CN101748381A - Method for preparing high-performance doped diamond-like film - Google Patents

Abstract

A method for preparing a high-performance doped diamond-like film, which is characterized in that the method first uses ultrasonic cleaning technology to remove the contamination layer on the surface of the substrate; then uses ion beam assisted deposition technology to prepare a gradient transition layer; finally uses ion beam deposition + magnetron sputtering In this step, in addition to passing any carbon-containing gas such as methane, acetylene, benzene, ethanol, acetone, etc. into the ion source, it also simultaneously passes into the ion source including silane, borane, phosphine, and four Any gas containing non-carbon element gas sources such as fluorinated carbon, and open the metal sputtering source to dope metal elements. The invention can synthesize a multi-component doped DLC film doped with metal elements and non-metal elements at the same time, give full play to the complementary advantages of doped metal elements and non-metal elements, and significantly improve the comprehensive performance of the DLC film.

Description

A kind of preparation method of high-performance doped diamond-like carbon film

Technical field:

The patent of the invention relates to a preparation technology of a high-performance diamond-like carbon (DLC) film doped with various elements, which belongs to the composite preparation technology of DLC film materials.

Background technique:

Diamond-like carbon films have high hardness, high elastic modulus, excellent friction and wear properties, chemical stability and biocompatibility, and have very broad application prospects. However, large internal stress, poor film/substrate bonding force, poor thermal stability, and high brittleness limit the application of DLC films in harsh service conditions.

The use of an optimized gradient transition layer can relieve the internal stress of the DLC film and improve the film/substrate bonding force of the DLC film; the formation of a multi-phase structure based on the amorphous carbon film by doping metal elements will improve the overall performance of the DLC film, but Doping metal will lead to a higher coefficient of friction of the DLC film, and a low coefficient of friction cannot be obtained. Doping non-metal elements F and H can significantly reduce the friction coefficient of DLC film under special conditions, and doping non-metal components such as Si and _SiO2 can regulate the structure and performance of DLC film. It is an effective way to obtain high-performance DLC films by simultaneously doping metal elements and non-metal elements in DLC films to realize the complementarity of different doping elements, but the research in this area has not been reported yet.

Invention content:

In order to overcome the shortcomings of the current DLC film preparation technology and doping scheme, the patent of the present invention proposes a new DLC film composite deposition technology, which is characterized in that: in the process of ion beam deposition and synthesis of DLC film, in addition to the ion source In addition to any carbon-containing gas such as methane, acetylene, benzene, ethanol, acetone, etc., any gas containing non-carbon element gas sources such as silane, borane, phosphine, and carbon tetrafluoride is simultaneously introduced. And turn on the metal sputtering source to dope the metal element, and synthesize the multi-element doped DLC film. The method includes the following steps:

(1) First use ultrasonic cleaning technology to remove the contamination layer on the surface of the substrate;

(2) Then utilize the ion beam assisted deposition technique to prepare the gradient transition layer;

(3) Finally, multiple doped DLC films were synthesized on the gradient transition layer by ion beam deposition and magnetron sputtering.

In the above preparation method, the ion source in step (2) can be any ion source in the anode layer ion source, Kafman ion source, Hall ion source, radio frequency inductively coupled ion source, electron cyclotron resonance ion source.

In the above preparation method, the composition of the ion beam generated by the ion source in step (2) is argon ions, argon/nitrogen mixed ions, argon/carbon mixed ions or argon/nitrogen/carbon mixed ions, and the ratio of different ions is controlled as required.

In the above preparation method, the ion energy of the ion beam in step (2) is 50eV-500eV.

In the above preparation method, the evaporation/sputtering source in step (2) can be any one of magnetron sputtering target, cathodic arc evaporation source, and hollow cathode arc evaporation source.

In the above preparation method, the evaporation/sputtering source target in step (2) is any metal of Ti, Cr, Zr, W, Nb.

In the above preparation method, according to the multi-component doped DLC film preparation method according to claim 1, it is characterized in that: the transition layer described in step (2) comprises Ti/TiN/TiCN/TiC, Cr/CrN/CrCN/CrC , Zr/ZrN/ZrCN/ZrC, W/WC, Nb/NbN/NbC and other gradient transition layers.

In the above preparation method, the ion source in step (3) can be any ion source in the anode layer ion source, Kafman ion source, Hall ion source, radio frequency inductively coupled ion source, electron cyclotron resonance ion source.

In the above-mentioned preparation method, in step (3), in addition to passing any carbon-containing gas such as methane, acetylene, benzene, ethanol, acetone, etc. Any gas containing non-carbon elements such as carbon dioxide.

In the above preparation method, the step (3) adjusts the doping amount of the non-metal element in the DLC film by controlling the flow ratio of the non-carbon element-containing gas source and the carbon-containing gas fed into the ion source.

In the above preparation method, the ion energy of the ion beam in step (3) is 50eV-1000eV.

In the above preparation method, the magnetron sputtering source in step (3) can adopt any magnetron sputtering method among DC magnetron sputtering, intermediate frequency magnetron sputtering and radio frequency magnetron sputtering.

In the above preparation method, the magnetron sputtering source target described in step (3) is any one of metal elements such as W, Cr, Ti, Nb, Mo, Zr, Ag, Cu, Co, etc.

In the above preparation method, step (3) adjusts the doping amount of metal elements in the DLC film by controlling the power of the magnetron sputtering target.

The advantage of the patent of the present invention is to give full play to the advantages of ion beam assisted deposition combination, ion beam deposition of multi-component mixed gas, and magnetron sputtering, and synthesize simultaneously doped metal elements and non- The multi-element doped DLC film realizes the complementary advantages of metal elements and non-metal elements, and significantly improves the comprehensive performance of the DLC film; by changing the gas type and flow rate of the ion source, sputtering target material and target power and other factors to control The type and content of doping elements are used to obtain a high-performance multi-component doped DLC film.

Implementation method:

The patent of the present invention will be described in further detail below in conjunction with specific examples, but not as a limitation to the patent of the present invention.

Example 1

First, use ultrasonic cleaning technology to remove the grease contamination layer on the surface of GCr15 bearings; then use the anode layer ion source to assist DC magnetron sputtering to deposit a gradient transition layer of Cr/CrN/CrCN/CrC, and the target material of magnetron sputtering is Cr, which is passed into the anode layer The gas of the ion source includes argon, nitrogen, and acetylene. The gradient transition of the transition layer is realized by gradually changing the flow of argon, nitrogen, and acetylene. The ion energy is -100~-800eV; finally, ion beam deposition + magnetron sputtering technology is used A DLC film doped with Cr, Si, and F is synthesized on the Cr/CrN/CrCN/CrC gradient transition layer. The ion source adopts the anode layer ion source, and the gas passed into the anode layer ion source includes argon, acetylene, silane and four. Carbon fluoride, the magnetron sputtering source adopts the DC magnetron sputtering method, and the target material is Cr; the multi-element doping is controlled by changing the flow rate of argon, acetylene, silane and carbon tetrafluoride, and the sputtering power of the chromium sputtering target Cr, Si, F content of DLC film.

Example 2

First, use ultrasonic cleaning technology to remove the grease contamination layer on the surface of the engine plunger; then use the anode layer ion source to assist DC magnetron sputtering to deposit a gradient transition layer of Cr/CrN/CrCN/CrC, the target material of the magnetron sputtering is Cr, and the The gas of the ion source of the anode layer includes argon, nitrogen, and benzene, and the gradient transition of the transition layer is realized by gradually changing the flow rate of argon, nitrogen, and benzene, and the ion energy is -100~-800eV; finally, ion beam deposition + magnetron sputtering is used Synthesize a DLC film doped with Cr, F, and N simultaneously on the Cr/CrN/CrCN/CrC gradient transition layer by means of radiation technology. Carbon fluoride, nitrogen, and magnetron sputtering adopt DC magnetron sputtering, and the target material is Cr; by changing the flow rate of argon, acetylene, carbon tetrafluoride, nitrogen, and the sputtering power of the chromium sputtering target, the multi-element doping The content of Cr, F, and N in the dopant DLC film.

Example 3

First, use ultrasonic cleaning technology to remove the grease contamination layer on the surface of high-speed steel tools; then use the anode layer ion source to assist cathodic arc deposition to prepare a Ti/TiN/TiCN/TiC gradient transition layer. Gases include argon, nitrogen, and methane. The gradient transition of the transition layer is achieved by gradually changing the flow of argon, nitrogen, and methane. The ion energy is -100~-800eV; A DLC film doped with Ti, Si, F, and SiO ₂ is synthesized on the TiN/TiCN/TiC gradient transition layer. The ion source adopts the anode layer ion source, and the gas flowing into the anode layer ion source includes hydrogen, methane, silane, and tetrafluoroethylene. Carbon dioxide, water vapor, magnetron sputtering adopts DC magnetron sputtering method, the target material is Ti; by changing the flow rate of hydrogen, methane, silane, carbon tetrafluoride, water vapor, and the sputtering power of titanium sputtering target Ti, Si, F, SiO ₂ content of multi-component doped DLC film.

Claims (8)

1. the preparation method of a multi-element doping quasi-diamond (DLC) film, it is characterized in that: in the process of the synthetic DLC film of ion beam depositing, except in ion source, feeding any carbonaceous gass such as methane, acetylene, benzene, ethanol, acetone, also feed simultaneously and comprise that silane, borine, phosphine, tetrafluoro-methane etc. contain any gas of non-carbon gas source, and opening metal sputtering source doped metallic elements, synthetic multi-element doping DLC film said method comprising the steps of:

(1) at first utilize ultrasonic cleaning technology to remove the matrix surface pollution layer;

(2) utilize ion beam assisted deposition to prepare gradient transitional lay then;

(3) on gradient transitional lay, utilize ion beam depositing+magnetron sputtering to synthesize multi-element doping DLC film at last.

2. according to the described multi-element doping DLC of claim 1 membrane preparation method, it is characterized in that: the ion source of step (2) can adopt any ion source in anode layer ion source, the graceful ion source of Kraft, hall ion source, radio-frequency induction coupling ion source, the electron cyclotron resonace ion source; The ionic fluid that ion source produces consist of argon ion, argon/nitrogen hybrid ionic, argon/carbon hybrid ionic or argon/nitrogen/carbon hybrid ionic, the ratio of different ions is controlled as required; The ion energy of ionic fluid is 50eV～500eV.

3, according to the described multi-element doping DLC of claim 1 membrane preparation method, it is characterized in that: the evaporation/sputtering source of step (2) can adopt any in magnetron sputtering target, cathodic arc evaporation source, the hollow cathode arc evaporation source; Evaporation/sputtering source target is any metal of Ti, Cr, Zr, W, Nb.

4. according to the described multi-element doping DLC of claim 1 membrane preparation method, it is characterized in that: the described transition layer of step (2) comprises Ti/TiN/TiCN/TiC, Cr/CrN/CrCN/CrC, Zr/ZrN/ZrCN/ZrC, W/WC, Nb/NbN/NbC constant gradient transition layer.

5. according to the described multi-element doping DLC of claim 1 membrane preparation method, it is characterized in that: the ion source of step (3) can adopt any ion source in anode layer ion source, the graceful ion source of Kraft, hall ion source, radio-frequency induction coupling ion source, the electron cyclotron resonace ion source.

6. according to the described multi-element doping DLC of claim 1 membrane preparation method, it is characterized in that: step (3) is except feeding any carbonaceous gass such as methane, acetylene, benzene, ethanol, acetone in ion source, also feeding comprises that silane, borine, phosphine, tetrafluoro-methane etc. contain any gas of non-carbon gas source simultaneously; Feed the non-metallic element incorporation that the ionogenic throughput ratio that contains non-carbon gas source and carbonaceous gas is adjusted the DLC film by control.

7. according to the described multi-element doping DLC of claim 1 membrane preparation method, it is characterized in that: the ion energy of step (2) ionic fluid is 50eV～1000eV.

8. according to the described multi-element doping DLC of claim 1 membrane preparation method, it is characterized in that: the controlled sputtering source of step (3) can adopt any magnetron sputtering mode in magnetically controlled DC sputtering, medium frequency magnetron sputtering, the rf magnetron sputtering.

9. according to the described multi-element doping DLC of claim 1 membrane preparation method, it is characterized in that: the described controlled sputtering source target of step (3) is any of metallic elements such as W, Cr, Ti, Nb, Mo, Zr, Ag, Cu, Co; Adjust the metallic element incorporation of DLC film by the power of control magnetron sputtering target.