High-throughput preparation device and method for large-area hydrogen-free diamond-like coating

Abstract

The high-flux preparation device comprises a reaction cavity, a vacuum control system and a gas path control system are arranged on the reaction cavity, a bias voltage power supply is arranged on the reaction cavity, an extraction opening and a working gas input opening are formed in the reaction cavity, and the vacuum control system, the gas path control system, the bias voltage power supply, the extraction opening and the working gas input opening are arranged on the reaction cavity. The four-target closed field unbalanced magnetron sputtering system comprises a cylindrical vacuum chamber, two groups of carbon target materials are arranged on the side wall of the cylindrical vacuum chamber, the carbon target materials form a closed field unbalanced system, the input end of the first group of carbon target materials is connected with the output end of a pulse direct current magnetron sputtering power supply, and the input end of the second group of carbon target materials is connected with the output end of a pulse direct current magnetron sputtering power supply. And the input end of the second group of carbon target materials is connected with the output end of the high-power pulse magnetron sputtering power supply. According to the method, the performance of the coating can be accurately controlled by regulating and controlling the parameters of the micropulses, the deposition rate is high, operation is easy and convenient, cost is low, and in addition, flammable and explosive acetylene gas is not adopted, so that the method is safer and more reliable.

Description

Technical Field

[0001] The invention relates to the technical field of carbon-based coating preparation, and in particular to a high-throughput preparation device for a large-area hydrogen-free diamond-like coating and a preparation method thereof. Background Art

[0002] A fuel cell is a device that converts chemical energy into electrical energy, and has the advantages of high efficiency, low pollution and zero emissions. Among them, metal bipolar plates, as one of the main components of fuel cells, directly affect the performance and service life of fuel cells. When using hydrogen-containing gases, such as acetylene gas and methane, reactive sputtering to prepare carbon-based compounds will leave residual hydrogen, which will cause the coating to crack, fall off and fail during use, seriously affecting the life of the metal bipolar plates.

[0003] Magnetron sputtering is a vacuum coating technology that introduces a magnetic field on the target cathode surface and uses the magnetic field to constrain charged particles to increase the plasma density and increase the sputtering rate, achieving high-speed, low-temperature, and low-damage sputtering. It has the advantages of simple equipment, easy control, large coating area, and strong adhesion. At present, magnetron sputtering has been widely used in the preparation of surface coatings for fuel cell metal bipolar plates.

[0004] In order to improve the performance and service life of fuel cells, it is necessary to prepare a hydrogen-free carbon-based coating to improve the conductivity and corrosion resistance of metal bipolar plates, while reducing the hydrogen-carbon content of the coating to improve the efficiency and stability of fuel cells. Therefore, a high-throughput preparation device and preparation method for a large-area hydrogen-free diamond-like coating is needed. Summary of the invention

[0005] The object of the present invention is to provide a high-throughput preparation device, method and system for large-area hydrogen-free diamond-like coating.

[0006] To achieve the above object, the present invention is implemented according to the following technical solutions:

[0007] The present invention includes a reaction chamber, on which a vacuum control system and a gas path control system are provided. The invention is characterized in that a bias power supply is provided on the reaction chamber, and an exhaust port and a working gas input port are provided on the reaction chamber. The four-target closed-field unbalanced magnetron sputtering system includes a cylindrical vacuum chamber, and the side walls of the cylindrical vacuum chamber are provided with two groups of carbon target materials, and the carbon target materials are arranged at 90° to each other to form a closed-field unbalanced system, and the input end of the first group of carbon target materials is connected to the output end of a pulsed DC magnetron sputtering power supply, and the input end of the second group of carbon target materials is connected to the output end of a high-power pulsed magnetron sputtering power supply.

[0008] Furthermore, high-power pulsed magnetron sputtering composite pulsed DC magnetron sputtering technology is combined with a closed-field non-equilibrium vacuum system, and the working gas is 99.99% argon or nitrogen. Large-area hydrogen-free carbon-based coatings with smooth and dense bonding are prepared at high speed on the surfaces of stainless steel, glass, ceramics and high molecular polymers.

[0009] Furthermore, the sputtering power is 8-10 kW, the micro pulse width is on time (4-10 μs) / off time (50 μs), the negative bias voltage is set to -400-500 V, the sample stage speed is 3 rpm, and the time is 10 min.

[0010] Furthermore, the coating deposition area is 1m×1m, the deposition rate is 20~100nm / s, the nano hardness is 15-100GPa, and the fracture toughness K IC Greater than 3MPa·m 1 / 2 .

[0011] Furthermore, the four-target closed-field unbalanced magnetron sputtering system and the pulsed magnetron sputtering power supply are coupled into a plasma source, and a vacuum control system and a gas path control system are controlled by a computer to adjust the working gas pressure, gas flow and pulsed power supply parameters.

[0012] A high-throughput preparation method for a large-area hydrogen-free diamond-like coating comprises the following steps:

[0013] A Sample loading: Clean the glass and silicon wafer samples for 30 minutes, blow dry with compressed air, and load the equipment into the sample loading chamber A. Wait until the vacuum pump system reaches the background vacuum of 1×10 -4 Below Pa;

[0014] B. Ion cleaning: 80-120 sccm of argon is introduced into the vacuum chamber, the pressure is set to 0.8-1.4 Pa, the negative bias voltage is set to -500~-800 V, and the time is 1~2 hrs;

[0015] C surface activation: change the sputtering power of the carbon target to 8-10kW, micro pulse width on time (4-10μs) / off time (50μs), negative bias voltage setting to -400-500V, sample stage speed 3rpm, time 10min;

[0016] D. Preparation of hydrogen-free carbon-based coating: Move the sample into the vacuum chamber C, start other targets respectively, adjust the sputtering power to 6-10kW, micro-pulse width on time (4-10μs) / off time (50μs), negative bias voltage to -100-500V, sample stage speed to 1-3rpm, time to 30min, and prepare a large-area hydrogen-free carbon-based coating with smooth and dense bonding surface at high speed. The coating thickness is about 20μm.

[0017] The beneficial effects of the present invention are:

[0018] The present invention is a high-throughput preparation device method and system for a large-area hydrogen-free diamond-like coating. Compared with the prior art, the present invention has the following technical effects:

[0019] The present invention can effectively deposit a coating area of ​​1m×1m, with a deposition rate of 20-100nm / s, a nano hardness of 15-100GPa, and a fracture toughness K IC Greater than 3MPa·m 1 / 2 By adjusting the parameters of the micro-pulse, the performance of the coating can be accurately controlled, the deposition rate is fast, the operation is simple and the cost is low. In addition, this method does not use flammable and explosive acetylene gas, which is safer and more reliable. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic structural diagram of a high-throughput preparation device for a large-area hydrogen-free diamond-like coating according to the present invention;

[0021] Figure 2 A high-throughput preparation method for a large-area hydrogen-free diamond-like coating according to the present invention is a schematic diagram of a sample photo;

[0022] Figure 3 A schematic diagram of coating of a sample of a high-throughput preparation method of a large-area hydrogen-free diamond-like coating according to the present invention;

[0023] Figure 4 A schematic diagram of hardness index of a sample coating in a high-throughput preparation method of a large-area hydrogen-free diamond-like coating according to the present invention;

[0024] Figure 5 A schematic diagram of coating of a coating tool of a high-throughput preparation device for large-area hydrogen-free diamond-like coating of the present invention;

[0025] Figure 6 A schematic diagram of coating hardness data of a coating tool of a high-throughput preparation device for a large-area hydrogen-free diamond-like coating according to the present invention; DETAILED DESCRIPTION

[0026] The present invention is further described below with specific examples. The illustrative examples and descriptions of the present invention are used to explain the present invention but are not intended to limit the present invention.

[0027] A high-throughput preparation method of a large-area hydrogen-free diamond-like coating comprises the following steps:

[0028] like Figure 1As shown, the present invention includes a reaction chamber, and the reaction chamber is provided with a vacuum control system and a gas path control system. It is characterized in that the reaction chamber is provided with a bias power supply, and the reaction chamber is provided with a gas extraction port and a working gas input port. The four-target closed-field unbalanced magnetron sputtering system includes a cylindrical vacuum chamber, and the side wall of the cylindrical vacuum chamber is provided with two groups of carbon target materials, and the carbon target materials are arranged at 90° to each other to form a closed-field unbalanced system, and the input end of the first group of carbon target materials is connected to the output end of the pulsed DC magnetron sputtering power supply, and the input end of the second group of carbon target materials is connected to the output end of the high-power pulsed magnetron sputtering power supply.

[0029] Case Study 1: Preparation of Hydrogen-Free Carbon-Based Coatings on Glass and Silicon Wafers

[0030] 1. Preparation of substrate materials: Install the purchased dust-free and clean glass and silicon wafer on the sample stage of the vacuum chamber, close the vacuum chamber, and evacuate the chamber.

[0031] 2. Vacuuming preparation: Use the vacuum pumping system to evacuate to a background vacuum of 1×10 -4 Pa.

[0032] 3. Sample surface ion cleaning: introduce argon gas 80-120sccm, set the pressure to 0.8-1.4Pa, and set the negative bias voltage

[0033] -500~-800V, time 1~2hrs.

[0034] 4. Surface activation: sputtering power 8-10kW, micro pulse width on time (4-10μs) / off time (50μs), negative bias setting -400-500V, sample stage speed 3rpm, time 10min.

[0035] 5. Preparation of hydrogen-free carbon-based coating: sputtering power 6-10kW, micro pulse width opening time (4-10μs) /

[0036] The closing time is 50 μs, the negative bias voltage is set to -100 to -500 V, the sample stage speed is 1 to 3 rpm, the time is 30 min, and the coating thickness is about 20 μm.

[0037] like Figure 2 and 3 As shown in the figure, the coating test data of the silicon wafer sample: no radial cracks are generated in the micron indentation, indicating that the fracture toughness is high, and the fracture toughness K IC Greater than 3MPa·m 1 / 2 ,like Figure 4 As shown in the figure, it is a schematic diagram of the sample surface hardness index. The surface hardness of the coating reaches 40GPa.

[0038] Implementation Case 2: Application of Hydrogen-free Carbon-based Coated Milling Cutters

[0039] 1. Preparation of matrix material: Clean the purchased milling cutter with acetone and ethanol in an ultrasonic water bath for 30 minutes, blow dry with compressed air, and then install it on the sample stage of the vacuum chamber, close the vacuum chamber, and evacuate it.

[0040] 2. Vacuuming preparation: Use the vacuum pumping system to evacuate to a background vacuum of 1×10 -4 Pa.

[0041] 3. Sample surface ion cleaning: introduce argon gas 80-120sccm, set the pressure to 0.8-1.4Pa, and set the negative bias voltage

[0042] -500~-800V, time 30-60min.

[0043] 4. Surface activation: sputtering power 6-8kW, micro pulse width on time (2-10μs) / off time (60μs), negative bias setting -500-800V, sample stage speed 2rpm, time 6-10min.

[0044] 5. Preparation of hydrogen-free carbon-based coating: sputtering power 8-10kW, argon flow rate 80-120sccm, gas pressure 0.8-1.5Pa, micro-pulse width on time (2-8μs) / off time (30 μs), negative bias setting -300-500V, sample stage speed 1-2rpm, time about 10min, coating thickness is about 3-5μm.

[0045] like Figure 5 This is a schematic diagram of the coating of the coated tool. There is no crack in the micron indentation, and the hardness value is HV4200. The coating on the blade is flat and the surface quality is high.

[0046] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-throughput preparation device for a large-area hydrogen-free diamond-like coating, comprising a reaction chamber, wherein a vacuum control system and a gas path control system are provided on the reaction chamber, characterized in that The reaction chamber is provided with a bias power supply, a vacuum port and a working gas input port, the four-target closed-field unbalanced magnetron sputtering system comprises a cylindrical vacuum chamber, the side wall of the cylindrical vacuum chamber is provided with two groups of carbon target materials, the carbon target materials are arranged at 90° to each other to form a closed-field unbalanced system, the input end of the first group of carbon target materials is connected to the output end of the pulsed DC magnetron sputtering power supply, and the input end of the second group of carbon target materials is connected to the output end of the high-power pulsed magnetron sputtering power supply.

2. A high-throughput preparation device for a large-area hydrogen-free diamond-like coating according to claim 1, characterized in that: High-power pulsed magnetron sputtering composite pulsed DC magnetron sputtering technology combined with a closed field non-equilibrium vacuum system, the working gas is 99.99% argon or nitrogen, and a large-area hydrogen-free carbon-based coating with smooth and dense bonding strength is prepared at high speed on the surfaces of stainless steel, glass, ceramics and high molecular polymers.

3. A high-throughput preparation device for a large-area hydrogen-free diamond-like coating according to claim 1, characterized in that: The sputtering power was 8-10 kW, the micro-pulse width was on time (4-10 μs) / off time (50 μs), the negative bias voltage was set to -400-500 V, the sample stage speed was 3 rpm, and the time was 10 min.

4. A high-throughput preparation device for a large-area hydrogen-free diamond-like coating according to claim 1, characterized in that: The coating deposition area is 1m×1m, the deposition rate is 20~100nm / s, the nano hardness is 15-100GPa, and the fracture toughness is K IC Greater than 3MPa·m 1 / 2 .

5. The high-throughput preparation device for large-area hydrogen-free diamond-like coating according to claim 1, characterized in that: The four-target closed-field unbalanced magnetron sputtering system and the pulsed magnetron sputtering power supply are coupled into a plasma source, and the vacuum control system and the gas path control system are controlled by a computer to adjust the working gas pressure, gas flow and pulsed power supply parameters.

6. A high-throughput preparation method for a large-area hydrogen-free diamond-like coating, characterized in that: The following steps are involved: A Sample loading: Clean the glass and silicon wafer samples for 30 min, blow dry with compressed air, and load the equipment into sample loading chamber A. Wait until the vacuum pump system reaches the background vacuum of 1×10 -4 Below Pa; B. Ion cleaning: 80-120 sccm of argon is introduced into the vacuum chamber, the pressure is set to 0.8-1.4 Pa, the negative bias is set to -500~-800 V, and the time is 1~2 hrs; C surface activation: change the sputtering power of the carbon target to 8-10kW, the micro pulse width on time (4-10μs) / off time (50μs), the negative bias voltage to -400-500V, the sample stage speed to 3rpm, and the time to 10min; D. Preparation of hydrogen-free carbon-based coating: Move the sample into the vacuum chamber C, start other targets respectively, adjust the sputtering power to 6-10kW, micro-pulse width on time (4-10μs) / off time (50μs), negative bias voltage to -100-500V, sample stage speed to 1-3rpm, time to 30min, and prepare a large-area hydrogen-free carbon-based coating with smooth and dense bonding surface at high speed. The coating thickness is about 20μm.

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