CN111748789B - A device and method for depositing pure DLC with graphite cathode arc enhanced glow discharge - Google Patents

Abstract

A graphite cathode arc enhanced glow discharge deposition pure DLC device and method, the invention relates to a graphite cathode arc enhanced glow discharge deposition pure DLC device and method. The purpose of the present invention is to solve the problem of "contamination" of DLC by metal elements when the DLC is prepared by the enhanced glow discharge of the metal cathode arc. The carbon-containing gas is ionized by the high-density electrons emitted by the graphite cathode arc and deposited on the surface of the workpiece to form pure DLC. The ratio of ions to atoms in carbon-containing plasma can be controlled by changing the discharge pattern between the cathode and anode and adjusting the discharge parameters. The invention avoids the bad influence of metal doping on the tribological properties when the metal target enhances the glow discharge to prepare the DLC. The invention is applied to the field of preparing DLC by plasma enhanced chemical vapor deposition.

Description

A kind of graphite cathode arc enhanced glow discharge deposition pure DLC device and method

technical field

The invention relates to a device and a method for a graphite cathode arc enhanced glow discharge deposition pure DLC.

Background technique

DLC (Diamond-like carbon) films have been widely used due to their low friction coefficient, high hardness, good wear resistance and chemical inertness, such as auto parts, seawater corrosion resistance of ship hulls, and processing of aluminum alloys.

There are many methods for depositing DLC, mainly based on plasma chemical vapor deposition (PECVD). The most widely used method in industry is the method of self-glow discharge of workpieces. This method uses the workpiece itself as the discharge source, and applies medium and high frequency bias on it, and the bias is generally higher than -300V. This method has the following problems: 1. It is greatly affected by the shape of the workpiece and the amount of furnace loading. If the workpiece changes, the process needs to be re-adjusted; 2. The strength of the glow discharge mainly depends on the bias voltage, so the structure and performance of the film Unable to adjust flexibly; 3. The working pressure is generally high, and it is difficult to handle workpieces with holes; 4. The deposition rate is low, generally less than 1.5μm/h;

The anode layer ion source introduced by AE company decouples ionization and bias voltage. However, due to the working characteristics of the ion source, the ion source is easy to ignite during coating, resulting in unstable coating process and even impurities generated by ignition. It is easy to enter the film, affecting the quality of the film, and the deposition rate of this technology is relatively low;

Using microwave discharge to deposit DLC, the deposition rate of DLC can be as high as 15 μm/h under the high density plasma excited by microwave. However, the process safety of microwave itself is not easy to control, and the equipment is complicated, the process window is narrow, and the cost is high;

The DLC is prepared by using a cage-mesh hollow cathode, and its deposition rate can reach 6 μm/h. However, because the workpiece is enclosed in the cage net, it is difficult to design the bottom layer and prepare metal-doped DLC, so it is difficult to meet the requirements of some working conditions;

A large number of electrons will be generated during the working process of the cathode arc, and the electrons can be extracted from the vicinity of the target through the external anode to ionize the gas in the vacuum chamber, which improves the intensity of the gas glow discharge and produces high-density plasma. The arc-enhanced glow discharge method is used to improve the ionization rate of Ar gas, which has a good effect in the process of Ar ion etching before coating, and improves the bonding force between the film and the substrate.

However, when the conventional metal arc enhanced glow discharge method is used to ionize acetylene to prepare DLC, in the process of electrons being drawn out by the anode, the metal ions will be pulled out along with the electrons and deposited on the surface of the film to form element-doped DLC. In application, it will adversely affect the tribological properties of DLC;

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the problem of "contamination" of DLC by metal elements in the preparation of DLC by metal cathode arc enhanced glow discharge, and to provide a device and method for depositing pure DLC by graphite cathode arc enhanced glow discharge.

The present invention is a device for depositing pure DLC with graphite cathode arc enhanced glow discharge, comprising a vacuum chamber, a turret, a bias power supply, a first graphite cathode arc, a second graphite cathode arc, a first metal cathode, a second metal cathode, The first anode, the second anode, the first high-pulse power supply, the second high-pulse power supply, the first DC power supply and the second DC power supply; an air inlet is opened at the bottom of the vacuum chamber; The frame is rotatably connected with the vacuum chamber, and four flanges are evenly arranged on the wall of the vacuum chamber along the circumferential direction, and the four flanges are respectively fixedly connected to the first graphite cathode arc, the first metal cathode, the second graphite cathode arc and the second metal cathode. Cathode; baffles are provided between the first graphite cathode arc and the second graphite cathode arc and the turret, and there are gaps between the two ends of the baffle and the inner wall of the vacuum; the first graphite cathode arc and the second graphite cathode arc are oppositely arranged the first metal cathode and the second metal cathode are arranged oppositely; the first anode is arranged between the first graphite cathode arc and the first metal cathode, and the second anode is arranged between the second graphite cathode arc and the second metal cathode; The first anode and the second anode are both composed of a base and an anode body, the anode body is fixedly connected to the base, an anode through hole is opened on the vacuum chamber, the anode base is inserted into the vacuum chamber through the anode through hole, and the anode body is located in the vacuum chamber. Inside the vacuum chamber; a first high-pulse power supply is connected between the first graphite cathode arc and the first anode, and a second high-pulse power supply is connected between the second graphite cathode arc and the second anode; the connection between the first metal cathode and the vacuum chamber is A first DC power supply is connected intermittently, a second DC power supply is connected between the second metal cathode and the vacuum chamber, and a bias power supply is connected between the turn frame and the vacuum chamber.

A method for depositing pure DLC with graphite cathode arc enhanced glow discharge of the present invention comprises the following steps: 1. ultrasonically cleaning the workpiece to be plated with alcohol, taking it out and drying it; The vacuum degree is less than 5×10 ^-3 Pa; 2. Ar ion bombardment cleaning of the workpiece to be plated: Pass Ar gas into the vacuum chamber from the air inlet to keep the air pressure of the vacuum chamber at 0.3-1.0Pa, and then turn on the bias power supply , adjust the bias voltage to -150--500V, the duty cycle is 10-80%; adjust the high pulse power supply, the current of the DC terminal is 30-150A, the average current of the pulse terminal is 30-200A,

The pulse discharge current is 50-5000A, the frequency is 10-20000Hz, the pulse width is 5-1000μs, or only the DC terminal is opened, the discharge current is 30-150A, the workpiece cleaning time is 5-100min, and the workpiece to be plated after cleaning is obtained;

3. Deposit a transition layer on the workpiece to be plated after cleaning; the transition layer is Cr/CrN/CrCN/Cr-C, Ti/TiN/TiCN/Ti-C, Ti/TiAlN, Cr/CrAlN or Si/Si- DLC;

4. Preparation of pure DLC by graphite cathode arc enhanced glow discharge: Pass argon gas and carbon-containing precursor gas into the vacuum chamber from the air inlet to maintain the pressure of the vacuum chamber at 0.1-5.0Pa; adjust the bias value of the bias power supply 50-10000V, duty cycle 5-80%; adjust the average current of high pulse power supply to 30-200A, pulse discharge current 50-50000A, frequency 10-20000Hz, pulse width 5-1000μs, DLC deposition time 5 -500min; wherein the carbon-containing precursor gas is one or more of CH ₄ , C ₂ H ₂ and C ₆ H ₆ mixed in any ratio;

The technical solution of the present invention has the following advantages:

The method for depositing pure DLC by graphite cathode arc enhanced glow discharge according to the present invention solves the problem of "contamination" of DLC by metal elements when conventional metal cathode arc enhanced glow discharge prepares DLC. At the same time, the decoupling of the bias source and the ionization source is realized, that is, the ionization process of the carbon-containing gas and the energy of the incident ions deposited on the workpiece can be independently controlled, making it easier to adjust the composition and properties of the film during the deposition process, and the process window is widened. ; The discharge electrons originate from cathodic arc discharge, so the density is high. The ratio of ions to atoms in the plasma can be adjusted by adjusting the discharge mode and pulse discharge parameters to obtain a high deposition rate. The discharge process of this process is cathodic arc discharge. , the voltage is low, so the discharge process is stable and there will be no sparking phenomenon, which has a high guarantee for the quality of the coating; the method can be carried out under low pressure, so the deep hole can be processed without being affected by the shape of the workpiece and the The influence of the structure; the ionization source of the method is independent, and the preparation of metal-doped DLC can be realized according to actual needs by configuring arc sources of other types of targets in the vacuum chamber. Since the discharge of the doping source and the ionization source are independent , so they will not interfere with each other, and the doping process is stable; the cathode material is graphite and the anode material is common metal materials (such as stainless steel, C steel, Al, Ti, Cr, Cu, etc.), the price is not expensive, so the cost of this method is not high ; This high deposition rate, low cost process is more suitable for industrial production. Using graphite as the target of the cathode arc, in the process of preparing DLC by the arc-enhanced glow discharge method, the "contamination" of the DLC film by the target elements from the cathode arc can be avoided, and the deposition of pure DLC can be achieved.

Description of drawings

1 is a schematic diagram of the device of the present invention;

Fig. 2 is the structural representation of the turret in the embodiment;

Fig. 3 graphite cathode arc enhanced glow discharge diagram (pulse current 500A);

Fig. 4 is the waveform diagram of graphite cathode arc under different discharge currents (the average pulse current is set to 20A, and the DC terminal is set to 55A);

Fig. 5 is the DLC physical map prepared by embodiment 1;

Fig. 6 is the XPS (C1s) test result of the DLC prepared by embodiment 1;

Fig. 7 is the surface morphology under the scanning electron microscope of the DLC film prepared in Example 2;

Fig. 8 is the sectional morphology under the scanning electron microscope of the DLC film prepared in Example 2;

Fig. 9 is the sectional morphology under the scanning electron microscope of the DLC film prepared in Example 3;

Fig. 10 is the Raman spectrum of the DLC film prepared by Example 5 and fitting peak splitting result;

Fig. 11 is the EDS test picture of comparative example DLC;

FIG. 12 is the EDS component analysis result of the comparative example.

Detailed ways

Embodiment 1: In this embodiment, a graphite cathode arc enhanced glow discharge deposition pure DLC device includes a vacuum chamber 9, a turret 2, a bias power supply 10, a first graphite cathode arc 1-1, and a second graphite cathode arc 1-2. First metal cathode 5-1, second metal cathode 5-2, first anode 3-1, second anode 3-2, first high pulse power supply 4-1, second high pulse power supply 4- 2. The first DC power supply 6-1 and the second DC power supply 6-2; the bottom of the vacuum chamber 9 is provided with an air inlet 7; , four flanges are evenly arranged on the wall of the vacuum chamber 9 along the circumferential direction, and the four flanges are respectively fixedly connected to the first graphite cathode arc 1-1, the first metal cathode 5-1, and the second graphite cathode arc 1-2 And the second metal cathode 5-2; the first graphite cathode arc 1-1 and the second graphite cathode arc 1-2 and the turret 2 are provided with a baffle 8, and the two ends of the baffle 8 are left with the inner wall of the vacuum chamber 9. There is a gap; the first graphite cathode arc 1-1 and the second graphite cathode arc 1-2 are arranged oppositely, the first metal cathode 5-1 and the second metal cathode 5-2 are arranged oppositely; the first graphite cathode arc 1- 1 and the first metal cathode 5-1 are provided with a first anode 3-1, a second anode 3-2 is provided between the second graphite cathode arc 1-2 and the second metal cathode 5-2; the first anode 3-1 and the second anode 3-2 are both composed of a base and an anode body, the anode body is fixedly connected to the base, an anode through hole is opened on the vacuum chamber 9, and the anode base is inserted into the vacuum chamber 9 through the anode through hole. On the top, the anode body is located inside the vacuum chamber 9; the first high-pulse power supply 4-1, the second graphite cathode arc 1-2 and the second anode are connected between the first graphite cathode arc 1-1 and the first anode 3-1 A second high pulse power supply 4-2 is connected between 3-2; a first DC power supply 6-1 is connected between the first metal cathode 5-1 and the vacuum chamber 9, and the second metal cathode 5-2 and the vacuum chamber are connected A second DC power supply 6-2 is connected between 9; a bias power supply 10 is connected between the turret 2 and the vacuum chamber 9.

In this embodiment, the DC terminal currents of the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2 are both 30-150A, the average currents at the pulse terminals are both 30-200A, and the pulse discharge currents are both 50-5000A. The frequency is 10-20000Hz, and the pulse width is 5-1000μs.

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the turret 2, the first graphite cathode arc 1-1, the second graphite cathode arc 1-2, the first metal cathode 5-1, and the second metal cathode The cathode 5 - 2 , the first anode 3 - 1 , the second anode 3 - 2 , and the baffle 8 are all insulated from the vacuum chamber 9 . Others are the same as the first embodiment.

In this embodiment, the turret 2, the first graphite cathode arc 1-1, the second graphite cathode arc 1-2, the first metal cathode 5-1, the second metal cathode 5-2, the first anode 3-1, the second The anode 3-2 and the baffle 8 are insulated from the vacuum chamber 9 by polytetrafluoroethylene.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the electrical connection end of the first anode 3-1 is electrically connected to the positive electrode of the first high-pulse power supply 4-1, and the first high-pulse power supply 4- The negative pole of 1 is electrically connected to the electrical connection terminal of the first graphite cathode arc 1-1; the electrical connection terminal of the second anode 3-2 is electrically connected to the positive pole of the second high-pulse power supply 4-2, and the second high-pulse power supply 4- The negative electrode of 2 is electrically connected to the electrical connection end of the second graphite cathode arc 1-2. Others are the same as in the first or second embodiment.

Embodiment 4: The difference between this embodiment and one of Embodiments 1 to 3 is that the electrical connection terminal of the first metal cathode 5-1 is electrically connected to the negative electrode of the first DC power supply 6-1, and the second metal cathode 5-1 is electrically connected to the negative electrode of the first DC power supply 6-1. The electrical connection terminal of -2 is electrically connected to the negative terminal of the second DC power supply 6-2, the negative terminal of the bias power supply 10 is electrically connected to the electrical connection terminal of the turret 2, and the electrical connection terminals of the vacuum chamber 9 are respectively connected to the first DC power supply. The positive electrode of 6-1, the positive electrode of the second DC power source 6-2, and the positive electrode of the bias power source 10 are electrically connected, and the vacuum chamber 9 is grounded. Others are the same as one of Embodiments 1 to 3.

Embodiment 5: A method for depositing pure DLC with graphite cathode arc enhanced glow discharge in this embodiment includes the following steps: 1. ultrasonically clean the workpiece to be plated with alcohol, take it out and blow dry; On the rack 2, the vacuum chamber 9 is evacuated to a degree of vacuum less than 5 × 10 ^-3 Pa; 2. Ar ion bombardment cleaning is performed on the workpiece to be plated: Ar gas is introduced into the vacuum chamber 9 from the air inlet 7 to maintain the vacuum chamber 9. The air pressure is 0.3-1.0Pa, then turn on the bias power supply 10, adjust the bias voltage to -150--500V, and the duty cycle is 10-80%; turn on the first high pulse power supply 4-1 and the second high pulse power supply 4 -2, the workpiece cleaning time is 5-100min, and the workpiece to be plated after cleaning is obtained; wherein the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2 turn on the DC terminal and the pulse terminal at the same time, and the current of the DC terminal is 30 -150A, the average current of the pulse terminal is 30-200A, the pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000μs; or only the DC terminal is turned on, the current of the DC terminal is 30-150A;

3. Turn off the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2, and deposit a transition layer on the cleaned workpiece to be plated; the transition layer is Cr/CrN/CrCN/Cr-C, Ti/TiN /TiCN/Ti-C, Ti/TiAlN, Cr/CrAlN or Si/Si-DLC;

4. Preparation of pure DLC by graphite cathode arc enhanced glow discharge: keep the first DC power supply 6-1 and the second DC power supply 6-2 closed, and then pass argon gas and carbon-containing gas into the vacuum chamber 9 from the air inlet 7 Precursor gas, maintain the air pressure of the vacuum chamber 9 at 0.1-5.0Pa; adjust the bias value of the bias power supply 10 to 50-10000V, and the duty cycle is 5-80%; adjust the first high pulse power supply 4-1 and the second High-pulse power supply 4-2, the deposition time of DLC is 5-500min; wherein the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2 turn on the DC terminal and the pulse terminal at the same time, the current of the DC terminal is 30-150A, and the pulse The average terminal current is 30-200A, the pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000μs; or only the DC terminal is turned on, the DC terminal current is 30-150A; the carbon-containing precursor gas is CH _4. One or more of C ₂ H ₂ and C ₆ H ₆ are mixed in any ratio.

Embodiment 6: The difference between this embodiment and Embodiment 5 is that in step 3, the transition layer is Cr/CrN/CrCN/Cr-C, and the deposition method is: turn off the first high pulse power supply 4-1 and the second high pulse power supply 4-1. Pulse power supply 4-2, feed Ar into the vacuum chamber 9, the flow rate is 100-500sccm, maintain the air pressure of the vacuum chamber 9 0.2-4.0Pa, turn on the first DC power supply 6-1 and the second DC power supply 6-2, The discharge current is DC 30-200A, the bias value of the bias power supply 10 is adjusted to -30--300V, the deposition time is 10-60min, and the Cr transition layer is prepared; then, the Ar gas is turned off, and the vacuum chamber 9 is fed at the same time. _N2 , the flow rate is _100-500sccm , the pressure of vacuum chamber 9 is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and the CrN transition layer is prepared _; The pressure of vacuum chamber 9 is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and the CrCN transition layer is prepared; then N ₂ is turned off, and Ar is introduced into the vacuum chamber 9, the flow rate is 100-500sccm, and the pressure of vacuum chamber 9 is maintained at 0.2 -4.0Pa, the deposition time is 10-60min, the deposition time is 10-60min, and a Cr-C transition layer is prepared. The first metal cathode 5-1 and the second metal cathode 5-2 are both Cr. Others are the same as the specific embodiments 1 to 5.

Embodiment 7: The difference between this embodiment and Embodiment 5 or 6 is: in step 3, when the transition layer is Ti/TiN/TiCN/Ti-C, the deposition method is: turn off the first high-pulse power supply 4-1 and The second high-pulse power supply 4-2, feeds Ar into the vacuum chamber 9, the flow rate is 100-500sccm, maintains the air pressure of the vacuum chamber 9 at 0.2-4.0Pa, and turns on the first DC power supply 6-1 and the second DC power supply 6-2, the discharge current is DC 30-200A, the bias voltage of the bias power supply 10 is adjusted to -30--300V, the deposition time is 10-60min, and the Ti transition layer is prepared; then, the Ar gas is turned off, and the vacuum chamber is turned off. Introduce N ₂ into 9, the flow rate is 100-500sccm, maintain the pressure of vacuum chamber 9 at 0.2-4.0Pa, and the deposition time is 10-60min, to prepare a TiN transition layer; then pass C ₂ H ₂ into the vacuum chamber 9, and the flow rate is 100-500sccm, maintain vacuum chamber 9 pressure 0.2-4.0Pa, deposition time is 10-60min, prepare TiCN transition layer; then turn off N ₂ , pass Ar into vacuum chamber 9, flow rate is 100-500sccm, maintain vacuum chamber 9. The gas pressure is 0.2-4.0Pa, the deposition time is 10-60min, and the Ti-C transition layer is prepared therein; the first metal cathode 5-1 and the second metal cathode 5-2 are both Ti. Others are the same as in the fifth or sixth embodiment.

Embodiment 8: The difference between this embodiment and one of Embodiments 5 to 7 is that: in step 3, when the transition layer is Ti/TiAlN, the deposition method is: turning off the first high pulse power supply 4-1 and the second high pulse Power supply 4-2, feed Ar into the vacuum chamber 9, the flow rate is 100-500sccm, maintain the air pressure of the vacuum chamber 9 at 0.2-4.0Pa, turn on the first DC power supply 6-1, the discharge current is DC 30-200A, adjust The bias value of the bias power supply 10 is -30--300V, the deposition time is 10-60min, and the Ti transition layer is prepared; then, the Ar gas and the first DC power supply 6-1 are turned off, and the second DC power supply 6-2 is turned on. At the same time, N ₂ is introduced into the vacuum chamber 9, the flow rate is 100-500sccm, the pressure of the vacuum chamber 9 is maintained at 0.2-4.0Pa, and the deposition time is 10-60min to prepare a TiAlN transition layer; the first metal cathode 5-1 is Ti, The second metal cathode 5-2 is TiAl. Others are the same as one of Embodiments 5 to 7.

Embodiment 9: The difference between this embodiment and one of Embodiments 5 to 8 is: in step 3, when the transition layer is Cr/CrAlN, the deposition method is: turn off the first high-pulse power supply 4-1 and the second high-pulse Power supply 4-2, feed Ar into the vacuum chamber 9, the flow rate is 100-500sccm, maintain the air pressure of the vacuum chamber 9 at 0.2-4.0Pa, turn on the first DC power supply 6-1, the discharge current is DC 30-200A, adjust The bias value of the bias power supply 10 is -30--300V, the deposition time is 10-60min, and the Cr transition layer is prepared; then, the Ar gas and the first DC power supply 6-1 are turned off, and the second DC power supply 6-2 is turned on. At the same time, N ₂ is introduced into the vacuum chamber 9, the flow rate is 100-500sccm, the pressure of the vacuum chamber 9 is maintained at 0.2-4.0Pa, and the deposition time is 10-60min to prepare a CrAlN transition layer; the first metal cathode 5-1 is Cr, The second metal cathode 5-2 is CrAl. Others are the same as one of Embodiments 5 to 8.

Embodiment 10: This embodiment differs from one of Embodiments 5 to 9 in that: in step 3, when the transition layer is Si/Si-DLC, the deposition method is as follows: Ar and SiH ₄ are introduced into the vacuum chamber 9 , The flow rate is 100-500sccm, the air pressure of the vacuum chamber 9 is maintained at 0.2-4.0Pa, the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2 are kept on, and the bias value of the bias power supply 10 is adjusted to -30 --300V, deposition time is 10-60min, prepare Si transition layer; continue to pass C ₂ H ₂ gas into vacuum chamber 9, flow rate is 100-500sccm, maintain air pressure 0.2-4.0Pa, deposition time is 10-60min, A Si-DLC transition layer is prepared; wherein the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2 turn on the DC terminal and the pulse terminal at the same time, the current of the DC terminal is 30-150A, and the average current of the pulse terminal is 30-200A, The pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000μs; or only the DC terminal is turned on, and the DC terminal current is 30-150A. Others are the same as one of the fifth to ninth embodiments.

Embodiment 11: The difference between this embodiment and Embodiments 5 to 11 is that the first DC power supply 6-1 and the second DC power supply 6-2 are kept closed, and then the vacuum chamber is directed from the air inlet 7 to the vacuum chamber. The mixed gas of argon, acetylene and TMS or HMDSN is introduced into 9, and the air pressure of the vacuum chamber 9 is maintained at 0.1-5.0Pa; the bias value of the bias power supply 10 is adjusted to 50-10000V, and the duty ratio is 5-80%; Adjust the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2, and the deposition time of the DLC is 5-500min; wherein the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2 simultaneously turn on the DC terminal and The pulse terminal, the current of the DC terminal is 30-150A, the average current of the pulse terminal is 30-200A, the pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000μs; or only the DC terminal is turned on, the current of the DC terminal is 30-150A, complete the graphite cathode arc-enhanced glow discharge to prepare element-doped DLC. When the feed gas is argon, acetylene and TMS, what is prepared is Si-DLC, and when the feed gas is argon, acetylene and TMS, what is prepared is (Si, N)-DLC, and the others are related to Embodiments 5 to 9. one is the same.

Embodiment 11: The difference between this embodiment and Embodiments 5 to 11 is that the second DC power supply 6-2 is turned on, and then a mixed gas of argon and acetylene is introduced into the vacuum chamber 9 from the air inlet 7 , maintain the air pressure of the vacuum chamber 9 at 0.1-5.0Pa; adjust the bias value of the bias power supply 10 to 50-10000V, the duty cycle is 5-80%; adjust the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the deposition time of DLC is 5-500min; wherein the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2 turn on the DC terminal and the pulse terminal at the same time, the current of the DC terminal is 30-150A, and the average current of the pulse terminal is is 30-200A, the pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000μs; Miscellaneous forms of DLC. The material of the cathode 5-2 can be Cr, Ti, CrAl or TiAl, respectively preparing DLC doped with corresponding elements. Others are the same as those of Embodiments 5 to 11.

The following experiments were carried out for verifying the beneficial effects of the present invention:

Example 1

1. Cleaning the workpiece to be plated: the workpiece to be plated is placed in alcohol, ultrasonically cleaned for 10 minutes, taken out and dried with hot air, placed on the workpiece tray 16 of the turret 2 in the vacuum chamber 9, and then the vacuum chamber 9 is evacuated To the degree of vacuum less than 5×10 ^-3 Pa;

2. Carry out Ar ion bombardment cleaning on the workpiece to be plated: Ar gas is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is kept at 0.5Pa, the bias power supply 10 is connected to the turn frame 2, and the pulse bias value is set Set to -200V, the duty cycle is 75%; turn on the DC terminals of the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the current is set to 60A, and the first graphite cathode arc 1-1 and the second high pulse power supply 4-2 are turned on. Between the first anodes 3-1, a discharge circuit is established between the second graphite cathode arc 1-2 and the second anode 3-2; the workpiece cleaning time is 40min;

3. Deposition of transition layer: Ar is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is maintained at 0.4Pa; the bias value of the bias power supply 10 is maintained at -200V; the first DC power supply 6-1 is turned on And the second DC power supply 6-2, the discharge current is DC 80A between the first metal cathode 5-1 and the vacuum chamber 9, between the second metal cathode 5-2 and the vacuum chamber 9 to establish a discharge, the deposition time is 15min , prepare the Cr transition layer; then turn off Ar, and at the same time pass N ₂ into the vacuum chamber 9, the flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0Pa; The discharge current of the DC power source 6-1 and the second DC power source 6-2 is DC 80A, the deposition time is 30min, and the CrN transition layer is prepared; N ₂ and C ₂ H ₂ are introduced into the vacuum chamber 9, and the flow rates are respectively 125sccm and 35sccm, maintaining the air pressure of the vacuum chamber 9 to be 1.0Pa, maintaining the bias voltage value of the bias power supply 10 to be -70V, and maintaining the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 to be DC 80A, The deposition time is 20min, and the CrCN transition layer is prepared; C ₂ H ₂ is introduced into the vacuum chamber 9, the flow rate is 50 sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5Pa; The discharge current of the DC power supply 6-1 and the second DC power supply 6-2 is DC 70A, the deposition time is 15min, and the Cr-C transition layer is prepared; wherein the first metal cathode 5-1 and the second metal cathode 5-2 Both are Cr;

4. Preparation of DLC by graphite cathode arc enhanced glow discharge: turn off the first DC power supply 6-1 and the second DC power supply 6-2, pass argon and C ₂ H ₂ into the vacuum chamber 9, and the flow rates are 75sccm and 75sccm, respectively. 75sccm, maintain the air pressure of the vacuum chamber 9 at 0.3Pa; adjust the bias value of the bias power supply 10 to 200V, and the duty cycle is 75%; adjust the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the average current is 75A, the DC terminal current is 55A, the pulse terminal average current is 20A, the pulse terminal peak current is 500A, the frequency is 520Hz, and the pulse width is 150μs; the deposition time of DLC is 60min, and the graphite cathode arc enhanced glow discharge is completed to prepare DLC; Fig. 2 is the photo of graphite cathode arc enhanced glow discharge. The deposition rate of DLC under this process can reach 2.1 μm/h.

FIG. 3 is a graph of graphite cathode arc enhanced glow discharge (pulse current 500A), illustrating the relative positions of the cathode and the anode in this embodiment, and verifying the feasibility.

Fig. 4 is a waveform diagram of graphite cathode arc under different discharge currents: it shows that this technology can realize two discharge modes of DC discharge and pulse discharge.

Fig. 5 is a graph of graphite cathode arc enhanced glow discharge deposition of DLC: the workpieces to be plated in this embodiment are aluminum and steel respectively, wherein a is aluminum foil, b is high-speed steel, and this method can deposit DLC on solid workpieces.

Figure 6 is the XPS (C1s) test result of preparing DLC in Example 1. It can be seen from Figure 6 that only C-C bonds and C-O exist, and no other bonds (such as C-Cr) exist, indicating that the prepared ones are pure DLC. The generation of C-O here is generated by long-term placement in the air.

Example 2

1. Cleaning the workpiece to be plated: The workpiece to be plated (single crystal silicon) is placed in alcohol, ultrasonically cleaned for 10 minutes, taken out and dried with hot air, placed on the workpiece tray 16 of the turret 2 in the vacuum chamber 9, and then Evacuate the vacuum chamber 9 to a degree of vacuum less than 5×10 ^{- 3} Pa;

2. Carry out Ar ion bombardment cleaning on the workpiece to be plated: Ar gas is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is kept at 0.5Pa, the bias power supply 10 is connected to the turn frame 2, and the pulse bias value is set Set to -200V, the duty cycle is 75%; turn on the DC terminals of the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the current is set to 60A, and the first graphite cathode arc 1-1 and the second high pulse power supply 4-2 are turned on. Between the first anodes 3-1, a discharge circuit is established between the second graphite cathode arc 1-2 and the second anode 3-2; the workpiece cleaning time is 40min;

3. Deposition of transition layer: Ar is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is maintained at 0.4Pa; the bias value of the bias power supply 10 is maintained at -200V; the first DC power supply 6-1 is turned on And the second DC power supply 6-2, the discharge current is DC 80A between the first metal cathode 5-1 and the vacuum chamber 9, between the second metal cathode 5-2 and the vacuum chamber 9 to establish a discharge, the deposition time is 15min , prepare the Cr transition layer; then turn off Ar, and at the same time pass N ₂ into the vacuum chamber 9, the flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0Pa; The discharge current of the DC power source 6-1 and the second DC power source 6-2 is DC 80A, the deposition time is 30min, and the CrN transition layer is prepared; N ₂ and C ₂ H ₂ are introduced into the vacuum chamber 9, and the flow rates are respectively 125sccm and 35sccm, maintaining the air pressure of the vacuum chamber 9 to be 1.0Pa, maintaining the bias voltage value of the bias power supply 10 to be -70V, and maintaining the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 to be DC 80A, The deposition time is 20min, and the CrCN transition layer is prepared; C ₂ H ₂ is introduced into the vacuum chamber 9, the flow rate is 50 sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5Pa; The discharge current of the DC power supply 6-1 and the second DC power supply 6-2 is DC 70A, the deposition time is 15min, and the Cr-C transition layer is prepared; wherein the first metal cathode 5-1 and the second metal cathode 5-2 Both are Cr;

4. Preparation of DLC by graphite cathode arc enhanced glow discharge: turn off the first DC power supply 6-1 and the second DC power supply 6-2, and pass argon and C ₂ H ₂ into the vacuum chamber 9 with the flow rates of 100 sccm and 100 sccm, respectively. 100sccm, maintain the air pressure of the vacuum chamber 9 at 0.3Pa; adjust the bias value of the bias power supply 10 to 200V, and the duty cycle is 75%; adjust the first high pulse power supply (4-1) and the second high pulse power supply 4-2, The average current is 75A, the DC terminal current is 55A, the pulse terminal average current is 20A, the pulse terminal peak current is 500A, the frequency is 800Hz, and the pulse width is 95μs; the DLC deposition time is 30min, and the graphite cathode arc enhanced glow discharge is completed to prepare DLC ; The deposition rate of DLC under this process can reach 1.8 μm/h. Figure 7 is the surface morphology of the DLC film prepared in Example 2 under the scanning electron microscope; the surface of the prepared DLC is magnified by 1000 times the photo, and Figure 8 is the cross-sectional morphology of the DLC film prepared in Example 2 under the scanning electron microscope; The microstructure of the cross-section thin films was obtained, and the deposition rate was evaluated.

Example 3

1. Cleaning the workpiece to be plated: The workpiece to be plated (single crystal silicon) is placed in alcohol, ultrasonically cleaned for 10 minutes, taken out and dried with hot air, placed on the workpiece tray 16 of the turret 2 in the vacuum chamber 9, and then Evacuate the vacuum chamber 9 to a degree of vacuum less than 5×10 ^{- 3} Pa;

2. Carry out Ar ion bombardment cleaning on the workpiece to be plated: Ar gas is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is kept at 0.5Pa, the bias power supply 10 is connected to the turn frame 2, and the pulse bias value is set Set to -200V, the duty cycle is 75%; turn on the DC terminals of the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the current is set to 60A, and the first graphite cathode arc 1-1 and the second high pulse power supply 4-2 are turned on. Between the first anodes 3-1, a discharge circuit is established between the second graphite cathode arc 1-2 and the second anode 3-2; the workpiece cleaning time is 40min;

3. Deposition of transition layer: Ar is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is maintained at 0.4Pa; the bias value of the bias power supply 10 is maintained at -200V; the first DC power supply 6-1 is turned on And the second DC power supply 6-2, the discharge current is DC 80A between the first metal cathode 5-1 and the vacuum chamber 9, between the second metal cathode 5-2 and the vacuum chamber 9 to establish a discharge, the deposition time is 15min , prepare the Cr transition layer; then turn off Ar, and at the same time pass N ₂ into the vacuum chamber 9, the flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0Pa; The discharge current of the DC power source 6-1 and the second DC power source 6-2 is DC 80A, the deposition time is 30min, and the CrN transition layer is prepared; N ₂ and C ₂ H ₂ are introduced into the vacuum chamber 9, and the flow rates are respectively 125sccm and 35sccm, maintaining the air pressure of the vacuum chamber 9 to be 1.0Pa, maintaining the bias voltage value of the bias power supply 10 to be -70V, and maintaining the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 to be DC 80A, The deposition time is 20min, and the CrCN transition layer is prepared; C ₂ H ₂ is introduced into the vacuum chamber 9, the flow rate is 50 sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5Pa; The discharge current of the DC power supply 6-1 and the second DC power supply 6-2 is DC 70A, the deposition time is 15min, and the Cr-C transition layer is prepared; wherein the first metal cathode 5-1 and the second metal cathode 5-2 Both are Cr;

4. Preparation of DLC by graphite cathode arc enhanced glow discharge: turn off the first DC power supply 6-1 and the second DC power supply 6-2, pass argon and C ₂ H ₂ into the vacuum chamber 9, and the flow rates are 75sccm and 75sccm, respectively. 75sccm, maintain the air pressure of vacuum chamber 9 at 0.3Pa; adjust the bias value of the bias power supply to 200V, and the duty cycle is 75%; adjust the first high pulse power supply 4-1 and the second high pulse power supply 4-2, DC terminal current At 75A, the pulse end was closed, the deposition time of DLC was 45min, and the preparation of DLC by graphite cathode arc enhanced glow discharge was completed; the deposition rate of DLC under this process could reach 3.8 μm/h.

FIG. 9 is the cross-sectional morphology of the DLC film prepared in Example 3 under the scanning electron microscope; the microstructure of the cross-sectional film can be seen, and the deposition rate is calculated.

Example 4

1. Cleaning the workpiece to be plated: The workpiece to be plated (single crystal silicon) is placed in alcohol, ultrasonically cleaned for 10 minutes, taken out and dried with hot air, placed on the workpiece tray 16 of the turret 2 in the vacuum chamber 9, and then Evacuate the vacuum chamber 9 to a degree of vacuum less than 5×10 ^{- 3} Pa;

2. Carry out Ar ion bombardment cleaning on the workpiece to be plated: Ar gas is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is kept at 0.5Pa, the bias power supply 10 is connected to the turn frame 2, and the pulse bias value is set Set to -200V, the duty cycle is 75%; turn on the DC terminals of the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the current is set to 60A, and the first graphite cathode arc 1-1 and the second high pulse power supply 4-2 are turned on. Between the first anodes 3-1, a discharge circuit is established between the second graphite cathode arc 1-2 and the second anode 3-2; the workpiece cleaning time is 40min;

3. Deposition of transition layer: Ar is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is maintained at 0.4Pa; the bias value of the bias power supply 10 is maintained at -200V; the first DC power supply 6-1 is turned on And the second DC power supply 6-2, the discharge current is DC 80A between the first metal cathode 5-1 and the vacuum chamber 9, between the second metal cathode 5-2 and the vacuum chamber 9 to establish a discharge, the deposition time is 15min , prepare the Cr transition layer; then turn off Ar, and at the same time pass N ₂ into the vacuum chamber 9, the flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0Pa; The discharge current of the DC power source 6-1 and the second DC power source 6-2 is DC 80A, the deposition time is 30min, and the CrN transition layer is prepared; N ₂ and C ₂ H ₂ are introduced into the vacuum chamber 9, and the flow rates are respectively 125sccm and 35sccm, maintaining the air pressure of the vacuum chamber 9 to be 1.0Pa, maintaining the bias voltage value of the bias power supply 10 to be -70V, and maintaining the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 to be DC 80A, The deposition time is 20min, and the CrCN transition layer is prepared; C ₂ H ₂ is introduced into the vacuum chamber 9, the flow rate is 50 sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5Pa; The discharge current of the DC power supply 6-1 and the second DC power supply 6-2 is DC 70A, the deposition time is 15min, and the Cr-C transition layer is prepared; wherein the first metal cathode 5-1 and the second metal cathode 5-2 Both are Cr;

4. Preparation of DLC by graphite cathode arc enhanced glow discharge: turn off the first DC power supply 6-1 and the second DC power supply 6-2, and pass argon and C ₂ H ₂ into the vacuum chamber 9 with the flow rates of 100 sccm and 100 sccm, respectively. 100sccm, maintain the air pressure of the vacuum chamber 9 at 0.3Pa; adjust the bias value of the bias power supply 10 to 200V, and the duty cycle is 75%; adjust the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the average current is 75A, the DC terminal current is 55A, the pulse terminal average current is 20A, the pulse terminal peak current is 500A, the frequency is 260Hz, and the pulse width is 260μs; the deposition time of DLC is 60min, and the graphite cathode arc enhanced glow discharge is completed to prepare DLC; this The deposition rate of DLC under the process can reach 2.7 μm/h.

Example 5

1. Cleaning the workpiece to be plated: The workpiece to be plated (single crystal silicon) is placed in alcohol, ultrasonically cleaned for 10 minutes, taken out and dried with hot air, placed on the workpiece tray 16 of the turret 2 in the vacuum chamber 9, and then Evacuate the vacuum chamber 9 to a degree of vacuum less than 5×10 ^{- 3} Pa;

2. Carry out Ar ion bombardment cleaning on the workpiece to be plated: Ar gas is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is kept at 0.5Pa, the bias power supply 10 is connected to the turn frame 2, and the pulse bias value is set Set to -200V, the duty cycle is 75%; turn on the DC terminals of the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the current is set to 60A, and the first graphite cathode arc 1-1 and the second high pulse power supply 4-2 are turned on. Between the first anodes 3-1, a discharge circuit is established between the second graphite cathode arc 1-2 and the second anode 3-2; the workpiece cleaning time is 40min;

3. Deposition of transition layer: Turn off the first high pulse power supply 4-1 and the second high pulse power supply 4-2, then pass Ar into the vacuum chamber 9, the flow rate is 300sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.4Pa; The bias value of the piezoelectric power supply 10 is -200V; the first DC power supply 6-1 and the second DC power supply 6-2 are turned on, and the discharge current is DC 80A, between the first metal cathode 5-1 and the vacuum chamber 9, A discharge is established between the second metal cathode 5-2 and the vacuum chamber 9, and the deposition time is 15 minutes to prepare a Cr transition layer; then Ar is turned off, and N ₂ is introduced into the vacuum chamber 9 at a flow rate of 125 sccm to maintain the vacuum chamber 9 The air pressure is 1.0Pa; the bias value of the bias power supply 10 is adjusted to -70V, the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 is kept at DC 80A, the deposition time is 30min, and the CrN transition is prepared. layer; feed N ₂ and C ₂ H ₂ into the vacuum chamber 9, the flow rates are 125sccm and 35sccm respectively, the air pressure of the vacuum chamber 9 is maintained at 1.0Pa, the bias value of the bias power supply 10 is maintained at -70V, and the first The discharge current of the DC power supply 6-1 and the second DC power supply 6-2 is DC 80A, the deposition time is 20min, and the CrCN transition layer is prepared; C ₂ H ₂ is introduced into the vacuum chamber 9, and the flow rate is 50 sccm, and the vacuum chamber is maintained. 9. The air pressure is 0.5Pa; the bias value of the bias power supply 10 is adjusted to -150V, the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 is adjusted to be DC 70A, and the deposition time is 15min to prepare Cr -C transition layer; wherein the first metal cathode 5-1 and the second metal cathode 5-2 are both Cr;

4. Preparation of DLC by graphite cathode arc enhanced glow discharge: Pour argon gas and C ₂ H ₂ into the vacuum chamber 9, the flow rates are 75 sccm and 75 sccm, maintain the air pressure at 0.5 Pa, and adjust the bias value of the bias power supply 10 to 200V, duty cycle 75%; turn on the DC terminals of the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the DC terminal current is 75A, and the first graphite cathode arc 1-1 and the first anode 3 Between -1, a discharge loop is established between the second graphite cathode arc 1-2 and the second anode 3-2; the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 is adjusted to 65A, and the Preparation of metal-doped DLC, the deposition time of Cr-DLC is 60min, and the preparation of DLC by graphite cathode arc enhanced glow discharge is completed;

FIG. 10 is the Raman spectrum of the DLC film prepared in this example and the fitting peak splitting result. This result shows a typical Raman peak of a DLC film, and the sub-peak result shows an ID/ _IG result of _0.55 . It is illustrated that the method of this embodiment can also be used to deposit doped DLC.

Example 6

1. Cleaning the workpiece to be plated: The workpiece to be plated (single crystal silicon) is placed in alcohol, ultrasonically cleaned for 10 minutes, taken out and dried with hot air, placed on the workpiece tray 16 of the turret 2 in the vacuum chamber 9, and then Evacuate the vacuum chamber 9 to a degree of vacuum less than 5×10 ^{- 3} Pa;

2. Carry out Ar ion bombardment cleaning on the workpiece to be plated: Ar gas is introduced into the vacuum chamber 9, the flow rate is 300sccm, the air pressure of the vacuum chamber 9 is kept at 0.5Pa, the bias power supply 10 is connected to the turn frame 2, and the pulse bias value is set Set to -200V, the duty cycle is 75%; turn on the DC terminals of the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the current is set to 60A, and the first graphite cathode arc 1-1 and the second high pulse power supply 4-2 are turned on. Between the first anodes 3-1, a discharge circuit is established between the second graphite cathode arc 1-2 and the second anode 3-2; the workpiece cleaning time is 40min;

3. Deposition of transition layer: Turn off the first high pulse power supply 4-1 and the second high pulse power supply 4-2, then pass Ar into the vacuum chamber 9, the flow rate is 300sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.4Pa; The bias value of the piezoelectric power supply 10 is -200V; the first DC power supply 6-1 and the second DC power supply 6-2 are turned on, and the discharge current is DC 80A, between the first metal cathode 5-1 and the vacuum chamber 9, A discharge is established between the second metal cathode 5-2 and the vacuum chamber 9, and the deposition time is 15 minutes to prepare a Cr transition layer; then Ar is turned off, and N ₂ is introduced into the vacuum chamber 9 at a flow rate of 125 sccm to maintain the vacuum chamber 9 The air pressure is 1.0Pa; the bias value of the bias power supply 10 is adjusted to -70V, the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 is kept at DC 80A, the deposition time is 30min, and the CrN transition is prepared. layer; feed N ₂ and C ₂ H ₂ into the vacuum chamber 9, the flow rates are 125sccm and 35sccm respectively, the air pressure of the vacuum chamber 9 is maintained at 1.0Pa, the bias value of the bias power supply 10 is maintained at -70V, and the first The discharge current of the DC power supply 6-1 and the second DC power supply 6-2 is DC 80A, the deposition time is 20min, and the CrCN transition layer is prepared; C ₂ H ₂ is introduced into the vacuum chamber 9, and the flow rate is 50 sccm, and the vacuum chamber is maintained. 9. The air pressure is 0.5Pa; the bias value of the bias power supply 10 is adjusted to -150V, the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 is adjusted to be DC 70A, and the deposition time is 15min to prepare Cr -C transition layer; wherein the first metal cathode 5-1 and the second metal cathode 5-2 are both AlCr;

4. Preparation of DLC by graphite cathode arc enhanced glow discharge: Pour argon gas and C ₂ H ₂ into the vacuum chamber 9, the flow rates are 75 sccm and 75 sccm, maintain the air pressure at 0.5 Pa, and adjust the bias value of the bias power supply 10 to 200V, duty cycle 75%; turn on the DC terminals of the first high pulse power supply 4-1 and the second high pulse power supply 4-2, the DC terminal current is 75A, and the first graphite cathode arc 1-1 and the first anode 3 Between -1, a discharge loop is established between the second graphite cathode arc 1-2 and the second anode 3-2; the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 is adjusted to 65A, and the For the preparation of metal-doped DLC, the deposition time of Cr-DLC was 60 min, and the DLC was prepared by graphite cathode arc enhanced glow discharge.

The graphite cathode arc enhanced glow discharge deposition DLC device used in Examples 1-6 includes a vacuum chamber 9, a turret 2, a bias power supply 10, a first graphite cathode arc 1-1, a second graphite cathode arc 1-2, The first metal cathode 5-1, the second metal cathode 5-2, the first anode 3-1, the second anode 3-2, the first high-pulse power supply 4-1, the second high-pulse power supply 4-2, the first The DC power supply 6-1 and the second DC power supply 6-2; the bottom of the vacuum chamber 9 is provided with an air inlet 7; Four flanges are evenly arranged on the wall of the vacuum chamber 9, and the four flanges are respectively fixedly connected to the first graphite cathode arc 1-1, the first metal cathode 5-1, the second graphite cathode arc 1-2 and the second metal cathode. Cathode 5-2; a baffle 8 is provided between the first graphite cathode arc 1-1 and the second graphite cathode arc 1-2 and the turret 2, and there are gaps between the two ends of the baffle 8 and the inner wall of the vacuum chamber 9; A graphite cathode arc 1-1 and a second graphite cathode arc 1-2 are arranged oppositely, the first metal cathode 5-1 and the second metal cathode 5-2 are arranged oppositely; the first graphite cathode arc 1-1 and the first A first anode 3-1 is arranged between the metal cathodes 5-1, a second anode 3-2 is arranged between the second graphite cathode arc 1-2 and the second metal cathode 5-2; the first anode 3-1 and The second anode 3-2 is composed of a base and an anode body, the anode body is fixedly connected to the base, the vacuum chamber 9 has an anode through hole, the anode base is inserted into the vacuum chamber 9 through the anode through hole, and the anode body Located inside the vacuum chamber 9; the first high pulse power supply 4-1, the second graphite cathode arc 1-2 and the second anode 3-2 are connected between the first graphite cathode arc 1-1 and the first anode 3-1. A second high pulse power supply 4-2 is connected intermittently; a first DC power supply 6-1 is connected between the first metal cathode 5-1 and the vacuum chamber 9, and a second metal cathode 5-2 is connected to the vacuum chamber 9. There is a second DC power supply 6-2; a bias power supply 10 is connected between the turret 2 and the vacuum chamber 9. In this embodiment, two air inlets 7 are opened, and the nozzle of the air inlet pipe of one of the air inlets 7 is located between the first graphite cathode arc 1-1 and the first anode 3-1, and the nozzle is connected to the first graphite cathode arc 1-1 and the first anode 3-1. The distance of the cathode arc 1-1 is 5-18cm; the nozzle of the air inlet pipe of the other air inlet 7 is located between the second graphite cathode arc 1-2 and the second anode 3-2, and the nozzle is connected to the second graphite cathode The distance of arcs 1-2 is 5-18 cm.

The turret 2 is a planetary turret, and the planetary turret includes a rotating shaft 11, a chain tray 12, a chain 13, a gear 14, a turntable 15, a rotating rod 17, a workpiece tray 16, a polytetrafluoroethylene insulating sleeve 18 and a polytetrafluoroethylene Vinyl spacer 19, chain tray 12 is fixed on the bottom of vacuum chamber 9, chain 13 is fixed on the upper surface of chain tray 12, and the top of rotating shaft 11 is provided with a turntable; rotating rod 17 is connected with the rotating disk 15 through bearings, and the bottom end of rotating rod 17 is provided with Gear 14, gear 14 meshes with chain 13, workpiece tray 16 is sleeved on rotating rod 17;

In the comparative example, the gas pressure was maintained at 0.5Pa by feeding Ar, the Cr arc current was 70A, the bias power supply voltage and duty ratio were adjusted to 950V and 75%, respectively, and the cleaning time was 10min, and metal ion cleaning was performed; Maintained at 0.5Pa, the graphite cathode arc was fixed at 60A, at the same time, the front-end baffle of the graphite arc was closed, the bias power supply was set to -200V, and the duration was 15min, and Ar ion cleaning was performed; Fix 80A, set the bias power supply to -200V, last for 15min, deposit a Cr transition layer; pass N2 to stabilize the air pressure at 1.0Pa, fix the Cr arc at 80A, set the bias power supply to -70V, last for 45min, deposit CrN transition layer; a mixed gas of _N2 and acetylene was introduced, the Cr arc was fixed at 80A, the flow ratio was _N2 :C2H2=100: ₁₅ (sccm), the air pressure was 1.0Pa, the bias power was set to -70V, and the deposition was performed. Time 20min, deposit CrCN transition layer; use Cr cathode arc to enhance glow discharge to prepare DLC, pass argon and acetylene gas mixture, the flow ratio is Ar:C2H2=75:100 (sccm), Cr cathode arc, the current is DC 55A , the average current of the composite pulse terminal is 20A, the pulse frequency is 200Hz, the frequency is 320μs, the pulse current is 300A, the air pressure is 0.5Pa, the bias power supply is set to -150V, and the deposition time is 30min.

Figure 11 is the EDS test picture of the DLC of this embodiment; Figure 12 is the EDS composition analysis result of this embodiment; the surface element ratio of DLC prepared by Cr cathode arc enhanced glow discharge is shown in Table 1.

Table 1

It can be seen that there is Cr in the DLC prepared by Cr cathode arc enhanced glow discharge, resulting in the pollution of element Cr.

Claims (10)

1. A graphite cathode arc enhanced glow discharge deposition pure DLC device is characterized by comprising a vacuum chamber (9), a rotating frame (2), a bias power supply (10), a first graphite cathode arc (1-1), a second graphite cathode arc (1-2), a first metal cathode (5-1), a second metal cathode (5-2), a first anode (3-1), a second anode (3-2), a first high-pulse power supply (4-1), a second high-pulse power supply (4-2), a first direct current power supply (6-1) and a second direct current power supply (6-2); the bottom of the vacuum chamber (9) is provided with an air inlet (7); the rotating frame (2) is positioned at the center of a circle at the bottom of the vacuum chamber (9), the rotating frame (2) is rotatably connected with the vacuum chamber (9), four flanges are uniformly arranged on the wall of the vacuum chamber (9) along the circumferential direction, and the four flanges are respectively and fixedly connected with a first graphite cathode arc (1-1), a first metal cathode (5-1), a second graphite cathode arc (1-2) and a second metal cathode (5-2); baffles (8) are arranged between the first graphite cathode arc (1-1) and the second graphite cathode arc (1-2) and the rotating frame (2), and gaps are reserved between the two ends of the baffles (8) and the inner wall of the vacuum chamber (9); the first graphite cathode arc (1-1) and the second graphite cathode arc (1-2) are oppositely arranged, and the first metal cathode (5-1) and the second metal cathode (5-2) are oppositely arranged; a first anode (3-1) is arranged between the first graphite cathode arc (1-1) and the first metal cathode (5-1), and a second anode (3-2) is arranged between the second graphite cathode arc (1-2) and the second metal cathode (5-2); the first anode (3-1) and the second anode (3-2) are both composed of a base and an anode body, the anode body is fixedly connected with the base, an anode through hole is formed in the vacuum chamber (9), the anode base is inserted in the vacuum chamber (9) through the anode through hole, and the anode body is positioned in the vacuum chamber (9); a first high pulse power supply (4-1) is connected between the first graphite cathode arc (1-1) and the first anode (3-1), and a second high pulse power supply (4-2) is connected between the second graphite cathode arc (1-2) and the second anode (3-2); a first direct current power supply (6-1) is connected between the first metal cathode (5-1) and the vacuum chamber (9), and a second direct current power supply (6-2) is connected between the second metal cathode (5-2) and the vacuum chamber (9); a bias power supply (10) is connected between the rotating frame (2) and the vacuum chamber (9).

2. The apparatus for deposition of pure DLC by graphite cathodic arc enhanced glow discharge according to claim 1, characterized in that the turret (2), the first graphite cathodic arc (1-1), the second graphite cathodic arc (1-2), the first metal cathode (5-1), the second metal cathode (5-2), the first anode (3-1), the second anode (3-2), the baffle (8) are all insulated from the vacuum chamber (9).

3. The device for graphite cathodic arc enhanced glow discharge deposition of pure DLC as claimed in claim 1 wherein the electrical connection of the first anode (3-1) is electrically connected to the positive electrode of the first high pulse power supply (4-1) and the negative electrode of the first high pulse power supply (4-1) is electrically connected to the electrical connection of the first graphite cathodic arc (1-1); the electric connection end of the second anode (3-2) is electrically connected with the anode of the second high pulse power supply (4-2), and the cathode of the second high pulse power supply (4-2) is electrically connected with the electric connection end of the second graphite cathode arc (2-2).

4. The apparatus for deposition of pure DLC by graphite cathodic arc enhanced glow discharge as claimed in claim 1 wherein the electrical connection of the first metal cathode (5-1) is electrically connected to the negative terminal of the first DC power supply (6-1), the electrical connection of the second metal cathode (5-2) is electrically connected to the negative terminal of the second DC power supply (6-2), the negative terminal of the bias power supply (10) is electrically connected to the electrical connection of the turret (2), the electrical connection of the vacuum chamber (9) is electrically connected to the positive terminal of the first DC power supply (6-1), the positive terminal of the second DC power supply (6-2), the positive terminal of the bias power supply (10), and the vacuum chamber (9) is grounded.

5. Method for graphite cathodic arc enhanced glow discharge deposition of pure DLC using the apparatus according to claim 1, characterized in that the method comprises the steps of: firstly, ultrasonically cleaning a workpiece to be plated by using alcohol, taking out and drying; then placing on a rotating frame (2) in a vacuum chamber (9), and pumping the vacuum chamber (9) to a vacuum degree of less than 5 x 10^-3Pa; secondly, performing Ar ion bombardment cleaning on the workpiece to be plated: introducing Ar gas into the vacuum chamber (9) from the gas inlet (7) to keep the air pressure of the vacuum chamber (9) at 0.3-1.0Pa, then starting the bias power supply (10), adjusting the bias value to-150 to-500V, and adjusting the duty ratio to 10-80%; starting a first high pulse power supply (4-1) and a second high pulse power supply (4-2), and cleaning the workpiece for 5-100min to obtain a cleaned workpiece to be plated; wherein the first high pulse power supply (4-1) and the second high pulse power supply (4-2) simultaneously start a direct current end and a pulse end, the current of the direct current end is 30-150A, the average current of the pulse end is 30-200A, the pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000 mus; or only starting the direct current end, wherein the current of the direct current end is 30-150A;

thirdly, depositing a transition layer on the cleaned workpiece to be plated; wherein the transition layer is Cr/CrN/CrCN/Cr-C, Ti/TiN/TiCN/Ti-C, Ti/TiAlN, Cr/CrAlN or Si/Si-DLC;

fourthly, preparing pure DLC by graphite cathode arc enhanced glow discharge: keeping the first direct current power supply (6-1) and the second direct current power supply (6-2) closed, then introducing argon and carbon-containing precursor gas into the vacuum chamber (9) from the gas inlet (7), and maintaining the pressure of the vacuum chamber (9) at 0.1-5.0 Pa; adjusting the bias voltage value of a bias voltage power supply (10) to be 50-10000V, and the duty ratio to be 5-80%; adjusting the deposition time of DLC for 5-500min by the first high pulse power supply (4-1) and the second high pulse power supply (4-2); wherein the first high pulse power supply (4-1) and the second high pulse power supply (4-2) simultaneously start a direct current end and a pulse end, the current of the direct current end is 30-150A, the average current of the pulse end is 30-200A, the pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000 mus; or only starting the direct current end, wherein the current of the direct current end is 30-150A;

wherein the carbon-containing precursor gas is CH₄、C₂H₂And C₆H₆In any ratio.

6. The method for depositing pure DLC by graphite cathode arc enhanced glow discharge as claimed in claim 5, wherein the transition layer in step three is Cr/CrN/CrCN/Cr-C, and the deposition method comprises: closing the first high pulse power supply (4-1) and the second high pulse power supply (4-2), introducing Ar into the vacuum chamber (9) at a flow rate of 100-500sccm, maintaining the air pressure of the vacuum chamber (9) at 0.2-4.0Pa, opening the first direct current power supply (6-1) and the second direct current power supply (6-2), adjusting the bias voltage value of the bias voltage power supply (10) to be-30-300V, and the deposition time to be 10-60min to prepare a Cr transition layer; then, the Ar gas is closed, and N is introduced into the vacuum chamber (9)₂The flow rate is 100-500sccm, the pressure in the vacuum chamber (9) is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and a CrN transition layer is prepared; then introducing C into the vacuum chamber (9)₂H₂The flow rate is 100-500sccm, the air pressure of the vacuum chamber (9) is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and a CrCN transition layer is prepared; then N is turned off₂Introducing Ar into the vacuum chamber (9) at a flow rate of 100-500sccm, maintaining the pressure of the vacuum chamber (9) at 0.2-4.0Pa, and depositing for 10-60min to prepare a Cr-C transition layer; wherein, the first metal cathode (5-1) and the second metal cathode (5-2) are both Cr.

7. The method for depositing pure DLC by graphite cathode arc enhanced glow discharge according to claim 5, wherein when the transition layer in step three is Ti/TiN/TiCN/Ti-C, the deposition method is as follows: closing the first high pulse power supply (4-1) and the second high pulse power supply (4-2), introducing Ar into the vacuum chamber (9) with a flow rate of 100-0) The bias voltage value is-30V to-300V, the deposition time is 10min to 60min, and a Ti transition layer is prepared; then, the Ar gas is closed, and N is introduced into the vacuum chamber (9)₂The flow rate is 100-500sccm, the air pressure of the vacuum chamber (9) is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and the TiN transition layer is prepared; then introducing C into the vacuum chamber (9)₂H₂The flow rate is 100-500sccm, the air pressure of the vacuum chamber (9) is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and a TiCN transition layer is prepared; then N is turned off₂Introducing Ar into the vacuum chamber (9) at a flow rate of 100-500sccm, maintaining the pressure of the vacuum chamber (9) at 0.2-4.0Pa, and depositing for 10-60min to prepare a Ti-C transition layer; wherein, the first metal cathode (5-1) and the second metal cathode (5-2) are both Ti.

8. The method for depositing pure DLC by graphite cathodic arc enhanced glow discharge as claimed in claim 5, wherein when the transition layer in step three is Ti/TiAlN, the deposition method is as follows: closing the first high pulse power supply (4-1) and the second high pulse power supply (4-2), introducing Ar into the vacuum chamber (9) at a flow rate of 100-500sccm, maintaining the air pressure of the vacuum chamber (9) at 0.2-4.0Pa, starting the first direct current power supply (6-1), adjusting the bias voltage value of the bias voltage power supply (10) to-30-300V and the deposition time to 10-60min, and preparing a Ti transition layer; then, the Ar gas and the first direct current power supply (6-1) are closed, the second direct current power supply (6-2) is opened, and N is introduced into the vacuum chamber (9) at the same time₂The flow rate is 100-500sccm, the air pressure of the vacuum chamber (9) is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and the TiAlN transition layer is prepared; the first metal cathode (5-1) is Ti, and the second metal cathode (5-2) is TiAl.

9. The method for depositing pure DLC by graphite cathode arc enhanced glow discharge according to claim 5, wherein when the transition layer in the third step is Cr/CrAlN, the deposition method comprises: closing the first high pulse power supply (4-1) and the second high pulse power supply (4-2), introducing Ar into the vacuum chamber (9) at a flow rate of 100-500sccm, maintaining the air pressure of the vacuum chamber (9) at 0.2-4.0Pa, turning on the first DC power supply (6-1), wherein the discharge current is DC 30-200A, the bias voltage value of the bias power supply (10) is adjusted to-30-300V, and the deposition time is 10Preparing a Cr transition layer after 60 min; then, the Ar gas and the first direct current power supply (6-1) are closed, the second direct current power supply (6-2) is started, and N is introduced into the vacuum chamber (9) at the same time₂The flow rate is 100-500sccm, the air pressure of the vacuum chamber (9) is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and a CrAlN transition layer is prepared; the first metal cathode (5-1) is Cr, and the second metal cathode (5-2) is CrAl.

10. The method for depositing pure DLC by graphite cathodic arc enhanced glow discharge as claimed in claim 5, wherein when the transition layer in step three is Si/Si-DLC, the deposition method is as follows: ar and SiH are introduced into a vacuum chamber (9)₄The flow rate is 100-500sccm, the air pressure of the vacuum chamber (9) is maintained at 0.2-4.0Pa, the first high pulse power supply (4-1) and the second high pulse power supply (4-2) are kept on, the bias voltage value of the bias voltage power supply (10) is adjusted to-30-300V, the deposition time is 10-60min, and the Si transition layer is prepared; continuously introducing C into the vacuum chamber (9)₂H₂Gas with the flow rate of 100-500sccm, the pressure of 0.2-4.0Pa and the deposition time of 10-60min are maintained, and a Si-DLC transition layer is prepared; wherein the first high pulse power supply (4-1) and the second high pulse power supply (4-2) simultaneously start a direct current end and a pulse end, the current of the direct current end is 30-150A, the average current of the pulse end is 30-200A, the pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000 mus; or only the direct current end is switched on, and the current at the direct current end is 30-150A.

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