High-throughput preparation method of gradient TiAlNb-based alloy film

Abstract

The invention relates to the technical field of light refractory high-entropy alloys, in particular to a high-throughput preparation method of a gradient TiAlNb-based alloy film. According to the preparation method, a TiTaNbVB alloy is used as a radio frequency magnetron sputtering target, a TiAl alloy is used as a direct current magnetron sputtering target, and a gradient TiAlNb-based alloy film is deposited on the surface of a horizontally-arranged substrate through double-target co-sputtering; wherein the target surface of the direct-current magnetron sputtering target and the target surface of the radio-frequency magnetron sputtering target form an included angle of 70-80 degrees with the horizontal direction. According to the high-throughput preparation method of the gradient TiAlNb-based alloy film, efficient and intelligent design of the high-hardness light refractory high-entropy alloy can be achieved, the influence of the content of strengthening elements on the alloy performance is explored, the problems that traditional alloy screening depends on experience, efficiency is low, and errors are large are solved, and the high-throughput preparation method of the gradient TiAlNb-based alloy film is suitable for industrial production. And the method is of great significance for exploring the optimal alloy element proportion.

Description

Technical Field

[0001] The present invention relates to the technical field of lightweight refractory high entropy alloys, and in particular to a high-throughput preparation method for a gradient TiAlNb-based alloy film. Background Art

[0002] High-hardness, lightweight, refractory high-entropy alloys are important strategic materials in the aerospace field. Although traditional high-temperature alloys such as nickel-based alloys have excellent high-temperature strength, their high density limits their application in lightweight structural materials. Titanium-based alloys have become one of the ideal candidate materials for high-temperature lightweight structures due to their high strength, low density and excellent corrosion resistance. However, in actual engineering applications, the hardness, strength and long-term stability of titanium-based alloys still need to be improved and still do not meet the requirements for use under extreme conditions. Therefore, how to improve titanium-based alloys to prepare lightweight high-temperature alloys with high hardness and high strength is a technical problem that needs to be solved urgently by those skilled in the art.

[0003] At the same time, the vast number of possible alloying compositions and complex microstructures of high-hardness, lightweight, refractory high-entropy alloys make systematic design extremely difficult through traditional experiments. Traditional lightweight refractory alloy design relies primarily on empirical experience and trial-and-error methods, which are time-consuming, costly, and inefficient. To overcome this material performance bottleneck, there is an urgent need to establish efficient and intelligent design methods for high-hardness, lightweight, refractory high-entropy alloys. Summary of the Invention

[0004] The purpose of the present invention is to provide a TiAlNb-based alloy film and a high-throughput preparation method for a gradient TiAlNb-based alloy film to solve the problems of the above-mentioned prior art. The TiAlNb-based alloy film provided by the present invention has a hardness of 8-12.5GPa, which can meet the high hardness requirements of the current aerospace field. At the same time, the film density is 6-7g / cm 3 , with an elastic modulus of 109.6-188.5 GPa. The high-throughput preparation method for gradient TiAlNb-based alloy films provided by this invention enables efficient and intelligent design of high-hardness, lightweight, refractory high-entropy alloys. This method explores the effect of strengthening element content on alloy properties, addresses the inefficiency and large error associated with traditional alloy screening, which relies on experience. This method is of great significance for exploring the optimal alloying element ratio.

[0005] To achieve the above object, the present invention provides the following solutions:

[0006] One of the technical solutions of the present invention: a TiAlNb-based alloy film, which comprises, in atomic percentage, 40% to 42.5% Ti, 11.9% to 24% Al, 20% to 30% Nb, 7.7% to 10.7% Ta, 5.2% to 8.2% V, and 0% to 1.45% B.

[0007] In the present invention, Nb and V are used as strengthening elements to improve the high temperature strength and stability of the metal through solid solution strengthening and lattice distortion. Ti is the main element of the alloy, providing low density (4.5g / cm 3 ) and excellent corrosion resistance. The addition of Al can further reduce the alloy density (3.7g / cm 3 ), while also improving strength by forming an α phase (hexagonal close-packed structure). Ta and Nb are used to increase the alloy's high-temperature strength and oxidation resistance. Excessive Nb content may lead to increased cost and the precipitation of brittle phases (such as Laves phase), while too low a Nb content may not meet high-temperature performance requirements. V is used to control lattice distortion to avoid embrittlement caused by increased strength. The addition of the light element boron refines the grain size and improves overall performance.

[0008] Optionally, the TiAlNb-based alloy film is a gradient TiAlNb-based alloy film, wherein the contents of Al, Nb, Ta, and V elements vary gradiently in the alloy film, and along the positive direction of the x-axis, the atomic percentage of Al increases from 11.9% to 23.65%, the atomic percentage of Nb decreases from 30% to 21.1%, the atomic percentage of Ta decreases from 10.67% to 7.7%, and the atomic percentage of V decreases from 8.2% to 5.21%.

[0009] The type and content of strengthening elements will directly affect the strengthening effect. In order to explore the optimal ratio of alloying elements and meet different needs, the present invention provides a gradient TiAlNb-based alloy film. This composition gradient film can provide a large number of composition combinations, which helps to quickly explore the performance of samples with different compositions, thereby accelerating the development of new high-hardness, lightweight, refractory high-entropy alloys.

[0010] Technical solution 2 of the present invention: The preparation method of the above-mentioned TiAlNb-based alloy film uses TiTaNbVB alloy as an RF magnetron sputtering target and TiAl alloy as a DC magnetron sputtering target to deposit the TiAlNb-based alloy film on the substrate surface by dual-target co-sputtering.

[0011] Compared with single-target sputtering, the advantage of using dual-target co-sputtering in the present invention is that a thin film with a composition gradient can be prepared by adjusting the target material composition and the angle between the target material and the substrate. The reason for using TiTaNbVB alloy as the RF magnetron sputtering target and TiAl alloy as the DC magnetron sputtering target is that based on the analysis of the composition, TiAl alloy has better conductivity than TiTaNbVB alloy. DC magnetron sputtering is suitable for target materials with good conductivity, while RF magnetron sputtering is suitable for target materials with insulating or poor conductivity.

[0012] Technical solution three of the present invention: The preparation method of the above-mentioned gradient TiAlNb-based alloy film uses TiTaNbVB alloy as an RF magnetron sputtering target and TiAl alloy as a DC magnetron sputtering target, and deposits the gradient TiAlNb-based alloy film on the surface of a horizontally arranged substrate by dual-target co-sputtering; wherein, the target surface of the DC magnetron sputtering target is at an angle of 70° to 80° with the horizontal direction; the target surface of the RF magnetron sputtering target is at an angle of 70° to 80° with the horizontal direction.

[0013] The present invention realizes the preparation of a gradient TiAlNb-based alloy film by adjusting the angle between the target surface and the horizontal direction, and can prepare a gradient TiAlNb-based alloy film including multiple component ratios at one time.

[0014] Preferably, in the above-mentioned technical solution 2 or technical solution 3 provided by the present invention, the TiTaNbVB alloy is Ti39.8Nb38.8Ta9.95V10B1.45.

[0015] Preferably, in the above-mentioned technical solution 2 or technical solution 3 provided by the present invention, the TiAl alloy is Ti50Al50.

[0016] The present invention regulates the atomic percentage gradient variation range in the film by limiting the molar ratio of elements in the TiTaNbVB alloy and the TiAl alloy.

[0017] Preferably, in the second or third technical solution provided by the present invention, the substrate is single-sided polished and has a crystal orientation of <111> silicon wafer.

[0018] Preferably, in the above-mentioned technical solution 2 or technical solution 3 provided by the present invention, the size of the RF magnetron sputtering target is Φ50mm×4.5mm; the size of the DC magnetron sputtering target is Φ50mm×4mm; the size of the substrate is Φ48mm×1mm.

[0019] Preferably, in the second or third technical solution provided by the present invention, the parameters of the dual-target co-sputtering include: substrate temperature 15-40°C, DC magnetron sputtering target power 50W, RF magnetron sputtering target power 80W, sputtering time 120min, starting gas pressure 3Pa, sputtering gas pressure 0.3Pa, vacuum degree 8×10 -4 Pa, argon atmosphere.

[0020] Substrate temperature (15-40°C): Maintaining it near room temperature helps reduce the impact of thermal stress on the film structure and avoids composition segregation or grain growth caused by high temperatures. This helps maintain the uniformity of the film's internal microstructure, which is particularly important when exploring the effects of different composition ratios on room-temperature properties.

[0021] DC magnetron sputtering target power (50W) and RF magnetron sputtering target power (80W): Selecting the appropriate power ensures efficient material deposition rates and good film quality. Lower DC magnetron sputtering target power helps control deposition rates, resulting in more precise and controllable composition distribution. Higher RF power, on the other hand, helps improve sputtering efficiency for less conductive targets, ensuring that composition gradients are achieved as intended.

[0022] Sputtering time (120 min): Sufficient sputtering time ensures the film reaches the desired thickness while allowing the composition to vary with position to form the desired gradient distribution. By adjusting the sputtering time, the film thickness and composition gradient can be precisely controlled to meet different experimental requirements.

[0023] Starting gas pressure (3Pa) and sputtering gas pressure (0.3Pa): A higher starting gas pressure helps to quickly start the sputtering process, while reducing the sputtering pressure to 0.3Pa can improve the quality and purity of the film and reduce the introduction of impurities, which is very important for the preparation of high-purity, high-performance alloy films.

[0024] Vacuum degree (8×10 -4 Pa): A high vacuum environment reduces the impact of background gases on the thin film deposition process, helping to improve the purity and density of the film, thereby improving its mechanical properties such as hardness and elastic modulus.

[0025] Argon atmosphere: Using inert gas argon as the working gas will not chemically react with the target material, but can effectively transfer energy to the atoms on the target surface, promoting their detachment from the target surface and deposition on the substrate to form a thin film of the desired composition.

[0026] Preferably, in the above-mentioned technical solution 2 or technical solution 3 provided by the present invention, pre-sputtering is performed at a gas pressure of 0.3 Pa for 3 minutes before dual-target co-sputtering.

[0027] Pre-sputtering before dual-target co-sputtering removes target surface oxides and contaminants, stabilizes the sputtering process, reduces particle shedding, and verifies equipment operation. This ensures the purity and uniformity of film deposition, improves the stability and reliability of the fabrication process, and lays the foundation for obtaining high-quality compositionally gradient films.

[0028] Preferably, in the second technical solution provided by the present invention, the distance between the DC magnetron sputtering target and the substrate is 7 cm; and / or the distance between the RF magnetron sputtering target and the substrate is 7 cm.

[0029] Preferably, in the third of the above-mentioned technical solutions provided by the present invention, the vertical distance between the center point of the DC magnetron sputtering target and the substrate is 7 cm; and / or the vertical distance between the center point of the RF magnetron sputtering target and the substrate is 7 cm; the DC magnetron sputtering target and the RF magnetron sputtering target are arranged relative to each other.

[0030] Preferably, in the third technical solution provided by the present invention, a rectangular coordinate system is established on the surface of the prepared film, and the unit length is 5 mm.

[0031] Preferably, in the third technical solution provided by the present invention, the EDS method is used to determine the content and distribution of Ti, Al, Nb, Ta, V, and B elements in the gradient TiAlNb-based alloy film; specifically, two points are taken near each coordinate point for measurement.

[0032] Preferably, in the third technical solution provided by the present invention, the hardness and elastic modulus of the gradient TiAlNb-based alloy film are measured by nanoindentation method; specifically, two points near the coordinate point are selected for measurement.

[0033] Preferably, in the third technical solution provided by the present invention, the weight of the Si wafer is weighed before and after magnetron sputtering, the thickness of the film is measured using a scanning electron microscope, and the approximate average density of the film is calculated using the density formula ρ=M / V.

[0034] Preferably, in the third technical solution provided by the present invention, the melting point distribution of the alloy film is estimated according to the linear mixing rule.

[0035] Preferably, in order to further evaluate the oxidation resistance of the gradient TiAlNb-based alloy film of the present invention, we conducted additional high-temperature heat treatment experiments on the prepared samples. The specific steps are as follows:

[0036] Heat treatment experiment: The prepared TiAlNb-based alloy film sample with composition gradient was placed in a high-temperature furnace, heat treated at 700°C for 5 hours, and then cooled; the cooling method was air cooling.

[0037] Scanning Electron Microscope Analysis: The surface morphology of each square grid (5 mm side) was observed using a scanning electron microscope (SEM) at 5k and 50k magnifications before and after heat treatment. By comparing the surface morphology before and after heat treatment, especially the formation of the oxide layer, the oxidation resistance of the different composition regions was evaluated.

[0038] The present invention discloses the following technical effects:

[0039] The present invention provides a TiAlNb-based alloy film with a hardness of 8-12.5 GPa, which can meet the high hardness requirements of materials in the current aerospace field. The hardness, strength and density of the Ti-based alloy are regulated by adding Al, Nb, Ta, V and B. The TiAlNb-based alloy film within the element range defined by the present invention has excellent hardness, strength and low density. Specifically, the film has a hardness of 8-12.5 GPa, an elastic modulus of 109.6-188.4 GPa, and a density as low as 6-7 g / cm 3 Furthermore, high-temperature heat treatment experiments verified the alloy film's excellent oxidation resistance. In particular, in regions containing high proportions of strengthening elements such as Ta and Nb, the film exhibited exceptional high-temperature oxidation resistance, which is particularly important for applications in extreme environments such as aerospace.

[0040] High-throughput material preparation technology is a method for screening new materials through high-throughput screening and collecting the correlation between the structure and performance of existing materials through a database to guide the design and development of new materials. Applying this preparation technology to the field of lightweight high-temperature alloys can accelerate the development of new materials, transform the development model of new lightweight high-temperature alloys, save manpower, material resources, and financial resources, build a reliable material gene database, realize resource sharing, and accelerate the optimization screening of the composition of high-hardness, lightweight, refractory, high-entropy alloys, thereby producing lightweight high-temperature alloys with excellent performance. To screen out high-hardness, lightweight, refractory, high-entropy alloys with new compositions, the present invention adds V, Ta, and B elements to a TiAlNb-based alloy and uses multi-target magnetron sputtering technology to prepare a film with a composition gradient on a substrate. Multi-target magnetron sputtering technology can simultaneously activate multiple deposition sources during the deposition process. Due to the certain tilt angle between each deposition source and the substrate, the resulting film will form a composition gradient in the horizontal direction. This composition gradient film can provide a large number of composition combinations, which helps to quickly explore the performance of samples with different compositions, thereby accelerating the development of new high-hardness, lightweight, refractory, high-entropy alloys.

[0041] The present invention provides a method for developing lightweight, high-temperature, high-strength TiAlNb-based high-entropy alloy compositions based on dual-target co-sputtering, and explores the strengthening effects of Ta, V, and B elements on TiAlNb-based alloys, solving the problem of traditional alloy screening relying on experience, low efficiency, and large errors. Preparation is performed using a dual-target co-sputtering magnetron sputtering instrument, and the change in the composition of the resulting sample can be controlled by adjusting the angle between the targets and the distance between the target and the substrate. This method not only allows for rapid exploration of multiple component ratios and selection of the optimal formula, but also ensures the practical application potential of thin film materials through experimental verification and performance evaluation. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] 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.

[0043] Figure 1 This is a schematic diagram of dual-target co-deposition magnetron sputtering according to Example 1 of the present invention;

[0044] Figure 2 Schematic diagram of film coordinate division in Example 1 of the present invention;

[0045] Figure 3 This is a distribution diagram of Ta element content in the TiAlNb-based alloy film prepared in Example 1 of the present invention;

[0046] Figure 4 This is a distribution diagram of the V element content in the TiAlNb-based alloy film prepared in Example 1 of the present invention;

[0047] Figure 5 This is a distribution diagram of Al element content in the TiAlNb-based alloy film prepared in Example 1 of the present invention;

[0048] Figure 6 This is a distribution diagram of Nb element content in the TiAlNb-based alloy film prepared in Example 1 of the present invention;

[0049] Figure 7 This is a distribution diagram of Ti element content in the TiAlNb-based alloy film prepared in Example 1 of the present invention;

[0050] Figure 8 This is a hardness distribution diagram of the TiAlNb-based alloy film prepared in Example 1 of the present invention;

[0051] Figure 9 This is a distribution diagram of the elastic modulus of the TiAlNb-based alloy film prepared in Example 1 of the present invention;

[0052] Figure 10 This is a theoretical melting point distribution diagram of the TiAlNb-based alloy film prepared in Example 1 of the present invention;

[0053] Figure 11 SEM images of three regions of the TiAlNb-based alloy film prepared in Example 1 of the present invention before heat treatment;

[0054] Figure 12 These are SEM images of three regions of the TiAlNb-based alloy film prepared in Example 1 of the present invention after heat treatment. DETAILED DESCRIPTION

[0055] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0056] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value within any stated value or stated range, and each smaller range between any other stated value or intermediate value within the stated range, is also encompassed within the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0057] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0058] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0059] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0060] The room temperature in the embodiment of the present invention is 25°C.

[0061] The raw materials used in the embodiments of the present invention are all commercially available products; among them:

[0062] TiTaNbVB alloy target, Ti39.8Nb38.8Ta9.95V10B1.45 with a purity of 99.99%, size Φ50mm×4.5mm;

[0063] TiAl alloy target, Ti50Al50 with a purity of 99.99%, size Φ50mm×4mm;

[0064] The Si substrate is single-sided polished and the crystal orientation is <111> The silicon wafer has a size of Φ48mm×1mm.

[0065] In an embodiment of the present invention, the vertical distance between the center point of the DC magnetron sputtering target and the substrate is 7 cm; the vertical distance between the center point of the RF magnetron sputtering target and the substrate is 7 cm, and the DC magnetron sputtering target and the RF magnetron sputtering target are arranged opposite to each other.

[0066] Example 1

[0067] In this embodiment, a two-target co-sputtering magnetron sputtering apparatus is used. A TiTaNbVB alloy target, a TiAl alloy target, and a Si substrate are placed in the magnetron sputtering apparatus. The TiTaNbVB alloy target is placed on an RF magnetron sputtering target, the TiAl alloy target is placed on a DC magnetron sputtering target, and the Si substrate is mounted on a fixture of the magnetron sputtering apparatus. The target surfaces of the TiTaNbVB alloy target and the TiAl alloy target are at an angle of 75° to the horizontal direction ( Figure 1 shown).

[0068] The preparation process of this embodiment needs to be carried out under high vacuum, and the specific operations are as follows:

[0069] (1) When the base pressure of the vacuum chamber is lower than 8×10 -4 When the pressure reaches 3 Pa, high-purity argon (99.999%) is injected into the vacuum chamber, and the pressure in the chamber reaches 3 Pa by adjusting the molecular pump valve and the argon flux;

[0070] (2) The TiTaNbVB alloy target (target 1) was selected with an RF sputtering power supply, and the TiAl alloy target (target 2) was selected with a DC sputtering power supply; the argon flux was 99 sccm (standard cubic centimeters per minute), the power was turned on, and the target was ignited; after ignition, the gas pressure was adjusted to 0.3 Pa, and the pre-sputtering time was 3 minutes. After the pre-sputtering was completed, sputtering was started and timing was set, and the sputtering time was 120 minutes; after the sputtering was completed, the instrument was turned off, and it was taken out after waiting for 60 minutes to obtain a TiAlNb-based alloy film with a composition gradient.

[0071] The parameters of the magnetron sputtering technology are as follows: the temperature of the Si substrate is room temperature, the power of the DC magnetron sputtering target is 50W, the power of the RF magnetron sputtering target is 80W, the sputtering time is 120min, the starting pressure is 3Pa, the sputtering pressure is 0.3Pa, and the vacuum degree is 8×10 - 4 Pa, argon atmosphere.

[0072] Effect Example 1

[0073] The film sample prepared in Example 1 was marked with a two-dimensional coordinate system ( Figure 2 As shown in the figure, the film surface is divided into multiple square grids with a side length of 5 mm. Two points are taken near each coordinate point to measure the composition, hardness and elastic modulus, as follows:

[0074] (1) The test method for determining the composition of the sample is X-ray energy dispersive spectrometer (EDS), which can obtain specific composition information. Figure 3-Figure 7 ;

[0075] Figure 3 It shows that the Ta content decreases along the positive direction of the x-axis and decreases along the positive direction of the y-axis, gradually decreasing from 10.67 at % to 7.7 at %.

[0076] Figure 4 It shows that the V content decreases along the positive direction of the x-axis and remains basically unchanged along the y-axis, gradually decreasing from 8.2at% to 5.21at%.

[0077] Figure 5 It shows that the Al content increases along the positive direction of the x-axis and remains basically unchanged along the y-axis, gradually increasing from 11.9at% to 23.65at%.

[0078] Figure 6 It shows that the Nb content decreases along the positive direction of the x-axis and remains basically unchanged along the y-axis, gradually decreasing from 30at% to 21.1at%.

[0079] Figure 7 It shows that the Ti content fluctuates between 40at% and 42.5at%, and the element content does not change significantly.

[0080] B is a light element and the error in measuring its content under a scanning electron microscope is large, so the content of element B was not measured. Elemental analysis by ICP-AES revealed that its content in the prepared TiAlNb-based alloy film did not change much, ranging from 0% to 1.45%.

[0081] (2) The hardness and elastic modulus of the film samples were tested using a nanoindentation tester from Hysitron Inc, Minneapolis, MN, with a loading force of 7 mN, a strain rate of 0.5 mN / s, and a loading time of 10 s to obtain the hardness distribution of the film samples. The results are shown in Figure 8-9 . Figure 8 TiAlNb-based alloy films with compositional gradients show a hardness distribution between 8 and 12.5 GPa due to varying concentrations of strengthening elements. The hardness gradient varies at different locations. This allows for rapid screening of samples with superior performance through a high-throughput method for a series of tests. Figure 9 It shows that the elastic modulus of TiAlNb-based alloy films with composition gradient reaches 109.6-188.4GPa.

[0082] (3) Estimate the melting point distribution of alloy films based on the linear mixing law. Figure 10The melting point of TiAlNb-based alloy films with composition gradient is shown to be distributed between 1716-1961℃.

[0083] (4) Additional high-temperature heat treatment experiments were conducted on the prepared samples. The details are as follows:

[0084] Heat treatment experiment: The TiAlNb-based alloy film sample with composition gradient prepared in Example 1 was placed in a high-temperature furnace, heat treated at 700° C. for 5 hours, and then cooled by air cooling.

[0085] Scanning electron microscopy analysis: The surface morphology of each square grid was observed using a scanning electron microscope (SEM) at 5k and 50k magnifications before and after heat treatment, respectively. Figure 11 SEM images of three selected areas before heat treatment ( Figure 11 In the figure, the coordinates of the three regions from top to bottom are (x, y) = (3, 1), (-3, -1), (2, -2). Figure 12 SEM images of three selected areas after heat treatment ( Figure 12 The coordinates of the three regions from top to bottom are (x, y) = (3, 1), (-3, -1), and (2, -2). By comparing the surface morphology before and after heat treatment, especially the formation of the oxide layer, the oxidation resistance of the regions with different compositions was evaluated.

[0086] Surface morphology changes: After heat treatment, no cracks or peeling were found in all areas. Most areas showed slight oxidation, while a few areas almost maintained a good original surface state.

[0087] Effect of ingredients on antioxidant properties: Combined with the ingredient distribution data in the previous Example 1 (such as Figure 3-Figure 7 As shown), it can be found that the TiAlNb-based alloy film within the scope of the present invention exhibits excellent oxidation resistance. This is because these elements help to form a protective oxide layer, thereby improving the overall oxidation resistance of the material.

[0088] Example 2

[0089] On the basis of the above-mentioned Example 1 and Effect Example 1, a TiAlNb-based alloy film with an atomic percentage of Ti 41%, Al 20%, Nb 24%, Ta 8%, V 6%, and B 1% was prepared, and its performance was verified using the scheme of Effect Verification Example 1. The results showed that its hardness was 12.11 GPa, elastic modulus was 177.9 GPa, and density was 6.14 g / cm 3 .

[0090] On the basis of the above-mentioned Example 1 and Effect Example 1, a TiAlNb-based alloy film with an atomic percentage of Ti 41%, Al 15%, Nb 28%, Ta 8%, V 7%, and B 1% was prepared, and its performance was verified using the scheme of Effect Verification Example 1. The results showed that its hardness was 12.35 GPa, elastic modulus was 183.3 GPa, and density was 6.53 g / cm 3 .

[0091] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A TiAlNb-based alloy film, characterized in that: In terms of atomic percentage, it includes: Ti 40% to 42.5%, Al 11.9% to 24%, Nb 20% to 30%, Ta 7.7% to 10.7%, V 5.2% to 8.2%, and B 0% to 1.45%.

2. The TiAlNb-based alloy thin film according to claim 1, characterized in that The TiAlNb-based alloy film is a gradient TiAlNb-based alloy film, in which the contents of Al, Nb, Ta, and V elements vary gradiently in the alloy film. Along the positive direction of the x-axis, the atomic percentage of Al increases from 11.9% to 23.65%, the atomic percentage of Nb decreases from 30% to 21.1%, the atomic percentage of Ta decreases from 10.67% to 7.7%, and the atomic percentage of V decreases from 8.2% to 5.21%.

3. A method for preparing a TiAlNb-based alloy thin film according to claim 1, characterized in that: The TiTaNbVB alloy is used as a radio frequency magnetron sputtering target, and the TiAl alloy is used as a direct current magnetron sputtering target, and the TiAlNb-based alloy film is deposited on the surface of the substrate through dual-target co-sputtering.

4. A method for preparing a TiAlNb-based alloy thin film according to claim 2, characterized in that: The gradient TiAlNb-based alloy film is deposited on the surface of a horizontally arranged substrate by dual-target co-sputtering using a TiTaNbVB alloy as a radio frequency magnetron sputtering target and a TiAl alloy as a direct current magnetron sputtering target; wherein the target surface of the direct current magnetron sputtering target forms an angle of 70° to 80° with the horizontal direction; and the target surface of the radio frequency magnetron sputtering target forms an angle of 70° to 80° with the horizontal direction.

5. The preparation method according to claim 3 or 4, characterized in that The TiTaNbVB alloy is Ti39.8Nb38.8Ta9.95V10B1.45; And / or, the TiAl alloy is Ti50Al50; And / or, the substrate is single-sided polished and has a crystal orientation of <111> silicon wafer.

6. The preparation method according to claim 3 or 4, characterized in that The size of the radio frequency magnetron sputtering target is Φ50 mm×4.5 mm; the size of the direct current magnetron sputtering target is Φ50 mm×4 mm; the size of the substrate is Φ48 mm×1 mm.

7. The preparation method according to claim 3 or 4, characterized in that The parameters of the dual-target co-sputtering include: The substrate temperature was 15-40°C, the DC magnetron sputtering target power was 50W, the RF magnetron sputtering target power was 80W, the sputtering time was 120min, the starting pressure was 3Pa, the sputtering pressure was 0.3Pa, and the vacuum degree was 8×10 -4 Pa, argon atmosphere.

8. The preparation method according to claim 7, characterized in that Before dual-target co-sputtering, pre-sputtering was performed at a pressure of 0.3 Pa for 3 minutes.

9. The preparation method according to claim 3, characterized in that The distance between the DC magnetron sputtering target and the substrate is 7 cm; and / or the distance between the RF magnetron sputtering target and the substrate is 7 cm.

10. The preparation method according to claim 4, characterized in that The vertical distance between the center point of the DC magnetron sputtering target and the substrate is 7 cm; and / or the vertical distance between the center point of the RF magnetron sputtering target and the substrate is 7 cm.

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