CN-122013115-A - Method for collaborative deposition of thick tetrahedral amorphous carbon films by self-relaxation effect, priming and ion energy modulation

CN122013115ACN 122013115 ACN122013115 ACN 122013115ACN-122013115-A

Abstract

The invention discloses a method for cooperatively depositing a thick tetrahedral amorphous carbon film by self-relaxation effect, adjusting a priming layer and ion energy regulation, which aims at solving the problem that the thick ta-C carbon film cannot be prepared due to high internal stress in the film layer in the existing process of preparing the ta-C carbon film. A method for depositing a thick tetrahedral amorphous carbon film comprises the steps of firstly cleaning the surface of a workpiece through glow, secondly cleaning the surface of the workpiece through arc light, thirdly depositing a priming layer on the workpiece, fourthly controlling the size of medium-frequency bias voltage to respectively deposit a soft layer rich in sp 2 components and a hard layer rich in sp 3 components, and fifthly, alternately depositing to obtain the thick tetrahedral amorphous carbon film. The invention adopts a deposition mode of short deposition and long cooling, and utilizes the self-relaxation effect of the ta-C carbon film to effectively release the intrinsic stress of the carbon film. The controllable sp 3 /sp 2 component structure is realized by utilizing high and low ion energy deposition modulated by bias voltage, the thickness of the deposited ta-C carbon film can reach 4.5 mu m, and the thickness of the ta-C carbon film is improved.

Inventors

WANG BENFU
TIAN XIUBO
ZHU BINHAI
HAO LIANG
GONG CHUNZHI
GENG HUIYUAN

Assignees

哈尔滨华德学院
哈尔滨工业大学

Dates

Publication Date: 20260512
Application Date: 20260213

Claims (10)

1. The method for depositing the thick tetrahedral amorphous carbon film in a synergic manner through self-relaxation effect, adjusting the priming layer and ion energy regulation is characterized by comprising the following steps: 1. glow cleaning the surface of the workpiece: Vacuumizing the vacuum chamber, introducing argon, fixing a workpiece on a workpiece rotating frame, connecting the negative output end of an intermediate frequency bias power supply with the workpiece rotating frame, connecting the positive output end of the intermediate frequency bias power supply with the ground, and carrying out glow cleaning by utilizing auxiliary anode ionized argon; 2. Arc cleaning the surface of a workpiece: closing the power supply of the auxiliary anode, and increasing the voltage of the medium-frequency bias power supply to perform arc cleaning; 3. and (3) depositing a priming layer: depositing a priming layer on the workpiece by using the priming target material to obtain a workpiece with the priming layer; 4. Tetrahedral amorphous carbon film deposition: starting a power supply of the graphite target, controlling the current of a direct current end of the graphite target to be 20-200A, the average current of a pulse end to be 20-200A, controlling the voltage of an intermediate frequency bias power supply to be-20 to-1000V, depositing for 1-5 min, stopping arc and cooling for 3-10 min, and preparing a soft layer rich in sp 2 components; Then, adjusting the current of a direct current end of the graphite target to be 20-200A, closing a power pulse end at the moment, setting the medium-frequency bias power voltage as a suspension bias voltage, setting the deposition time to be 1-5 min, stopping arc and cooling for 3-10 min, and obtaining a hard layer rich in sp 3 components; 5. Thick amorphous carbon film deposition: And (3) repeating the process of preparing the sp 2 -rich soft layer and the sp 3 -rich hard layer in the step four, and alternately depositing the sp 2 -rich soft layer and the sp 3 -rich hard layer to obtain the thick tetrahedral amorphous carbon film.
2. The method of claim 1, wherein the workpiece in step one is a high-speed steel, a hot work die steel, a maraging steel or a ceramic material.
3. The method for collaborative deposition of a thick tetrahedral amorphous carbon film by self-relaxation effect, priming layer adjustment and ion energy modulation according to claim 1, characterized in that in step one, the glow cleaning time is controlled to be 20-40 min.
4. The method for collaborative deposition of a thick tetrahedral amorphous carbon film by self-relaxation effect, priming and ion energy modulation according to claim 1, wherein the arc cleaning time is controlled to be 10-30 min in step two.
5. Method for the collaborative deposition of thick tetrahedral amorphous carbon films by self-relaxation effects, tuning of the underlayer and ion energy modulation according to claim 1 characterized in that the underlayer deposited in step three is Cr, ti, crTi alloy, ta, al or CrAl alloy.
6. The method for collaborative deposition of a thick tetrahedral amorphous carbon film by self-relaxation effect, adjustment of underlayer and ion energy modulation according to claim 1, characterized in that the underlayer thickness deposited in step three is 0.2-3 μm.
7. The method for collaborative deposition of a thick tetrahedral amorphous carbon film by self-relaxation effect, priming and ion energy modulation according to claim 1, wherein in step four, the gas pressure is controlled to be 0.05-0.15 Pa during the deposition of the tetrahedral amorphous carbon film.
8. The method for collaborative deposition of a thick tetrahedral amorphous carbon film by self-relaxation effect, priming and ion energy modulation according to claim 1, characterized in that the thickness of the soft layer rich in sp 2 component is 20-25 nm and the thickness of the hard layer rich in sp 3 component is 110-120 nm in step four and step five.
9. The method for collaborative deposition of a thick tetrahedral amorphous carbon film through self-relaxation effect, adjustment of a priming layer and ion energy regulation according to claim 1, which is characterized in that in the fourth step, a power supply of a graphite target is started, direct current end current of the graphite target is controlled to be 40-60A, average current of a pulse end is controlled to be 20-40A, voltage of an intermediate frequency bias power supply is controlled to be-1000V, deposition time is 1 min, arc stopping cooling is 3 min, and a soft layer rich in sp 2 components is prepared; And then, regulating the direct current end current of the graphite target to be 60-100A, regulating the pulse end current to be 0A, setting the medium-frequency bias power supply voltage to be a suspension bias voltage, setting the deposition time to be 2 min, stopping arc and cooling to be 4 min, and obtaining the hard layer rich in sp 3 components.
10. The method for collaborative deposition of a thick tetrahedral amorphous carbon film by self-relaxation effect, priming and ion energy modulation according to claim 1, characterized in that the thickness of the thick tetrahedral amorphous carbon film in step five is 1-4.5 μm.

Description

Method for collaborative deposition of thick tetrahedral amorphous carbon films by self-relaxation effect, priming and ion energy modulation Technical Field The invention belongs to the technical field of material manufacturing, and particularly relates to a method for preparing a thick tetrahedral amorphous carbon film (ta-C) by self-relaxation effect, controllable sp 3/sp2 component content and adjustment of a priming layer. Background The high intrinsic stress limits the thickness of the film during the preparation of the Ta-C carbon film. As the thickness of the carbon film increases, internal stress continues to build up, and once the bonding strength of the carbon-based network itself is exceeded, film collapse and delamination may be initiated. Therefore, the existence of high intrinsic stress makes the process of depositing a thicker ta-C carbon film very difficult, and further severely restricts the application range of the carbon film under different parts and working conditions. However, in the parts such as piston rings, piston pins, lifters and the like of automobile engines, certain requirements are put on the thickness of the ta-C carbon film in order to ensure the application requirements in severe environments such as high temperature, high pressure and the like. To overcome the limitations of residual stress on film thickness, researchers have tried various methods of reducing stress and controlling coating temperature. However, the thickness of the ta-C carbon film is still difficult to break through by 1-2 μm due to the high residual stress of the carbon film itself and the difference between the thermal expansion coefficients of the carbon film and the base material. Researchers have tried various methods to solve the limitation of the high intrinsic stress of the ta-C carbon film on the thickness of the film. These methods include element doping, thermal annealing, designing multilayer film structures, applying different energy ion bombardment, and the like. However, metal doping will cause a reduction in the optical transparency of the film. Although thermodynamic annealing is effective in reducing internal stress, high temperature treatment is not applicable to temperature sensitive matrix materials. The carbide interlayer after high energy ion bombardment shows good bonding strength, but the matrix must be a carbide-formed material. The high internal stress of the Ta-C carbon film is mainly due to the high Gibbs free energy required for sp 3 bonds to form during deposition. However, the excellent mechanical and tribological properties of Ta-C carbon films are highly dependent on the higher sp 3 bond content. This constitutes a key contradiction in that to achieve high performance of ta—c carbon films, a high sp 3 bond ratio must be maintained, while a high sp 3 content causes significant internal stress build up, thus limiting the film thickness. The method for preparing the thick ta-C carbon film is particularly important in combination with the fact that the working condition environment of the existing carbon film coated workpiece is more severe. Disclosure of Invention The invention aims at solving the problem that the thick ta-C carbon film cannot be prepared due to high internal stress in the film layer in the existing process of preparing the ta-C carbon film, and provides a method for depositing a thick tetrahedral amorphous carbon film through the cooperation of self-relaxation effect, adjustment of a priming layer and ion energy regulation. The method for cooperatively depositing the thick tetrahedral amorphous carbon film by self-relaxation effect, adjusting the priming layer and ion energy regulation is realized according to the following steps: 1. glow cleaning the surface of the workpiece: Vacuumizing the vacuum chamber, introducing argon, fixing a workpiece on a workpiece rotating frame, connecting the negative output end of an intermediate frequency bias power supply with the workpiece rotating frame, connecting the positive output end of the intermediate frequency bias power supply with the ground, and carrying out glow cleaning by utilizing auxiliary anode ionized argon; 2. Arc cleaning the surface of a workpiece: closing the power supply of the auxiliary anode, and increasing the voltage of the medium-frequency bias power supply to perform arc cleaning; 3. and (3) depositing a priming layer: depositing a priming layer on the workpiece by using the priming target material to obtain a workpiece with the priming layer; 4. Tetrahedral amorphous carbon film deposition: starting a power supply of the graphite target, controlling the current of a direct current end of the graphite target to be 20-200A, the average current of a pulse end to be 20-200A, controlling the voltage of an intermediate frequency bias power supply to be-20 to-1000V, depositing for 1-5 min, stopping arc and cooling for 3-10 min, and preparing a soft layer rich in sp 2 components; Then, adjusting th