CN108677144B - Method for preparing aluminum-nitrogen co-doped diamond-like carbon composite film - Google Patents
Method for preparing aluminum-nitrogen co-doped diamond-like carbon composite film Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- IWBUYGUPYWKAMK-UHFFFAOYSA-N [AlH3].[N] Chemical compound [AlH3].[N] IWBUYGUPYWKAMK-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 27
- 239000010439 graphite Substances 0.000 claims abstract description 27
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 230000008020 evaporation Effects 0.000 claims abstract description 22
- 238000004544 sputter deposition Methods 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 238000000541 cathodic arc deposition Methods 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 238000005137 deposition process Methods 0.000 claims abstract description 3
- 239000012495 reaction gas Substances 0.000 claims abstract description 3
- 239000013077 target material Substances 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 62
- 229910052786 argon Inorganic materials 0.000 claims description 37
- 150000002500 ions Chemical class 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 25
- 238000004140 cleaning Methods 0.000 claims description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 argon ions Chemical class 0.000 claims description 10
- 230000001276 controlling effect Effects 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
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- 231100000719 pollutant Toxicity 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010884 ion-beam technique Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000005728 strengthening Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 8
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 85
- 230000035882 stress Effects 0.000 description 12
- 229910018509 Al—N Inorganic materials 0.000 description 9
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 4
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
- C23C14/0611—Diamond
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing an aluminum-nitrogen co-doped diamond-like carbon composite film. Adopting an ion source assisted cathodic arc deposition technology, and configuring two double-excitation-source cathodic arc coating devices with different characteristics, wherein one is a direct current arc evaporation cathode source for mounting an aluminum target material, and the other is a pulse arc evaporation cathode source for mounting a graphite target; in the deposition process, nitrogen is used as reaction gas, and an ion source is used for introducing nitrogen (N)2) Ionised to ionic nitrogen (N)+) The sputtering deposition on the surface of the workpiece is realized by rotating the workpiece and enabling the aluminum target and the graphite target which are arranged on the direct current arc evaporation cathode source and the pulse arc evaporation cathode source to obtain the aluminum-nitrogen co-doped diamond-like composite film with controllable components. In the invention, N is doped in an ion form to promote the diamond-like carbon composite film to form hard aluminum nitride (AlN) and metal Al nanocrystalline particles; has the advantages of smooth surface, high hardness, high toughness and low stress.
Description
Technical Field
The invention relates to a method for preparing an aluminum-nitrogen co-doped diamond-like carbon composite film, and belongs to the technical field of preparation of diamond-like carbon composite films.
Background
Diamond-like carbon films are widely used in high-speed cutting tools, die protection, and the like as the most important film in solid lubricating coatings. However, the diamond-like thin film itself still has some problems to be solved: the diamond-like carbon film has the problems of low film-substrate bonding strength and the like caused by high internal stress and high internal stress, and is delaminated, peeled or failed; meanwhile, the problem of the reduction of the film hardness caused by doping metal elements in order to solve the internal stress is solved. Therefore, it is very critical and urgent to solve the above-mentioned problems restricting the application of the diamond-like carbon film.
The interfacial stress or thermal stress caused by the mismatch of the thermal expansion coefficients of the diamond-like thin film and the base material is one of the reasons for the low film-to-substrate bonding strength. By integrating the research and analysis at home and abroad, in order to reduce the difference of physical properties between film bases, foreign elements are often doped in the diamond-like carbon film to relieve the problems of internal stress accumulation and film brittleness of the diamond-like carbon film. Research shows that the film-substrate bonding strength and mechanical strength can be improved by reasonably controlling the bonding mode of the mutual-crosslinking carbon matrix network in the doping element and the diamond-like carbon film, the surface chemical state of the film and the film components. First, for the metal element Al doped diamond-like carbon film, the Al element with the medium hardness is doped into the diamond-like carbon film to form weak bonding carbide with carbon, which greatly improves the toughness of the film, but reduces the hardness of the film to a certain extent. After the non-metal element N is doped into the diamond-like carbon film, the N atom replaces the carbon atom in the C-C bond in the film to promote sp in the film2Hybridized bond to sp3The hybrid bonds are transformed to improve the diamond properties of the film, but not to significantly improve the toughness of the film. However, studies on Al and N double-element co-doped diamond-like carbon films are rare.
Disclosure of Invention
The invention aims to provide a method for preparing an aluminum-nitrogen co-doped diamond-like carbon composite film, which combines the advantages of metal-doped diamond-like carbon films and nonmetal-doped diamond-like carbon films, selects nonmetal N elements and metal Al elements as dopants, and can prepare the aluminum-nitrogen co-doped diamond-like carbon composite film containing an AlN nanoparticle strengthening phase and a simple substance Al nanoparticle toughening phase by reasonably regulating and controlling the microstructure and components of the film.
In the invention, N is doped in an ion form to promote the formation of aluminum nitride AlN and metal Al nanocrystalline particles in the diamond-like carbon composite film; the aluminum nitride nanocrystalline particles can be used as a mechanical strengthening phase to improve the hardness of the diamond-like carbon film, the Al nanocrystalline particles are uniformly embedded in the amorphous carbon network matrix, the plastic deformation effect of metal can be fully exerted, and the toughness of the film is greatly improved by releasing strain. Preparing Al and N pairs by cathodic arc deposition technologyIn the process of element co-doping of the diamond-like carbon film, the metal target and the graphite target are easy to generate a large amount of macro particles under the action of high-temperature electric arc, so that the surface of the film becomes rough, and the performance of the film is greatly reduced. In order to eliminate the adverse effect of macro particles in the process of depositing diamond-like carbon film, the invention changes the doping mode of nitrogen source, and inert nitrogen (N) is added by ion source assisted cathodic arc deposition technology2) Ionization to highly active ionic nitrogen (N)+) And preparing the aluminum-nitrogen co-doped diamond-like composite film with a smooth surface on the surface of the workpiece by matching with a direct current and pulse double-excitation-source cathode plasma deposition device. The optimal matching of the toughness and the hardness of the diamond-like carbon film can be achieved by reasonably controlling the contents of the aluminum and the nitrogen in the film. The method is very important for further popularization of the application of the diamond-like carbon film in the engineering field.
The invention provides a method for preparing an aluminum-nitrogen co-doped diamond-like composite film, which adopts an ion source assisted cathodic arc deposition technology and is provided with two double excitation source cathodic arc coating devices with different characteristics, wherein one of the two double excitation source cathodic arc coating devices is a direct current arc evaporation cathode source and is used for installing an aluminum target material, and the other one is a pulse arc evaporation cathode source and is used for installing a graphite target; before the film deposition, Ar and N are firstly introduced2The mixed gas is used for carrying out sputtering cleaning on the surface of the workpiece by adopting an ion source; in the film deposition process, nitrogen is used as a reaction gas, and an ion source is used for introducing nitrogen (N)2) Ionised to ionic nitrogen (N)+) The aluminum targets and the graphite targets which are arranged on the direct current arc evaporation cathode source and the pulse arc evaporation cathode source are enabled to realize sputtering deposition on the surface of the workpiece by rotating the workpiece, and the aluminum-nitrogen co-doped diamond-like composite film with controllable components and containing the AlN nanoparticle strengthening phase and the simple substance Al nanoparticle toughening phase is obtained.
The double excitation source cathode arc coating device comprises a vacuum chamber, a direct current aluminum cathode target and a pulse graphite cathode target; a direct current aluminum cathode arc power supply and a pulse graphite cathode arc power supply are installed on the rear wall of the vacuum chamber, an upper group of deflection magnetic filtering devices and a lower group of deflection magnetic filtering devices which are combined are arranged outside an aluminum cathode target, a circular rotating sample table is installed at the bottom of the vacuum chamber, and the lower end of the sample table is connected with a bias power supply outside the vacuum chamber; a pulse graphite anode target is arranged below the pulse graphite cathode target; a sputtering ion source is arranged below the direct current cathode target; an air exhaust channel is arranged below the rear wall of the vacuum chamber, the outer side of the vacuum chamber is connected with a vacuumizing device, the upper part and the side surface of the vacuum chamber are respectively provided with an argon gas inlet and a nitrogen gas inlet, and the outer part of the air inlet is connected with a gas flowmeter.
The preparation method of the aluminum-nitrogen co-doped diamond-like carbon composite film specifically comprises the following steps:
(1) surface treatment of a workpiece: sequentially putting the workpiece into an acetone solution, an ethanol solution and deionized water, respectively carrying out ultrasonic cleaning for 10 min, removing surface grease and other pollutants, and then putting the substrate into an oven for drying for later use;
(2) fixing the processed workpiece on a rotating sample table in a vacuum chamber of a double-excitation-source cathode arc coating device, wherein a high-purity aluminum target and a graphite target are respectively arranged on evaporators of a direct-current cathode arc and a pulse cathode arc;
(3) the vacuum chamber is vacuumized by a vacuumizing device to ensure that the vacuum degree reaches 4 multiplied by 10−4~6×10−4Pa; introducing argon into the vacuum chamber through the air inlet, controlling the flow of the argon by the flow meter, and adjusting the air inlet flow of the argon flow meter to stabilize the air pressure of the vacuum chamber at 3 × 10−2~8×10−2Pa; starting a rotary sample table, carrying out sputtering cleaning on the surface of a workpiece by adopting an ion source, and then cooling to room temperature;
(4) closing the argon inlet, opening the nitrogen inlet, and regulating the gas flow of the nitrogen flowmeter to stabilize the pressure of the vacuum chamber at 3 × 10−2~8×10−2Pa; ionization of nitrogen (N) by ion source2) Generating a nitrogen ion beam (N)+) (ii) a Simultaneously starting a direct current cathode arc evaporation power supply and a pulse cathode arc evaporation source, and adjusting the direct current cathode voltage to be 60-90V and the direct current cathode current to be 60-70A; and adjusting the voltage of a pulse cathode to be 300-350V, and the pulse frequency to be 3-10 Hz, and depositing the aluminum-nitrogen co-doped diamond-like carbon composite film on the rotating workpiece.
In the preparation method, in the step (3), the ion source for sputtering cleaning is argon ions, the argon flow is 30-60 sccm, and sputtering is performedThe jet cleaning time is 10-15 min, and the energy and beam density of argon ions are 2-4 keV and 15-25A/m respectively2。
In the preparation method, in the step (4), the nitrogen flow is introduced at 20-50 sccm, and the energy of nitrogen ions is 120-150 eV.
In the above preparation method, when the diamond-like carbon film is prepared by pulsed cathodic arc in the step (4), the number of pulses is 370-3000.
In the preparation method, the rotating speed of the sample stage is 1-3r/min when the film is sputtered, cleaned and deposited in the steps (3) and (4).
In the preparation method, the film thickness of the obtained composite film is 1.0-1.2 μm.
The aluminum-nitrogen co-doped diamond-like composite film prepared by the method can form aluminum nitride nanocrystals with stable thermodynamics, the nanocrystals can be isolated by an amorphous carbon matrix on one hand, so that internal stress is easily released, further expansion of cracks is prevented, and dislocation and grain boundary slippage can be prevented on the other hand, so that the hardness of the composite film can be effectively improved, and the internal stress of the film is reduced.
The invention has the beneficial effects that:
(1) the invention installs an ion source on a conventional cathodic arc deposition device for exciting N2Generating N+The nitrogen is doped in an ion form, so that the bonding effect among Al atoms, C atoms and N atoms in the film is improved, the roughness of the surface of the film is reduced, and the surface quality of the film is greatly improved.
(2) By adopting the preparation method, the energy density of the plasma can be controlled by changing the pulse frequency of the current of the pulse cathodic arc evaporation source and the current of the direct-current cathodic arc evaporation power supply, and the content of aluminum and nitrogen elements in the film can be regulated and controlled, so that the preparation of the diamond-like composite film with high hardness and high toughness can be realized.
(3) The Al atoms not bonded to carbon can further improve the toughness of the thin film by exerting the characteristic of strong plastic deformation of the metal. Compared with the pure diamond-like carbon film, the aluminum-nitrogen co-doped diamond-like carbon composite film has the advantages that the residual stress is obviously reduced, the hardness and the toughness are greatly improved, and the abrasion resistance is enhanced.
Drawings
FIG. 1 is a schematic view of a coating apparatus according to the present invention;
FIG. 2 is an atomic force microscope three-dimensional photograph of the surface of the Al-N co-doped diamond-like composite film prepared in example 1;
FIG. 3 is an atomic force microscope three-dimensional photograph of the surface of the Al-N co-doped diamond-like composite film prepared in example 2;
FIG. 4 is an Al2p XPS spectrum and its fitting peak of the Al-N co-doped diamond-like composite film prepared in example 1;
FIG. 5 is an Al2p XPS spectrum and its fitting peak of the Al-N co-doped diamond-like composite film prepared in example 2;
FIG. 6 is a microscope photograph of scratches on the surface of the Al-N co-doped diamond-like composite film prepared in example 1;
FIG. 7 is a photomicrograph of a scratch on the surface of the Al-N co-doped diamond-like composite film prepared in example 2;
in fig. 1: 1. a vacuum chamber; 2. a direct current aluminum cathode arc power supply; 3. a pulsed graphite cathodic arc power supply; 4. a direct current aluminum cathode target; 5. a deflection magnetic filter device; 6. rotating the sample table; 7. a pulsed graphite cathode target; 8. a bias power supply; 9. a pulsed graphite anode target; 10. an air extraction channel; 11. a vacuum pumping device; 12. an argon gas inlet; 13. argon gas flowmeter, 14, ion source; 15. a nitrogen inlet; 16. a nitrogen gas flow meter.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
firstly, providing a coating device adopted in the process of modifying the surface of a substrate, namely the direct current and pulse double excitation source cathode arc coating device, as shown in figure 1, the device comprises a vacuum chamber 1, a direct current aluminum cathode target 4 and a pulse graphite cathode target 7; a direct current aluminum cathode arc power supply 2 and a pulse graphite cathode arc power supply 3 are installed on the rear wall of a vacuum chamber 1, an upper group and a lower group of combined deflection magnetic filtering devices 5 are arranged outside a direct current aluminum cathode target 4, a circular rotating sample table 6 is installed at the bottom of the vacuum chamber 1, and the lower end of the sample table is connected with a bias power supply 8 outside the vacuum chamber; a pulse graphite anode target 9 is arranged below the pulse graphite cathode target 7, and a sputtering ion source 14 is arranged below the direct current aluminum cathode target; an air pumping channel 10 is arranged below the rear wall of the vacuum chamber 1, the outer side of the air pumping channel is connected with a vacuum pumping device 11, and the upper part of the vacuum chamber 1 is arranged; an air exhaust channel is arranged below the rear wall of the vacuum chamber, the outer side of the vacuum chamber is connected with a vacuum extractor, the upper part and the side surface of the vacuum chamber are respectively provided with an argon gas inlet hole 12 and a nitrogen gas inlet hole 15, and the outside of the argon gas inlet hole 12 is connected with an argon gas flowmeter 13 and a nitrogen gas flowmeter 16.
The embodiment provides a method for preparing a high-hardness and high-toughness aluminum-nitrogen co-doped diamond-like composite film on the surface of a workpiece by adopting the device. The workpiece is tested, and the operation steps are as follows:
(1) surface treatment of a workpiece: sequentially putting the workpiece into acetone solution, ethanol solution and deionized water, respectively carrying out ultrasonic cleaning for 10 min to remove surface grease and other pollutants, and then putting the substrate into an oven for drying for later use;
(2) fixing the pretreated workpiece on a rotary sample table 6 in a vacuum chamber 1 of a cathode arc device shown in figure 1, wherein a direct current aluminum cathode target 4 and a pulse graphite cathode target 7 are respectively arranged on evaporators of a direct current aluminum cathode arc power supply 2 and a pulse cathode arc power supply 3;
(3) the vacuum chamber 1 is vacuumized by a vacuum-pumping device 11 to make the vacuum degree reach 6 x 10−4Pa; introducing argon gas into the vacuum chamber 1 through an air inlet 12, controlling the flow of the argon gas by a gas flowmeter 13, adjusting the inflow rate of the argon gas to 35sccm, and stabilizing the pressure of the vacuum chamber at 5 x 10−2Pa; starting the rotary sample table 6, and carrying out sputtering cleaning on the surface of the workpiece by adopting an ion source 14, wherein the energy and the beam density of argon ions are respectively 3 keV and 25A/m2Cleaning for 15min, and then cooling to room temperature;
(4) closing the argon inlet 12, opening the nitrogen inlet 15, adjusting the inlet flow of the nitrogen flowmeter 16 to 35sccm, and adjusting the vacuum chamber pressure to 5 × 10−2. Nitrogen gas (N) ionization using ion source 142) Generating a nitrogen ion beam (N)+). Simultaneously turning on the DC cathodeThe electric arc evaporation power supply 2 and the pulse cathode electric arc evaporation source 3 adjust the direct current cathode voltage to 80V and the direct current cathode current to 60A; and adjusting the voltage of a pulse cathode to 350V and the pulse frequency to 6 Hz, and preparing the aluminum-nitrogen co-doped diamond-like carbon composite film on the rotating workpiece.
Example 2:
this example provides a method for preparing a high hardness, high toughness aluminum-nitrogen co-doped diamond-like composite film using the apparatus described in example 1, comprising the steps of:
(1) surface treatment of a workpiece: sequentially putting the workpiece into acetone solution, ethanol solution and deionized water, respectively carrying out ultrasonic cleaning for 10 min to remove surface grease and other pollutants, and then putting the substrate into an oven for drying for later use;
(2) fixing the pretreated workpiece on a rotary sample table 6 in a vacuum chamber 1 of a cathode arc device shown in figure 1, wherein a direct current aluminum cathode target 4 and a pulse graphite cathode target 7 are respectively arranged on evaporators of a direct current aluminum cathode arc power supply 2 and a pulse cathode arc power supply 3;
(3) the vacuum chamber 1 is vacuumized by a vacuum-pumping device 11 to make the vacuum degree reach 6 x 10−4Pa; introducing argon gas into the vacuum chamber 1 through an air inlet 12, controlling the flow of the argon gas by a gas flowmeter 13, adjusting the inflow rate of the argon gas to be 50sccm, and stabilizing the pressure of the vacuum chamber at 8 x 10−2Pa; starting the rotary sample table 6, and carrying out sputtering cleaning on the surface of the workpiece by adopting an ion source 14, wherein the energy and the beam density of argon ions are respectively 2 keV and 20A/m2Cleaning for 15min, and then cooling to room temperature;
(4) closing the argon inlet 12, opening the nitrogen inlet 15, adjusting the inlet flow of the nitrogen flowmeter 16 to 50sccm, and adjusting the vacuum chamber pressure to 8 × 10−2. Nitrogen gas (N) ionization using ion source 142) Generating a nitrogen ion beam (N)+). Simultaneously starting a direct current cathode arc evaporation power supply 2 and a pulse cathode arc evaporation source 3, and adjusting the direct current cathode voltage to 80V and the direct current cathode current to 80A; and adjusting the voltage of a pulse cathode to 350V and the pulse frequency to 10 Hz, and preparing the aluminum-nitrogen co-doped diamond-like carbon composite film on the rotating workpiece.
Comparative example:
the example provides a method for preparing a non-doped diamond-like film on the surface of a workpiece by adopting the prior art to test the workpiece, and the operation steps are as follows:
(1) surface treatment of a workpiece substrate: sequentially putting the workpiece into acetone solution, ethanol solution and deionized water, respectively carrying out ultrasonic cleaning for 10 min to remove surface grease and other pollutants, and then putting the substrate into an oven for drying for later use;
(2) fixing the pretreated workpiece on a rotary sample table in a vacuum chamber, and installing a graphite target on an evaporator of a pulse cathode arc;
(3) the vacuum chamber is vacuumized by a vacuumizing device to ensure that the vacuum degree reaches 6 multiplied by 10−4Pa; introducing argon gas into the vacuum chamber through the gas inlet, wherein the flow rate of the argon gas is controlled by a flowmeter, so that the pressure of the vacuum chamber is stabilized at 5 x 10−2Pa; starting a rotary sample table, and carrying out sputtering cleaning on the silicon substrate by adopting an ion source, wherein the energy and the beam density of argon ions are respectively 3 keV and 25A/m2Cleaning for 15min, and then cooling to room temperature;
(4) and (3) closing an argon gas inlet, starting a pulse cathode electric arc power supply, adjusting the cathode voltage to 300V, and depositing a diamond-like single-layer film on the surface of the rotating workpiece, wherein the pulse number is 1500, and the rotating speed of the sample table is 2 r/min.
The resulting product was tested for properties as follows:
as shown in FIGS. 2 and 3, the Al-N co-doped diamond-like composite film prepared by the method of the present invention under different process parameters shows the surface morphology of the nano structure, and the particle size and the roughness of the surface of the film are closely related to the process parameters.
The Al2p XPS spectra shown in FIGS. 4 and 5 show that Al-N co-doped diamond-like composite films containing Al-N, Al-O and Al metal bonds form a hard aluminum nitride ceramic phase and elemental aluminum with high ductility.
The microscopic photos of the scratches of the aluminum-nitrogen co-doped diamond-like composite film shown in fig. 6 and 7 show that the scratches on the surface of the film have different groove depths under different process parameters, the toughness of the film is improved, no obvious cracks are formed around the grooves, and the crack propagation resistance is high.
The mechanical properties of the aluminum-nitrogen co-doped diamond-like carbon composite film prepared by the invention and the pure diamond-like carbon film prepared in the comparative example are compared as follows: the mechanical properties of the film are tested through a Stroni stress test and a nano indentation test, and test results show that the residual stress of the aluminum-nitrogen co-doped diamond-like carbon composite film in the embodiment 1 and the embodiment 2 is respectively 0.83 GPa and 1.81 GPa, the nano hardness (H) is respectively 23.5 GPa and 30 GPa, and the plastic deformation resistance index (H/E) is respectively 0.092 and 0.080; while the residual stress, nano-hardness and plastic deformation resistance index of the pure diamond-like carbon film are respectively 3.51GPa, 19.2GPa and 0.061. . Therefore, the method of the invention obviously reduces the residual stress of the diamond-like carbon-based composite film and improves the hardness, the wear resistance and the toughness.
Claims (7)
1. A method for preparing an aluminum-nitrogen co-doped diamond-like carbon composite film is characterized by comprising the following steps: adopting an ion source assisted cathodic arc deposition technology, and configuring two double-excitation-source cathodic arc coating devices with different characteristics, wherein one is a direct current arc evaporation cathode source for mounting an aluminum target material, and the other is a pulse arc evaporation cathode source for mounting a graphite target; before the film deposition, Ar and N are firstly introduced2The mixed gas is used for carrying out sputtering cleaning on the surface of the workpiece by adopting an ion source; in the film deposition process, nitrogen is used as reaction gas, an ion source is utilized to ionize the nitrogen into ion nitrogen, and sputtering deposition on the surface of a workpiece is realized by rotating the workpiece to enable an aluminum target and a graphite target which are arranged on a direct current arc evaporation cathode source and a pulse arc evaporation cathode source to obtain an aluminum nitrogen co-doped diamond-like composite film with controllable components and containing an AlN nanoparticle strengthening phase and a simple substance Al nanoparticle toughening phase;
the method for preparing the aluminum-nitrogen co-doped diamond-like composite film comprises the following steps:
(1) surface treatment of a workpiece: sequentially putting the workpiece into an acetone solution, an ethanol solution and deionized water, respectively carrying out ultrasonic cleaning for 10 min, removing surface grease and other pollutants, and then putting the substrate into an oven for drying for later use;
(2) fixing the processed workpiece on a rotating sample table in a vacuum chamber of a double-excitation-source cathode arc coating device, wherein a high-purity aluminum target and a graphite target are respectively arranged on evaporators of a direct-current cathode arc and a pulse cathode arc;
(3) the vacuum chamber is vacuumized by a vacuumizing device to ensure that the vacuum degree reaches 4 multiplied by 10−4~6×10−4Pa; introducing argon into the vacuum chamber through the air inlet, controlling the flow of the argon by the flow meter, and adjusting the air inlet flow of the argon flow meter to stabilize the air pressure of the vacuum chamber at 3 × 10−2~6×10−2Pa; starting a rotary sample table, carrying out sputtering cleaning on the surface of a workpiece by adopting an ion source, and then cooling to room temperature;
(4) closing the argon inlet, opening the nitrogen inlet, and regulating the gas flow of the nitrogen flowmeter to stabilize the pressure of the vacuum chamber at 3 × 10−2~6×10−2Pa; ionizing nitrogen by using an ion source to generate a nitrogen ion beam; simultaneously starting a direct current cathode arc evaporation power supply and a pulse cathode arc evaporation source, and adjusting the direct current cathode voltage to be 60-90V and the direct current cathode current to be 60-70A; and adjusting the voltage of a pulse cathode to be 300-350V, and the pulse frequency to be 3-10 Hz, and depositing the aluminum-nitrogen co-doped diamond-like carbon composite film on the rotating workpiece.
2. The method for preparing the aluminum-nitrogen co-doped diamond-like composite film according to claim 1, wherein: in the step (3), the ion source for sputtering cleaning is argon ions, the flow of the argon ions is 30-60 sccm, the sputtering cleaning time is 10-15 min, and the energy and the beam density of the argon ions are 2-4 keV and 15-25A/m respectively2。
3. The method for preparing the aluminum-nitrogen co-doped diamond-like composite film according to claim 1, wherein: in the step (4), the flow rate of the introduced nitrogen is 30-60 sccm, and the energy of the nitrogen ions is 120-150 eV.
4. The method for preparing the aluminum-nitrogen co-doped diamond-like composite film according to claim 1, wherein: when the diamond-like carbon film is prepared by pulse cathodic arc in the step (4), the number of pulses is 370-3000.
5. The method for preparing the aluminum-nitrogen co-doped diamond-like composite film according to claim 1, wherein: and (4) in the steps (3) and (4), the rotating speed of the sample stage is 1-3r/min when the film is sputtered, cleaned and deposited.
6. The method for preparing the aluminum-nitrogen co-doped diamond-like composite film according to claim 1, wherein: the film thickness of the obtained composite film is 1.0-1.2 μm.
7. The method for preparing the aluminum-nitrogen co-doped diamond-like composite film according to claim 1, wherein: the double excitation source cathode arc coating device comprises a vacuum chamber, a direct current aluminum cathode target and a pulse graphite cathode target; a direct current aluminum cathode arc power supply and a pulse graphite cathode arc power supply are installed on the rear wall of the vacuum chamber, an upper group of deflection magnetic filtering devices and a lower group of deflection magnetic filtering devices which are combined are arranged outside an aluminum cathode target, a circular rotating sample table is installed at the bottom of the vacuum chamber, and the lower end of the sample table is connected with a bias power supply outside the vacuum chamber; a pulse graphite anode target is arranged below the pulse graphite cathode target; a sputtering ion source is arranged below the direct current cathode target; an air exhaust channel is arranged below the rear wall of the vacuum chamber, the outer side of the vacuum chamber is connected with a vacuumizing device, the upper part and the side surface of the vacuum chamber are respectively provided with an argon gas inlet and a nitrogen gas inlet, and the outer part of the air inlet is connected with a gas flowmeter.
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| CN110205589B (en) * | 2019-07-12 | 2023-12-08 | 江苏徐工工程机械研究院有限公司 | Pulse carbon ion excitation source device |
| CN111906144B (en) * | 2020-07-17 | 2022-02-22 | 太原理工大学 | Method for improving interface bonding strength of titanium/aluminum composite board |
| CN111850484B (en) * | 2020-07-24 | 2022-05-17 | 太原理工大学 | Device and method for preparing tough amorphous carbon-based multiphase hybrid film |
| CN112038481B (en) * | 2020-09-01 | 2023-09-22 | 武汉大学 | Heavy rare earth doped ZnO columnar crystal preferred orientation piezoelectric film material and preparation method thereof |
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| CN116219391A (en) * | 2023-05-09 | 2023-06-06 | 艾瑞森表面技术（苏州）股份有限公司 | AlN doped diamond-like coating process |
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| CN106011745A (en) * | 2016-06-15 | 2016-10-12 | 太原理工大学 | Device and method for preparing amorphous carbon and nitrogen thin films on surface of silicon |
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