CN108977767B - Wear-resistant delta-TaN film and preparation method and application thereof - Google Patents

Wear-resistant delta-TaN film and preparation method and application thereof Download PDF

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CN108977767B
CN108977767B CN201811021251.2A CN201811021251A CN108977767B CN 108977767 B CN108977767 B CN 108977767B CN 201811021251 A CN201811021251 A CN 201811021251A CN 108977767 B CN108977767 B CN 108977767B
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tan
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CN108977767A (en
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符立才
谭聘
周灵平
朱家俊
杨武霖
李德意
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Hunan University
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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
    • C23C14/0641—Nitrides
    • 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
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering

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Abstract

The invention relates to a wear-resistant delta-TaN film and a preparation method and application thereof; belongs to the technical field of wear-resistant material design and preparation. Texture coefficient I of the delta-TaN film(200)/[I(200)+I(111)]0.2 to 0.8; the crystal structure of the film is delta-TaN of a NaCl crystal form. The atomic ratio of Ta/N in the film is about 0.72 to 1.33. The preparation method comprises adopting radio frequency reaction magnetron sputtering, using nitrogen and argon as working gas, tantalum target as tantalum source, and fixing flow ratio of nitrogen and argon; the film grain texture coefficient is regulated and controlled by changing the working air pressure and/or the tantalum target power. Applications of the resulting film include use as a dicing apparatus, a diffusion barrier layer for electronic packaging, and the like. The invention creates a brand new method for regulating and controlling the crystal grain texture coefficient of the film; the obtained product has excellent performance and is convenient for high-precision and large-scale production and application.

Description

Wear-resistant delta-TaN film and preparation method and application thereof
Technical Field
The invention relates to a wear-resistant delta-TaN film and a preparation method and application thereof; belongs to the technical field of wear-resistant material design and preparation.
Background
At present, the cutting tool adopts a coating technology to effectively improve the cutting efficiency and reduce the processing cost, a base material has high strength and high toughness, a coating has high hardness and wear resistance, and the coating are combined to obtain more excellent comprehensive performance, so that the wear resistance of the cutting tool is improved, and the toughness of the cutting tool is not lost. Common coating materials include carbides, oxides, borides, silicides, nitrides, carbonitrides, diamonds, composite coatings, and the like; the technology is the most mature and widely applied TiN and TiC coatings, the TiN coating is easy to oxidize and ablate at 500 ℃ along with the development of the modern metal cutting technology, the hardness of the TiN coating cannot meet the requirement, the transition metal Ta has high hardness and melting point and good corrosion resistance, and the heat resistance of the cutter can be greatly improved and the good hardness can be kept by adopting the PVD technology to prepare the TaN coating.
The quality of the cutter coating is influenced by the process of the cutter coating, the residual stress and the adhesive force in the coating are influenced by the deposition temperature, and the coating prepared by a CVD (chemical vapor deposition) method has high temperature and large internal stress of the coating, so that the coating is easy to crack and the strength of the section of a matrix is reduced; PVD (physical vapor deposition) can reduce deposition temperature, increase film-substrate binding force, and improve anti-adhesion and abrasion resistance of the cutter.
The reaction magnetron sputtering deposition technology is used for preparing the TaN coating, and the TaN coating has high hardness, high melting point, chemical inertness, corrosion resistance and wear resistance (N.R. Moody, addition and fraction of Tatalum nitride films. actamat. Vol.46, No.2, pp.585-597,1998.). These excellent properties make TaN extremely suitable for use as a protective coating for cutting wear resistant tools. Adjusting the phase structure and preferred orientation can change the mechanical properties of the material to different degrees. The atomic ratio and arrangement of tantalum and nitrogen determine different crystal structures, such as: hexagonal phase Ta2N, NaCl type delta-TaN, hexagonal phase TaN, Ta5N6Ta of tetragonal phase4N5And Ta of an orthogonal structure3N5(Kun-Yuan Liu,Jyh-Wei Lee,Fabrication and tribologicalbehavior of sputtering TaN coatings.Surface&Coatings Technology 259(2014) 123-128). Compared with other phase structures, the NaCl type delta-TaN has excellent high-temperature stability (M.Grosser, M.Munch, the insulation of substrate properties and thermal insulation on Tatalum nitride films, Applied Surface Science 258(2012)2894 and 2900.), has stable phase structure and is not easy to decompose at high temperature, so that the components are controlled in a stoichiometric ratio range and have different orientations, the TaN coating with high hardness, good oxidation resistance and good friction and wear resistance can be obtained, and the wear resistance and the service life of the cutter are greatly improved.
The delta-TaN of the NaCl crystal form is a face-centered cubic structure (commonly called as FCC-TaN) formed by non-monoatomic molecular stacks, the main crystal faces of the delta-TaN have (111), (200), (220) and (311), and the prepared texture mainly grows along the (111) or (200) crystal face. If a polycrystalline material consisting of a stack of monoatomic molecules grows along (111) lattice planes, the resulting surface energy is minimal (C. Quaeyhaeegens, Experimental study of the growth evaluation from random orientations a (111) precursor orientation of PVD TiN coatings, Thin Solidfilms258(1995) I70 35173.), but the NaCl form of delta-TaN is not a polycrystalline material consisting of a simple stack of monoatomic molecules, and consists of two mosaic face cubes, the total surface energy is not minimal when the (111) plane is parallel to the substrate surface, but instead (200) has the lowest surface energy (C. -S. shine, Development of the deposition in a crystalline NaCl-structure delta-TaN layer growth by growth reaction of crystal lattice J.2002. 92. introduction. J. 2002. 31. introduction. 9. surface. J. the surface energy of the crystal is not minimal.
The metal nitride or carbide ceramic coating which is widely used at present and takes TiN, TiC and the like as the basis has the defects of knife adhesion phenomenon in the use process, easy failure at the temperature of above 600-700 ℃ and the like when cutting high-carbon steel, hard alloy and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a wear-resistant delta-TaN film and a preparation method and application thereof.
The invention relates to a wear-resistant delta-TaN film; the film has strong preferred orientation and texture coefficient I(200)/[I(200)+I(111)]0.2 to 0.8.
The invention relates to a wear-resistant delta-TaN film; the crystal structure of the film is delta-TaN of a NaCl crystal form.
The invention relates to a wear-resistant delta-TaN film; the atomic ratio of Ta/N is about 0.72 to 1.33.
The invention relates to a wear-resistant delta-TaN film; the thickness of the film is 1-4 μm.
The invention relates to a wear-resistant delta-TaN film; the film has excellent film-substrate bonding strength. The bonding strength with the film base is more than or equal to 25N.
The invention relates to a wear-resistant delta-TaN film; the nano-indentation hardness of the film is more than or equal to 15 GPa. Preferably up to 38 GPa.
The invention relates to a wear-resistant delta-TaN film; the film has excellent wear-resisting and friction-reducing performances. The dry friction coefficient is less than or equal to 0.3; when the wear-resistant alloy is used for opposite grinding with bearing steel, hard alloy, high-carbon steel and the like, the wear-resistant performance is excellent, and after 2.5-hour wear test, the film still keeps intact. The film wear rate is lower than 2.5X 10-6mm3/N·m。
The invention discloses a preparation method of a wear-resistant delta-TaN film, which is characterized by comprising the following steps: adopting radio frequency reaction magnetron sputtering, taking nitrogen and argon as working gases, taking a tantalum target as a tantalum source, and fixing the flow ratio of the nitrogen to the argon; the film grain texture coefficient is regulated and controlled by changing the working air pressure and/or the tantalum target power.
The invention relates to a preparation method of a wear-resistant delta-TaN film, which is characterized in that in the preparation process, the cross section of the film is changed from columnar crystal to isometric crystal by controlling the texture coefficient of the film.
In the preparation method of the wear-resistant delta-TaN film, the flow ratio of nitrogen to argon is a fixed value selected from 0.08-0.5, preferably 0.1-0.3, and more preferably 0.15-0.2.
The invention relates to a preparation method of a wear-resistant delta-TaN film, wherein in the preparation process, the power of tantalum target power is selected from 60-300W.
According to the preparation method of the wear-resistant delta-TaN film, the substrate temperature is maintained at about 20 ℃ in the preparation process.
The invention relates to a preparation method of a wear-resistant delta-TaN film, and the used equipment is a reactive magnetron sputtering coating instrument.
The invention relates to a preparation method of a wear-resistant delta-TaN film, wherein the substrate comprises WC-Co, 45# steel, high-speed steel and other substrates.
The invention relates to a preparation method of a wear-resistant delta-TaN film, which uses hard alloy WC-10Co, 45# steel, high-speed steel and the like as substrate materials; respectively polishing the substrate materials, sequentially putting the substrate materials into acetone, alcohol and deionized water for ultrasonic cleaning, drying the substrate materials by a blast drying oven, and putting the substrate materials on the equidistant circumference of the center of a sample table of a vacuum chamber. In the deposition process, circulating cooling water is introduced into the sample table to ensure that the temperature of the substrate is maintained at about 20 ℃ in the experimental process.
The invention relates to a preparation method of a wear-resistant delta-TaN film, which is characterized in that a pure Ta (99.95%) target material is fixed on a target head, the target is vertical to the upper part of a substrate, and the distance between the target material and the substrate is adjusted to 8 mm. After the vacuum chamber door is closed, the vacuum chamber is pumped by using a mechanical pump and a molecular pump in sequence, and when the vacuum degree is 5.0 multiplied by 10-4After pa, argon gas was introduced into the vacuum chamber to make the pressure in the vacuum chamber 1.2X 10-4Pa, starting a low-energy ion source (600V, 50mA), performing low-energy cleaning on the sample for ten minutes, and pumping the background hollow again to be better than 5.0 multiplied by 10-4pa, introducing a mixed gas of nitrogen and argon into the vacuum chamber, wherein the ratio N of the nitrogen to the argon is2/(N2+ Ar) fixation; regulating the air pressure of the vacuum chamber to an experimental value by using a molecular pump gate valve, carrying out pre-sputtering for 5 minutes after a Ta target power supply is turned on to the experimental value, removing an oxide layer on the surface of the target material, rotating a sample provided with the substrate to be right below the Ta target material, starting timing, and carrying out formal deposition; the deposition time is generally more than 1.5 hours.
The invention controls the size of working air pressure through a molecular pump gate valve, adjusts the working air pressure and target power by using radio frequency power supplies with fixed frequency and different duty ratios, keeps the rotating speed of a sample stage to be more than two revolutions per minute, and prepares the delta-TaN film with different preferred orientations.
The delta-TaN film designed and prepared by the invention can work normally when used at the temperature of above 600-700 ℃.
The invention relates to application of a wear-resistant delta-TaN film, which comprises at least one of a diffusion barrier layer used as a cutting device and an electronic packaging layer. The cutting device is preferably a knife. In particular use, the film is in the form of a coating attached to at least the cutting edge of the tool.
The invention relates to application of a wear-resistant delta-TaN film, which is used for a cutter without the phenomenon of cutter sticking.
Principles and advantages
The invention adopts the radio frequency reaction magnetron sputtering method to prepare the TaN coating, and firstly explores that the stoichiometric ratio and the film grain texture coefficient of the delta-TaN film are regulated and controlled by changing the sputtering power and/or the working air pressure under the condition that the flow ratio of nitrogen and argon is not changed. This provides the necessary condition for obtaining high quality delta-TaN film. Meanwhile, the product obtained by the optimization of the invention has excellent mechanical and tribological properties. And meanwhile, the TaN film with preferred orientation is obtained, so that the heat resistance, the cutting efficiency and the service life of the cutter are greatly improved. This provides the necessary condition for widening the application range of the delta-TaN film. Meanwhile, when the delta-TaN film obtained by the invention is used in high-speed steel cutters, hard alloy cutters and the like, the performance of the existing product is shown.
The invention adopts the delta-TaN coating deposited by reactive magnetron sputtering, and successfully prepares a new delta-TaN film material with different preferred orientations by fixing the proportion of nitrogen and argon and changing the working pressure and the target power, and has the advantages that:
1) when the delta-TaN coating deposited by the radio frequency reaction magnetron sputtering is adopted, the ratio N of nitrogen to argon is kept2/(N2+ Ar) is fixed, the orientation can be changed from (111) to (200) only by adjusting working air pressure or tantalum target power, and the method for obtaining different preferred orientations delta-TaN is convenient; this provides the necessary conditions for precise control of the microstructure of the product. The difficulty of control is far lower than that of the prior art.
2) The delta-TaN coating deposited by reactive magnetron sputtering is adopted, so that the proportion of nitrogen and argon is maintained at a lower level, the problem of target poisoning generated in the long-time deposition process is avoided, and the utilization rate of the tantalum target is improved;
3) when the delta-TaN coating deposited by reactive magnetron sputtering is adopted, the selected process parameters can obtain good film-substrate bonding strength;
4) the delta-TaN film with the stoichiometric ratio deposited by reactive magnetron sputtering has excellent high-temperature stability, is difficult to oxidize at high temperature, has stable chemical structure, and is difficult to decompose into other phase structures in the friction and wear process;
5) the invention has the delta-TaN coating with preferred orientation, and has excellent wear-resisting and antifriction properties;
6) when the oriented delta-TaN coating is subjected to opposite grinding with AISI52100 steel, 45# steel and the like, the delta-TaN coating has small abrasion loss, and the oriented delta-TaN coating is subjected to large abrasion loss with AISI52100 balls and the like subjected to opposite grinding with the delta-TaN coating, so that the oriented delta-TaN coating is suitable for cutting high-carbon steel and the like.
Drawings
FIG. 1 is an XRD pattern of the delta-TaN films prepared in examples 1, 3 and 4;
FIG. 2 is a TEM (transmission electron microscope) topography of the section of the delta-TaN thin film prepared in the examples 1, 3 and 4;
FIG. 3 is a force-displacement curve obtained from nanoindentation measurements of the delta-TaN films prepared in examples 1, 3, and 4.
In FIG. 1, a is the XRD characterization curve of the delta-TaN film prepared in example 1; b is an XRD characterization curve of the delta-TaN film prepared in the example 3; c is the XRD characterization curve of the delta-TaN film prepared for example 4; as can be seen from the curve a of FIG. 1, the delta-TaN film obtained in example 1 has a strong (111) preferred orientation; as can be seen from the b curve of FIG. 1, the delta-TaN film obtained in example 3 has a strong (200) preferred orientation; as can be seen from the c-curve of FIG. 1, the delta-TaN film obtained in example 4 has isotropic characteristics.
In FIG. 2, a is a TEM morphology of the delta-TaN film prepared in example 1, and the upper right corner is a corresponding selected area electron diffraction pattern, which verifies that the film is delta-TaN in NaCl crystal form; b is a dark field image of the delta-TaN film prepared in example 3, which shows that the film grows in a columnar crystal mode, and the diameter of the columnar crystal is 50 nm; the upper right corner is a corresponding selected electron diffraction pattern, and the selected area electron diffraction verifies that the film is a NaCl crystal form; b and c are TEM morphology images of the delta-TaN film prepared in example 4, which show that the film grows in an isometric crystal mode, and the diameter of the isometric crystal is about 50 nm; the upper right corner is the corresponding selected electron diffraction pattern, and the selected area electron diffraction verifies that the film is delta-TaN with a NaCl crystal form.
In FIG. 3, a represents the force-displacement curve obtained from the nanoindentation measurement of the δ -TaN film prepared in example 1;
from a, the nano-indentation hardness is 15 GPa; b represents the curve of the nano-indentation measurement result of the delta-TaN film prepared in example 3; from b it can be seen that the nanoindentation hardness is 29 GPa; c represents the curve of the nano-indentation measurement result of the delta-TaN film prepared in example 4; from c it can be seen that the nanoindentation hardness is 38 GPa.
Detailed Description
Example 1
Placing the cleaned WC-Co substrate on a sample table, introducing cooling water into the sample table, positioning each sample at a concentric circle with an equiaxial distance from the center of the sample table, fixing the target material to the surface of the sample by 80mm,the Ta target power was adjusted to 130W and the nitrogen/argon flow ratio was fixed at 0.2, i.e., 10sccm for nitrogen, 50sccm for argon, and 2 hours for deposition. The working gas pressure is adjusted from 0.2Pa to 1.5Pa, and TaN films with different orientations can be obtained. XRD analysis is carried out on the sample, the structure diagram is shown in figure 1a, and the film has a crystal structure of NaCl crystal form and has strong (111) preferred orientation; its texture coefficient I(200)/[I(200)+I(111)]Is 0.26. And (3) carrying out transmission electron microscope analysis on the sample, wherein a figure 2a is a delta-TaN film section TEM morphology figure, the upper right corner is a corresponding selected area electron diffraction figure, and the selected area electron diffraction verifies that the film is delta-TaN with a NaCl crystal form. The hardness and elastic modulus indentation depth of the delta-TaN film in example 1 were measured to be 500nm using nanoindentation. The results showed that the (111) -oriented delta-TaN film had a hardness of 15GPa and an elastic modulus of 245 GPa. The result of a film scratch test shows that the film-substrate bonding strength of the film is 33N; the abrasion resistance of the delta-TaN film deposited on the WC-Co is tested by adopting a frictional wear test, the test time is 120min, and the result shows that the friction coefficient is 0.15.
Example 2
Placing the cleaned WC-Co substrate on a sample table, introducing cooling water into the sample table, enabling each sample to be located in a concentric circle with an isometric distance from the center of the sample table, enabling the distance between a fixed target and the surface of each sample to be 80mm, enabling the working pressure to be 1Pa, enabling the flow ratio of nitrogen to argon to be 0.2, namely enabling nitrogen to be 10sccm, argon to be 50sccm, and enabling the deposition time to be 2 hours. Adjusting the power of the carbon target from 60W to 260W to obtain different Ta/N atomic ratios; when the power of the tantalum target is 80W, the atomic ratio of Ta/N is 0.85; when the tantalum target power is 210W, the Ta/N atomic ratio is 1.12.
Example 3
Placing the cleaned WC-Co substrate on a sample table, introducing cooling water into the sample table, positioning each sample on a concentric circle with an equiaxial distance from the center of the sample table, fixing the distance between a target material and the surface of the sample to be 80mm, adjusting the power of a Ta target to be 100W, the working pressure to be 1Pa, fixing the nitrogen/argon flow ratio to be 0.2, namely, the nitrogen intake is 10sccm, the argon intake is 50sccm, the deposition time is 2.5 hours, the thickness of a film is about 2.7 mu m, carrying out XRD analysis on the samples,the structure diagram is shown in figure 1b, the prepared delta-TaN film has strong (200) preferred orientation and texture coefficient I(200)/[I(200)+I(111)]Is 0.8. Analyzing the sample by a transmission electron microscope, wherein a dark field image of the delta-TaN film is shown in figure 2b, which shows that the film grows in a columnar crystal mode and the diameter of the columnar crystal is 50 nm; the upper right corner is the corresponding selected electron diffraction pattern, and the selected area electron diffraction verifies that the film is in a NaCl crystal form.
Example 4
Placing the cleaned WC-Co substrate on a sample table, introducing cooling water into the sample table, positioning each sample at a concentric circle with an equiaxial distance from the center of the sample table, fixing the distance between a target material and the surface of the sample to be 80mm, adjusting the power of a Ta target to be 160W, the working pressure to be 1Pa, fixing the nitrogen/argon flow ratio to be 0.8, namely, the nitrogen intake is 10sccm, the argon intake is 50sccm, the deposition time is 2 hours, the thickness of the film is about 3.1 mu m, carrying out XRD analysis on the samples, and the structural diagram of the prepared delta-TaN film is shown in figure 1c, wherein the prepared delta-TaN film has the isotropic characteristic of texture coefficient I(200)/[I(200)+I(111)]Is 0.51. Analyzing a sample by a transmission electron microscope, and showing that the film grows in an isometric crystal mode and the diameter of the isometric crystal is about 50nm as shown in a figure 2c which is a TEM topography of the delta-TaN film; the upper right corner is the corresponding selected electron diffraction pattern, and the selected area electron diffraction verifies that the film is delta-TaN with a NaCl crystal form. The hardness and elastic modulus indentation depth of the delta-TaN film in the sample are measured by adopting nano indentation to be 500 nm. The results show isotropic delta-TaN films with hardness up to 38GPa, elastic modulus of 455GPa, and a residual indentation depth of 230nm as shown by the loading-unloading curve in FIG. 3 c. The film is ground with AISI52100 under the conditions of load of 5N, rotation speed of 100r/min and film breakage after 150 min. The abraded sample was subjected to energy spectrum analysis, and as c in table 1, the content of W was 0.0%, indicating that the film was intact.
TABLE 1 energy spectra of wear scars
Figure BDA0001787378180000061
Please note that a and b in Table 1 represent sample numbers, respectively, as in FIGS. 1-3.
Example 5
Placing the cleaned WC-Co substrate on a sample table, introducing cooling water into the sample table, enabling each sample to be located in a concentric circle with an isometric distance from the center of the sample table, fixing the distance between a target material and the surface of the sample to be 80mm, adjusting the power of a Ta target to be 260W, setting the working pressure to be 1Pa, fixing the nitrogen/argon flow ratio to be 0.8, namely, setting the nitrogen inlet to be 20sccm, setting the argon inlet to be 25sccm, setting the deposition time to be 1 hour, and setting the thickness of the film to be 3.2 mu m, wherein the prepared TaN film has a hexagonal structure and the nano indentation hardness to be 10.2 GPa. The film was broken by a 30min counter-grinding with AISI52100 under a load of 5N and a rotation speed of 100 r/min. The fixed value of the nitrogen/argon flow ratio influences the structure of the deposited film and reduces the wear resistance of the film.
As can be seen from example 5 and the comparative examples of the other examples, the preferred fixed nitrogen/argon flow ratio has a critical influence on the material.

Claims (3)

1. A wear resistant delta-TaN film; the method is characterized in that:
the crystal structure of the film is delta-TaN of a NaCl crystal form;
the wear-resistant delta-TaN film is prepared by the following steps:
placing the cleaned WC-Co substrate on a sample table, introducing cooling water into the sample table, enabling each sample to be located in a concentric circle with an isometric distance from the center of the sample table, enabling the distance between a fixed target and the surface of each sample to be 80mm, enabling the working pressure to be 1Pa, enabling the flow ratio of nitrogen to argon to be 0.2, namely enabling the nitrogen to be 10sccm, the argon to be 50sccm and enabling the deposition time to be 2 hours; adjusting the power of the carbon target from 60W to 260W to obtain different Ta/N atomic ratios; when the power of the tantalum target is 80W, the atomic ratio of Ta/N is 0.85; when the power of the tantalum target is 210W, the atomic ratio of Ta/N is 1.12;
or
Placing the cleaned WC-Co substrate on a sample table, introducing cooling water into the sample table, positioning each sample on a concentric circle with an equiaxial distance from the center of the sample table, fixing the distance between a target material and the surface of the sample to be 80mm, adjusting the power of a Ta target to be 100W, setting the working pressure to be 1Pa, and fixing the nitrogen/argon flow ratio to be 0.2, namely, the nitrogen intake is 10sccm, argon gas inlet of 50sccm, deposition time of 2.5 hours, film thickness of about 2.7 μm, prepared delta-TaN film with strong (200) preferred orientation and texture coefficient I(200)/ [I(200)+I(111)]Is 0.8; the transmission electron microscope analysis is carried out on the sample, which shows that the film grows in a columnar crystal mode, and the diameter of the columnar crystal is 50 nm;
or
Placing the cleaned WC-Co substrate on a sample table, introducing cooling water into the sample table, positioning each sample at a concentric circle with an equiaxial distance from the center of the sample table, fixing the distance between a target material and the surface of the sample to be 80mm, adjusting the power of a Ta target to be 160W, working pressure to be 1Pa, fixing the nitrogen/argon flow ratio to be 0.2, namely nitrogen inlet gas to be 10sccm, argon inlet gas to be 50sccm, depositing time to be 2 hours, and the thickness of the film to be 3.1 mu m, wherein the prepared delta-TaN film has the isotropic characteristic and the texture coefficient I(200)/ [I(200)+I(111)]Is 0.51; the transmission electron microscope analysis is carried out on the sample, which shows that the film grows in an isometric crystal mode, and the diameter of the isometric crystal is 50 nm; adopting nano indentation to measure the hardness and elastic modulus indentation depth of the delta-TaN film in the sample to be 500 nm; the result shows that the isotropic delta-TaN film has the hardness as high as 38GPa and the elastic modulus of 455 GPa; the film is ground with AISI52100 under the conditions of load of 5N, rotation speed of 100r/min and film breakage after 150 min.
2. Use of the abrasion resistant delta-TaN film of claim 1 in at least one of a dicing tool and a diffusion barrier layer for electronic packaging.
3. Use of a wear resistant delta-TaN film according to claim 2; the cutting apparatus includes a knife.
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