CN111748789B

CN111748789B - Device and method for depositing pure DLC (Diamond like carbon) by enhancing glow discharge through graphite cathode arc

Info

Publication number: CN111748789B
Application number: CN202010663232.0A
Authority: CN
Inventors: 田修波; 胡健; 巩春志
Original assignee: Harbin Institute of Technology
Current assignee: Harbin Institute of Technology
Priority date: 2020-07-10
Filing date: 2020-07-10
Publication date: 2022-06-24
Anticipated expiration: 2040-07-10
Also published as: CN111748789A

Abstract

The invention relates to a device and a method for depositing pure DLC by enhancing glow discharge of graphite cathodic arc. The invention aims to solve the problem of pollution of metal elements to DLC (diamond-like carbon) during the preparation of DLC by the conventional metal cathodic arc enhanced glow discharge. The ratio of ions to atoms in the 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 adverse effect of metal doping on tribological performance when the metal target enhances glow discharge to prepare DLC. The method is applied to the field of preparing DLC by plasma enhanced chemical vapor deposition.

Description

Device and method for depositing pure DLC (Diamond like carbon) by enhancing glow discharge through graphite cathode arc

Technical Field

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

Background

DLC (Diamond-like carbon) films are widely used because of their low coefficient of friction, high hardness, good wear resistance and their chemical inertness, such as automotive parts, ship hull resistance to seawater corrosion and processing of aluminum alloys.

DLC methods are numerous and are mainly based on plasma chemical vapor deposition (PECVD). The most industrially used is the method of self-glow discharge of the workpiece. The method is to use the workpiece itself as a discharge source, and apply medium and high frequency bias voltage on the workpiece, wherein the magnitude of the bias voltage is generally higher than-300V. This method has the following problems: 1. the influence of the shape of the workpiece and the charging amount is great, and if the workpiece changes, the process needs to be readjusted; 2. the intensity of glow discharge mainly depends on the magnitude of bias voltage, so that the structure and the performance of the film cannot be flexibly regulated and controlled; 3. the working air pressure is generally very high, and the treatment of the workpiece with holes is difficult; 4. the deposition rate is low, generally less than 1.5 mu m/h;

the anode layer ion source proposed by AE company decouples ionization and bias voltage, but due to the working characteristics of the ion source, the ion source is easy to ignite during film coating, so that the film coating process is unstable, even impurities generated by ignition are easy to enter a film, the film quality is influenced, and meanwhile, the deposition rate of the technology is lower;

DLC is deposited using microwave discharge, and the deposition rate of DLC can be as high as 15 μm/h under microwave-excited high-density plasma. But the process safety of the microwave is not easy to control, and the equipment is complex, the process window is narrow and the manufacturing cost is expensive;

the deposition rate of DLC prepared by the cage-type hollow cathode can reach 6 μm/h. But because the workpiece is sealed inside the cage net, the design of the bottom layer and the preparation of the metal-doped DLC are difficult to carry out, so that the requirements of some working conditions are difficult to meet;

a large amount of electrons can be generated in the working process of the cathode arc, and the electrons can be led out from the vicinity of the target through the external anode to ionize the gas in the vacuum chamber, so that the intensity of gas glow discharge is improved, and high-density plasma is generated. The method of arc enhanced glow discharge is utilized to improve the ionization rate of Ar gas, thereby having good effect in the Ar ion etching process before film coating and improving the binding force between the film and the substrate.

However, when acetylene is ionized to prepare DLC by a conventional metal arc enhanced glow discharge method, in the process that electrons are led out by an anode, metal ions are drawn out along with the electrons and deposited on the surface of a film to form the DLC doped with elements, and the DLC has adverse effect on the tribological performance of DLC in application;

disclosure of Invention

The invention aims to solve the problem of pollution of metal elements to DLC when DLC is prepared by the conventional metal cathodic arc enhanced glow discharge, and provides a device and a method for depositing pure DLC by graphite cathodic arc enhanced glow discharge.

The invention relates to a device for depositing pure DLC by graphite cathode arc enhanced glow discharge, which comprises a vacuum chamber, a rotating frame, a bias power supply, a first graphite cathode arc, a second graphite cathode arc, a first metal cathode, a second metal cathode, a first anode, a second anode, a first high-pulse power supply, a second high-pulse power supply, a first direct-current power supply and a second direct-current power supply, wherein the vacuum chamber is provided with a vacuum chamber; the bottom of the vacuum chamber is provided with an air inlet; the rotating frame is positioned at the center of a circle at the bottom of the vacuum chamber, the rotating frame is rotationally connected with the vacuum chamber, four flanges are uniformly arranged on the wall of the vacuum chamber along the circumferential direction, and the four flanges are respectively and fixedly connected with a first graphite cathode arc, a first metal cathode, a second graphite cathode arc and a second metal cathode; baffles are arranged between the first graphite cathode arc and the rotating frame and between the second graphite cathode arc and the rotating frame, and gaps are reserved between the two ends of each baffle and the inner wall of the vacuum chamber; the first graphite cathode arc and the second graphite cathode arc are oppositely arranged, and the first metal cathode and the second metal cathode are oppositely arranged; a first anode is arranged between the first graphite cathode arc and the first metal cathode, and a 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 with the base, an anode through hole is formed in the vacuum chamber, the anode base is inserted into the vacuum chamber through the anode through hole, and the anode body is positioned 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; a first direct current power supply is connected between the first metal cathode and the vacuum chamber, and a second direct current power supply is connected between the second metal cathode and the vacuum chamber; a bias power supply is connected between the rotating frame and the vacuum chamber.

The invention relates to a method for depositing pure DLC by graphite cathode arc enhanced glow discharge, which comprises the following steps: firstly, ultrasonically cleaning a workpiece to be plated by using alcohol, taking out and drying; then placing on a rotating frame in a vacuum chamber, and pumping the vacuum chamber to a vacuum degree of less than 5 × 10^-3Pa; secondly, performing Ar ion bombardment cleaning on the workpiece to be plated: introducing Ar gas into the vacuum chamber from the gas inlet to keep the pressure of the vacuum chamber at 0.3-1.0Pa, then starting a bias power supply, adjusting the bias value to-150-500V, and adjusting the duty ratio to 10-80%; adjusting the high-pulse power supply, the current at the direct current end is 30-150A, the average current at the pulse end is 30-200A,

pulse discharge current 50-5000A, frequency 10-20000Hz, pulse width 5-1000 mus, or opening DC end only, discharge current 30-150A, workpiece cleaning time 5-100min to obtain cleaned workpiece to be plated;

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: introducing argon and carbon-containing precursor gas into the vacuum chamber from the gas inlet, and maintaining the pressure of the vacuum chamber at 0.1-5.0 Pa; adjusting the bias voltage value of the bias voltage power supply to 50-10000V, and the duty ratio to 5-80%; adjusting the average current of high-pulse power supply to 30-200A, the pulse discharge current to 50-50000A, the frequency to 10-20000Hz, the pulse width to 5-1000 mus, and the deposition time of DLC to 5-500 min; wherein the carbon-containing precursor gas is CH₄、C₂H₂And C₆H₆One or more of them are mixed according to any ratio;

the technical scheme of the invention has the following advantages:

the method for depositing pure DLC by graphite cathode arc enhanced glow discharge solves the problem of pollution of DLC caused by metal elements in the conventional preparation of DLC by metal cathode arc enhanced glow discharge. Meanwhile, the decoupling of a bias source and an ionization source is realized, namely, the ionization process of the carbon-containing gas and the energy of incident ions deposited on a workpiece can be respectively and independently controlled, so that the components and the performance of a film in the deposition process are easier to adjust, and a process window is widened; the discharge electrons are from cathode arc discharge, so the density is high, the adjustment of the proportion of ions and atoms in the plasma can be realized through the discharge mode and the regulation and control of pulse discharge parameters, and the high deposition rate is obtained; the discharge process of the process is cathode arc discharge, and the voltage is lower, so that the discharge process is stable, the phenomenon of sparking cannot occur, and the quality of a coated film is guaranteed very well; the method can be carried out under low air pressure, so that the deep hole can be processed without being influenced by the shape and the structure of a workpiece; the ionization source of the method is independent, the preparation of the metal doped DLC can be realized according to the actual requirement by configuring the arc source of other target materials in the vacuum chamber, and because the discharge of the doping source and the ionization source is independent, the mutual interference can not be caused, and the doping process is stable; the cathode material is graphite, the anode material is common metal material (such as stainless steel, C steel, Al, Ti, Cr, Cu and the like), and the price is not expensive, so the cost of the method is not high; the process method with high deposition rate and low cost is more suitable for industrial production. The graphite is used as the target material of the cathode arc, and the DLC film is prevented from being polluted by the target material elements from the cathode arc in the process of preparing the DLC by the arc enhanced glow discharge method, so that the deposition of pure DLC can be realized.

Drawings

FIG. 1 is a schematic view of an apparatus of the present invention;

FIG. 2 is a schematic structural view of a turret according to an embodiment;

FIG. 3 is a graph of graphite cathodic arc enhanced glow discharge (pulsed current 500A);

FIG. 4 is a waveform diagram of graphite cathode arc under different discharge currents (pulse average current setting 20A, DC end setting 55A);

FIG. 5 is a pictorial representation of a DLC prepared in example 1;

FIG. 6 shows the XPS (C1s) test results for DLC prepared in example 1;

FIG. 7 shows the surface morphology of the DLC film prepared in example 2 under a scanning electron microscope;

FIG. 8 is a cross-sectional view of the DLC film prepared in example 2 under a scanning electron microscope;

FIG. 9 shows the cross-sectional morphology of the DLC film prepared in example 3 under a scanning electron microscope;

FIG. 10 shows the Raman spectrum and the fitting peak separation result of the DLC film prepared in example 5;

FIG. 11 is an EDS test picture of DLC of comparative example;

FIG. 12 shows the results of the EDS composition analysis of the comparative example.

Detailed Description

The first embodiment is as follows: the device for depositing pure DLC by graphite cathode arc enhanced glow discharge comprises 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 rotationally 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 inside 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 turret 2 and the vacuum chamber 9.

In the embodiment, the direct current end current of the first high pulse power supply 4-1 and the direct current end current of the second high pulse power supply 4-2 are both 30-150A, the average current of the pulse ends is 30-200A, the pulse discharge current is 50-5000A, the frequency is 10-20000Hz, and the pulse width is 5-1000 mus.

The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the rotating frame 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 anode 3-2, and the baffle plate 8 are all insulated from the vacuum chamber 9. The rest is the same as the first embodiment.

In the embodiment, the rotating frame 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 anode 3-2 and the baffle plate 8 are all insulated from the vacuum chamber 9 through polytetrafluoroethylene.

The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the electric connection end of the first anode 3-1 is electrically connected with the anode of a first high-pulse power supply 4-1, and the cathode of the first high-pulse power supply 4-1 is electrically connected with the electric connection end of a first graphite cathode 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 1-2. The others are the same as in the first or second embodiment.

The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is: the electric connection end of the first metal cathode 5-1 is electrically connected with the negative electrode of the first direct current power supply 6-1, the electric connection end of the second metal cathode 5-2 is electrically connected with the negative electrode of the second direct current power supply 6-2, the negative electrode of the bias power supply 10 is electrically connected with the electric connection end of the rotating frame 2, the electric connection end of the vacuum chamber 9 is respectively electrically connected with the positive electrode of the first direct current power supply 6-1, the positive electrode of the second direct current power supply 6-2 and the positive electrode of the bias power supply 10, and the vacuum chamber 9 is grounded. The rest is the same as one of the first to third embodiments.

The fifth concrete implementation mode: this implementationThe method for depositing pure DLC by graphite cathode arc enhanced glow discharge comprises the following steps: 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 × 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-150-500V, 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 turn on 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, turning off the first high pulse power supply 4-1 and the second high pulse power supply 4-2, and 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 the bias voltage power supply 10 to 50-10000V, and the duty ratio to 5-80%; adjusting the first high pulse power supply 4-1 and the second high pulse power supply 4-2, and the deposition time of DLC is 5-500 min; wherein the first high pulse power supply 4-1 and the second high pulse power supply 4-2 simultaneously turn on 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.

The sixth specific implementation mode: this and the detailed description of the preferred embodimentsThe five differences are as follows: in the third step, the transition layer is Cr/CrN/CrCN/Cr-C, and the deposition method comprises the following steps: 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 the 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-30-300V and the deposition time to 10-60min, and preparing a Cr transition layer; then, Ar gas is turned off, and N is introduced into the vacuum chamber 9₂The flow rate is 100-500sccm, the pressure of 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 C is introduced into the vacuum chamber 9₂H₂The flow rate is 100-500sccm, the 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 and 10-60min to prepare a Cr-C transition layer; the first metal cathode 5-1 and the second metal cathode 5-2 are both Cr. The rest is the same as the first to fifth embodiments.

The seventh embodiment: the fifth or sixth embodiment is different from the fifth or sixth embodiment in that: when the transition layer in the third step is Ti/TiN/TiCN/Ti-C, the deposition method comprises the following steps: 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 and 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 power supply 10 to be-30 to-300V, and the deposition time to be 10 to 60min to prepare a Ti transition layer, wherein the discharge current is direct current of 30 to 200A; then, Ar gas is turned off, and N is introduced into the vacuum chamber 9₂The flow rate is 100-500sccm, the pressure of the vacuum chamber 9 is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and a TiN transition layer is prepared; then C is introduced into the vacuum chamber 9₂H₂The flow rate is 100-500sccm, the 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; first, theOne metal cathode 5-1 and the second metal cathode 5-2 are both Ti. The other is the same as the fifth or sixth embodiment.

The specific implementation mode is eight: the difference between this embodiment mode and one of the fifth to seventh embodiment modes is that: in the third step, when the transition layer is Ti/TiAlN, the deposition method comprises the following steps: 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-; 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 simultaneously introduced into the vacuum chamber 9₂The flow rate is 100-500sccm, the pressure of the vacuum chamber 9 is maintained at 0.2-4.0Pa, the deposition time is 10-60min, and a TiAlN transition layer is prepared; the first metal cathode 5-1 is Ti, and the second metal cathode 5-2 is TiAl. The rest is the same as one of the fifth to seventh embodiments.

The specific implementation method nine: the fifth to eighth embodiments are different from the fifth to eighth embodiments in that: when the transition layer in the third step is Cr/CrAlN, the deposition method comprises the following steps: 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-; 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 9₂The 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. The rest is the same as the fifth to eighth embodiments.

The specific implementation mode is ten: the present embodiment differs from one of the fifth to ninth embodiments in that: in the third step, when the transition layer is Si/Si-DLC, the deposition method comprises the following steps: ar and SiH are introduced into the vacuum chamber 9₄The flow rate is 100-500sccm, the pressure in the vacuum chamber 9 is maintained at 0.2-4.0Pa, and the first high pulse is maintainedStarting a charging source 4-1 and a second high pulse power source 4-2, adjusting the bias voltage value of a bias power source 10 to be-30 to-300V, and depositing for 10 to 60min to prepare a Si transition layer; c is continuously introduced into the vacuum chamber 9₂H₂Gas 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 open 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 opening the direct current end, wherein the current of the direct current end is 30-150A. The others are the same as in one of the fifth to ninth embodiments.

The concrete implementation mode eleven: the present embodiment differs from one of the fifth to tenth embodiments in that: keeping the first direct current power supply 6-1 and the second direct current power supply 6-2 closed, then introducing mixed gas of argon, acetylene and TMS or HMDSN into the vacuum chamber 9 from the air inlet 7, and maintaining the air pressure of the vacuum chamber 9 at 0.1-5.0 Pa; adjusting the bias voltage value of the bias voltage power supply 10 to 50-10000V, and the duty ratio to 5-80%; adjusting the first high pulse power supply 4-1 and the second high pulse power supply 4-2, and the deposition time of DLC is 5-500 min; wherein the first high pulse power supply 4-1 and the second high pulse power supply 4-2 simultaneously open 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 opening the direct current end, wherein the current of the direct current end is 30-150A, and the preparation of the DLC in the element doping form by graphite cathode arc enhanced glow discharge is completed. When argon gas, acetylene and TMS are introduced, Si-DLC is prepared, and when argon gas, acetylene and TMS are introduced, (Si, N) -DLC is prepared, and the rest is the same as one of the fifth to ninth embodiments.

The concrete implementation mode eleven: the present embodiment differs from one of the fifth to tenth embodiments in that: starting a second direct current power supply 6-2, introducing a mixed gas of argon and acetylene into the vacuum chamber 9 from the air inlet 7, and maintaining the air pressure of the vacuum chamber 9 at 0.1-5.0 Pa; adjusting the bias voltage value of the bias voltage power supply 10 to 50-10000V, and the duty ratio to 5-80%; adjusting the first high pulse power supply 4-1 and the second high pulse power supply 4-2, and the deposition time of DLC is 5-500 min; wherein the first high pulse power supply 4-1 and the second high pulse power supply 4-2 simultaneously open 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 opening the direct current end, wherein the current of the direct current end is 30-150A, and the preparation of the DLC in the element doping form by graphite cathode arc enhanced glow discharge is completed. The cathode 5-2 can be made of Cr, Ti, CrAl or TiAl, and DLC doped with corresponding elements is prepared respectively. The others are the same as in one of the fifth to tenth embodiments.

The following experiments were performed to verify the beneficial effects of the present invention:

example 1

Firstly, cleaning a workpiece to be plated: placing the workpiece to be plated in alcohol, ultrasonic cleaning for 10min, taking out, drying with hot air, placing on the workpiece tray 16 of the rotary frame 2 in the vacuum chamber 9, and pumping the vacuum chamber 9 to vacuum degree of less than 5 × 10^-3Pa；

Secondly, performing Ar ion bombardment cleaning on the workpiece to be plated: introducing Ar gas into the vacuum chamber 9 at a flow rate of 300sccm, maintaining the pressure of the vacuum chamber 9 at 0.5Pa, connecting the bias power supply 10 to the rotating frame 2, setting the pulse bias value to-200V, and setting the duty ratio to 75%; starting direct current ends of a first high pulse power supply 4-1 and a second high pulse power supply 4-2, setting the current to be 60A, and establishing a discharge circuit between a first graphite cathode arc 1-1 and a first anode 3-1 and between a second graphite cathode arc 1-2 and a second anode 3-2; the workpiece cleaning time is 40 min;

thirdly, deposition of a transition layer: introducing Ar into the vacuum chamber 9 at a flow rate of 300sccm, and maintaining the air pressure of the vacuum chamber 9 at 0.4 Pa; keeping the bias voltage value of the bias power supply 10 at-200V; starting a first direct current power supply 6-1 and a second direct current power supply 6-2, establishing discharge between a first metal cathode 5-1 and a vacuum chamber 9 and between a second metal cathode 5-2 and the vacuum chamber 9 by using direct current 80A, and preparing a Cr transition layer, wherein the deposition time is 15 min; then Ar is closed and N is introduced into the vacuum chamber 9₂The flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0 Pa; adjusting the bias voltage value of the bias power supply 10 to-70V to maintain the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2Direct current 80A is adopted, the deposition time is 30min, and a CrN transition layer is prepared; introducing N into the vacuum chamber 9₂And C₂H₂Respectively controlling the flow rates to be 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, maintaining the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 80A, and depositing for 20min to prepare a CrCN transition layer; introducing C into the vacuum chamber 9₂H₂The flow rate is 50sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5 Pa; adjusting the bias voltage value of the bias voltage power supply 10 to-150V, adjusting the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 70A, and preparing a Cr-C transition layer, wherein the deposition time is 15 min; wherein the first metal cathode 5-1 and the second metal cathode 5-2 are both Cr;

fourthly, preparing DLC by graphite cathode arc enhanced glow discharge: the first direct current power supply 6-1 and the second direct current power supply 6-2 are closed, and argon and C are introduced into the vacuum chamber 9₂H₂The flow rates are respectively 75sccm and 75sccm, and the gas pressure of the vacuum chamber 9 is maintained at 0.3 Pa; adjusting the bias voltage value of the bias power supply 10 to 200V, and the duty ratio to 75%; adjusting a first high pulse power supply 4-1 and a second high pulse power supply 4-2, wherein the average current is 75A, the direct current end current is 55A, the pulse end average current is 20A, the pulse end peak current is 500A, the frequency is 520Hz, and the pulse width is 150 mus; the deposition time of DLC is 60min, and the DLC is prepared by graphite cathode arc enhanced glow discharge; fig. 2 is a photograph of a graphite cathode arc enhanced glow discharge. The deposition rate of DLC under the process can reach 2.1 mu m/h.

Fig. 3 is a graph of a graphite cathodic arc enhanced glow discharge (pulsed current 500A) illustrating the relative positions of the cathode and anode of this example, demonstrating the feasibility.

FIG. 4 is a waveform diagram of graphite cathode arc under different discharge currents: the technology can realize two discharge modes of direct current discharge and pulse discharge.

FIG. 5 is a pictorial view of graphite cathodic arc enhanced glow discharge deposition of DLC: in the embodiment, the workpieces to be plated are respectively aluminum and steel, wherein a is aluminum foil and b is high-speed steel, and the method can be used for depositing DLC on a solid workpiece.

FIG. 6 shows the XPS (C1s) test result of DLC prepared in example 1, and it can be seen from FIG. 6 that only C-C bond and C-O exist, and no other bond (e.g., C-Cr) exists, indicating that pure DLC is prepared. Where the production of C-O is produced by long term exposure to air.

Example 2

Firstly, cleaning a workpiece to be plated: putting the workpiece (monocrystalline silicon) to be plated in alcohol, ultrasonically cleaning for 10min, taking out, drying with hot air, placing on the workpiece tray 16 of the rotary frame 2 in the vacuum chamber 9, and pumping the vacuum chamber 9 to a vacuum degree of less than 5 × 10^- ³Pa；

thirdly, deposition of a transition layer: introducing Ar into the vacuum chamber 9 at a flow rate of 300sccm, and maintaining the air pressure of the vacuum chamber 9 at 0.4 Pa; keeping the bias voltage value of the bias power supply 10 at-200V; starting a first direct current power supply 6-1 and a second direct current power supply 6-2, establishing discharge between a first metal cathode 5-1 and a vacuum chamber 9 and between a second metal cathode 5-2 and the vacuum chamber 9 by using the discharge current of direct current 80A, and preparing a Cr transition layer, wherein the deposition time is 15 min; then Ar is closed and N is introduced into the vacuum chamber 9₂The flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0 Pa; adjusting the bias voltage value of the bias voltage power supply 10 to-70V, keeping the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 80A, and preparing a CrN transition layer with the deposition time of 30 min; introducing N into the vacuum chamber 9₂And C₂H₂Respectively controlling the flow rates to be 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, maintaining the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 80A, and depositing for 20min to prepare a CrCN transition layer; introducing C into the vacuum chamber 9₂H₂The flow rate is 50sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5 Pa; adjusting the bias voltage value of the bias voltage power supply 10 to-150V, adjusting the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 70A, and preparing a Cr-C transition layer, wherein the deposition time is 15 min; wherein the first metal cathode 5-1 and the second metal cathode 5-2 are both Cr;

fourthly, preparing DLC by graphite cathode arc enhanced glow discharge: the first direct current power supply 6-1 and the second direct current power supply 6-2 are closed, and argon and C are introduced into the vacuum chamber 9₂H₂The flow rates are respectively 100sccm and 100sccm, and the gas pressure of the vacuum chamber 9 is maintained at 0.3 Pa; adjusting the bias voltage value of the bias power supply 10 to 200V, and the duty ratio to 75%; adjusting a first high pulse power supply (4-1) and a second high pulse power supply (4-2), wherein the average current is 75A, the current of a direct current end is 55A, the average current of a pulse end is 20A, the peak current of the pulse end is 500A, the frequency is 800Hz, and the pulse width is 95 mus; the deposition time of DLC is 30min, and the DLC is prepared by graphite cathode arc enhanced glow discharge; the deposition rate of DLC under the process can reach 1.8 mu m/h. FIG. 7 shows the surface morphology of the DLC film prepared in example 2 under a scanning electron microscope; the surface of the DLC film prepared in example 2 is magnified 1000 times and FIG. 8 is the cross-sectional profile of the DLC film prepared in example 2 under a scanning electron microscope; the microstructure of the cross-sectional film can be seen, as well as the deposition rate evaluated.

Example 3

fourthly, preparing DLC by graphite cathode arc enhanced glow discharge: the first direct current power supply 6-1 and the second direct current power supply 6-2 are turned off, argon and C are introduced into the vacuum chamber 9₂H₂The flow rates are respectively 75sccm and 75sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.3 Pa; adjusting the bias voltage value of the bias power supply to 200V, and the duty ratio to 75%; adjusting the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2, wherein the current of a direct current end is 75A, closing the pulse end, and the deposition time of DLC is 45min to complete the preparation of DLC by graphite cathode arc enhanced glow discharge; the deposition rate of DLC under the process can reach 3.8 mu m/h.

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

Example 4

thirdly, deposition of a transition layer: introducing Ar into the vacuum chamber 9 at a flow rate of 300sccm, and maintaining the air pressure of the vacuum chamber 9 at 0.4 Pa; keeping the bias voltage value of the bias power supply 10 at-200V; starting a first direct current power supply 6-1 and a second direct current power supply 6-2, establishing discharge between a first metal cathode 5-1 and a vacuum chamber 9 and between a second metal cathode 5-2 and the vacuum chamber 9 by using the discharge current of direct current 80A, and preparing a Cr transition layer, wherein the deposition time is 15 min; then Ar is closed and N is introduced into the vacuum chamber 9₂The flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0 Pa; adjusting the bias voltage value of a bias voltage power supply 10 to-70V, keeping the discharge current of a first direct current power supply 6-1 and a second direct current power supply 6-2 to be direct current 80A, and preparing a CrN transition layer with the deposition time of 30 min; introducing N into the vacuum chamber 9₂And C₂H₂Respectively controlling the flow rates to be 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, maintaining the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 80A, and depositing for 20min to prepare a CrCN transition layer; introducing C into the vacuum chamber 9₂H₂The flow rate is 50sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5 Pa; adjusting the bias voltage value of the bias power supply 10 to-150V, adjusting the discharge current of the first DC power supply 6-1 and the second DC power supply 6-2 to DC 70A, and depositingIn 15min, preparing a Cr-C transition layer; wherein the first metal cathode 5-1 and the second metal cathode 5-2 are both Cr;

fourthly, preparing DLC by graphite cathode arc enhanced glow discharge: the first direct current power supply 6-1 and the second direct current power supply 6-2 are closed, and argon and C are introduced into the vacuum chamber 9₂H₂The flow rates are respectively 100sccm and 100sccm, and the gas pressure of the vacuum chamber 9 is maintained at 0.3 Pa; adjusting the bias voltage value of the bias voltage power supply 10 to 200V, and the duty ratio is 75%; adjusting a first high pulse power supply 4-1 and a second high pulse power supply 4-2, wherein the average current is 75A, the direct current end current is 55A, the average current of the pulse end is 20A, the peak current of the pulse end is 500A, the frequency is 260Hz, and the pulse width is 260 mus; the deposition time of DLC is 60min, and the DLC is prepared by graphite cathode arc enhanced glow discharge; the deposition rate of DLC under the process can reach 2.7 mu m/h.

Example 5

thirdly, deposition of a transition layer: closing the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2, then introducing Ar into the vacuum chamber 9 at the flow rate of 300sccm, and maintaining the air pressure of the vacuum chamber 9 at 0.4 Pa; keeping the bias voltage value of the bias power supply 10 at-200V; starting a first direct current power supply 6-1 and a second direct current power supply 6-2, setting the discharge current as direct current 80A, establishing discharge between a first metal cathode 5-1 and a vacuum chamber 9 and between a second metal cathode 5-2 and the vacuum chamber 9, setting the deposition time as 15min, and preparing CrA transition layer; then Ar is closed and N is introduced into the vacuum chamber 9₂The flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0 Pa; adjusting the bias voltage value of a bias voltage power supply 10 to-70V, keeping the discharge current of a first direct current power supply 6-1 and a second direct current power supply 6-2 to be direct current 80A, and preparing a CrN transition layer with the deposition time of 30 min; introducing N into the vacuum chamber 9₂And C₂H₂Respectively controlling the flow rates to be 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, maintaining the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 80A, and depositing for 20min to prepare a CrCN transition layer; introducing C into the vacuum chamber 9₂H₂The flow rate is 50sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5 Pa; adjusting the bias voltage value of the bias voltage power supply 10 to-150V, adjusting the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 70A, and preparing a Cr-C transition layer, wherein the deposition time is 15 min; wherein the first metal cathode 5-1 and the second metal cathode 5-2 are both Cr;

fourthly, preparing DLC by graphite cathode arc enhanced glow discharge: introducing argon and C into the vacuum chamber 9₂H₂The flow rates are respectively 75sccm and 75sccm, the gas pressure is maintained at 0.5Pa, the bias voltage value of the bias voltage power supply 10 is adjusted to be 200V, and the duty ratio is 75%; starting direct current ends of a first high pulse power supply 4-1 and a second high pulse power supply 4-2, wherein the current of the direct current ends is 75A, and establishing a discharge loop between a first graphite cathode arc 1-1 and a first anode 3-1 and between a second graphite cathode arc 1-2 and a second anode 3-2; adjusting the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to 65A, preparing metal-doped DLC, and depositing Cr-DLC for 60min to complete the preparation of DLC by graphite cathode arc enhanced glow discharge;

fig. 10 shows the raman spectrum and fitting peak separation result of the DLC film prepared in this example. The results show the Raman peak of a typical DLC film, and the peak separation results show I_D/I_GThe result was 0.55. Illustrating that the method of this embodiment can also be used to deposit doped DLC.

Example 6

Firstly, cleaning a workpiece to be plated: putting a workpiece to be plated (monocrystalline silicon) in alcohol, and ultrasonically cleaningWashing for 10min, taking out, drying with hot air, placing on the workpiece tray 16 of the rotary frame 2 in the vacuum chamber 9, and vacuumizing the vacuum chamber 9 to a vacuum degree of less than 5 × 10^- ³Pa；

thirdly, deposition of a transition layer: closing the first high-pulse power supply 4-1 and the second high-pulse power supply 4-2, then introducing Ar into the vacuum chamber 9 at the flow rate of 300sccm, and maintaining the air pressure of the vacuum chamber 9 at 0.4 Pa; keeping the bias voltage value of the bias power supply 10 at-200V; starting a first direct current power supply 6-1 and a second direct current power supply 6-2, wherein the discharge current is direct current 80A, and establishing discharge between a first metal cathode 5-1 and a vacuum chamber 9 and between a second metal cathode 5-2 and the vacuum chamber 9, wherein the deposition time is 15min, and preparing a Cr transition layer; then Ar is closed and N is introduced into the vacuum chamber 9₂The flow rate is 125sccm, and the air pressure of the vacuum chamber 9 is maintained at 1.0 Pa; adjusting the bias voltage value of a bias voltage power supply 10 to-70V, keeping the discharge current of a first direct current power supply 6-1 and a second direct current power supply 6-2 to be direct current 80A, and preparing a CrN transition layer with the deposition time of 30 min; introducing N into the vacuum chamber 9₂And C₂H₂Respectively controlling the flow rates to be 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, maintaining the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 80A, and depositing for 20min to prepare a CrCN transition layer; introducing C into the vacuum chamber 9₂H₂The flow rate is 50sccm, and the air pressure of the vacuum chamber 9 is maintained at 0.5 Pa; adjusting the bias voltage value of the bias voltage power supply 10 to-150V, adjusting the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to be direct current 70A, and preparing a Cr-C transition layer, wherein the deposition time is 15 min; wherein the first metal cathode 5-1 and the second metal cathode5-2 poles are all AlCr;

fourthly, preparing DLC by graphite cathode arc enhanced glow discharge: introducing argon and C into the vacuum chamber 9₂H₂The flow rates are respectively 75sccm and 75sccm, the gas pressure is maintained at 0.5Pa, the bias voltage value of the bias voltage power supply 10 is adjusted to be 200V, and the duty ratio is 75%; starting direct current ends of a first high pulse power supply 4-1 and a second high pulse power supply 4-2, wherein the current of the direct current ends is 75A, and establishing a discharge circuit between a first graphite cathode arc 1-1 and a first anode 3-1 and between a second graphite cathode arc 1-2 and a second anode 3-2; and adjusting the discharge current of the first direct current power supply 6-1 and the second direct current power supply 6-2 to 65A, preparing the metal-doped DLC, and depositing the Cr-DLC for 60min to finish the preparation of DLC by graphite cathode arc enhanced glow discharge.

The apparatus for deposition of DLC by graphite cathodic arc enhanced glow discharge used in examples 1 to 6 comprises a vacuum chamber 9, a turret 2, a bias power supply 10, a first graphite cathodic arc 1-1, a second graphite cathodic 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 dc power supply 6-1 and a second dc 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 rotationally 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 each baffle 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 turret 2 and the vacuum chamber 9. In the embodiment, two air inlets 7 are opened, wherein the pipe orifice of the air inlet pipe of one air inlet 7 is positioned between the first graphite cathode arc 1-1 and the first anode 3-1, and the distance between the pipe orifice and the first graphite cathode arc 1-1 is 5-18 cm; the pipe orifice of the air inlet pipe of the other air inlet 7 is positioned between the second graphite cathode arc 1-2 and the second anode 3-2, and the distance between the pipe orifice and the second graphite cathode arc 1-2 is 5-18 cm.

The rotating frame 2 is a planetary rotating frame which comprises a rotating shaft 11, a chain tray 12, a chain 13, a gear 14, a rotating disc 15, a rotating rod 17, a workpiece tray 16, a polytetrafluoroethylene insulating sleeve 18 and a polytetrafluoroethylene cushion block 19, wherein the chain tray 12 is fixedly arranged at the bottom of the vacuum chamber 9, the chain 13 is fixed on the upper surface of the chain tray 12, and the rotating disc is arranged at the top end of the rotating shaft 11; the rotating rod 17 is connected with the rotating disc 15 through a bearing, a gear 14 is arranged at the bottom end of the rotating rod 17, the gear 14 is meshed with the chain 13, and a workpiece tray 16 is sleeved on the rotating rod 17; the planet rotating frame is insulated from the vacuum chamber by a polytetrafluoroethylene insulating sleeve 18 and a polytetrafluoroethylene cushion block 19.

In the comparative example, Ar is introduced to maintain the air pressure at 0.5Pa, the Cr arc current is 70A, the bias power supply voltage and the duty ratio are respectively adjusted to 950V and 75 percent, the cleaning time is 10min, and metal ion cleaning is carried out; introducing Ar to maintain the air pressure at 0.5Pa, fixing the graphite cathode arc by 60A, closing a baffle plate at the front end of the graphite arc, setting a bias power supply to-200V, and keeping the time for 15min to perform Ar ion cleaning; introducing Ar to maintain the air pressure at 0.4Pa, fixing the Cr arc by 80A, setting a bias voltage power supply to-200V, lasting for 15min, and depositing a Cr transition layer; introducing N2 to stabilize the air pressure at 1.0Pa, fixing Cr arc at 80A, setting bias voltage power supply at-70V, lasting for 45min, and depositing a CrN transition layer; introducing mixed gas of N2 and acetylene, fixing Cr arc by 80A, and controlling the flow ratio to be N₂:C₂H₂100:15(sccm), gas pressure 1.0Pa, bias voltageSetting a power supply to be 70V below zero, depositing for 20min, and depositing a CrCN transition layer; the DLC is prepared by utilizing Cr cathode arc enhanced glow discharge, argon and acetylene mixed gas is introduced, the flow ratio of Ar to C2H2 is 75 to 100(sccm), the Cr cathode arc is obtained, the current is direct current 55A, the average current of a composite pulse end is 20A, the pulse frequency is 200Hz, the frequency is 320 mus, the pulse current is 300A, the air pressure is 0.5Pa, the bias power supply is set to-150V, and the deposition time is 30 min.

FIG. 11 is an EDS test picture of DLC of the present example; FIG. 12 shows the result of EDS composition analysis in this example; the surface element ratio of DLC produced by Cr cathodic arc enhanced glow discharge is shown in table 1.

TABLE 1

From this, it is found that Cr is present in DLC produced by Cr cathodic arc enhanced glow discharge, and contamination with Cr element is caused.

Claims

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;

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.