, and sputtering target 4 to perform three-target composite co-sputtering and complete the coating deposition. Set the voltage of the DC bias power supply 11 to 0V~500V and the deposition time to 0h~10h. The working gas is nitrogen, oxygen, or acetylene, and the flow rate is 5Sccm~100Sccm. Example

[0039] This embodiment uses a TiSiAlCrMoN coating as an example to illustrate the process characteristics of the method of the present invention during sputtering discharge and coating deposition.

[0040] In this embodiment, the first sputtering target 2 is a Mo target, the second sputtering target 3 is an AlCr target, and the third sputtering target 4 is a TiSi alloy target. The diameter of the three sputtering targets is 2 inches. The purity of the TiSi alloy target (Ti:Si=70:30, at.%) and the AlCr alloy target (Al:Cr =30:70, at.%) is 99.9%, and the purity of the Mo target is 99.95%.

[0041] The specific process parameters for this embodiment are as follows: The background vacuum level is 8.5 × 10⁻⁶. -4 The sputtering pressure was 0.65 Pa. High-power pulsed magnetron sputtering was performed on both Mo and AlCr targets at a frequency of 2 kHz. The pulse width for the Mo target was 20 ms (4% duty cycle), and the pulse width for the AlCr target was 10 ms (2% duty cycle). The interval between the AlCr and Mo targets was 100 ms (to promote low-pressure ignition of the second sputtering target). Modulated pulsed magnetron sputtering was performed on the TiSi target at a frequency of 100 Hz. The auxiliary sputtering pulse width was 100 ms, and the main sputtering pulse width was 300 ms (4% duty cycle). The power of the TiSi and AlCr targets was fixed at 80 W and 110 W, respectively.

[0042] The composition and microstructure of the coating can be controlled by changing the nitrogen / argon flow ratio and the Mo target power.

[0043] Figure 3 and Figure 4 The voltage and current waveforms of the three sputtering targets are shown when the Mo target power is 80W and 90W, respectively, with the nitrogen flow rate being 20 Sccm and the argon flow rate being 10 Sccm. Figure 5 The voltage and current waveforms of the three sputtering targets are shown when the argon flow rate is 30 Sccm, the nitrogen flow rate is 0 Sccm, and the Mo target power is 90 W. The surface SEM images of the coatings obtained with different parameters are shown below. Figure 6As shown in the figure, when nitrogen gas is introduced, the resulting coatings are all crystalline coatings with agglomeration of nanocrystals. Furthermore, when the Mo target power increases from 80 W to 90 W, the atomic percentage of Mo in the coating increases from 14.89% to 17.91%. However, when the nitrogen flow rate is 0 Sccm, the resulting coating is a dense, featureless amorphous structure, and the percentage of Mo in the coating increases to approximately 30.99% due to the change in sputtering yield.

[0044] Figure 7 The GIXRD patterns of the coatings obtained with different parameters are shown. It can be observed that when the nitrogen flow rate is 0 Sccm, the coating does not exhibit any diffraction peaks. However, after nitrogen is introduced, the coating shows obvious (111), (200), and (220) diffraction peaks, indicating that the TiSiAlCrMoN coating obtained by introducing nitrogen is a solid solution with a NaCl(B1) type FCC structure. This is consistent with... Figure 6 The results are consistent. Meanwhile, the average grain sizes of the 80W and 90W coatings, calculated using the Scherrer formula, are approximately 5.6 nm and 5.0 nm, respectively. The coating hardness obtained using nanoindentation at a nitrogen flow rate of 0 Sccm is approximately 8.7 GPa, while at a nitrogen flow rate of 20 Sccm, the hardness of the Mo target power coatings at 80W and 90W are approximately 16.4 GPa and 20.2 GPa, respectively.

[0045] Figure 8 These are polarization curves for a 65Mn steel substrate and coatings obtained with different parameters. The corrosion potential and corrosion current density of the 65Mn steel are approximately -0.658V and 9.337V, respectively. 10 -6 A / cm 2 When the nitrogen flow rate was 20 sccm and the Mo target power was 80 W and 90 W, the corrosion potentials of the coatings were approximately -0.234 V and -0.232 V, respectively, and the corrosion current densities were 1.69 V and 1.69 sccm, respectively. 10 -7 A / cm 2 and 1.62 10 -7 A / cm 2 The corrosion potential and corrosion current density of the coating obtained when the nitrogen flow rate is 0 Sccm are approximately -0.237 V and 1.77 V, respectively. 10 -8 A / cm 2 In addition, the composition, microstructure, mechanical properties, and corrosion resistance of high-entropy alloy coatings can be controlled by changing parameters such as duty cycle, pulse interval time, and substrate bias amplitude.

[0046] The three-target composite co-sputtering high-entropy alloy coating method of the present invention combines the advantages of high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering. It has a wide process window, high ion energy, high deposition efficiency, and stable glow discharge, and is particularly suitable for controlling the composition, phase composition, microstructure and properties of high-entropy alloy coatings.

[0047] The foregoing has shown and described the main features and advantages of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0048] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for applying a high-entropy alloy coating using a three-target composite co-sputtering process, characterized in that, Includes the following steps: Step 1: Install sputtering target 1, sputtering target 2, and sputtering target 3. Sputtering target 1 and sputtering target 2 are connected to the main circuit of the dual-target high-power pulsed magnetron co-sputtering power supply, and sputtering target 3 is connected to the main circuit of the modulated pulsed magnetron sputtering power supply. The main circuits of the dual-target high-power pulsed magnetron co-sputtering power supply and the modulated pulsed magnetron sputtering power supply are both connected to a DC power supply. Sputtering target 1, sputtering target 2, and sputtering target 3 are subjected to high-power pulsed magnetron sputtering, high-power pulsed magnetron sputtering, and modulated pulsed magnetron sputtering, respectively. Step 2: Install the ultrasonically cleaned and dried sample onto the sample stage, and connect the sample stage to a bias DC power supply. Step 3: Close the vacuum chamber, turn on the circulating water, and evacuate the vacuum chamber until the background vacuum level is below 1×10⁻⁶. -3 Pa, then argon gas is introduced into the vacuum chamber at a flow rate of 5 Sccm to 100 Sccm to make the pressure in the vacuum chamber 0.05 to 10 Pa; Step 4: Set the sputtering frequency of the dual-target high-power pulsed magnetron co-sputtering power supply to 1KHz~5KHz, the period to 200ms~1000ms, the pulse width of both the first and second sputtering targets to 10ms~100ms, and the duty cycle to 1%~10%. Set the pulse interval between the first and second sputtering targets to promote the low-voltage ignition of the second sputtering target. Set the sputtering frequency of the modulated pulse magnetron sputtering power supply to 20Hz~200Hz, with a period more than 20 times the period of the first or second sputtering target. Set the auxiliary sputtering pulse width and the main sputtering pulse width so that the duty cycle is 1%~10% and the total pulse width is ≤ the period of the dual-target high-power pulse magnetron co-sputtering power supply. Step 5: Set the DC power supply voltage to 300V~2000V and the sputtering pressure to 0.05Pa~5Pa. Turn on the glow discharge sequentially in the order of sputtering target No. 1, sputtering target No. 2 and sputtering target No. 3 to perform pre-sputtering. Step 6: After pre-sputtering, introduce working gas and adjust the sputtering pressure to 0.1Pa~5Pa. Set the input voltage of the DC power supply to 300V~3000V. The sputtering power of sputtering target 1, sputtering target 2, and sputtering target 3 is 10W~1000W. Turn on glow discharge sequentially in the order of sputtering target 1, sputtering target 2, and sputtering target 3 to perform three-target composite co-sputtering and complete the coating deposition. Set the voltage of the DC bias power supply to 0V~500V, the deposition time to 0h~10h, and the flow rate of the working gas to 5Sccm~100Sccm.

2. The method for three-target composite co-sputtering high-entropy alloy coating according to claim 1, characterized in that, The target materials of the No. 1 sputtering target, the No. 2 sputtering target, and the No. 3 sputtering target are homogeneous or heterogeneous target materials.

3. The method for three-target composite co-sputtering high-entropy alloy coating according to claim 2, characterized in that, The target material is an alloy or an element, and contains ≥5 types of elements.

4. A method for three-target composite co-sputtering high-entropy alloy coating according to any one of claims 1 to 3, characterized in that, The first sputtering target is a permanent magnet target, while the second and third sputtering targets are either permanent magnet targets or strong magnetic targets.

5. The method for three-target composite co-sputtering high-entropy alloy coating according to claim 1, characterized in that, The pre-sputtering time is 0 min to 30 min.

6. The method for three-target composite co-sputtering high-entropy alloy coating according to claim 1, characterized in that, The working gas is nitrogen, oxygen, or acetylene.

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