A high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy film, a preparation method therefor, and an application thereof

Abstract

The application provides a high-hardness titanium-zirconium-niobium-hafnium-nickel (TiZrNbHfNi) amorphous high-entropy alloy film as well as a preparation method and application thereof, and relates to the field of high-entropy alloy materials. The application introduces the metal element Ni into the TiZrNbHf alloy, and simultaneously changes the Ni content to regulate the microstructure of the alloy, so that the TiZrNbHfNi high-entropy alloy film with high strength / hardness is obtained. The microstructure of the TiZrNbHfNi high-entropy alloy film is amorphous structure, and the film has the characteristics of high density, good combination with a substrate and high hardness, and can be used for a corrosion-resistant coating. The application uses the method of co-sputtering of elemental metal targets to avoid the preparation of a complex alloy target, and greatly reduces the preparation cost of the alloy film. In addition, compared with the TiZrNbHf alloy film without Ni, the hardness of the TiZrNbHfNi high-entropy alloy film is at least increased by 23.8%.

Description

Technical Field

[0001] The present invention relates to the field of high entropy alloy materials, and in particular to a high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high entropy alloy film, a preparation method thereof, and applications thereof. Background Art

[0002] In the past decade, high-entropy alloys (HEAs) have garnered significant attention due to their vast alloy design space and exceptional mechanical, physical, and chemical properties, such as superior high-temperature strength, extremely high low-temperature fracture toughness, and high corrosion and wear resistance. Unlike traditional alloy design strategies, which rely on the addition of trace alloying elements to a single primary element (as is typical with aluminum, titanium, and nickel alloys), HEAs typically consist of five or more elements in equimolar or near-equimolar ratios, with the molar percentage of each element ranging from 5 to 35%. These alloys possess extremely high mixing entropy and tend to form simple solid solutions rather than complex intermetallic compounds, such as face-centered cubic (FCC) and body-centered cubic (BCC) crystal structures, or even amorphous structures.

[0003] Refractory high-entropy alloys (RHEAs) are typically composed of ten high-melting-point metallic elements: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, and Re. These alloys exhibit high hardness and high-temperature strength. Their excellent high-temperature mechanical properties hold great promise for applications in aerospace propulsion systems, gas turbines, and heat exchangers. Among reported RHEAs, TiZrNbHf and its derivatives exhibit excellent room-temperature tensile ductility (over 10%) and compressive ductility (over 50%), whereas other RHEAs often exhibit brittleness at room temperature. However, while TiZrNbHf alloys exhibit good room-temperature ductility, their hardness and strength are lower than those of most other RHEAs. Therefore, significantly improving their hardness and strength is of great scientific significance and engineering value.

[0004] At present, the main methods for preparing high-entropy alloys are vacuum melting and powder metallurgy. The size and application scenarios of bulk high-entropy alloys prepared by these methods are limited, and the alloy composition control process is relatively complicated. High-entropy alloy films can be prepared by physical and chemical vapor deposition, and their thickness can be controlled at the nanometer to micrometer level. They can be widely used in surface modification, such as in the field of protective coatings. The most commonly used method for preparing high-entropy alloy films is magnetron sputtering. There are mainly two types of targets for preparing high-entropy alloy films by magnetron sputtering: (1) Prepare a high-entropy alloy bulk target by smelting, and then complete the preparation of high-entropy alloy films, such as patent application number 202110344020.0 "A NbMoTaWAl refractory high-entropy alloy and its preparation method" and 202110998558.3 ​​"A high-entropy amorphous film and its preparation method and application". Although this method can well control the elemental composition of the high-entropy alloy film, changing the content of one or more elements requires the re-preparation of the corresponding alloy target. The preparation process of the alloy target is time-consuming and cumbersome, which is not conducive to the design of composition control. Therefore, its preparation cost is often higher than that of most traditional alloys. (2) Select metal powders for mixing and pressurizing the mixed powder to make a high-entropy alloy target. For example, patent application number 20191028.504.6 is "A method for preparing a multi-element high-entropy alloy". However, it is difficult to mix the powders uniformly, and it is difficult to ensure that a high-entropy alloy film with uniform composition is obtained. In addition, there are few reports on the preparation of quaternary or higher high-entropy alloy films using single metal targets.

[0005] Therefore, the present invention uses single metal target co-sputtering to prepare titanium zirconium niobium hafnium nickel (TiZrNbHfNi) high entropy alloy film, and prepares a TiZrNbHf high entropy alloy film with high hardness, uniform component composition and precise controllable by precisely controlling the Ni element content. Summary of the Invention

[0006] The present invention provides a high-hardness titanium-zirconium-niobium-hafnium-nickel (TiZrNbHfNi) amorphous high-entropy alloy film, a preparation method thereof, and an application thereof, the purpose of which is to solve the above-mentioned problems existing in the background technology.

[0007] Since the physical properties of each element are different to a certain extent, such as the size of the atomic radius and the elastic modulus, by adding suitable metal elements for alloying, the alloy system produces a larger lattice distortion, which increases the strength of the material. In order to achieve the above-mentioned purpose, an embodiment of the present invention provides a high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy film and its preparation method and application. The present invention intends to introduce the metal element Ni into the TiZrNbHf alloy, because the atomic radius and elastic modulus of Ni are quite different from those of the four matrix elements Ti, Zr, Nb, and Hf, which is conducive to producing a larger lattice distortion effect. At the same time, the alloy microstructure can be regulated by adjusting the Ni content, thereby obtaining a TiZrNbHfNi high-entropy alloy with high strength / hardness.

[0008] An embodiment of the present invention provides a high-hardness titanium-zirconium-niobium-hafnium-nickel (TiZrNbHfNi) amorphous high-entropy alloy film, wherein Ti: 11-20%, Zr: 11-20%, Nb: 11-20%, Hf: 17-32%, and Ni: 8-50%.

[0009] Preferably, Ti: 13~20%, Zr: 13~20%, Nb: 13~20%, Hf: 22~32%, Ni: 8~39%.

[0010] Preferably, Ti: 15%, Zr: 15%, Nb: 15%, Hf: 25%, Ni: 30%.

[0011] Preferably, the thickness of the high-hardness TiZrNbHfNi amorphous high-entropy alloy film is 100-6000 nm.

[0012] Based on a general concept of the invention, an embodiment of the present invention further provides a method for preparing the above-mentioned high-hardness TiZrNbHfNi amorphous high-entropy alloy film, comprising the following steps:

[0013] S1: Target preparation and installation: Ti target, Zr target, Nb target, Hf target, and Ni target are used as target materials. Each target material is installed in the target cavity of the deposition chamber. Then the substrate is sent to the deposition chamber. The distance between the substrate and each target material is adjusted, and the vacuum of the deposition chamber is pumped to 5×10 -5 Pa;

[0014] S2: Cleaning the substrate: introduce argon gas, adjust the pressure of the deposition chamber, and clean it; use Ar + The purpose of bombarding the substrate surface is to remove impurities on the surface, so that the atoms in the film can directly combine with the substrate surface, which is beneficial to increase the contact sites and thus improve the bonding ability between the film and the substrate;

[0015] S3: Target pre-sputtering; Pre-sputtering is used to remove oxides and other contaminants on the target surface;

[0016] S4: Sputtering deposition: First, turn on the rotating motor connected to the substrate, set the sputtering power of each target material, and after the sputtering power of each target material reaches stability, open the cover of each target material at the same time to perform sputtering deposition; after the sample is fully cooled in a vacuum, take it out to obtain a high-hardness TiZrNbHfNi amorphous high-entropy alloy film.

[0017] Preferably, in step S1, the purity of the Ti target is 99.999%, the purity of the Zr target is 99.9%, the purity of the Nb target is 99.9%, the purity of the Hf target is 99.9%, and the purity of the Ni target is 99.95%; the distance between the substrate and each target material is kept consistent, which is 88~108mm.

[0018] Preferably, in step S2, the gas pressure in the deposition chamber is 1-3 Pa, the argon flow rate is 50-200 sccm, and the purity of the argon is 99.999%.

[0019] Preferably, in step S3, the pre-sputtering working gas is argon, and the working pressure is 1-2 Pa; the pre-sputtering power of each target material is set to 50-100 W, and the pre-sputtering time is 5-20 minutes.

[0020] Preferably, in step S4, the sputtering deposition working pressure is 1~2 Pa, the argon flow rate is 50~100 sccm, and the time is 0.5~6 h; the sputtering power of each target material is: Ti 45~140 W, Zr 30~94 W, Nb 29~90 W, Hf 34~106 W, Ni 46~168 W, and the plating rate of each target material is: Ti 0.0227~0.0705 nm / s, Zr 0.03~0.0941 nm / s, Nb 0.0234~0.0725 nm / s, Hf 0.0460~0.14353 nm / s, Ni 0.01764~0.0644 nm / s; the sample cooling time is 1~3 h. Setting different deposition times can obtain film samples of different thicknesses; sampling after cooling is because the sputtered atoms bombard the substrate for a long time during the deposition process, causing it to have a certain temperature rise. After the deposition is completed, it is placed in the cavity of the high vacuum coating chamber for cooling to prevent the film from debonding and breaking from the substrate due to internal stress, and to prevent the film from oxidation, so that the deposited atoms can fully diffuse to form the final TiZrNbHfNi high-entropy alloy film.

[0021] An embodiment of the present invention also provides an application of a high-hardness TiZrNbHfNi amorphous high-entropy alloy film obtained by the above-mentioned and / or preparation methods, wherein the high-hardness TiZrNbHfNi amorphous high-entropy alloy film is applied to a corrosion-resistant coating.

[0022] The above solution of the present invention has the following beneficial effects:

[0023] (1) The titanium zirconium niobium hafnium nickel (TiZrNbHfNi) high entropy alloy film prepared by the present invention has an amorphous microstructure, is dense, has good bonding with the substrate, and has high hardness, and can be used for corrosion-resistant coatings; compared with the amorphous high entropy ceramic film formed by adding non-metallic elements such as N, O, B, and C, the TiZrNbHfNi amorphous high entropy alloy film will have better toughness.

[0024] (2) Compared with the TiZrNbHf alloy film without Ni, the hardness of the TiZrNbHfNi high entropy alloy film of the present invention is increased by at least 23.8%.

[0025] (3) The present invention utilizes a method of co-sputtering a single metal target to avoid the complicated preparation of alloy targets, thereby greatly reducing the preparation cost of alloy films.

[0026] (4) The present invention can achieve the regulation of element content (alloy composition) by changing the power of the single-element target material. The operation is simple and easy to implement, which greatly improves the preparation efficiency of multi-element alloy films and is conducive to high-throughput experimental design. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0028] Figure 1 Ti of Example 1 of the present invention 22.8 Zr 19.1 Nb 19.7 Hf 30 Ni 8.4 SEM image and element distribution spectrum of high entropy alloy film surface;

[0029] Figure 2 Ti of Example 2 of the present invention 16.7 Zr 15.1 Nb 15.1 Hf 24.6 Ni 28.5 SEM image and element distribution spectrum of high entropy alloy film surface;

[0030] Figure 3 Ti of Example 3 of the present invention 13.9 Zr 12.9 Nb 12.4 Hf 22.3 Ni 38.5SEM image and element distribution spectrum of high entropy alloy film surface;

[0031] Figure 4 is the Ti of Comparative Example 1 of the present invention 20.5 Zr 22.7 Nb 22.1 Hf 34.7 SEM image and element distribution spectrum of high entropy alloy film surface;

[0032] Figure 5 is an XRD diffraction pattern of a TiZrNbHfNi high entropy alloy film according to an embodiment of the present invention;

[0033] Figure 6 Ti of Example 1 of the present invention 22.8 Zr 19.1 Nb 19.7 Hf 30 Ni 8.4 TEM and HRTEM images of high entropy alloy films;

[0034] Figure 7 Ti of Example 3 of the present invention 13.9 Zr 12.9 Nb 12.4 Hf 22.3 Ni 38.5 TEM and HRTEM images of high entropy alloy films;

[0035] Figure 8 is the Ti of Comparative Example 1 of the present invention 20.5 Zr 22.7 Nb 22.1 Hf 34.7 TEM and HRTEM images of high entropy alloy films;

[0036] Figure 9 It is the nanohardness of the TiZrNbHfNi high entropy alloy film according to the embodiment of the present invention. DETAILED DESCRIPTION

[0037] In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, a detailed description will be given below with reference to the accompanying drawings and specific embodiments.

[0038] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0039] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0040] In response to the existing problems, the present invention provides a high-hardness titanium-zirconium-niobium-hafnium-nickel (TiZrNbHfNi) amorphous high-entropy alloy film, a preparation method thereof, and an application thereof.

[0041] Equipment conditions: equipped with 5 independent magnetron sputtering target guns, at least one with RF power supply, and the rest with DC power supply; the ultimate backing vacuum is better than 5×10 -5 Pa. Since Ni target has strong magnetism, RF power supply is used, while other targets use DC power supply.

[0042] The raw materials and specifications are as follows: Ti target (purity of 99.999%), Zr target (purity of 99.9%), Nb target (purity of 99.9%), Hf target (purity of 99.9%), Ni target (purity of 99.95%). The size of all targets is 2 inches. 6 mm; the working gas is high-purity argon with a purity of 99.999%; the substrate is single crystal Si (100), with a size of 2 inches 0.4mm, single-sided polishing, resistivity less than 0.1 ohm·cm.

[0043] (Note: The substrate can be replaced according to the specific application scenario. This embodiment only takes the Si substrate as an example but is not limited to the Si substrate).

[0044] Example 1

[0045] A high hardness TiZrNbHf 1.6 Ni 0.4 The preparation process of the high entropy alloy film is designed with the atomic percentage of each element as Ti-20%, Zr-20%, Nb-20%, Hf-32%, and Ni-8%. The specific steps are as follows:

[0046] (1) Install Ti target (purity of 99.999%), Zr target (purity of 99.9%), Nb target (purity of 99.9%), Hf target (purity of 99.9%), and Ni target (purity of 99.95%) in the deposition chamber, then fix the single crystal silicon substrate on the tray, and send it into the vacuum deposition chamber through the mechanical rod, and then pump the vacuum to 5×10 -5 Pa.

[0047] (2) Clean the silicon wafer by introducing high-purity argon gas with a purity of 99.999% and an argon flow rate of 70 sccm, so that the working gas pressure reaches 1.4 Pa. Then turn on the bias power supply with a power of 50 W and the cleaning time is 5 minutes.

[0048] (3) Target pre-sputtering: the working pressure is 1.4 Pa, the argon flow rate is 70 sccm, the target pre-sputtering time is 5 minutes, and the power is 50 W.

[0049] (4) Alloy thin film deposition: The working pressure was 1.4 Pa, the argon flow rate was 70 sccm, and the sputtering powers of the targets were: Ti-140W, Zr-94W, Nb-90W, Hf-106W, and Ni-46W. The plating rates of the targets at these powers were: Ti-0.0705nm / s, Zr-0.0941nm / s, Nb-0.0725nm / s, Hf-0.14353nm / s, and Ni-0.01764nm / s. Deposition began with the cover of each target open for 50 minutes. The samples were cooled in vacuum for 1 hour before removal, and the sample thickness was measured to be 1038nm.

[0050] Example 2

[0051] A high hardness TiZrNbHf 1.6 Ni 2.0 The preparation process of the high entropy alloy film is designed with the atomic percentage of each element as Ti-15%, Zr-15%, Nb-15%, Hf-25%, and Ni-30%. The specific steps are as follows:

[0052] (1) Install Ti target (purity of 99.999%), Zr target (purity of 99.9%), Nb target (purity of 99.9%), Hf target (purity of 99.9%), and Ni target (purity of 99.95%) in the deposition chamber, then fix the single crystal silicon substrate on the tray, and send it into the vacuum deposition chamber through the mechanical rod, and then pump the vacuum to 5×10 -5 Pa.

[0053] (2) Clean the silicon wafer by introducing high-purity argon gas with a purity of 99.999% and an argon flow rate of 70 sccm, so that the working gas pressure reaches 1.4 Pa. Then turn on the bias power supply with a power of 50 W and the cleaning time is 5 minutes.

[0054] (3) Target pre-sputtering: the working pressure is 1.4 Pa, the argon flow rate is 70 sccm, the target pre-sputtering time is 5 minutes, and the power is 50 W.

[0055] (4) Alloy thin film deposition: The working pressure was 1.4 Pa, the argon flow rate was 70 sccm, and the sputtering powers of the targets were: Ti-100W, Zr-67W, Nb-64W, Hf-76W, and Ni-146W. The plating rates of the targets at these powers were: Ti-0.0504nm / s, Zr-0.0641nm / s, Nb-0.0516nm / s, Hf-0.1029nm / s, and Ni-0.05598nm / s. Deposition began with the cover of each target opened for 60 minutes. The samples were cooled in vacuum for 1 hour before removal, and the sample thickness was measured to be 1170nm.

[0056] Example 3

[0057] A high hardness TiZrNbHf 1.6 Ni 3.0 The preparation process of the high entropy alloy film is designed with the atomic percentage of each element as Ti-13%, Zr-13%, Nb-13%, Hf-22%, and Ni-39%. The specific steps are as follows:

[0058] (1) Install Ti target (purity of 99.999%), Zr target (purity of 99.9%), Nb target (purity of 99.9%), Hf target (purity of 99.9%), and Ni target (purity of 99.95%) in the deposition chamber, then fix the single crystal silicon substrate on the tray, and send it into the vacuum deposition chamber through the mechanical rod, and then pump the vacuum to 5×10 -5 Pa.

[0059] (2) Clean the silicon wafer by introducing high-purity argon gas with a purity of 99.999% and an argon flow rate of 70 sccm, so that the working gas pressure reaches 1.4 Pa. Then turn on the bias power supply with a power of 50 W and the cleaning time is 5 minutes.

[0060] (3) Target pre-sputtering: the working pressure is 1.4 Pa, the argon flow rate is 70 sccm, the target pre-sputtering time is 5 minutes, and the power is 50 W.

[0061] (4) Alloy thin film deposition: The working pressure was 1.4 Pa, the argon flow rate was 70 sccm, and the sputtering powers of the targets were 70 W for Ti, 47 W for Zr, 45 W for Nb, 60 W for Hf, and 171 W for Ni. The plating rates of the targets at these powers were 0.03525 nm / s for Ti, 0.04705 nm / s for Zr, 0.03625 nm / s for Nb, 0.08124 nm / s for Hf, and 0.06557 nm / s for Ni. The cover of each target was opened to begin deposition, and the deposition time was 60 minutes. The samples were cooled in vacuum for 1 hour before being removed. The sample thickness was measured to be 1047 nm.

[0062] Comparative Example 1

[0063] TiZrNbHf 1.6 The preparation process of the high entropy alloy film is designed with the atomic percentage of each element being Ti-21.7%, Zr-21.7%, Nb-21.7%, and Hf-34.9%. The specific steps are as follows:

[0064] (1) Install Ti target (purity of 99.999%), Zr target (purity of 99.9%), Nb target (purity of 99.9%), and Hf target (purity of 99.9%) in the deposition chamber, then fix the single crystal silicon substrate on the tray, and send it into the vacuum deposition chamber through the mechanical rod, and then pump the vacuum to 5×10 -5 Pa.

[0065] (2) Clean the silicon wafer by introducing high-purity argon gas with a purity of 99.999% and an argon flow rate of 70 sccm, so that the working gas pressure reaches 1.4 Pa. Then turn on the bias power supply with a power of 50 W and the cleaning time is 5 minutes.

[0066] (3) Target pre-sputtering: the working pressure is 1.4 Pa, the argon flow rate is 70 sccm, the target is pre-sputtered for 20 minutes for the first time, and the power is 50 W.

[0067] (4) Alloy thin film deposition: The operating pressure was 1.4 Pa, the argon flow rate was 70 sccm, and the sputtering powers for the targets were 140 W for Ti, 94 W for Zr, 90 W for Nb, and 106 W for Hf. The plating rates for the targets at these powers were: 0.0705 nm / s for Ti, 0.0941 nm / s for Zr, 0.0725 nm / s for Nb, and 0.14353 nm / s for Hf. Deposition began with the covers of each target open for 45 minutes. The samples were cooled in vacuum for 1 hour before being removed. The sample thickness was measured to be 987 nm.

[0068] The samples prepared in Examples 1, 2, and 3, as well as Comparative Example 1, were analyzed using an energy dispersive X-ray spectrometer (EDS). The atomic percentages of the elements were as follows: Example 1: Ti-22.8%, Zr-19.1%, Nb-19.7%, Hf-30%, Ni-8.4%; Example 2: Ti-16.7%, Zr-15.1%, Nb-15.1%, Hf-24.6%, Ni-28.5%; Example 3: Ti-13.9%, Zr-12.9%, Nb-12.4%, Hf-22.3%, Ni-38.5%; Comparative Example 1: Ti-20.5%, Zr-22.7%, Nb-22.1%, Hf-34.7%. The results show that the actual atomic percentages of the elements are essentially consistent with the initial design composition, and that the elements are evenly distributed, with no apparent aggregation or clustering. Figure 1-4 The crystal structures of Examples 1, 2, 3 and Comparative Example 1 were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD results showed that the diffraction peaks of the TiZrNbHfNi films in Examples 1, 2, and 3 were low in intensity and broad, exhibiting typical amorphous structural characteristics; while the TiZrNbHf in Comparative Example 1 was a BCC crystal structure, as shown in the attached figure. Figure 5 TEM results further verified the amorphous structure characteristics of TiZrNbHfNi thin films, which showed that the atomic arrangement was short-range ordered but long-range disordered, as shown in the attached Figure 6 and attached Figure 7 As shown; while the TiZrNbHf in Comparative Example 1 has a typical BCC crystal structure, and its grain morphology is columnar crystal, as shown in the attached Figure 8 As shown. The hardness of the TiZrNbHfNi films in Examples 1, 2, and 3 was measured by nanoindentation to be 5.93±0.2GPa, 6.48±0.1GPa, and 6.15±0.18GPa, respectively; the hardness of the TiZrNbHf in Comparative Example 1 was 4.79±0.2GPa. Compared with the TiZrNbHf alloy film without Ni, the hardness of the TiZrNbHfNi alloy films in Examples 1, 2, and 3 was increased by 23.8%, 35.3%, and 28.4%, respectively. Figure 9 The above results show that the present invention can accurately control the content of each element in TiZrNbHfNi, and the alloy elements are evenly distributed; compared with the TiZrNbHf alloy film without Ni, the hardness of TiZrNbHfNi is significantly improved.

[0069] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy film, characterized in that: Ti: 11-20%, Zr: 11-20%, Nb: 11-20%, Hf: 17-32%, Ni: 8-50%; the method for preparing the high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy film comprises the following steps: S1: Target preparation and installation: Ti target, Zr target, Nb target, Hf target, and Ni target are used as target materials. Each target material is installed in the target cavity of the deposition chamber. Then the substrate is sent to the deposition chamber, the distance between the substrate and each target material is adjusted, and the vacuum of the deposition chamber is pumped to 5×10 - 5 Pa; S2: Cleaning the substrate: introducing argon gas, adjusting the pressure in the deposition chamber, and cleaning; S3: target pre-sputtering; S4: Sputtering deposition: First, turn on the rotating motor connected to the substrate, set the sputtering power of each target material, and after the sputtering power of each target material reaches stability, open the cover of each target material at the same time to perform sputtering deposition; after the sample is fully cooled in a vacuum, take it out to obtain a high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy film; among them, the sputtering power of each target material is: Ti45~140W, Zr 30~94W, Nb 29~90W, Hf 34~106W, Ni 46~168W, and the plating rate of each target material is: Ti 0.0227~0.0705nm / s, Zr 0.03~0.0941nm / s, Nb 0.0234~0.0725nm / s, Hf 0.0460~0.14353n / s, Ni 0.01764~0.0644nm / s.

2. The high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy thin film according to claim 1, characterized in that: Ti: 13~20%, Zr: 13~20%, Nb: 13~20%, Hf: 22~32%, Ni: 8~39%.

3. The high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy thin film according to claim 2, characterized in that Ti: 15%, Zr: 15%, Nb: 15%, Hf: 25%, Ni: 30%.

4. The high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy thin film according to claim 3, characterized in that: The thickness of the high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy film is 100-6000 nm.

5. The method for preparing a high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy thin film according to any one of claims 1 to 4, characterized in that: The steps include: S1: Target preparation and installation: Ti target, Zr target, Nb target, Hf target, and Ni target are used as target materials. Each target material is installed in the target cavity of the deposition chamber. Then the substrate is sent to the deposition chamber, the distance between the substrate and each target material is adjusted, and the vacuum of the deposition chamber is pumped to 5×10 - 5 Pa; S2: Cleaning the substrate: introducing argon gas, adjusting the pressure in the deposition chamber, and cleaning; S3: target pre-sputtering; S4: Sputtering deposition: First, turn on the rotating motor connected to the substrate, set the sputtering power of each target material, and after the sputtering power of each target material reaches stability, open the cover of each target material at the same time to perform sputtering deposition; after the sample is fully cooled in a vacuum, take it out to obtain a high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy film; among them, the sputtering power of each target material is: Ti45~140W, Zr 30~94W, Nb 29~90W, Hf 34~106W, Ni 46~168W, and the plating rate of each target material is: Ti 0.0227~0.0705nm / s, Zr 0.03~0.0941nm / s, Nb 0.0234~0.0725nm / s, Hf 0.0460~0.14353n / s, Ni 0.01764~0.0644nm / s.

6. The preparation method according to claim 5, characterized in that In step S1, the purity of the Ti target is 99.999%, the purity of the Zr target is 99.9%, the purity of the Nb target is 99.9%, the purity of the Hf target is 99.9%, and the purity of the Ni target is 99.95%; the distance between the substrate and each target material is kept consistent, ranging from 88 to 108 mm.

7. The preparation method according to claim 6, characterized in that In step S2 , the gas pressure in the deposition chamber is 1-3 Pa, the argon flow rate is 50-200 sccm, and the purity of the argon is 99.999%.

8. The preparation method according to claim 7, characterized in that In step S3 , the pre-sputtering working gas is argon, and the working pressure is 1-2 Pa; the pre-sputtering power of each target material is kept consistent, 50-100 W, and the pre-sputtering time is 5-20 minutes.

9. The preparation method according to claim 8, characterized in that In step S4, the sputtering deposition working pressure is 1-2 Pa, the argon gas flow rate is 50-100 sccm, and the time is 0.5-6 h; the sample cooling time is 1-3 h.

10. Use of the high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy thin film according to any one of claims 1 to 4 or the high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy thin film obtained by the preparation method according to any one of claims 7 to 9, characterized in that: The high-hardness titanium-zirconium-niobium-hafnium-nickel amorphous high-entropy alloy film is applied to corrosion-resistant coatings.

Images