CN111270207A - Preparation method of high-entropy alloy thin film material with layered structure - Google Patents

Preparation method of high-entropy alloy thin film material with layered structure Download PDF

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CN111270207A
CN111270207A CN202010097935.1A CN202010097935A CN111270207A CN 111270207 A CN111270207 A CN 111270207A CN 202010097935 A CN202010097935 A CN 202010097935A CN 111270207 A CN111270207 A CN 111270207A
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entropy alloy
evaporation
layered structure
metal
film
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任卫
朱楠楠
张永超
杨朝宁
李璐
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Xian University of Posts and Telecommunications
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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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/54—Controlling or regulating the coating process

Abstract

The invention relates to a preparation method of a high-entropy alloy film with a laminated structure, which comprises the following steps: under the condition of high vacuum, adopting high-energy electron beams to sequentially heat different types of metal evaporation materials so as to sequentially evaporate the metal evaporation materials, then sequentially depositing the evaporated metal materials, repeating the steps to prepare a multilayer film with periodically arranged metal materials, and finally performing annealing treatment at 800 ℃ in the air to form a high-entropy alloy film with a layered structure; compared with the traditional method, the preparation method of the high-entropy alloy film with the layered structure has the advantages that the required process equipment is simple, the process flow is reliable, the process is simple and convenient, the process parameters are controllable, and the key processes (the thickness of each deposition layer, the proportion and the sequence of deposition elements are changed) are easy to operate; the prepared film has good film forming quality and uniform element component distribution.

Description

Preparation method of high-entropy alloy thin film material with layered structure
Technical Field
The invention belongs to the technical field of preparation and characterization of materials, and particularly relates to a preparation method of a high-entropy alloy film with a layered structure.
Background
The professor of Taiwan scholars in leaf of China firstly provides a multi-component high-entropy alloy system in 2004, and the system breaks through the traditional alloy system framework and greatly widens the range of the alloy research field. High entropy alloys refer to an alloy system having 5 or more major elements, typically between 5 and 13 element species, and 35% or less of each element. Due to the high entropy effect of the high entropy alloy system, the high entropy alloy has more metal elements and tends to form a simple solid solution structure, and the special element mixture and crystal structure enable the high entropy alloy to have excellent mechanical properties, chemical properties and physical properties such as high hardness, high plasticity, high work hardening, wear resistance, corrosion resistance, high temperature oxidation resistance, softening resistance and the like.
The research direction of the traditional high-entropy alloy system mainly focuses on the improvement of the component proportion and the mechanical property of the block material. With the development of the times, higher requirements are put forward on the surface functional modification of some components, and the components have the characteristics of chemical corrosion resistance, high-temperature oxidation resistance, mechanical wear resistance and the like if needed. The high-entropy alloy film coating material has the characteristics of simple and various preparation processes, low raw material cost consumption, wider application and the like, is more suitable for being used in extreme environments in modern industry, and quickly becomes a hot spot for research on the high-entropy alloy film coating material.
The main methods for preparing the high-entropy alloy film coating material are magnetron sputtering, thermal spraying and electrochemical deposition. The high-entropy alloy films prepared by the methods are all in a state with more uniform components, and various mechanical, chemical and electrical properties are in a stable final state on the surface and in the film. However, in the process of converting the pure metal/low-entropy alloy into the high-entropy alloy, the mutual diffusion and mutual mixing processes of different metal components along with the temperature rise have great influence on the structural performance of the high-entropy alloy thin film. Its diffusion mechanism to form high entropy alloys remains unclear.
Disclosure of Invention
The invention provides a preparation method of a high-entropy alloy film with a laminated structure, which comprises the following steps: under the condition of high vacuum, high-energy electron beams are adopted to sequentially heat different types of metal evaporation materials so that the metal evaporation materials are sequentially evaporated, then the evaporated metal materials are sequentially deposited, the steps are repeated, multilayer films with metal materials arranged periodically are prepared, and finally annealing treatment at 800 ℃ is carried out in the air, so that the high-entropy alloy film with the layered structure is formed.
The preparation method of the high-entropy alloy film with the layered structure comprises the following steps:
s1, placing the cleaned high-purity silicon substrate in an electron beam evaporation device, and placing the required different kinds of metal evaporation materials into different graphite crucibles;
s2, starting a vacuum pump system to reduce the vacuum degree of an evaporation cavity of the electron beam evaporation device to 6.4 multiplied by 10-4Below Pa, simultaneously heating the high-purity silicon substrate to 310 ℃ by using a resistance wire heating system of an electron beam evaporation device, and maintaining the temperature of the substrate at a constant temperature of 310 ℃;
s3, starting an electron gun, emitting high-energy electron beams, and pre-melting the required metal evaporation materials respectively;
s4, after the pre-melting is finished, cleaning an ion source, and cleaning residual gas in the evaporation cavity and gaseous waste metal generated by the pre-melting;
s5, setting the evaporation sequence of different metal evaporation materials, the thickness of each metal evaporation material deposition layer and the repeated period of evaporation of the metal evaporation materials, and starting coating when the vacuum degree reaches the evaporation condition;
and S6, taking out the multilayer film sample after the evaporation of the multilayer film is finished and the temperature in the cavity is reduced to room temperature, and annealing the sample in the air at 800 ℃ to obtain the high-entropy alloy film with the laminated structure.
The types of the metal evaporation materials are more than five (including five).
The metal evaporation materials are five in type, and sequentially comprise aluminum (Al), iron (Fe), chromium (Cr), copper (Cu) and nickel (Ni).
The purities of the metal evaporation material and the high-purity silicon substrate are more than 99.95 percent.
The high-purity silicon substrate is a single-side polished Si (100) single crystal wafer with the resistivity of 10k omega cm, and is cut into 2 x 2cm by adopting a laser cutting mode2The chip of (1).
The specific process for cleaning the high-purity silicon substrate comprises the following steps: putting the high-purity silicon substrate into a mixed solution containing concentrated sulfuric acid and hydrogen peroxide (the ratio is 3:1), heating the mixed solution on a heating furnace to boil at 120 ℃ for 8 minutes; the high purity silicon substrate was then removed from the solution and ultrasonically cleaned in acetone, absolute ethanol and deionized water for 10 minutes, respectively.
The concentrated sulfuric acid concentration is 96%, and the hydrogen peroxide concentration is 30%.
The vapor deposition rate of the chromium (Cr) is
Figure BDA0002385856110000031
The current range of the electron gun is 993-996 mA.
The evaporation rate of the copper (Cu) is
Figure BDA0002385856110000032
The current range of the electron gun is 1263-1267 mA.
The evaporation rate of the nickel (Ni) is
Figure BDA0002385856110000033
The current range of the electron gun is 1108-1110 mA.
The evaporation rate of the aluminum (Al) is
Figure BDA0002385856110000034
The current range of the electron gun is 1291-1295 mA.
The evaporation rate of the iron (Fe) is
Figure BDA0002385856110000035
The current range of the electron gun is 1187-1189 mA.
The distance between the metal evaporation material and the high-purity silicon substrate is 75-100 cm.
Compared with the prior art, the invention has the beneficial effects that: compared with the traditional method, the preparation method of the high-entropy alloy film with the layered structure has the advantages that the required process equipment is simple, the process flow is reliable, the process is simple and convenient, the process conditions and parameters are controllable, and the key processes (changing the thickness of each deposition layer, the proportion and the sequence of deposition elements) are easy to operate; the prepared film has good film forming quality and uniform element component distribution. The method also provides a new idea for researching the influence of the mutual diffusion of elements on the performance of the film material in the process of forming the high-entropy alloy film. The evaporation sequence of different metal layers, the thickness of each deposition layer and the repetition period have scientific significance on the influence of the high-entropy alloy film and have important application value in the technology.
The present invention will be described in further detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is an X-ray diffraction pattern of a high-entropy alloy thin film having a layered structure prepared.
FIG. 2 is a Raman spectrum of the prepared high-entropy alloy thin film with a laminated structure.
FIG. 3 is a first scanning electron microscope image of the prepared high-entropy alloy thin film with a laminated structure.
FIG. 4 is a second scanning electron microscope image of the prepared high-entropy alloy thin film with a laminated structure.
FIG. 5 is a scanning electron microscope photograph III of the prepared high-entropy alloy thin film having a layered structure.
FIG. 6 is a scanning electron microscope image IV of the prepared high-entropy alloy thin film with a laminated structure.
FIG. 7 is a first AC impedance spectrum of the prepared high-entropy alloy thin film with a laminated structure.
FIG. 8 is a second AC impedance spectrum of the prepared high-entropy alloy thin film with a laminated structure.
FIG. 9 is a third AC impedance spectrum of the prepared high-entropy alloy thin film with a laminated structure.
FIG. 10 is a fourth AC impedance spectrum of the prepared high-entropy alloy thin film with a laminated structure.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the intended purpose, the following detailed description of the embodiments, structural features and effects of the present invention will be made with reference to the accompanying drawings and examples.
Example 1
The invention provides a preparation method of a high-entropy alloy film with a layered structure as shown in figures 1-10, which comprises the following steps: under the condition of high vacuum, high-energy electron beams are adopted to sequentially heat different types of metal evaporation materials, so that the metal evaporation materials are sequentially evaporated and deposited on a substrate to form a film, the steps are repeated, a multilayer film with periodically arranged metal materials is prepared, and finally, annealing treatment at 800 ℃ is carried out in the air to form the high-entropy alloy film with a laminated structure. The temperature of the silicon substrate during the evaporation process was maintained at 310 ℃. Finally, the sample is annealed in the air at 800 ℃. The following examples design four typical multilayer thin film schemes with different metal layer deposition sequences.
The substrate temperature is maintained in a vacuum environment of 310 ℃ in the evaporation process, the main purpose is to remove gas and impurities adsorbed on the surface of the substrate, improve the mobility of deposited metal atoms on the surface of the substrate and reduce the surface stress of a metal film, and meanwhile, a stable system environment can be provided for the deposition growth of the film in the vacuum environment. Annealing is carried out at 800 ℃ in the air, and the metal atoms are mutually diffused under the heating state to promote the re-fusion and reaction bonding between different metal atoms, so that the high-entropy alloy film with uniform and compact components and a layered structure is formed, and the influence of high-temperature annealing on the performance of the high-entropy alloy film material is conveniently researched.
Further, the preparation method of the high-entropy alloy film with the laminated structure comprises the following steps:
s1, placing the cleaned high-purity silicon substrate in an electron beam evaporation device, and placing the required different kinds of metal evaporation materials into different graphite crucibles;
s2, starting a vacuum pump system to reduce the vacuum degree of an evaporation cavity of the electron beam evaporation device to 6.4 multiplied by 10-4Below Pa, simultaneously heating the high-purity silicon substrate to 310 ℃ by using a resistance wire heating system of an electron beam evaporation device, and maintaining the temperature of the substrate at a constant temperature of 310 ℃;
s3, starting an electron gun, emitting high-energy electron beams, and pre-melting the required metal evaporation materials respectively;
s4, after the pre-melting is finished, cleaning an ion source, and cleaning residual gas in the evaporation cavity and gaseous waste metal generated by the pre-melting;
s5, setting the evaporation sequence of different metal evaporation materials, the thickness of each metal evaporation material deposition layer and the repeated period of evaporation of the metal evaporation materials, and starting coating when the vacuum degree reaches the evaporation condition;
s6, taking out the multilayer film sample after the evaporation of the multilayer film is finished and the temperature in the cavity is reduced to room temperature, and annealing the sample in the air at 800 ℃, wherein the annealing time is 1 hour, and the temperature rise rate is set to be 5 ℃/min in the annealing process. And then, preserving the heat for 10 minutes when the temperature reaches 300 ℃, and naturally cooling along with the furnace to finally obtain the high-entropy alloy film with the laminated structure.
Furthermore, the types of the metal evaporation materials are more than five (including five).
In the high-entropy alloy thin film described in this embodiment, the types of the metal evaporation materials used are five, and aluminum (Al), iron (Fe), chromium (Cr), copper (Cu), and nickel (Ni) are sequentially used.
Furthermore, the purity of the five metal evaporation materials and the purity of the high-purity silicon substrate are both more than 99.95%.
Further, the high-purity silicon substrate is a single-side polished Si (100) single crystal wafer with the resistivity of 10k omega cm. Cutting a high-purity silicon substrate into 2 multiplied by 2cm in area by adopting a laser cutting mode2The chip of (1).
Further, the deposition rate of the metal material is
Figure BDA0002385856110000062
The deposition rate may have some effect on the growth mode of the film. If the thickness of the film is larger, the method of firstly adjusting the deposition rate to be lower and then adjusting the deposition rate to be higher can be adopted to improve the crystallization quality of the deposited film and the deposition efficiency of the film; however, if the film thickness is small, the variation in the deposition rate has little influence on the film. This deposition rate is a more optimal deposition rate that is experimentally derived.
Further, the specific process of cleaning the high-purity silicon substrate is as follows: putting the high-purity silicon substrate into a mixed solution containing concentrated sulfuric acid and hydrogen peroxide (the ratio is 3:1), heating the mixed solution on a heating furnace to boil at 120 ℃ for 8 minutes; the high purity silicon substrate was then removed from the solution and ultrasonically cleaned in acetone, absolute ethanol and deionized water for 10 minutes, respectively.
The concentrated sulfuric acid concentration is 96%, and the hydrogen peroxide concentration is 30%.
The vapor deposition rate of the chromium (Cr) is
Figure BDA0002385856110000061
The current range of the electron gun is 993-996 mA.
The evaporation rate of the copper (Cu) is
Figure BDA0002385856110000071
The current range of the electron gun is 1263-1267 mA.
The evaporation rate of the nickel (Ni) is
Figure BDA0002385856110000072
The current range of the electron gun is 1108-1110 mA.
The evaporation rate of the aluminum (Al) is
Figure BDA0002385856110000073
The current range of the electron gun is 1291-1295 mA.
The evaporation rate of the iron (Fe) is
Figure BDA0002385856110000074
The current range of the electron gun is 1187-1189 mA.
Further, the distance between the metal evaporation material and the high-purity silicon substrate is 75-100 cm. The distance between the metal evaporation material and the filament of the electron gun is 20-30 mm; when the electron beam heats the metal evaporation material, if the silicon substrate is too close to the metal evaporation material, the evaporation rate of the metal evaporation material is higher at the initial moment when the metal evaporation material is converted from a solid state/a liquid state into a gaseous state, the film forming quality is difficult to control, and the final film forming quality and uniformity can be influenced. In addition, if the evaporation material is heated unevenly, the phenomenon of bursting and collapsing of metal evaporation material particles can occur. The collapsing vaporized material particles can also affect film quality if they are sputtered onto the substrate. Through repeated tests, the rising rate of the metal vapor and the relative gas density of the metal vapor are more uniform when the distance between the substrate and the evaporation material is 75-100 cm, and the growth of a high-quality film is facilitated.
Example 2
In this example, the method of example 1 was used to prepare a high-entropy alloy thin film with a layered structure, five metal evaporation materials were used, and the evaporation sequence of the metal evaporation materials (from the silicon substrate upwards in sequence) and the thickness of each deposition layer were Cr (40nm), Cu (40nm), Ni (40nm), Al (40nm), Fe (40nm) in sequence, the repetition period was 1 time, the total thickness of the thin film was 200nm, and the mark was crcuninalfe.
Example 3
In this example, five kinds of metal evaporation materials were used to prepare a high-entropy alloy thin film having a layered structure by using the method of example 1, and the evaporation sequence of the metal evaporation materials (from the silicon substrate to the top in sequence) and the thickness of each deposition layer were Al (10nm), Fe (10nm), Cr (10nm), Cu (10nm), and Ni (10nm) in sequence, the repetition period was 4 times, the total thickness of the thin film was 200nm, and the mark was alfecrccuni.
Example 4
In this example, five kinds of metal evaporation materials were used to prepare a high-entropy alloy thin film having a layered structure by using the method of example 1, and the evaporation sequence of the metal evaporation materials (from the silicon substrate to the top in sequence) and the thickness of each deposition layer were Al (10nm), Fe (10nm), Cr (10nm), Cu (10nm), and Ni (10nm) in sequence, the repetition period was 4 times, the total thickness of the thin film was 200nm, and the mark was alfecrccuni.
Example 5
In this example, five kinds of metal evaporation materials were used, and the evaporation sequence of the metal evaporation materials and the thickness of each deposited film layer were Fe (10nm), Cr (10nm), Cu (10nm), Ni (10nm), and Al (10nm), the repetition period was 4 times, and the total nominal thickness of the film was 200nm, and the mark was fecrccunai, in the method of example 1.
Further, the alternating current impedance spectrum analysis is carried out on the prepared high-entropy alloy film with the laminated structure by adopting a three-electrode system, and the result shows that all samples have two or more than two electrical interfaces, and the high-temperature annealing can oxidize the surface layer or subsurface metal layer of the film into a more compact oxide layer so as to protect the interior of the film from being corroded by corrosive liquid. The etching solution used was 3.5% NaCl solution.
Further, the high-entropy alloy thin films of the layered metal arrangement structures prepared in examples 1 to 4 were analyzed by an X-ray diffractometer, a raman spectrometer, a scanning electron microscope and an ac impedance spectrometer, and the characterization results are shown in fig. 1 to 10. The results in fig. 1 show that different deposition sequences and the thickness and repetition period of each deposition layer have little influence on the experimental results, and more diffraction peaks appear in the sample under the high-temperature annealing treatment at 800 ℃, which indicates that the intermetallic compounds appear in the multilayer metal film at higher temperature. The results in FIG. 2 show that different evaporation sequences have different Raman peaks of the corresponding high-entropy alloy thin films. And the difference of the Raman peak of the sample treated by high-temperature annealing and the sample not treated by high-temperature annealing is more dependent on the characteristics of the outermost metal (air contact layer) element. The results of fig. 3 to 6 show that the thin film subjected to the high temperature annealing treatment has different degrees of dot-like precipitates on the surface, and the distribution of the dot-like precipitates differs depending on the surface elements. The results of FIGS. 7-10 show that the negative impedance spectra of all high entropy alloy films can be viewed as consisting of at least two semicircles. Since the sheet resistance generally includes grain resistance and grain boundary resistance, and the grain boundary resistance is generally much larger than the grain resistance, it indicates that the layered high-entropy alloy thin film forms two or more electrical interfaces. In addition, the corrosion resistance of the film after high-temperature annealing treatment is better than that of a sample without annealing treatment, and the possible reason is that metal elements on the surface layer are oxidized by oxygen in the air at high temperature to form a compact oxide layer, so that the internal components of the film are protected from being corroded by corrosive liquid. Compared with the traditional preparation method, the method for preparing the high-entropy alloy film has certain innovativeness in the aspect of preparation method, the film preparation process is simple, the film forming quality is good, the cost is low, and a new way is provided for the industrial production of the high-quality high-entropy alloy film.
In conclusion, compared with the traditional method, the preparation method of the high-entropy alloy film with the layered structure has the advantages that the required process equipment is simple, the process flow is reliable, the process is simple and convenient, the process conditions and parameters are controllable, and the key processes (changing the thickness of each deposition layer, the proportion and the sequence of deposition elements) are easy to operate; the prepared film has good film forming quality and uniform element component distribution. The method also provides a new idea for researching the influence of the mutual diffusion of elements on the performance of the film material in the process of forming the high-entropy alloy film. The evaporation sequence of different metal layers, the thickness of each deposition layer and the repetition period have scientific significance on the influence of the performance of the high-entropy alloy film and have important application value in the technology.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (10)

1. A preparation method of a high-entropy alloy film with a layered structure is characterized by comprising the following steps: under the condition of high vacuum, high-energy electron beams are adopted to sequentially heat different types of metal evaporation materials so that the metal evaporation materials are sequentially evaporated, then the evaporated metal materials are sequentially deposited, the steps are repeated, multilayer films with metal materials arranged periodically are prepared, and finally annealing treatment at 800 ℃ is carried out in the air, so that the high-entropy alloy film with the layered structure is formed.
2. A method for producing a high-entropy alloy thin film of a layered structure as defined in claim 1, comprising the steps of:
s1, placing the cleaned high-purity silicon substrate in an electron beam evaporation device, and placing the required different kinds of metal evaporation materials into different graphite crucibles;
s2, starting a vacuum pump system to reduce the vacuum degree of an evaporation cavity of the electron beam evaporation device to 6.4 multiplied by 10-4Below Pa, simultaneously heating the high-purity silicon substrate to 310 ℃ by using a resistance wire heating system of an electron beam evaporation device, and maintaining the temperature of the substrate at a constant temperature of 310 ℃;
s3, starting an electron gun, emitting high-energy electron beams, and pre-melting the required metal evaporation materials respectively;
s4, after the pre-melting is finished, cleaning an ion source, and cleaning residual gas in the evaporation cavity and gaseous waste metal generated by the pre-melting;
s5, setting the evaporation sequence of different metal evaporation materials, the thickness of each metal evaporation material deposition layer and the repeated period of evaporation of the metal evaporation materials, and starting coating when the vacuum degree reaches the evaporation condition;
and S6, taking out the multilayer film sample after the evaporation of the multilayer film is finished and the temperature in the cavity is reduced to room temperature, and annealing the sample in the air at 800 ℃ to obtain the high-entropy alloy film with the laminated structure.
3. A method for producing a high-entropy alloy thin film of a layered structure as defined in claim 1, wherein: the types of the metal evaporation materials are more than five (including five).
4. A method for producing a high-entropy alloy thin film of a layered structure as defined in claim 3, wherein: the metal evaporation materials are five in type, and sequentially comprise aluminum (Al), iron (Fe), chromium (Cr), copper (Cu) and nickel (Ni).
5. A method for producing a high-entropy alloy thin film of a layered structure as defined in claim 2, wherein: the purities of the metal evaporation material and the high-purity silicon substrate are more than 99.95 percent.
6. A method for producing a high-entropy alloy thin film of a layered structure as defined in claim 2, wherein: the high-purity silicon substrate is a single-side polished Si (100) single-crystal wafer with the resistivity of 10k omega cm, and is cut into 2 x 2cm by adopting a laser cutting mode2The chip of (1).
7. A method for producing a high-entropy alloy thin film of a layered structure as defined in claim 2, characterized in that: the specific process for cleaning the high-purity silicon substrate comprises the following steps: putting the high-purity silicon substrate into a mixed solution containing concentrated sulfuric acid and hydrogen peroxide (the ratio is 3:1), heating the mixed solution on a heating furnace to boil at 120 ℃ for 8 minutes; the high purity silicon substrate was then removed from the solution and ultrasonically cleaned in acetone, absolute ethanol and deionized water for 10 minutes, respectively.
8. The method for producing a high-entropy alloy thin film of a layered structure as claimed in claim 7, characterized in that: the concentrated sulfuric acid concentration is 96%, and the hydrogen peroxide concentration is 30%.
9. The method for producing a high-entropy alloy thin film of a layered structure as claimed in claim 4, characterized in that: the vapor deposition rate of the chromium (Cr) is
Figure FDA0002385856100000021
The current range of the electron gun is 993-996 mA; the evaporation rate of the copper (Cu) is
Figure FDA0002385856100000022
The current range of the electron gun is 1263-1267 mA; the evaporation rate of the nickel (Ni) is
Figure FDA0002385856100000023
The current range of the electron gun is 1108-1110 mA; the evaporation rate of the aluminum (Al) is
Figure FDA0002385856100000024
The current range of the electron gun is 1291-1295 mA; the evaporation rate of the iron (Fe) is
Figure FDA0002385856100000025
The current range of the electron gun is 1187-1189 mA.
10. The method for preparing a high-entropy alloy thin film with a layered structure as defined in claim 2, wherein: the distance between the metal evaporation material and the high-purity silicon substrate is 75-100 cm.
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