Preparation method for cathode integrated coating, device and altin coating

Abstract

The present application relates to the technical field of coating preparation, and provides a preparation method for a cathode integrated coating, a device and an AlTiN coating. The method of the present application comprises: performing cathode integrated high-power pulse magnetron sputtering on a substrate to obtain a coating, the cathode discharge mode of the cathode integrated high-power pulse magnetron sputtering being high-current and high-voltage discharge, the peak current of the high-current and high-voltage discharge being 200-2000 A, the peak voltage being 200-2000 V, and the discharge waveform being square. The preparation method provided by the present application can achieve high ionization rate and high deposition rate, and prepare coatings integrating the advantages of AIP and MS; utilizing the discharge characteristics can easily adjust the grain size, preferred orientation and phase structure of coatings by means of parameter adjustment, so as to adjust the hardness and toughness of coatings, thus greatly improving coating performance, and widening process windows by targetedly adjusting the coating performance.

Description

Cathode integrated coating preparation method and device and AlTiN coating

[0001] The present application claims priority to the Chinese patent application No. CN202410650336.6, filed on May 23, 2024, and entitled "Cathode integrated coating preparation method and device and AlTiN coating", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present application relates to the technical field of coating preparation, in particular to a cathode integrated coating preparation method, device and AlTiN coating. BACKGROUND

[0003] PVD tool coating refers to a coating formed by using physical vapor deposition method (PVD method) to coat materials on the surface of a tool, which can improve the hardness, wear resistance and chemical stability of the tool.

[0004] At present, the PVD technology used for coating deposition mainly includes two types of magnetic sputtering (MS) and arc ion plating (AIP). The traditional arc ion plating technology has the characteristics of large current discharge, high ionization rate and fast deposition rate. However, the coating prepared by this method is prone to "large particle" pollution. Large particles refer to neutral particle clusters continuously generated by the rolling and burning of arc cathode spots on the surface of the target material. These clusters are ejected together with the plasma and fall onto the surface of the growing thin film, thereby causing surface contamination of the thin film, increasing the roughness of the coating and reducing the adhesion.

[0005] High power impulse magnetron sputtering technology (HiPiMS) can improve the compactness and film-substrate adhesion of the deposited thin film and avoid the problem of large particle pollution. Although the traditional HiPiMS can achieve instantaneous high power and high current, the peak current and peak power cannot achieve sustained discharge, the ionization rate is low, and the deposition rate is low (the deposition rate is mostly 0.1-0.5 μm / H).

[0006] SUMMARY

[0007] Therefore, the present application provides a cathode integrated coating preparation method, device and AlTiN coating. The cathode integrated coating method provided by the present application adopts a high-current and high-voltage discharge mode, the discharge waveform is a square waveform, the peak current can be sustained for a long time, the ionization rate is high, and the deposition rate is high.

[0008] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0009] A cathode integrated coating preparation method, comprising the following steps:

[0010] Cathode integrated high-power pulse magnetron sputtering is performed on the substrate to obtain a coating; the cathode discharge mode of the cathode integrated high-power pulse magnetron sputtering is high-current and high-voltage discharge; the peak current of the high-current and high-voltage discharge is 200-2000 A, the peak voltage is 200-2000 V, and the discharge waveform is square.

[0011] Preferably, the mode of the cathode integrated high-power pulse magnetron sputtering is a constant current mode or a constant power mode.

[0012] The conditions of the cathode integrated high-power pulse magnetron sputtering include: the cathode peak current is 200-2000 A, the cathode peak voltage is 200-2000 V, the cathode average power is 4-40 KW, the cathode pulse frequency is 200-3000 Hz, and the cathode duty cycle is 3-40%.

[0013] The flow ratio of Ar and N2 is 1.4-3.5, the cavity pressure is 0.35-1 Pa, and the cavity temperature is 500±50℃.

[0014] The substrate negative bias is -20 to -200 V, the bias power frequency is 20-50 KHz, and the bias power duty cycle is 30%-90%.

[0015] Preferably, the number of target materials of the cathode integrated high-power pulse magnetron sputtering is 2; the target material is an AlTi alloy; and the coating is an AlTiN coating.

[0016] Preferably, the grain of the AlTiN coating is one or more of coarse columnar crystals, fine columnar crystals and dense crystals.

[0017] The coarse columnar crystal is a columnar crystal with a width of 160-200 nm, the crystal phase of the coarse columnar crystal includes c-AlTiN, and the 200 / 111 peak intensity of the c-AlTiN in the coarse columnar crystal is less than 1.5.

[0018] The fine columnar crystal is a columnar crystal with a width of 80-140 nm, the crystal type of the fine columnar crystal includes c-AlTiN, and the 200 / 111 peak intensity of the c-AlTiN in the fine columnar crystal is between 1.5 and 4.

[0019] The dense crystal is a columnar crystal with a width of 20-60 nm, the crystal type of the dense crystal includes c-AlTiN, and the 200 / 111 peak intensity of the c-AlTiN in the dense crystal is greater than 4.

[0020] Preferably, when the crystal grain of the AlTiN coating is coarse columnar crystal, the cathode integrated high power pulse magnetron sputtering conditions for preparing the AlTiN coating include: a cathode peak current of 450±100 A, a cathode peak voltage of 700±50 V, a nitrogen flow rate of 130±5 sccm, and a substrate bias voltage of 40±10 V.

[0021] When the crystal grain of the AlTiN coating is fine columnar crystal, the cathode integrated high power pulse magnetron sputtering conditions for preparing the AlTiN coating include: a cathode peak current of 600±100 A, a cathode peak voltage of 720±50 V, a nitrogen flow rate of 140±5 sccm, and a substrate bias voltage of 70±10 V.

[0022] When the crystal grain of the AlTiN coating is dense crystal, the cathode integrated high power pulse magnetron sputtering conditions for preparing the AlTiN coating include: a cathode peak current of 750±100 A, a cathode peak voltage of 750±50 V, a nitrogen flow rate of 165±5 sccm, and a substrate bias voltage of 70±10 V.

[0023] Preferably, the AlTiN coating includes a bottom layer and a surface layer; the bottom layer is fine columnar crystal, and the surface layer is dense crystal; the total thickness of the AlTiN coating is 3-10 μm; and the thickness ratio of the surface layer to the bottom layer is 2-6.

[0024] Preferably, before the cathode integrated high power pulse magnetron sputtering, the method further includes cleaning the substrate with chemical solution, glow cleaning, and ion etching.

[0025] The gas used in the glow cleaning is Ar and H2; the conditions of the glow cleaning include: a substrate bias voltage of -30 to -90 V, an Ar flow rate of 100-300 sccm, an H2 flow rate of 100-300 sccm, an Ar to H2 flow rate ratio of 1.5-2.5, and a cleaning time of 40-60 min.

[0026] The gas used in the ion etching is Ar; the conditions of the ion etching include: an Ar flow rate of 200-500 sccm, a substrate bias voltage of -100 to -300 V, and a chamber pressure of 0.8-2 Pa.

[0027] The application also provides a cathode integrated magnetron sputtering device used in the method, which includes a vacuum chamber, a heater, a substrate table, an etching module, a cathode, and a cathode power supply, wherein the cathode is connected to the cathode power supply; and the cathode power supply is used to control the cathode to discharge at high current and high voltage.

[0028] The application also provides an AlTiN coating prepared by the method.

[0029] The application also provides the application of the AlTiN coating in a tool.

[0030] The application provides a cathode integrated coating preparation method, comprising the following steps: performing cathode integrated high-power pulse magnetron sputtering on a substrate to obtain a coating; the cathode discharge mode of the cathode integrated high-power pulse magnetron sputtering is high-current and high-voltage discharge; the peak current of the high-current and high-voltage discharge is 200-2000 A, the peak voltage is 200-2000 V, and the discharge waveform is square. The application has the following beneficial effects:

[0031] The "cathode integrated high-power pulse magnetron sputtering" refers to platform sustained discharge on the basis of traditional HiPiMS. The discharge waveform of the traditional HiPiMS is a triangular waveform, which realizes instantaneous high power and high current, low ionization rate and low deposition rate. The discharge waveform of the "cathode integrated HiPiMS" is a square waveform, the peak current can be sustained for ms, the ionization rate is high, the deposition rate is high, and the deposition rate is 0.5-5 μm / H. The discharge mode of the application combines the large-current discharge characteristics of AIP and the large-voltage discharge characteristics of traditional MS. The prepared coating has a smooth surface without droplets, excellent adhesion, fast deposition rate and low internal stress.

[0032] Further, the discharge waveform of the traditional HiPiMS technology is a triangular waveform, the peak current and peak power cannot realize sustained discharge, the total energy of the ionized plasma density is low, and the adjustment of the power supply parameters has limited adjustment on the total energy. The high-energy pulse of the "cathode integration" can realize sustained discharge of the peak current and peak power, the plasma realizes high density and high energy, and by adjusting the power supply parameters and process parameters, the adjustment of the coating grain size, preferred orientation and phase structure is easy to realize, and then the adjustment of the hardness and toughness of the coating is realized, which greatly improves the performance of the coating. At the same time, the performance of the coating can also be adjusted specifically, and the process window is widened.

[0033] Taking the AlTiN coating as an example, the traditional HiPiMS technology is difficult to realize the precise adjustment of the preferred orientation of c-AlTiN and the control of c-AlN phase and w-AlN phase. The "cathode integrated" HiPiMS technology can easily control the preferred orientation of c-AlTiN, the 200 / 111 peak intensity of c-AlTiN is less than 1.5, the coating presents a relatively large columnar crystal, and has a more excellent adhesion. The 200 / 111 peak intensity of c-AlTiN can also be adjusted to be greater than 4, so that the coating tends to form a dense crystal, and the coating has higher compactness, higher hardness and better wear resistance. The "cathode integrated" HiPiMS technology can be used to control and avoid the generation of c-AlN phase and w-AlN phase, so that the coating has better high-temperature stability, and the generation of soft phase is avoided, and the hardness of the coating is improved. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is a schematic diagram of the structure of the cathode integrated coating device used in the present application (a) and a schematic diagram of the cathode discharge waveform (b); in Figure 1: 1 is a first cathode, 1-1 is a first cathode power supply, 2 is a second cathode, 2-2 is a second cathode power supply, 3 is a heater 1 / 2, 4 is a heater 3 / 4, 5 is a heater 5 / 6, 6 is an etching module, 7 is a substrate table, 8 is a substrate carrier;

[0035] Figure 2 is a SEM image of the cross-section of the AlTiN coating obtained in Example 1, Scheme 1;

[0036] Figure 3 is a SEM image of the cross-section of the AlTiN coating obtained in Example 1, Scheme 2;

[0037] Figure 4 is a SEM image of the cross-section of the AlTiN coating obtained in Example 1, Scheme 3;

[0038] Figure 5 is a SEM image of the cross-section of the AlTiN coating obtained in Example 1, Scheme 4;

[0039] Figure 6 is an XRD pattern of the AlTiN coatings obtained in Example 1, Scheme 3, Scheme 2 and Scheme 5;

[0040] Figure 7 is a comparison of the tool wear of the AlTiN coatings obtained in Example 1, Scheme 4 and Scheme 5 under turning 316 working conditions;

[0041] Figure 8 is a SEM image of the surface of the AlTiN coating obtained in Example 1, Scheme 4. DETAILED DESCRIPTION

[0042] Glossary: In the present application, "cathode integrated high power pulsed magnetron sputtering" refers to a high power pulsed magnetron sputtering method that simultaneously has high current (200-2000 A adjustable) and high voltage (200-2000 V adjustable) discharge and can sustain a certain discharge time (μs-ms).

[0043] The present application provides a cathode integrated coating preparation method, comprising the following steps:

[0044] cathode integrated high power pulsed magnetron sputtering of the substrate to obtain a coating; the cathode discharge mode of the cathode integrated high power pulsed magnetron sputtering is high current and high voltage discharge; the peak current of the high current and high voltage discharge is 200-2000 A, the peak voltage is 200-2000 V, and the discharge waveform is square.

[0045] In the application, the deposition rate of the cathode integrated high power pulse magnetron sputtering is 0.5-5 μm / H; the sustainable discharge time of the peak current can reach ms level, and the highest can reach 10 ms, in the specific embodiment of the application, the sustainable discharge time of the peak current is ≤10 ms, preferably 0.1-10 ms, and further preferably 0.2-1 ms.

[0046] In the application, the substrate is preferably cemented carbide, specifically cemented carbide blades and square test blocks; the type of the cemented carbide is preferably WC.

[0047] In the application, before the cathode integrated high power pulse magnetron sputtering is performed, preferably, the substrate is further subjected to chemical cleaning, glow cleaning and ion etching; the cleaning agent used in the chemical cleaning is preferably a neutral cleaning agent, and the application does not have special requirements for the type of the neutral cleaning agent, and the well-known one in the art can be used, specifically DH-316, 1102H cleaning agent; the chemical cleaning is used to remove glue, oil stains and wax on the surface of the substrate; the gas used in the glow cleaning is preferably Ar and H2; the conditions of the glow cleaning preferably include: the substrate bias is -30 to -90 V, preferably -50 to -70 V, the Ar flow rate is 100-300 sccm, preferably 150-250 sccm, the H2 flow rate is 100-300 sccm, preferably 130-200 sccm, the flow rate ratio of the Ar to H2 is 1.4-2.5, the cleaning time is 40-60 min, and the cavity pressure is preferably 1-2 Pa, and more preferably 1.2 Pa; the glow cleaning is used to further remove oil stains on the surface of the substrate; the gas used in the ion etching is preferably Ar; the conditions of the ion etching preferably include: the Ar flow rate is 200-500 sccm, preferably 300-400 sccm, the substrate bias is -100 to -300 V, preferably -150 to -250 V, and the cavity pressure is 0.8-2 Pa, preferably 1-1.5 Pa; the ion etching is used to further clean the stubborn impurities on the surface of the substrate, and to improve the surface roughness of the substrate and the bonding force between the coating and the substrate.

[0048] In the specific embodiment of the application, after the chemical cleaning is completed, the substrate is preferably placed in a vacuum coating machine, and vacuumized to ≤5×10 -3 Pa, then the heating module is started to make the cavity temperature reach the working temperature, the working temperature is preferably 500±50℃, then the glow cleaning is performed under the above conditions, after the glow cleaning is completed, the bias is increased to the bias required for ion etching, and the H2 is closed, only the Ar is introduced, and the ion etching is performed under the above conditions.

[0049] After the ion etching, the substrate after the ion etching is subjected to cathode integrated high-power pulse magnetron sputtering to obtain a coating on the surface of the substrate. In the present application, the mode of the cathode integrated high-power pulse magnetron sputtering is preferably a constant current mode or a constant power mode; the operating conditions of the cathode integrated high-power pulse magnetron sputtering preferably include: a cathode peak current of 200-2000 A, preferably 300-800 A, a peak voltage of 200-2000 V, preferably 300-800 V, a cathode average power of 8-30 KW, preferably 10-25 KW, a cathode pulse frequency of 200-3000 Hz, preferably 250-2000 Hz, a cathode duty cycle of 3-40%, preferably 5-20%, an Ar and N2 flow ratio of 1.5-3.5, preferably 2-3, a cavity pressure of 0.35-1 Pa, preferably 0.4-0.8 Pa, a cavity temperature of 500±50℃, a substrate negative bias of -20 to -120 V, preferably -30 to -90 V, a bias power frequency of 20-50 KHz, a bias power duty cycle of 30%-90%, preferably 40%-80%.

[0050] In the present application, the number of target materials of the cathode integrated high-power pulse magnetron sputtering is preferably 2, and the target materials are preferably symmetrically arranged on both sides of the substrate carrier.

[0051] In specific embodiments of the present application, the target material is preferably an AlTi alloy, the content of Al in the AlTi alloy is preferably 70 at.%, and the content of Ti is preferably 30 at.%; when the AlTi alloy is used as the target material, the coating is an AlTiN coating.

[0052] In the present application, the cathode integrated high-power pulse magnetron sputtering can realize continuous discharge of peak current and peak power, high density and high energy of plasma, and easy adjustment of coating grain size, preferred orientation and phase structure through adjustment of power supply parameters and process parameters, thereby greatly improving the performance of the coating. The following will be specifically described taking the AlTiN coating as an example.

[0053] In the present application, the crystal grains of the AlTiN coating are one or more of coarse columnar crystals, fine columnar crystals and dense crystals; the coarse columnar crystals are columnar crystals with a width of 160-200 nm, and the crystal form of the coarse columnar crystals includes c-AlTiN; the 200 / 111 peak intensity of the c-AlTiN in the coarse columnar crystals is less than 1.5, preferably greater than or equal to 1 and less than 1.5; the fine columnar crystals are columnar crystals with a width of 80-140 nm, and the crystal form of the fine columnar crystals includes c-AlTiN; the 200 / 111 peak intensity of the c-AlTiN in the fine columnar crystals is preferably 1.5-4; the dense crystals are columnar crystals with a width of 20-60 nm, and the crystal form of the dense crystals includes c-AlTiN; the 200 / 111 peak intensity of the c-AlTiN in the dense crystals is greater than 4, preferably 4-6.

[0054] When the crystal grains of the AlTiN coating are coarse columnar crystals, the conditions for preparing the AlTiN coating by cathode-integrated high-power pulsed magnetron sputtering preferably include: a cathode peak current of 450±100 A, preferably 450±30 A, a cathode peak voltage of 700±50 V, a nitrogen flow rate of 130±5 sccm, and a substrate bias voltage of 40±10 V.

[0055] When the crystal grains of the AlTiN coating are fine columnar crystals, the conditions for preparing the AlTiN coating by cathode-integrated high-power pulsed magnetron sputtering preferably include: a cathode peak current of 600±100 A, preferably 600±30 A, a cathode peak voltage of 720±50 V, a nitrogen flow rate of 140±5 sccm, preferably 142 sccm, and a substrate bias voltage of 70±10 V.

[0056] When the crystal grains of the AlTiN coating are dense crystals, the conditions for preparing the AlTiN coating by cathode-integrated high-power pulsed magnetron sputtering preferably include: a cathode peak current of 750±100 A, preferably 750±30 A, a cathode peak voltage of 750±50 V, a nitrogen flow rate of 165±5 sccm, and a substrate bias voltage of 70±10 V.

[0057] In the present application, the AlTiN coating preferably includes a bottom layer and a surface layer; the bottom layer is fine columnar crystals, and the surface layer is dense crystals; the total thickness of the AlTiN coating is preferably 3-10 μm; and the thickness ratio of the surface layer to the bottom layer is preferably 2-6, more preferably 3-5. In the present application, the AlTiN coating with fine columnar crystals has higher adhesion to the substrate, and the AlTiN coating with dense crystals has higher hardness. The present application combines a fine columnar crystal bottom layer and a dense crystal surface layer, the bottom layer can ensure high adhesion, the surface layer can increase the hardness of the coating and improve the ability of the coating to resist crack propagation, and this combination of a bottom layer and a surface layer is suitable for use scenarios that require high adhesion and high hardness.

[0058] After the cathode integrated high-power pulsed magnetron sputtering is completed, the application preferably degasses; after the coating preparation is completed, the process gas exists in the cavity, the application preferably maintains the mechanical pump and the molecular pump to be continuously opened for a period of time, and the process gas is pumped away, so that the cavity is restored to the bulk vacuum degree, and the leak hunting of the equipment is used.

[0059] After degassing is completed, the application preferably cools down, and after the vacuum coating machine is reduced to a set temperature (≤200℃), the substrate (i.e., the coating product) is taken out.

[0060] The application also provides a cathode integrated coating device used in the method described in the above scheme, which comprises a vacuum chamber, a heater, a substrate table, an etching module, a cathode, and a cathode power supply, wherein the cathode and the cathode power supply are connected; and the cathode power supply is used to control the cathode to perform high-current and high-voltage discharge.

[0061] In the application, the substrate table is preferably arranged at the central part of the vacuum chamber; a plurality of substrate carriers are arranged on the substrate table; and the substrate carriers are used to place substrates, and each substrate carrier can place a plurality of substrates, so as to facilitate the simultaneous sputtering of the plurality of substrates.

[0062] In the application, the heater is preferably 6, and two are a pair (referred to as a heating module), and the three pairs of heaters are preferably uniformly arranged around the substrate carrier; in the specific embodiment of the application, the three pairs of heaters are respectively referred to as heater 1 / 2, heater 3 / 4, and heater 5 / 6.

[0063] In the application, the cathode is preferably 2, and the two cathodes are symmetrically arranged on the two sides of the substrate carrier; the number of the cathode power supply is preferably 2, and each cathode is connected with one cathode power supply; the cathode comprises a back plate and a target material arranged on the back plate; in the specific embodiment of the application, the two cathodes are respectively referred to as a first cathode and a second cathode, the cathode power supply connected with the first cathode is referred to as a first cathode power supply, and the cathode power supply connected with the second cathode is referred to as a second cathode power supply. In the application, the cathode power supply is used to control the cathode to perform high-current and high-voltage discharge and control the square wave; the application does not have special requirements for the cathode power supply, and a commercially available power supply can be used as long as it can realize the high-current and high-voltage discharge of the cathode.

[0064] The application does not have special requirements for the structure and position of the etching module, and a structure well known to those skilled in the art can be used, which can be arranged on one side of the substrate carrier.

[0065] The application further provides an AlTiN coating prepared by the method described in the above scheme; in specific embodiments of the application, the AlTiN coating is preferably a coating with fine columnar crystals in the bottom layer and dense crystals in the surface layer, and the specific thickness and preparation method are not described herein again.

[0066] The application further provides the application of the AlTiN coating described in the above scheme in a cutter; in specific embodiments of the application, the AlTiN coating is directly applied to the cutter as a substrate for film plating; the application does not have special requirements for the type of the cutter, and any cutter known to those skilled in the art can be used. The AlTiN coating of the application prepared on the surface of the cutter can effectively improve the hardness and wear resistance of the cutter, and the adhesion between the coating and the cutter substrate is strong.

[0067] The technical solutions in the application will be described clearly and completely in the embodiments in the application. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0068] Embodiment 1

[0069] 1. Pretreatment (chemical cleaning): The surface oil and oxide of the substrate are cleaned by using a cleaning agent, and the substrate is WC cemented carbide.

[0070] 2. Vacuumizing: The substrate is placed in a vacuum film plating machine, so that the vacuum degree in the vacuum film plating machine reaches 5x10 -3 Pa.

[0071] 3. Heating: The heating module is started, so that the cavity temperature reaches the working temperature of 500℃.

[0072] 4. Glow cleaning and ion etching: Ar and H2 are introduced under a bias voltage of -60V, the flow rate of Ar is 200sccm, the flow rate of H2 is 100sccm, the glow cleaning is performed for 60min, the main purpose is to remove the oil stains on the surface of the cutter, the flow rate ratio of Ar to H2 is 2, and the cavity pressure is 1.2Pa. After the glow cleaning is completed, the bias voltage is increased, H2 is closed, only Ar 300sccm is introduced, the bias voltage is controlled to be -240, the cavity pressure is 1.05Pa, ion etching is performed, the stubborn impurities on the surface of the plated substrate cutter are further cleaned, the surface roughness of the substrate is improved, and the adhesion between the coating and the substrate is improved.

[0073] 5. Coating deposition:

[0074] (1) The specific coating device and target cathode discharge waveform is shown in Figure 1. When preparing, Cathode 1 and 2 are opened at the same time, and the two cathode targets work together. The cathode target material used is an AlTi7030 at.% target material.

[0075] (2) The peak current of the coating is set, and the constant current mode is used. The peak current and peak voltage are shown in Table 1.

[0076] (3) The pulse frequency of the cathode is set to 600 Hz, and the duty cycle is 12%. The holding time of the peak current in the following scheme is 200 μs.

[0077] (4) The ratio of Ar and N2 is 1.4, the nitrogen flow is shown in Table 1, and the chamber pressure is 0.7 Pa.

[0078] (5) The substrate negative bias is shown in Table 1, the frequency of the substrate power supply is 30 KHz, and the duty cycle is 80%.

[0079] 6. Degassing: After the coating is completed, there is process gas in the chamber. This step refers to maintaining the mechanical pump and molecular pump for a period of time after the coating is completed to remove the process gas and restore the chamber to the base vacuum degree, which is used for leak detection of the equipment.

[0080] 7. Cooling: Cooling and obtaining the plated product. After the coating is completed, the vacuum coating equipment is cooled, and after being reduced to the set temperature, the coated substrate (knife finished product) is taken out of the vacuum coating equipment, and the coating is completed. The hardness of the obtained film layer is tested, and the test results are shown in Table 1.

[0081] Table 1: Test parameter data table

[0082] Coating detection:

[0083] 1. SEM cross-section analysis: Using a scanning electron microscope, the coating cross-section is magnified to 10K-60K, and the growth morphology of the grain size is observed. The observation results of the coatings obtained in schemes 1-3 are shown in Figures 2-4. According to Figures 2-4, columnar crystals and dense crystals with adjustable grain size can be prepared by setting the process parameters. For some use scenarios that require high adhesion and high hardness, the combination of fine columnar crystals in the bottom layer and dense crystals on the surface layer is recommended (scheme 4). The bottom layer can ensure high adhesion, and the surface layer can increase the hardness of the coating and improve the ability to resist crack propagation. The observation results of the coating obtained in scheme 4 are shown in Figure 5.

[0084] 2. Crystal orientation analysis by XRD: The coatings obtained by scheme 3 (preferably dense crystal), scheme 2 (preferably columnar crystal) and scheme 5 (not recommended) were tested by XRD, and the results are shown in Figure 6. By comparing the intensity of (111) and (200) peaks, it is preferred that the ratio of (200) / (111) peak intensity of the bottom layer is between 1.5 and 4, so that the coating presents fine columnar crystal, has high bonding force, and the ratio of (200) / (111) peak intensity of the surface layer is greater than 4, and most preferably 4 to 6, so that the coating presents dense columnar crystal, has high density and high hardness, and controls the generation of c-AlN and w-AlN in the coating, so that the coating has better high-temperature stability and higher hardness.

[0085] 3. Hardness analysis by nanoindentation: The nanoindenter of Anton Paar was used for testing, the indenter test depth was less than 1 / 10 of the coating thickness, 15 points were selected for each sample, and the average value was taken to obtain the hardness of the coating. The specific test results are shown in Table 1. According to the test results, when c-AlN and w-AlN phases appear in the coating of scheme 5, the hardness of the coating is the lowest, and the hardness of the coating of coarse columnar crystal is the second.

[0086] 4. Cutting test: Figure 7 is a comparison of tool wear of coatings obtained by scheme 4 and scheme 5 under turning 316 working conditions. The tool base is a cemented carbide turning blade, and the specific machining parameters are: Vc=260 / min, fn=0.4mm / min, ap=1.0mm, and water cooling. According to the wear comparison chart, the service life of the preferred coating scheme 4 is more than 60% higher than that of the non-recommended coating scheme 5, which fully shows that the preferred coating scheme 4 has better wear resistance.

[0087] 5. SEM test of coating surface

[0088] Figure 8 is an SEM image of the coating surface obtained by scheme 4. According to Figure 8, it can be seen that the coating surface is smooth without droplets.

[0089] The above example results show that the cathode integrated coating preparation method provided in the application can realize high ionization rate and high deposition rate, and the deposition rate is usually 0.5-5μm / H, which is significantly better than the traditional HiPiMS; by using the discharge characteristics, the columnar crystal and dense crystal of the coating can be adjusted, the ratio of (200) and (111) peak intensity of c-AlTiN can be adjusted, the c-AlN and w-AlN phase structure can be adjusted, the hardness, toughness and bonding force of the coating can be adjusted, the coating performance can be targetedly adjusted, the process window is widened, and the performance of the coating is greatly improved; in addition, the application can prepare a coating which combines the advantages of AIP coating and MS, i.e. has smooth surface without droplets, high deposition rate, high ionization rate, low stress and the like.

[0090] The above merely describes the preferred embodiments of the present application, and it should be pointed out that, for those skilled in the art, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for producing a cathode-integrated coating, characterized by, The method comprises the following steps: The substrate is subjected to cathode integrated high-power pulse magnetron sputtering to obtain a coating; the cathode discharge mode of the cathode integrated high-power pulse magnetron sputtering is high-current and high-voltage discharge; the peak current of the high-current and high-voltage discharge is 200-2000 A, the peak voltage is 200-2000 V, and the discharge waveform is square.

2. The production method according to claim 1, characterized by, The mode of the cathode integrated high-power pulse magnetron sputtering is a constant current mode or a constant power mode. The conditions of the cathode integrated high-power pulse magnetron sputtering include: the cathode peak current is 200-2000 A, the cathode peak voltage is 200-2000 V, the cathode average power is 4-40 KW, the cathode pulse frequency is 200-3000 Hz, and the cathode duty cycle is 3-40%. The flow ratio of Ar and N2 is 1.4-3.5, the cavity pressure is 0.35-1 Pa, and the cavity temperature is 500±50℃. The substrate negative bias is -20 to -200 V, the bias power frequency is 20-50 KHz, and the bias power duty cycle is 30%-90%.

3. The production method according to claim 1 or 2, characterized by, The sustainable discharge time of the peak current is ≤10 ms.

4. The production method according to claim 3, characterized by, The sustainable discharge time of the peak current is 0.1-10 ms.

5. The production method according to claim 1 or 2, characterized by, The number of target materials of the cathode integrated high-power pulse magnetron sputtering is 2.

6. The production method according to claim 5, wherein The target material is an AlTi alloy; and the coating is an AlTiN coating.

7. The production method according to claim 6, wherein The crystal grains of the AlTiN coating are one or more of coarse columnar crystals, fine columnar crystals and dense crystals. The coarse columnar crystals are columnar crystals with a width of 160-200 nm, the crystal phase of the coarse columnar crystals includes c-AlTiN, and the 200 / 111 peak intensity of c-AlTiN in the coarse columnar crystals is less than 1.

5. The fine columnar crystals are columnar crystals with a width of 80-140 nm, the crystal type of the fine columnar crystals includes c-AlTiN, and the 200 / 111 peak intensity of c-AlTiN in the fine columnar crystals is between 1.5 and 4. The dense crystals are columnar crystals with a width of 20-60 nm, the crystal type of the dense crystals includes c-AlTiN, and the 200 / 111 peak intensity of c-AlTiN in the dense crystals is greater than 4. When the crystal grains of the AlTiN coating are coarse columnar crystals, the cathode integrated high-power pulse magnetron sputtering conditions for preparing the AlTiN coating include: the cathode peak current is 450±100 A, the cathode peak voltage is 700±50 V, the nitrogen flow rate is 130±5 sccm, and the substrate bias is 40±10 V.

8. The production method according to claim 2 or 7, characterized by, When the crystal grains of the AlTiN coating are fine columnar crystals, the cathode integrated high-power pulse magnetron sputtering conditions for preparing the AlTiN coating include: the cathode peak current is 600±100 A, the cathode peak voltage is 720±50 V, the nitrogen flow rate is 140±5 sccm, and the substrate bias is 70±10 V. ​ When the crystal grain of the AlTiN coating is dense crystal, the cathode integrated high power pulse magnetron sputtering condition for preparing the AlTiN coating comprises: a cathode peak current of 750±100 A, a cathode peak voltage of 750±50 V, a nitrogen flow rate of 165±5 sccm, and a substrate bias voltage of 70±10 V.

9. The production method according to claim 8, characterized by, The AlTiN coating comprises a bottom layer and a surface layer; the bottom layer is fine columnar crystal, and the surface layer is dense crystal; the total thickness of the AlTiN coating is 3-10 μm; and the thickness ratio of the surface layer to the bottom layer is 2-6.

10. The method of claim 1, wherein, Before the cathode integrated high power pulse magnetron sputtering, the substrate is subjected to chemical cleaning, glow cleaning and ion etching. The gas used in the glow cleaning is Ar and H2; the conditions of the glow cleaning comprise: a substrate bias voltage of-30 to-90 V, an Ar flow rate of 100-300 sccm, an H2 flow rate of 100-300 sccm, an Ar to H2 flow rate ratio of 1.5-2.5, a cleaning time of 40-60 min, and a cavity pressure of 1-2 Pa; The gas used in the ion etching is Ar; the conditions of the ion etching comprise: an Ar flow rate of 200-500 sccm, a substrate bias voltage of-100 to-300 V, and a cavity pressure of 0.8-2 Pa.

11. The cathode-integrated magnetron sputtering device used in the method of any one of claims 1-10, comprising a vacuum chamber, a heater, a substrate table, an etching module, a cathode, and a cathode power supply, wherein the cathode is connected to the cathode power supply; and wherein the device further comprises a gas source, a gas inlet, a gas outlet, and a gas flow controller. The cathode power supply is used to control the cathode to discharge at high current and high voltage.

12. The cathode-integrated magnetron sputtering device of claim 11, wherein, The number of the cathodes is 2, and the number of the cathode power supplies is 2, each cathode being connected to one cathode power supply.

13. An AlTiN coating, characterized in that, Prepared by the method of any one of claims 1-10.

14. Use of the AlTiN coating of claim 13 in a cutting tool.

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