CN114703452B

CN114703452B - CoCrFeNi high-entropy alloy doped amorphous carbon film and preparation method thereof

Info

Publication number: CN114703452B
Application number: CN202210199226.3A
Authority: CN
Inventors: 周野飞; 韩世超; 邢晓磊; 陈琳; 杨庆祥
Original assignee: Yanshan University
Current assignee: Yanshan University
Priority date: 2022-03-02
Filing date: 2022-03-02
Publication date: 2023-03-21
Anticipated expiration: 2042-03-02
Also published as: CN114703452A

Abstract

The invention discloses a CoCrFeNi high-entropy alloy doped amorphous carbon film and a preparation method thereof, and the CoCrFeNi high-entropy alloy with higher stacking fault forming capability is used as a doping component, argon is used as sputtering gas, and the CoCrFeNi nano twin crystal structure doped amorphous carbon film material is prepared by a physical vapor deposition device. The film is characterized by the incorporation of a high entropy phase in the amorphous carbon. Different from single-component or multi-component doping, the film can solve the problem of high residual stress of the amorphous carbon film by utilizing the characteristic of high-entropy phase deformation induced plasticity, and has the advantages of high hardness, high toughness, low friction coefficient and high film-substrate binding force by forming a high-entropy phase twin crystal structure. In view of the above description, the invention can provide a basic theory and a method for the design of the high-performance self-lubricating material, and expand the application of the amorphous carbon film in mechanical engineering and other fields.

Description

CoCrFeNi high-entropy alloy doped amorphous carbon film and preparation method thereof

Technical Field

The invention relates to a carbon-based composite film and a preparation method thereof, in particular to a CoCrFeNi high-entropy alloy doped amorphous carbon film and a preparation method thereof.

Background

The amorphous carbon film is formed by sp of diamond structure ³ Hybridization of carbon atoms and sp of graphitic structure ² The amorphous structure or amorphous-nanocrystalline composite structure formed by the three-dimensional network formed by the hybridized carbon atoms has excellent performances of high hardness, high elastic modulus, low friction coefficient, high wear resistance and the like, and shows better application prospect in various technical fields. High energy of amorphous carbon film during depositionThe C-C bond length/angle changes caused by particle bombardment deform the complex and highly crosslinked carbon matrix to an increased extent, resulting in residual stresses on the GPa scale. The residual Stress gradually accumulates with the increase of the deposition thickness of the amorphous carbon film, resulting in the decrease of the bonding property of the amorphous carbon film to the substrate [ Ferrari AC, rodil S E, robertson J, mille W L.is Stress near to the substrate sp ³ bonding in diamond-like carbon[J].Diamond and Related Materials,2002,11(3-6):994-999.]. Different from the mode that the residual stress of the metal crystal material is released through relaxation, the amorphous carbon film does not have a long-range ordered crystal structure, namely, the residual stress cannot be relieved through dislocation formation and slippage, and the fracture toughness of the amorphous carbon film is often lower. The realization of the residual stress regulation and control in the amorphous carbon film deposition preparation process and the obtainment of the amorphous carbon film with low friction, long service life and high reliable service performance are hot spots and difficult problems of the industry research.

The heterogeneous element doping is an effective means for regulating and controlling the residual stress and the comprehensive performance of the amorphous carbon film. When a small amount of Ti, nb, W or Cr is doped, the doping atoms are in the interstitial positions of the carbon matrix network or exist in the carbon matrix in the form of simple substances, so that the residual stress generated in the carbon matrix network due to the bond angle distortion is reduced. After the doping amount is increased, a part of doping atoms are bonded with C atoms to generate hard nanocrystalline carbide, so that sp is generated ³ The reduction of hybrid bonds results in a reduction of the residual stress of the film and also in a reduction of the tribological properties. The invention patent CN108149193A provides a diamond-like carbon-based film and a preparation method thereof, the Cu element is doped, the nano-crystalline state exists in the amorphous carbon film, the effective regulation and control of the residual stress are realized by occupying a certain lattice position, the tribological performance of the film is improved, but the overall strength of the Cu element doped diamond-like carbon-based film is reduced to some extent due to the low strength of the Cu. The invention patent CN103938211A is a low-stress corrosion-resistant multilayer diamond-like film, and the residual stress of the film is reduced to about 2GPa by doping hydrogen and plating a multilayer film. The invention patent CN105132878A prepares a Ti-doped diamond multilayer film with a residual stress of 1.6E1.8GPa. Although the two inventions can reduce the residual stress, the final residual stress value is still larger. The invention patent CN102817008A provides a method for preparing Ag and Ti co-doped amorphous carbon film, which improves the carbon network structure and obtains good performance by doping two elements to act on a diamond-like coating synergistically on the basis of doping of a single element and co-doping noble metal Ag and transition metal Ti. The invention patent CN108677144B provides a method for preparing an aluminum-nitrogen co-doped diamond-like carbon composite film, a non-metal N element and a metal Al element are selected as doping agents, aluminum nitride AlN and metal Al nanocrystalline particles are formed in the diamond-like carbon composite film, the residual stress of the amorphous carbon film is effectively reduced, and the toughness and the hardness of the amorphous carbon film are improved. In fact, through multi-component synergy, sp in the film is changed ³ And sp ² The hybrid bond proportion, the bond angle and bond length distortion are adjusted, the rearrangement of the amorphous carbon matrix network structure is promoted, and the residual stress and the performance of the amorphous carbon film can be improved. In general, the multicomponent doped amorphous carbon film has lower residual stress and more excellent comprehensive performance compared with single components. However, the multi-component doped amorphous carbon film with the residual stress of the slow-release film takes two components as dopants, the doping research of three, four or more components is less, and almost no mature theory and invention experiment research exists. Compared with the traditional component doping, the multi-component doping amorphous carbon film is more complex in process, and the key and complex problem is how to select multiple types of doping components and play a good synergistic effect.

Disclosure of Invention

Aiming at the technical problems, the invention aims to provide a CoCrFeNi high-entropy alloy doped amorphous carbon film and a preparation method thereof aiming at the problem that the traditional doped amorphous carbon film material has poor stress relief, toughness and friction performance. Through the TWIP effect of the CoCrFeNi high-entropy doped phase, the self-relieving and self-releasing of the residual stress in the deposition process of the CoCrFeNi doped amorphous carbon-based film are realized.

The technical scheme adopted by the invention is as follows:

in a plurality of high-entropy alloy systems, the solidification structure of the CoCrFeNi high-entropy alloy is a single-phase solid solution with a face-centered cubic structure, the CoCrFeNi high-entropy alloy has a stacking layer fault energy range suitable for forming a twin crystal structure, and atoms in the CoCrFeNi high-entropy alloy are stacked layer by layer under the action of continuous stress, so that the twin crystal structure is formed. The CoCrFeNi high-entropy alloy with higher stacking fault forming capability is doped in the amorphous carbon film, and the doped phase can be induced to generate plastic deformation by utilizing the GPa-level residual stress generated in the deposition process of the amorphous carbon film so as to generate a twin crystal structure. Essentially, in the deposition process, the in-situ twinning reaction of the CoCrFeNi high-entropy alloy doped phase is used for relieving the residual stress of the amorphous carbon film and playing a role in improving the synergy by the cooperation of mechanical properties, so that the amorphous carbon film with low stress, high hardness, low friction coefficient and high film-substrate binding force is prepared.

The CoCrFeNi high-entropy alloy doped amorphous carbon film comprises a substrate, and sequentially comprises a priming layer combined with the substrate, a transition layer combined with the priming layer and a CoCrFeNi high-entropy alloy doped amorphous carbon layer combined with the transition layer from the substrate to the surface of the film.

Furthermore, a nanometer twin crystal structure is introduced into the amorphous carbon film by doping a CoCrFeNi component with stacking fault forming capacity, the stress of the CoCrFeNi high-entropy alloy doped amorphous carbon film is 0.3-0.8 GPa, the film thickness is 0.3-15 μm, the hardness is 15-25 GPa, the bonding force is 35-65N, and the friction coefficient is 0.08-0.21.

The CoCrFeNi high-entropy alloy doped amorphous carbon film is prepared by a physical vapor deposition device, and deposition raw materials comprise a CoCrFeNi high-entropy alloy target, metal targets such as Ti/Cr/W/Zr and the like and a graphite target.

A preparation method of a CoCrFeNi high-entropy alloy doped amorphous carbon film comprises the following steps:

step S1: cleaning and drying the polishing substrate, and mounting the substrate on a sample table of a rotating frame;

step S2: processing the surface of the sample by using a plasma cleaning technology;

and step S3: depositing a simple substance metal priming coat;

and step S4: depositing a metal carbide, metal nitride or metal carbonitride transition layer;

step S5: and depositing a CoCrFeNi high-entropy alloy doped amorphous carbon layer.

Further, the substrate comprises stainless steel, silicon wafers, hard alloy or glass; the specific size of the matrix can be selected by a craftsman according to the requirements of the actual plated parts.

Preferably, the substrate comprises stainless steel, bearing steel, titanium alloy, magnesium alloy, hard alloy, silicon chip and glass.

Further, in step S1, specifically: and placing the substrate in acetone and absolute ethyl alcohol in sequence for ultrasonic cleaning treatment, then placing the substrate in a vacuum high-temperature drying oven for drying, and mounting the substrate on a sample table of a rotating frame after drying.

Further, the ion source of the plasma cleaning technique in step S2 includes any one of an anode layer ion source, a kaffman ion source, a hall ion source, a radio frequency inductively coupled ion source, and an electron cyclotron resonance ion source; the ion energy of the ion beam is 50eV to 1500eV. Starting a heater to set the temperature to be 100-150 ℃, and pumping the vacuum degree of the vacuum cavity to be 1.0 multiplied by 10 ^-5 Then, high-purity argon gas was introduced into the reactor to maintain the pressure at 5X 10 ^-1 And setting ion beam voltage between 1000 and 2000V and bias voltage between-600 and-2000V between-3 Pa, and carrying out ion cleaning on the sample for 30 to 90min.

Further, the target evaporation/sputtering power source used in the deposition in steps S3 to S5 includes any one of a magnetron sputtering power source, a cathode arc evaporation source, a hollow cathode arc evaporation source, and a hot wire arc evaporation source.

Further, the magnetron sputtering power supply comprises any one of a direct current magnetron sputtering power supply, a medium frequency magnetron sputtering power supply, a radio frequency magnetron sputtering power supply and a high power pulse magnetron sputtering power supply.

Further, the elementary metal priming layer in the step S3 comprises Ti, cr, W or Zr; and S4, the transition layer comprises TiC, crC, tiN, crN, tiCN or CrCN.

Further, the sputtering target material of the CoCrFeNi high-entropy alloy doped amorphous carbon layer is prepared by a method of vacuum melting and isostatic pressing sintering, and the purity of the sputtering target material is higher than 99.9%.

Further, the Co element in the CoCrFeNi high-entropy alloy doped amorphous carbon layer: cr element: fe element: the proportion of the Ni element is 1-2:1-2:1-2:1-2.

Further, depositing an elemental metal primer layer, specifically: the evaporated/sputtered target material is made of any one or more metals of Ti, cr, W, zr and the like. The target evaporation/sputtering power source can adopt any one of a magnetron sputtering source, a cathode arc evaporation source, a hollow cathode arc evaporation source, a hot wire arc evaporation source and the like. The magnetron sputtering power supply can adopt any one of a direct-current magnetron sputtering power supply, a medium-frequency magnetron sputtering power supply, a radio-frequency magnetron sputtering power supply and a high-power pulse magnetron sputtering power supply. Similarly, in the preparation of the metal carbide/nitride/carbonitride transition layer and the deposited CoCrFeNi high-entropy alloy doped amorphous carbon layer, the selection of the target evaporation/sputtering source is also the same.

Further, depositing a metal carbide, metal nitride or metal carbonitride transition layer, specifically: the deposited transition layer is any one or more of carbide/nitride/carbonitride such as TiC, crC, tiN, crN, tiCN or CrCN.

Further, depositing a CoCrFeNi high-entropy alloy doped amorphous carbon layer, specifically: selecting 1-2:1-2:1-2:1-2 molar ratio of CoCrFeNi high-entropy alloy target material and graphite target material for codeposition, and selecting magnetron sputtering technology or enhanced cathode arc technology to prepare the alloy according to different equipment conditions and process requirements

Further, preparing CoCrFeNi high-entropy alloy doped amorphous carbon films with different hydrogen contents, specifically comprising the following steps: in the deposition process of the amorphous carbon layer, CH with the gas flow of 5-80 sccm is introduced ₄ Or C ₂ H ₂ The gases are mixed and ionized to dope hydrogen ions of different concentrations into the film and thereby improve the film performance.

The above experimental parameter range is the preferable working parameter range, and particularly, in the film deposition process, an ion beam assisted deposition technology can be adopted, and the voltage can be selected to be 0-2000V. A person skilled in the art can select different ion source voltages to fine tune the film deposition performance, and can adjust and control the doping amount of the CoCrFeNi high-entropy alloy in the amorphous carbon film by changing the evaporation/sputtering power supply current so as to introduce a crystalline doping phase with the best performance to relieve the residual stress and cooperatively improve the mechanical property.

In conclusion, the CoCrFeNi high-entropy alloy doped amorphous carbon film with the thickness of 0.3-15 mu m is prepared by a physical vapor deposition device.

Compared with the prior art of doping the amorphous carbon by the heterogeneous metal elements, the method has the following beneficial effects:

the invention is creative in thinking, and the CoCrFeNi high-entropy alloy with high entropy effect (thermodynamics), delayed diffusion effect (kinetics), lattice distortion effect (structure) and cocktail effect (performance) is doped in the amorphous carbon film, and the residual stress of the film is relieved through the twinning reaction spontaneously formed by the crystalline doping phase under the action of high deposition stress of the film, thereby providing an effective thinking for the research of low-stress and high-performance amorphous carbon films.

The present invention incorporates a high entropy phase into amorphous carbon. Different from single-component or multi-component doping, the film can solve the problem of high residual stress of the amorphous carbon film by utilizing the characteristic of high-entropy phase deformation induced plasticity, and has the advantages of high hardness, high toughness, low friction coefficient and high film-substrate binding force by forming a high-entropy phase twin crystal structure. In view of the above description, the invention can provide a basic theory and a method for the design of the high-performance self-lubricating material, and expand the application of the amorphous carbon film in mechanical engineering and other fields.

Drawings

FIG. 1 is a schematic structural diagram of a CoCrFeNi high-entropy alloy doped amorphous carbon film layer.

In the figure, 1, a substrate; 2. priming a bottom layer; 3. a transition layer; 4. the CoCrFeNi high-entropy alloy is doped with an amorphous carbon layer.

FIG. 2 is TEM and HRTEM analysis images of CoCrFeNi nanocrystalline doped amorphous carbon thin film.

In the figure, a, bright field image and electron diffraction; b. a dark field phase; c. nano twin crystal high resolution phase; d. and a nano twin crystal/amorphous carbon matrix high-resolution phase.

FIG. 3 is a graph showing the residual stress results and the curvature of the silicon wafer surface before and after thin film plating in example 1.

FIG. 4 is a graph of the residual stress results and the wafer surface curvature before and after film plating for example 2.

FIG. 5 is a graph of the residual stress results and the curvature of the silicon wafer surface before and after thin film plating of example 3.

FIG. 6 is a graph showing the residual stress results and the curvature of the silicon wafer surface before and after thin film plating in the comparative example.

FIG. 7 is a graph showing the residual stress in examples 1 to 3 in comparison with the comparative example.

Detailed Description

The preparation and performance of the CoCrFeNi high-entropy alloy doped amorphous carbon film of the invention are further explained by the following specific examples, which are not intended to limit the invention.

The specific structure of the CoCrFeNi high-entropy alloy doped amorphous carbon film is shown in figure 1, and the CoCrFeNi high-entropy alloy doped amorphous carbon film sequentially comprises a matrix 1, a priming layer 2 of Ti/Cr/W/Zr and the like, a transition layer 3 of TiC/CrC/TiN/CrN/TiCN/CrCN and the like and a CoCrFeNi high-entropy alloy doped amorphous carbon layer 4.

Example 1

Equipment: the preparation process of the film is carried out on a magnetron sputtering and cathode arc ion enhanced physical vapor deposition device. The device comprises a heater, a Ti target magnetron sputtering/cathode arc evaporation source, a CoCrFeNi alloy target magnetron sputtering/cathode arc evaporation source, a graphite target magnetron sputtering/cathode arc evaporation source, an anode layer ion source, an autorotation rotating frame, a revolution rotating frame and the like. The sample holder is connected with a pulse bias power supply (0-100 KHz) for applying negative bias.

The coating process comprises the following steps: the method comprises the following process steps:

step S1: samples were selected, washed and mounted. Selecting a stainless steel sheet with the size of 40 multiplied by 20mm and a polished silicon sheet with the size of 20 multiplied by 20mm as sample matrixes, sequentially placing the samples in acetone and absolute ethyl alcohol, respectively treating for 20 minutes by using ultrasonic waves, cleaning oil stains and dust on the surface, then placing the samples in a vacuum high-temperature drying oven for drying to ensure the cleanness of the surfaces of the samples, and then installing the samples on a clamp table which is opposite to the ion source at the position of 12 cm.

Step S2: and carrying out ion beam cleaning on the sample. Setting the heater at 150 deg.C to improve the pumping efficiency, and pumping the vacuum degree of the vacuum chamber to 1.0 × 10 by using molecular pump ^-3 Introducing high-purity argon with the purity of 99.99 percent under Pa, wherein the gas flow is 25sccm, and the vacuum cavity pressure is maintained at 8 multiplied by 10 ^-1 Pa, setting ion beam voltage to 1300V and bias voltage to 600V to carry out ion beam cleaning on the sample for 30min.

And step S3: and depositing a Ti bottom layer. Introducing high-purity argon with the purity of 99.99%, wherein the flow rate is 30sccm, the vacuum cavity pressure is kept at 1.0Pa, the current of a magnetron sputtering source of the Ti target is set to be 4A, the power supply power is 1600W, the bias voltage is-600V, the duty ratio is 20%, meanwhile, the ion beam voltage is set to be 1300V for auxiliary deposition, after 30min, a Ti film layer 250nm is prepared, and the Ti target is shielded and protected against other targets in work, so that target pollution is avoided.

And step S4: and depositing a TiC transition layer. Introducing high-purity argon with the purity of 99.99 percent, wherein the flow rate is 25sccm, and the pressure of the vacuum cavity is kept at 8 multiplied by 10 ^-1 Pa, setting the current of a magnetron sputtering source of a Ti target and a graphite target to be 2.5A, the power supply power of the two targets to be 1000W, the bias voltage to be-600V, the duty ratio to be 20 percent, simultaneously setting the ion beam voltage to be 1300V for auxiliary deposition, and preparing the TiC film layer to be 300nm after 30min. The Ti and graphite targets should be shielded and protected during working, so that target pollution is avoided.

Step S5: and depositing a CoCrFeNi doped amorphous carbon layer. Introducing high-purity argon with the purity of 99.99 percent, wherein the flow rate is 25sccm, and the pressure of the vacuum cavity is kept at 8 multiplied by 10 ^-1 Pa, opening the two graphite targets simultaneously, setting the current of the graphite target magnetron sputtering source to be 3A, the power supply power of the two targets to be 1200W, setting the current of the CoCrFeNi alloy target magnetron sputtering source to be 1.5A, the power to be 600W, the bias voltage to be-400V, the duty ratio to be 10%, simultaneously setting the ion beam voltage to be 1300V for auxiliary deposition, and preparing the CoCrFeNi doped amorphous carbon film layer with the thickness of 1600nm after 300 min. The graphite and CoCrFeNi high-entropy alloy target can shield and protect other targets in work, so that target pollution is avoided.

And (3) performance characterization: the film thickness is 2.15 μm; the hardness is 21.3GPa; the binding force is 45N; massage deviceThe coefficient of friction was 0.13 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress analysis of the coating is carried out by an AlphaStep D-100 step instrument, a polished silicon wafer with the thickness of 25mm multiplied by 5mm is selected and respectively scanned by the step instrument before and after coating plating, and the specific residual stress is carried out according to the Stoney formula through the curvature change of the pretreatment and the post-treatment

And (4) calculating. In the formula, E _S 、V _S The modulus of elasticity and the poisson's ratio of the substrate, respectively; t is t _S And t _f Is the thickness of the substrate and the film; r is the curvature radius of the substrate, and the residual stress is measured to be 0.59GPa; the specific results and the surface curvature of the silicon wafer before and after the film plating are shown in the attached figure 3.

Example 2

Equipment: the same as in example 1.

step S1: the same as the step S1 of the coating process in example 1.

Step S2: the same as the step S2 of the coating process in example 1.

And step S3: the same as the step S3 of the plating process in example 1.

And step S4: the same as the step S4 of the coating process in example 1.

Step S5: and depositing a CoCrFeNi doped amorphous carbon layer. Introducing high-purity argon with the purity of 99.99 percent, wherein the flow rate is 25sccm, and the pressure of the vacuum cavity is kept at 8 multiplied by 10 ^-1 Pa, opening the two graphite targets simultaneously, setting the current of the graphite target magnetron sputtering source to be 3A, the power supply power of the two targets to be 1200W, setting the current of the CoCrFeNi alloy target magnetron sputtering source to be 1A, the power to be 800W, the bias voltage to be-400V and the duty ratio to be 10 percent, simultaneously setting the ion beam voltage to be 1300V for auxiliary deposition, and after 300min, preparing the CoCrFeNi doped amorphous carbon film layer with the thickness of 1500nm. The graphite and CoCrFeNi alloy target should shield and protect other targets in work, and target pollution is avoided.

And (3) performance characterization: the film thickness is 2.05 μm; the hardness is 23.4GPa; the binding force is 53N; the coefficient of friction was 0.14 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60 percent of humidity, the film does not generate phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.66GPa, the measurement method was the same as that of example 1, and the specific result and the surface curvature of the silicon wafer before and after the thin film plating are shown in FIG. 4.

Example 3

Equipment: the same as in example 1.

step S1: the same as the step S1 of the coating process in example 1.

Step S2: the same as the step S2 of the coating process in example 1.

And S3, depositing a Ti transition layer. Introducing high-purity argon with the purity of 99.99%, keeping the gas flow of 30sccm, keeping the pressure of a vacuum cavity at 1.0Pa, setting the current of an arc evaporation source of a Ti target cathode to be 50A, the power of a power supply to be 1600W, the bias voltage to be-100V and the duty ratio to be 20%, closing an ion source in the deposition process, and shielding and protecting the ion source to avoid pollution. The Ti film layer with the thickness of 0.6 mu m is prepared after 20min, and the Ti target can shield and protect other targets in work so as to avoid target pollution.

And step S4: and depositing a TiC transition layer. Introducing high-purity argon with the purity of 99.99 percent, wherein the flow rate is 25sccm, and the pressure of the vacuum cavity is kept at 8 multiplied by 10 ^-1 Pa, setting the current of the cathode arc evaporation source of the Ti target and the graphite target to be 50A, the power of the power supplies of the two targets to be 1600W, the bias voltage to be-100V and the duty ratio to be 20 percent, closing the ion source in the deposition process, and shielding and protecting the ion source to avoid pollution. After 20min, a TiC film layer with the diameter of 1.0 μm is prepared. The Ti and graphite targets should be shielded and protected during working, so that target pollution is avoided.

Step S5: and depositing a CoCrFeNi doped amorphous carbon layer. Introducing high-purity argon with the purity of 99.99 percent, wherein the flow rate is 25sccm, and the pressure of the vacuum cavity is kept at 8 multiplied by 10 ^-1 Pa, opening the two graphite targets simultaneously, setting the current of a cathode arc evaporation source of the graphite target to be 60A, setting the power of a power supply of the two targets to be 1800W, and setting the cathode arc of the CoCrFeNi alloy targetThe evaporation source current is 20A, the power is 600W, the bias voltage is-400V, the duty ratio is 10%, the ion source is closed in the deposition process, and the ion source is shielded and protected to avoid pollution. After 30min, a CoCrFeNi doped amorphous carbon film layer with the thickness of 4.2 mu m is prepared. The graphite and CoCrFeNi alloy target should shield and protect other targets in work, and target pollution is avoided.

And (3) performance characterization: the film thickness is 5.8 mu m; the hardness is 22.7GPa; the binding force is 63N; the coefficient of friction was 0.21 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60 percent of humidity, the film does not generate phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.39GPa, the measurement method was the same as that of example 1, and the specific result and the surface curvature of the silicon wafer before and after the thin film plating are shown in FIG. 5.

Example 4

The Ti target in step S3 of example 1 was replaced with a Cr target, i.e., a Cr primer layer was deposited on the surface of the substrate. The rest of the procedure was the same as in example 1. Respectively preparing the CoCrFeNi high-entropy alloy doped amorphous carbon film with Cr as the bottom layer.

And (3) performance characterization: the film thickness is 2.20 μm; the hardness is 21.5GPa; the binding force is 40N; the coefficient of friction was 0.12 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.55GPa.

Example 5

The Ti target in step S3 of example 1 was replaced with a W target, i.e., a W primer layer was deposited on the surface of the substrate. The rest of the procedure was the same as in example 1. Respectively preparing the CoCrFeNi high-entropy alloy doped amorphous carbon film with the bottom layer of W.

And (3) performance characterization: the film thickness is 2.23 μm; the hardness is 20.4GPa; the binding force is 38N; the coefficient of friction was 0.11 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.59GPa.

Example 6

The Ti target in step S3 of example 1 was replaced with a Zr target, i.e., a Zr primer layer was deposited on the surface of the substrate. The rest of the procedure was the same as in example 1. Respectively preparing the CoCrFeNi high-entropy alloy doped amorphous carbon film with Zr as the bottom layer.

And (3) performance characterization: the film thickness is 2.11 μm; the hardness is 19.3GPa; the binding force is 40N; the coefficient of friction was 0.13 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.56GPa.

Example 7

The Ti target and graphite target in step S4 of example 1 were replaced with a Cr target and a graphite target, i.e., a CrC transition layer was deposited on the basis of step S3. The rest of the procedure was the same as in example 1. Respectively preparing the CoCrFeNi high-entropy alloy doped amorphous carbon film with the CrC transition layer.

And (3) performance characterization: the film thickness is 2.23 μm; the hardness is 18.9GPa; the binding force is 38N; the coefficient of friction was 0.11 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.57GPa.

Example 8

The Ti target and the graphite target in step S4 of example 1 were replaced with Ti targets (N was introduced and ionized) ₂ ) Namely, depositing a TiN transition layer on the basis of the step S3. The rest of the procedure was the same as in example 1. Respectively preparing the CoCrFeNi high-entropy alloy doped amorphous carbon film with the transition layer of TiN.

And (3) performance characterization: the film thickness is 2.25 μm; the hardness is 19.9GPa; the binding force is 40N; the coefficient of friction was 0.14 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.59GPa.

Example 9

The Ti target and the graphite target in step S4 of example 1 were replaced with Cr targets (N was introduced and ionized) ₂ ) Namely, a CrN transition layer is deposited on the basis of the step S3. The rest of the procedure was the same as in example 1. Respectively preparing the CoCrFeNi high-entropy alloy doped amorphous carbon film with the CrN transition layer.

And (3) performance characterization: the film thickness is 2.30 μm; the hardness is 19.8GPa; the binding force is 41N; the coefficient of friction was 0.13 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.55GPa.

Example 10

The Ti target and the graphite target in step S4 of example 1 were replaced with the Ti target and the graphite target (N was introduced and ionized) ₂ ) I.e. depositing a TiCN transition layer on the basis of step S3. The rest of the procedure was the same as in example 1. And respectively preparing the CoCrFeNi high-entropy alloy doped amorphous carbon film with the TiCN as the transition layer.

And (3) performance characterization: the film thickness is 2.24 mu m; the hardness is 20.1GPa; the binding force is 37N; the coefficient of friction was 0.12 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60 percent of humidity, the film does not generate phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.52GPa.

Example 11

The Ti target and the graphite target in step S4 of example 1 were replaced with a Cr target and a graphite target (N was introduced and ionized) ₂ ) I.e. a CrCN transition layer is deposited on the basis of step S3. The rest of the procedure was the same as in example 1. And respectively preparing the CoCrFeNi high-entropy alloy doped amorphous carbon film with the CrCN transition layer.

And (3) performance characterization: the film thickness is 2.26 mu m; the hardness is 20.3GPa; the binding force is 43N; the coefficient of friction was 0.10 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 0.56GPa.

Comparative example 1

Equipment: the same as in example 1.

step S1: the same as the step S1 of the coating process in example 1.

Step S2: the same as the step S2 of the coating process in example 1.

And step S3: the same as the step S3 of the coating process in example 1.

And step S4: the same as the step S4 of the coating process in example 1.

Step S5: a pure amorphous carbon layer is deposited. Introducing high-purity argon with the purity of 99.99 percent, wherein the flow rate is 25sccm, and the pressure of the vacuum cavity is kept at 8 multiplied by 10 ^-1 Pa, opening the two graphite targets simultaneously, setting the current of the graphite target magnetron sputtering source to be 3A, the power supply power of the two targets to be 1200W, the bias voltage to be 400V, the duty ratio to be 10 percent, simultaneously setting the ion beam voltage to be 1300V for auxiliary deposition, and preparing the pure amorphous carbon film layer of 1450nm after 360 min. The graphite and CoCrFeNi high-entropy alloy target can shield and protect other targets in work, so that target pollution is avoided.

And (3) performance characterization: the film thickness is 2.0 μm; the hardness is 16.3GPa; the binding force is 26N; the coefficient of friction was 0.18 (GCr 15 for the friction couple ball). After the film is stored for three months under the conditions of 30 ℃ and 60% of humidity, the film does not generate the phenomena of foaming, cracking, falling off and the like. The friction coefficient and the wear rate of the carbon film are not obviously changed before and after storage. The residual stress was measured to be 1.1GPa, the measurement method is the same as that of example 1, and the specific result and the surface curvature of the silicon wafer before and after the film plating are shown in the attached figure 6.

The residual stress of the example is compared to the sample of comparative example 1, see figure 7.

In conclusion, the CoCrFeNi high-entropy alloy doped amorphous carbon film prepared by the invention has low stress and good other mechanical properties, and has outstanding comprehensive properties compared with the prior art.

The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims

1. A CoCrFeNi high-entropy alloy doped amorphous carbon film is characterized in that: the CoCrFeNi high-entropy alloy doped amorphous carbon film comprises a substrate, and sequentially comprises a priming layer combined with the substrate, a transition layer combined with the priming layer and a CoCrFeNi high-entropy alloy doped amorphous carbon layer combined with the transition layer from the substrate to the surface of the film; the Co element in the CoCrFeNi high-entropy alloy doped amorphous carbon layer: cr element: fe element: the proportion of the Ni element is 1 to 2.

2. The CoCrFeNi high-entropy alloy doped amorphous carbon film of claim 1, which is characterized in that: a nanometer twin crystal structure is introduced into an amorphous carbon film by doping a CoCrFeNi component with stacking fault forming capability, the stress of the CoCrFeNi high-entropy alloy doped amorphous carbon film is 0.3-0.8GPa, the film thickness is 0.3-15 mu m, the hardness is 15-25GPa, the bonding force is 35-65N, and the friction coefficient is 0.08-0.21.

3. The preparation method of the CoCrFeNi high-entropy alloy doped amorphous carbon film as claimed in claim 1 or 2, characterized in that: the method comprises the following steps:

and step S3: depositing a simple substance metal priming coat;

4. The production method according to claim 3, characterized in that: the substrate comprises stainless steel, bearing steel, titanium alloy, magnesium alloy, hard alloy, silicon chip and glass.

5. The production method according to claim 3, characterized in that: s2, the ion source of the plasma cleaning technology comprises any one of an anode layer ion source, a Kaffman ion source, a Hall ion source, a radio frequency induction coupling ion source and an electron cyclotron resonance ion source; the ion energy of the ion beam is 50eV to 1500eV.

6. The production method according to claim 3, characterized in that: the target evaporation/sputtering power source adopted in the deposition in the steps S3-S5 comprises any one of a magnetron sputtering power source, a cathode arc evaporation source, a hollow cathode arc evaporation source and a hot wire arc evaporation source; the magnetron sputtering power supply comprises any one of a direct-current magnetron sputtering power supply, a medium-frequency magnetron sputtering power supply, a radio-frequency magnetron sputtering power supply and a high-power pulse magnetron sputtering power supply.

7. The production method according to claim 3, characterized in that: s3, the elementary metal priming coat comprises Ti, cr, W or Zr; and S4, the transition layer comprises TiC, crC, tiN, crN, tiCN or CrCN.

8. The production method according to claim 3, characterized in that: the sputtering target material of the CoCrFeNi high-entropy alloy doped amorphous carbon layer is prepared by vacuum melting and isostatic pressing sintering, and the purity of the sputtering target material is higher than 99.9%.

9. The production method according to claim 3, characterized in that: co element in the CoCrFeNi high-entropy alloy doped amorphous carbon layer: cr element: fe element: the ratio of the Ni element is 1 to 2.

10. The production method according to claim 3, characterized in that: s5, when the CoCrFeNi high-entropy alloy doped amorphous carbon layer is deposited, introducing CH with the gas flow of 5-80sccm ₄ Or C ₂ H ₂ And is ionized.