Composite co-deposition method of high power pulsed magnetron sputtering and modulated pulsed magnetron sputtering

Abstract

The present invention discloses a composite co-deposition method of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering, and belongs to the technical field of material surface modification. Aiming at the problem that existing methods such as single-target high-power pulse magnetron sputtering (modulated pulse magnetron sputtering), DC-high-power pulse magnetron co-sputtering, and homogeneous multi-target modulated pulse magnetron sputtering composite co-deposition are difficult to achieve systematic regulation of the composition and microstructure of multi-element alloy coatings, the present invention combines the plasma and pulse discharge characteristics of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering, and achieves regulation of the coating composition and microstructure by controlling parameters such as sputtering power, sputtering frequency, duty cycle, pulse time interval, peak current, and bias amplitude.

Description

Technical Field

[0001] The invention belongs to the technical field of material surface modification, and in particular relates to a composite co-deposition method of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering. Background Art

[0002] Magnetron sputtering is one of the commonly used physical vapor deposition technologies, which can be used to prepare various coatings, including direct current sputtering (DCMS), radio frequency sputtering (RFMS), high power pulsed magnetron sputtering (HiPIMS) and modulated pulsed magnetron sputtering (MPPMS). Since the structure of the coating obtained by magnetron sputtering mainly depends on the plasma characteristics and discharge characteristics of the sputtering target, compared with traditional DC sputtering and radio frequency sputtering, the duty cycle of high power pulsed magnetron sputtering is 0.5% to 10%, and the peak power of the target surface is 0.5kw / cm 2 ~10kw / cm 2 , which can make the sputtered material highly ionized on the basis of lower average power, and through the bombardment of high-energy ion beam, the microstructure of the coating can be effectively controlled. However, the shortcomings of HiPIMS are low deposition rate and poor discharge stability. The modulated pulse magnetron sputtering that has been developed since then has realized the multi-segment pulse discharge configuration of high-power pulse magnetron sputtering (HiPIMS) technology by editing the micro-pulse waveform. In the pre-sputtering stage, low voltage is used to pre-ionize the plasma, and in the main sputtering stage, high voltage is used to highly ionize the sputtered material. The main pulse width can reach 3ms, and the duty cycle can even reach 28%. Although the pulse current and pulse power of MPPMS are slightly lower, they improve the deposition rate and the stability of pulse discharge (Gui Binhua, Zhou Hui, Zheng Jun, Ma Zhanji, Yang Lamaocao, Zhang Yanshuai, Effect of bias voltage on the structure and properties of AlTiSiN nanocomposite coating prepared by MPPMS, Surface Technology, 49 (2020) 228-236, 275. and Wu Zhili, Li Yuge, Wu Bi, Lei Mingkai, Research on structure regulation and properties of TiAlSiN nanocomposite coating deposited by high power modulated pulse magnetron sputtering, Journal of Inorganic Materials, 30 (2015) 1254-1260.), and can also achieve effective regulation of the coating microstructure.

[0003] For multi-element alloy coatings such as high entropy alloys (composed of 5 or more elements in equal or nearly equal molar ratios) and medium entropy alloys (2 to 4 main elements), if a single target (a multi-element alloy single target prepared by powder metallurgy or vacuum melting or a combined single target made of different single-element targets) is used to prepare the multi-element alloy coating, the composition of the obtained coating depends on the content of each element in the target. The content of alloy elements in the coating can only be systematically controlled by preparing targets with different element ratios (Wang Zhenyu, Xu Sheng, Zhang Dong, Liu Xincai, Ke Peiling, Wang Aiying, Effect of N2 flow rate on the structure and mechanical properties of TiSiN coating prepared by HiPIMS, Acta Metallurgica Sinica, 50 (2014) 540-546. and JC Oliveira, F. Fernandes, F. Ferreira, A. Cavaleiro, Tailoring the nanostructure of Ti–Si–N thin films by HiPIMS in deep oscillation magnetron sputtering (DOMS) mode, Surface and Coatings Technology, 264 (2015) 140-149. and CY Lee, P Chen, S J Lin, J W Yeh, Mechanical performance of high-entropy (AlCrNbSiTi) N films fabricated by high-power impulse magnetron sputtering over a wide compositional window, Ceramics International, 49 (2023) 38392-38397) However, the target material preparation cycle is long, the cost is high, the process is complicated, and the percentage of target elements is difficult to achieve continuous changes, otherwise it may affect the stability of magnetron sputtering glow discharge, especially high entropy alloy targets or spliced ​​targets containing certain non-metallic elements, such as Si elements. In addition, the single-target sputtering deposition rate is also low. Therefore, researchers consider using multiple sputtering targets for co-deposition to achieve the regulation of coating composition and microstructure.Among them, Swedish scholars G. Greczynski et al. (G. Greczynski, B. Bakhit, L. Hultman, M. Odén, High Si content TiSiN films with superior oxidation resistance, Surface and Coatings Technology, 398 (2020) 126087.) successfully prepared TiSiN coatings on Si wafers using heterogeneous dual-target DCMS-HiPIMS composite co-deposition. However, due to the low ionization rate of DC sputtering, it is impossible to effectively control the microstructure of the coating. Chinese scholars Wu Zhili et al. (Wu Zhili, Li Yuge, Wu Bi, Lei Mingkai, Research on the structure control and performance of TiAlSiN nanocomposite coatings deposited by high-power modulated pulse magnetron sputtering, Journal of Inorganic Materials, 30 (2015) 1254-1260.) prepared TiAlSiN nanocomposite coatings by using homogeneous four-target modulated pulse magnetron sputtering composite co-deposition, and achieved effective control of the coating microstructure by changing the process parameters, but the four target materials have the same composition, so it is difficult to achieve systematic and continuous control of the coating alloy element content by changing the process parameters. In addition, unlike DC co-sputtering, the pulse discharge characteristics of modulated pulse magnetron sputtering composite co-deposition determine that the phase relationship between the discharge voltage pulses of each sputtering target should be determined, otherwise the uniformity of the coating composition and the repeatability and consistency of the test results are difficult to guarantee. Summary of the invention

[0004] In view of the problem that it is difficult to achieve systematic regulation of the composition and microstructure of multi-element alloy coatings by existing methods such as single-target high-power pulse magnetron sputtering (modulated pulse magnetron sputtering), DC-high-power pulse magnetron co-sputtering, and homogeneous multi-target modulated pulse magnetron sputtering composite co-deposition, the present invention combines the plasma and pulse discharge characteristics of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering, and proposes a method for phase-controllable high-power pulse magnetron sputtering and modulated pulse magnetron sputtering composite co-deposition.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A composite co-deposition method of high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering, wherein the device used in the composite co-deposition method is a composite deposition device, including a vacuum chamber, two sputtering targets, a sample stage, a composite co-deposition power supply, a mass flow controller, a heating power supply, a mechanical pump, a molecular pump and a vacuum gauge, etc.;

[0007] Two sputtering targets and a sample stage are arranged in a vacuum chamber;

[0008] The cathode of the first sputtering target is connected to the cathode output terminal of the high-power pulse magnetron sputtering circuit, the anode of the sputtering target is connected to the anode output terminal of the high-power pulse magnetron sputtering circuit and is grounded, the anode input terminal of the high-power pulse magnetron sputtering circuit is connected to the anode of the DC power supply and is grounded, and the cathode input terminal of the high-power pulse magnetron sputtering circuit is connected to the cathode of the DC power supply;

[0009] The second sputtering target is connected to the cathode output terminal of the modulated pulse magnetron sputtering circuit, the sputtering target anode is connected to the anode output terminal of the modulated pulse magnetron sputtering circuit and is grounded, the anode input terminal of the modulated pulse magnetron sputtering is connected to the anode of the DC power supply and is grounded, and the cathode input terminal of the modulated pulse magnetron sputtering circuit is connected to the cathode of the DC power supply for modulated pulse magnetron sputtering;

[0010] The sample stage is connected to the cathode output terminal of the bias circuit, the anode of the bias circuit is connected to the anode of the bias DC power supply and is grounded, and the cathode input terminal of the bias circuit is connected to the cathode of the bias DC power supply;

[0011] The composite co-deposition method comprises the following steps:

[0012] Step 1, respectively installing target materials on two sputtering targets, and installing the sample on a sample table;

[0013] Step 2: evacuate the vacuum chamber to make the background vacuum degree less than 1×10 -2 Pa, heat the sample to the specified temperature, then introduce argon into the vacuum chamber to make the pressure in the vacuum chamber 0.05~10Pa;

[0014] Step 3, set the frequency of the modulated pulse magnetron sputtering circuit sputtering target to 0KHz~2KHz, and the pre-sputtering pulse width τ M预 Set to 0μs~500μs, main sputtering pulse width τ M主 Set to 0μs~3000μs, so that the duty cycle is 1%~30%; set the pulse width τ of the sputtering target of the high-power pulse magnetron sputtering circuit with the same frequency H Set to 0μs~1000μs, pulse delay D is set to 0μs~1000μs;

[0015] Setting the pulse width τ of synchronous pulse bias in modulated pulse magnetron sputtering 偏-M 0μs~1000μs, pulse delay D 偏-M 0μs~1000μs, high power pulse magnetron sputtering synchronous pulse bias pulse width τ 偏-H 0μs~1000μs, pulse delay D 偏-H 0μs~1000μs;

[0016] Step 4, pre-sputtering: setting the input voltages of the high-power pulsed magnetron sputtering circuit and the modulated pulsed magnetron sputtering circuit to 300V to 1000V, the sputtering pressure to 0.1Pa to 5Pa, and the pre-sputtering time to 3min to 30min;

[0017] Step 5, coating deposition: after pre-sputtering, introduce working gas, adjust the sputtering pressure to 0.1Pa~5Pa, set the input voltage of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering to 300V~3000V, and the sputtering power to 10W~1000W; set the pulse bias to 0V~1000V, set the deposition time to 0h~10h, and complete the deposition.

[0018] Furthermore, the composite deposition device is also provided with a human-machine interaction interface, a circulating water circuit, and a mechanical pump and a molecular pump; the human-machine interaction interface is used to control sputtering parameters related to the high-power pulse magnetron sputtering circuit, the modulated pulse magnetron sputtering circuit and the bias circuit, including sputtering frequency, pulse width and pulse delay; the circulating water circuit is used to cool the sputtering target, the molecular pump and the vacuum chamber; the mechanical pump and the molecular pump are used to evacuate the vacuum chamber.

[0019] Furthermore, the vacuum chamber is provided with two inlets for working gas and argon gas, and control valves are respectively provided on the pipelines and connected to the mass flow controller.

[0020] Furthermore, a heating device is provided inside the sample stage, and heating is provided by a heating power supply.

[0021] Furthermore, the target materials of the two sputtering targets in step 1 are homogeneous target materials or heterogeneous target materials.

[0022] Furthermore, in step 2, the flow rate of the argon gas introduced is 5 Sccm to 200 Sccm.

[0023] Furthermore, the working gas is nitrogen, oxygen or acetylene.

[0024] Furthermore, in step 5, the flow rate of the working gas is 5 Sccm to 200 Sccm.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] 1. The present invention adopts a composite co-deposition method of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering. While improving the deposition rate, it can also combine the plasma and pulse discharge characteristics of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering. Through the bombardment of the substrate with high-density and high-energy ions, the coating microstructure can be more effectively regulated.

[0027] 2. The present invention can use heterogeneous target materials. By adjusting the power, duty cycle and peak power of the sputtering target, the systematic and continuous regulation of the coating composition can be achieved, thereby avoiding the problem of relatively fixed coating composition prepared by using a single alloy target. The coating composition of the present invention does not depend on the target structure and composition, and has a wide range of applications.

[0028] 3. The phase between the high-power pulse magnetron sputtering, modulated pulse magnetron sputtering and substrate pulse bias of the present invention is controllable, thereby ensuring the uniformity of the coating composition structure and the repeatability and consistency of the test results. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of a high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition device in a specific implementation mode 1. 1 is a vacuum chamber, 2 is a sputtering target, 3 is a sample stage, 4 is a composite co-deposition power supply, 4-1 is a high-power pulsed magnetron sputtering circuit, 4-2 is a modulated pulsed magnetron sputtering circuit, and 4-3 is a bias circuit.

[0030] Figure 2 It is a circuit schematic diagram of a high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition power supply based on dual DC power supply control in a specific implementation mode one.

[0031] Figure 3 It is a timing diagram of the gate drive signal of the composite co-deposition power supply IGBT in the first specific implementation mode.

[0032] Figure 4 is a composite co-deposition voltage waveform curve in a specific embodiment.

[0033] a) The TiSi target voltage is 85W and the Ti target voltage is 80W; b) The TiSi target voltage is 70W and the Ti target voltage is 80W.

[0034] Figure 5 It is the SEM spectrum of the coating obtained with different parameters in the specific embodiment.

[0035] a) The TiSi target voltage is 85W and the Ti target voltage is 80W; b) The TiSi target voltage is 70W and the Ti target voltage is 80W.

[0036] Figure 6 It is the XRD spectrum of the coating obtained with different parameters in the specific embodiment. DETAILED DESCRIPTION

[0037] Example 1

[0038] The high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite deposition device mainly includes a vacuum chamber, two sputtering targets, a sample stage, a composite co-deposition power supply, a mechanical pump, a molecular pump, a heating power supply, a mass flow controller and a vacuum gauge, etc. The two sputtering targets and the sample stage are arranged in the vacuum chamber;

[0039] The first sputtering target is connected to the cathode output terminal of the high-power pulse magnetron sputtering circuit, the sputtering target anode is connected to the anode output terminal of the high-power pulse magnetron sputtering circuit and is grounded, the anode input terminal of the high-power pulse magnetron sputtering circuit is connected to the anode of the DC power supply and is grounded, and the cathode input terminal of the high-power pulse magnetron sputtering circuit is connected to the cathode of the DC power supply for high-power pulse magnetron sputtering;

[0040] The second sputtering target is connected to the cathode output terminal of the modulated pulse magnetron sputtering circuit, the sputtering target anode is connected to the anode output terminal of the modulated pulse magnetron sputtering circuit and is grounded, the anode input terminal of the modulated pulse magnetron sputtering is connected to the anode of the DC power supply and is grounded, and the cathode input terminal of the modulated pulse magnetron sputtering circuit is connected to the cathode of the DC power supply for modulated pulse magnetron sputtering;

[0041] The sample stage is connected to the cathode output end of the bias circuit, the anode of the bias circuit is connected to the anode of the bias DC power supply and is grounded, and the cathode input end of the bias circuit is connected to the cathode of the bias DC power supply.

[0042] Figure 2 It is the schematic diagram of the main circuit of modulated pulse magnetron sputtering and the main circuit of high-power pulse magnetron sputtering of the composite power supply.

[0043] Among them, V1 in the MPPMS circuit is a DC power supply with its positive pole grounded, R1 is the output load (sputtering target), R2 and R3 are resistors, C1, C2, C3, and C4 are capacitors, D1, D2, and D3 are diodes, L1 and L2 are inductors, and Q1 is an insulated gate bipolar transistor (IGBT).

[0044] In the HiPIMS circuit, V2 is a DC power supply with its positive pole grounded, R4 is an output load (sputtering target), R5, R6, R7, and R8 are resistors, C5, C6, C7, C7, C8, and C9 are capacitors, D4 is a diode, TVS1, TVS2, and TVS3 are transient diodes, and Q2 is an IGBT.

[0045] Figure 3 This is the timing diagram of the IGBT gate drive signal for modulated pulse magnetron sputtering, high-power pulse magnetron sputtering, and bias. M Pre and τ M The main ones are the MPPMS pre-sputtering and main sputtering macro pulse widths, and the internal micro pulse duty ratios of the two are different. H is the HiPIMS pulse width, τ 偏-M With τ偏-H is the bias pulse width.

[0046] The delay of the high-power pulsed magnetron sputtering signal relative to the modulated pulsed magnetron sputtering signal is D;

[0047] The delay of the bias signal relative to the pulse signal of modulated pulse magnetron sputtering is D 偏-M ;

[0048] The delay of the bias signal relative to the high power pulse magnetron sputtering signal is D 偏-H ;

[0049] All the above parameters can be controlled through the LCD human-machine interface connected to the PLC.

[0050] At the same time, the control circuit has short circuit, overcurrent and overvoltage detection and feedback modules. When the above faults occur three times in a row, the PLC will reset to shut down the gate drive signal of the IGBT to protect the power supply system. After the fault is eliminated, the power supply system can be reset automatically or manually.

[0051] The high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition method comprises the following steps:

[0052] Step 1, mounting the target materials on two sputtering targets respectively, and fixing the cleaned sample on a rotatable sample table in a vacuum chamber;

[0053] Step 2: evacuate the vacuum chamber to make the background vacuum degree less than 1×10 -2 Pa, then the sample is heated to the specified temperature, and argon gas is introduced into the vacuum chamber to make the pressure in the vacuum chamber 0.05~10Pa;

[0054] Step 3: Set the frequency of modulated pulse magnetron sputtering to 0KHz~2KHz, and the pre-sputtering pulse width τ M预 Set to 0μs~500μs, main sputtering pulse width τ M主 Set to 0μs~3000μs, so that the duty cycle is 1%~30%; through PLC, the pulse width τ of high-power pulse magnetron sputtering with the same frequency H Set to 0μs~1000μs, pulse delay D is set to 0μs~1000μs; set the pulse width τ of the modulated pulse magnetron sputtering synchronous pulse bias 偏-M 0μs~1000μs, pulse delay D 偏-M 0μs~1000μs, high power pulse magnetron sputtering synchronous pulse bias pulse width τ 偏-H 0μs~1000μs, pulse delay D 偏-H 0μs~1000μs;

[0055] Step 4, pre-sputtering: setting the input voltages of the high-power pulsed magnetron sputtering circuit and the modulated pulsed magnetron sputtering circuit to 300V to 1000V, the sputtering pressure to 0.1Pa to 5Pa, and pre-sputtering for 3min to 30min;

[0056] Step 5, coating deposition: after pre-sputtering, the working gas is passed to make the sputtering pressure 0.1Pa~5Pa, the input voltages of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering are set to 300V~3000V, and the sputtering powers are both 10W~1000W; the pulse bias is set to 0V~1000V, the deposition time is set to 0h~10h, and the deposition is completed.

[0057] Furthermore, the composite deposition device is also provided with a human-machine interaction interface, a circulating water circuit, and a mechanical pump and a molecular pump; the human-machine interaction interface is used to control relevant parameters of a high-power pulsed magnetron sputtering circuit, a modulated pulsed magnetron sputtering circuit, and a bias circuit; the circulating water circuit is used to cool the sputtering target, the molecular pump, and the vacuum chamber; the mechanical pump and the molecular pump are used to evacuate the vacuum chamber.

[0058] Furthermore, the vacuum chamber is provided with two inlets for working gas and argon gas, and is connected to a mass flow controller through a pipeline.

[0059] Furthermore, a heating device is provided inside the sample stage, and heating is provided by a heating power supply.

[0060] Furthermore, the target materials of the two sputtering targets in step 1 are homogeneous target materials or heterogeneous target materials.

[0061] Furthermore, in step 2, the flow rate of the argon gas introduced is 5 Sccm to 200 Sccm.

[0062] Furthermore, the working gas is nitrogen, oxygen or acetylene.

[0063] Furthermore, in step 5, the flow rate of the working gas is 5 Sccm to 100 Sccm.

[0064] Example 2

[0065] Ti 1-x Si x Taking N coating as an example, the process characteristics of the composite co-deposition device based on heterogeneous dual-target high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering in the sputtering discharge and coating deposition process are explained.

[0066] The heterogeneous dual targets used a Ti target with a diameter of 50.8 mm and a purity of 99.95% and a TiSi alloy target with a diameter of 50.8 mm and a purity of 99.9% (Ti:Si=85:15, at.%). The background vacuum degree was 1×10 -3Pa, the sputtering gas is high-purity argon and high-purity nitrogen, with flow rates of 30 Sccm and 10 Sccm respectively, the sputtering pressure is 1.2 Pa, and the substrate temperature is 200 ° C. The Ti target is subjected to modulated pulse magnetron sputtering, and the TiSi target is subjected to high-power pulse magnetron sputtering. The sputtering frequency is set to 200 Hz, the Ti target pre-sputtering pulse width is set to 50 μs, the main sputtering pulse width is set to 300 μs, the same frequency high-power pulse magnetron sputtering pulse width is set to 150 μs, and the pulse delay is set to 450 μs.

[0067] By controlling the sputtering power, the content of different elements in the coating can be effectively controlled, thereby achieving the regulation of the coating composition and microstructure. Taking the Ti target sputtering power of 80W and the corresponding TiSi target sputtering power of 85W and 70W respectively as an example, the TiSi target / Ti target voltage waveform curve in one discharge cycle is as follows: Figure 4 As shown in Figure 2, when the sputtering power of the TiSi target changes, the Ti 1-x Si x The Si content in the N coating is 28.32% and 21.17% respectively. Figure 5 ) It can be seen that the obtained coating is uniform and dense, but it shows a change in the organizational structure. When the TiSi target sputtering power is reduced from 85W to 70W, the grain size increases. The grazing incidence X-ray diffraction pattern ( Figure 6 ), combined with the Scherrer formula to analyze the crystal structure, it can be seen that the coating phases of the TiSi target sputtering power of 85W and 70W are both TiN, and the grain sizes are about 9nm and 13nm respectively, which is consistent with Figure 5 The results obtained are basically consistent. In addition, the TiO2O3 can be controlled by changing the sputtering frequency, duty cycle, pulse time interval, peak current and bias amplitude. 1-x Si x The composition and microstructure of the N coating are controlled.

[0068] The composite co-deposition method of high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering based on homogeneous or heterogeneous dual targets combines the advantages of high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering, with a wide process window, high ion energy and high deposition efficiency, and is particularly suitable for regulating the composition and microstructure of multi-element alloy coatings.

[0069] The contents not described in detail in the present specification belong to the prior art known to the professional and technical personnel in the field. Although the above content describes the specific implementation methods of the present specification to facilitate the understanding of the present invention by the technical personnel in the field, it should be clear that the present invention is not limited to the scope of the specific implementation methods. For the ordinary technical personnel in the field, as long as the various changes are within the spirit and scope of the present invention defined and determined by the attached claims, these changes are obvious, and all inventions and creations using the concept of the present invention are protected.

Claims

1. A composite co-deposition method of high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering, characterized in that: The device used in the composite co-deposition method is a composite deposition device, including a vacuum chamber, two sputtering targets, a sample stage, a composite co-deposition power supply, a mass flow controller, a heating power supply, a mechanical pump, a molecular pump and a vacuum gauge; Two sputtering targets and a sample stage are arranged in a vacuum chamber; The cathode of the first sputtering target is connected to the cathode output terminal of the high-power pulse magnetron sputtering circuit, the anode of the sputtering target is connected to the anode output terminal of the high-power pulse magnetron sputtering circuit and is grounded, the anode input terminal of the high-power pulse magnetron sputtering circuit is connected to the anode of the DC power supply and is grounded, and the cathode input terminal of the high-power pulse magnetron sputtering circuit is connected to the cathode of the DC power supply; The second sputtering target is connected to the cathode output terminal of the modulated pulse magnetron sputtering circuit, the sputtering target anode is connected to the anode output terminal of the modulated pulse magnetron sputtering circuit and is grounded, the anode input terminal of the modulated pulse magnetron sputtering is connected to the anode of the DC power supply and is grounded, and the cathode input terminal of the modulated pulse magnetron sputtering circuit is connected to the cathode of the DC power supply for modulated pulse magnetron sputtering; The sample stage is connected to the cathode output terminal of the bias circuit, the anode of the bias circuit is connected to the anode of the bias DC power supply and is grounded, and the cathode input terminal of the bias circuit is connected to the cathode of the bias DC power supply; The composite co-deposition method comprises the following steps: Step 1, respectively installing target materials on two sputtering targets, and installing the sample on a sample table; Step 2: evacuate the vacuum chamber to make the background vacuum degree less than 1×10 -2 Pa, heat the sample to the specified temperature, then introduce argon into the vacuum chamber to make the pressure in the vacuum chamber 0.05~10Pa; Step 3, set the frequency of the modulated pulse magnetron sputtering circuit sputtering target to 0KHz~2KHz, and the pre-sputtering pulse width τ M预 Set to 0μs~500μs, main sputtering pulse width τ M主 Set to 0μs~3000μs, so that the duty cycle is 1%~30%; set the pulse width τ of the sputtering target of the high-power pulse magnetron sputtering circuit with the same frequency H Set to 0μs~1000μs, pulse delay D is set to 0μs~1000μs; Setting the pulse width τ of synchronous pulse bias voltage for modulated pulse magnetron sputtering 偏-M 0μs~1000μs, pulse delay D 偏-M 0μs~1000μs, high power pulse magnetron sputtering synchronous pulse bias pulse width τ 偏-H 0μs~1000μs, pulse delay D 偏-H 0μs~1000μs; Step 4, pre-sputtering: setting the input voltages of the high-power pulsed magnetron sputtering circuit and the modulated pulsed magnetron sputtering circuit to 300V to 1000V, the sputtering pressure to 0.1Pa to 5Pa, and the pre-sputtering time to 3min to 30min; Step 5, coating deposition: after pre-sputtering, introduce working gas, adjust the sputtering pressure to 0.1Pa~5Pa, set the input voltage of high-power pulse magnetron sputtering and modulated pulse magnetron sputtering to 300V~3000V, and the sputtering power to 10W~1000W; set the pulse bias voltage to 0V~1000V, set the deposition time to 0h~10h, and complete the deposition; In the step 1, the target materials of the two sputtering targets are homogeneous target materials or heterogeneous target materials.

2. The high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition method according to claim 1, characterized in that: The composite deposition device is also provided with a human-machine interaction interface, a circulating water circuit, a mechanical pump and a molecular pump; the human-machine interaction interface is used to control sputtering parameters related to the high-power pulse magnetron sputtering circuit, the modulated pulse magnetron sputtering circuit and the bias circuit, including sputtering frequency, pulse width and pulse delay; The circulating water circuit is used to cool the sputtering target, the molecular pump and the vacuum chamber; The mechanical pump and the molecular pump are used to evacuate the vacuum chamber.

3. The high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition method according to claim 1, characterized in that: The vacuum chamber is provided with two inlets for working gas and argon gas, and control valves are respectively provided on the pipelines and connected with the mass flow controller.

4. The high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition method according to claim 1, characterized in that: The sample stage is provided with a heating device inside, which is heated by a heating power supply.

5. The high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition method according to claim 1, characterized in that: The flow rate of the argon gas introduced in step 2 is 5 Sccm to 200 Sccm.

6. The high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition method according to claim 3, characterized in that: The working gas is nitrogen, oxygen or acetylene.

7. The high-power pulsed magnetron sputtering and modulated pulsed magnetron sputtering composite co-deposition method according to claim 1, characterized in that: The flow rate of the working gas in step 5 is 5 Sccm to 200 Sccm.

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