CN114921757A - A kind of amorphous high-entropy alloy thick film preparation equipment and preparation method - Google Patents

Abstract

The invention discloses an amorphous high-entropy alloy thick film preparation equipment and preparation method. The ion beam bombards the target material to cause cascade collision effect in several atomic layers on the surface of the target material, thereby sputtering a large number of high-energy particles. The high-energy particles are rapidly deposited on the low-temperature substrate and solidify before nucleation, which greatly improves the glass-forming ability of single-phase high-entropy alloys. At the same time, the auxiliary ion source carries out low-energy bombardment on the surface of the substrate, which enhances the diffusion and migration of the deposited atoms, densifies the metal film, and improves the coating quality.

Description

A kind of amorphous high-entropy alloy thick film preparation equipment and preparation method

technical field

The invention relates to a high-entropy alloy thick film preparation equipment and a process method, and the fields of material science and condensed matter physics.

Background technique

Amorphous alloys are metastable metal materials. Amorphous alloys have no crystal defects such as dislocations and grain boundaries. The structural characteristics of short-range order and long-range disorder make them have unique mechanical and functional properties. Compared with traditional crystalline materials, amorphous alloys have higher yield strength, fracture toughness and elastic limit. The thermodynamically stable phase structures with the same composition as these amorphous materials are usually intermetallic compounds or eutectic structures (Literature 1: Wang WH, Lewandowski JJ, Greer AL. Understanding the glass-forming ability of Cu ₅₀ Zr ₅₀ alloys in terms of ametastable eutectic. Journal of Materials Research, 2005, 20(09):2307-2313.). However, it has been reported that high-entropy alloys with a single-phase solid solution structure can also be prepared into amorphous alloys (Reference 2: Ma L, Wang L, Zhang T, et al. Bulk Glass Formation of Ti-Zr-Hf-Cu-M ( M=Fe, Co, Ni) Alloys. Materials Transactions, 2002, 43(2):277-280.). High-entropy alloys have the characteristics of high strength, high toughness, strong thermal stability at high temperature, excellent wear resistance and corrosion resistance, superconducting properties and high catalytic performance. We believe that the amorphization of this novel material will surely bring about new materials with abnormal mechanical, physical and chemical behaviors. Amorphous materials are primarily obtained by rapid solidification or vacuum coating methods that provide cooling rates fast enough to inhibit grain nucleation and growth, resulting in an amorphous state far from equilibrium. Although high-entropy alloys are single-phase solid solution alloys like most traditional engineering metal materials, high-entropy alloys have slow kinetics due to atomic diffusion (Reference 3: TsaiMH, Yeh JW, Gan JY. Diffusion barrier properties of AlMoNbSiTaTiVZr high- entropy alloy layer between copper and silicon. Thin Solid Films, 2008, 516(16): 5527-5530.), so amorphous high-entropy alloys have relatively strong thermal stability in terms of thermodynamics, which is also the energy of single-phase high-entropy alloys. The reason for the preparation of amorphous alloys by vacuum coating methods such as magnetron sputtering.

In recent years, many amorphous high-entropy alloys have been developed and studied. The cooling and solidification of bulk high-entropy alloys usually form a single-phase solid solution structure, while the metal films prepared by sputter deposition can obtain an amorphous structure. This is because each element in the target is bombarded by the ion beam, sputtering out the atoms of the target and depositing on the substrate at a very high cooling rate (about 10 ⁹ K/s). The deposited particles solidify before they can nucleate. Based on this "quick quenching effect", an amorphous high-entropy alloy thin film is finally obtained. Feng et al. prepared WNbMoTaV alloy targets by powder metallurgy (Reference 4: Feng CS, Lu TW, Wang TL, et al. A novel high-entropy amorphous thin film with high electrical resistivity and outstanding corrosion resistance. Acta Metallurgica Sinica, 2021, 34 ( 11): 1537-1545.), Amorphous thin films of target composition were obtained in a pulsed laser deposition system. The resistivity of the WNbMoTaV amorphous high-entropy film is about 320.6 mW×cm and the corrosion current density is 0.088 mA/cm ² . The excellent resistivity and corrosion resistance are derived from the high-entropy effect and amorphous structure caused by multi-components .

However, the amorphous high-entropy alloy system still has many shortcomings. The high-entropy effect tends to produce stable solid solutions, which makes many materials with low glass-forming ability and cannot be prepared into amorphous films. The thickness of the prepared samples is limited by the existing preparation technology, which is not conducive to performance characterization and engineering applications. Therefore, developing a method that can provide a higher cooling rate and can prepare a thicker alloy film can make high-entropy alloys with more composition systems prepared into amorphous high-entropy alloy films with considerable thickness, thereby making up for the difference between the nature of glass and the Glass transition and other basic scientific research and engineering application vacancies.

SUMMARY OF THE INVENTION

In order to solve the problems of the prior art, the purpose of the present invention is to overcome the deficiencies of the prior art, and to provide a preparation equipment and a preparation method for an amorphous high-entropy alloy thick film, which can efficiently and economically prepare an amorphous high-entropy alloy thick film. The preparation process and method of the membrane, the prepared membrane is dense, large in size, and uniform in thickness, which meets the requirements of most performance characterization and industrial applications.

In order to achieve the above-mentioned purpose of invention and creation, the present invention adopts the following technical solutions:

An amorphous high-entropy alloy thick film preparation device, comprising a vacuum chamber and a vacuum pumping system; a low-temperature substrate stage, a baffle plate, a rotating target stage, a main ion source, an auxiliary ion source, and a low-temperature liner are arranged in the vacuum chamber. The bottom platform, the baffle plate, the fixed part of the rotating target platform, the main ion source and the auxiliary ion source are fixed on the wall surface of the vacuum chamber; the substrate is arranged on the low temperature substrate platform, and the target material is arranged on the rotating target platform;

The vacuum chamber is provided with an observation window;

The low-temperature substrate table can be installed with various substrates, and the low-temperature substrate table has a built-in circulating cooling liquid to take away the heat generated during the preparation of the amorphous high-entropy alloy thick film, so that the temperature of the low-temperature substrate table can be maintained. within the set range;

A circulating cooling water system is arranged in the rotating target platform;

The emission port of the main ion source is aligned with the rotating target platform, and the ion beam generated by the main ion source is emitted toward the rotating target platform;

The emission port of the auxiliary ion source is aligned with the low-temperature substrate stage, and the ion beam generated by the auxiliary ion source is emitted toward the low-temperature substrate stage;

The baffle is installed between the target stage and the cryogenic substrate stage;

The vacuum pumping system includes a mechanical pump and a molecular pump. The mechanical pump is used for first-level vacuuming of the vacuum chamber. The air inlet of the mechanical pump is connected to the air outlet of the molecular pump. The molecular pump is used to pump the vacuum chamber. The chamber is evacuated in two stages, and the air inlet of the molecular pump is connected to the air outlet of the vacuum chamber;

A gas cylinder is provided, and the gas cylinder provides working gas to the vacuum chamber to complete the preparation of the amorphous high-entropy alloy thick film.

Preferably, the temperature range provided by the low temperature substrate table is -271°C to room temperature.

Preferably, the degree of vacuum provided by the vacuum chamber is not higher than 1'10 ^-3 Pa.

Preferably, the energy range of the ion beam provided by the main ion source during coating is 150-1500 eV, and the beam current range is 0-100 mA.

Preferably, the energy range of the ion beam provided by the auxiliary ion source during coating is 150-1000 eV, and the beam current range is 0-100 mA.

Preferably, the main ion source and the auxiliary ion source are selected from Kaufman type ion source, radio frequency type ion source or ERC type ion source.

A method for preparing an amorphous high-entropy alloy thick film, using the device for preparing an amorphous high-entropy alloy thick film of the present invention to perform sputtering coating, is characterized in that, comprising the following steps:

1) Clean the surface of the target material, remove oxide scale or other impurities, and install the target material on the rotating target table; preferably use electric brush, sandpaper or high-pressure water gun to clean the surface of the target material;

2) Install the clean substrate on the low-temperature substrate stage in the vacuum chamber, open the baffle; start the vacuum system, and pump the air pressure in the vacuum chamber to no higher than 1×10 ^-3 Pa;

3) Pour the working gas into the vacuum chamber, keep the air pressure stable, open the cooling system of the low-temperature substrate stage, regulate and set the substrate temperature, and wait for the temperature to be constant;

4) Turn on the auxiliary ion source to generate an energy of 150-1000 eV and a beam current of 0-100 mA; then, close the baffle to bombard and clean the substrate with the auxiliary ion source; after the cleaning of the substrate, open the baffle and close the Auxiliary ion source, turn on the main ion source, bombard and clean the target with energy of 150-1500eV and beam current of 0-100mA to remove oxides or other impurities on the surface of the target; The energy and beam current are used for short-term bombardment cleaning, so as to change the surface activity of the substrate, improve the bonding force between the substrate and the film and the purity of the coating;

5) After cleaning the target, turn on the auxiliary ion source to generate an energy of 50-150 eV and a beam current of 0-50 mA; close the baffle to start coating; the auxiliary ion source bombards the substrate surface with a certain energy and beam current, Enhance the diffusion and migration of deposited atoms on the surface, and make the particles that are not tightly bound become more tightly bound or detached from the surface of the metal film under bombardment, thereby reducing structural defects such as holes in the growth process, making the metal film denser and improving the coating. quality, increase the thickness of the metal film;

6) After the deposition setting time, that is, after the coating is completed, the coating is stopped, and the cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system of the low-temperature substrate table are closed in turn; After stopping the coating, wait for at least After 2 hours, the vacuum chamber was inflated to atmospheric pressure, and then the substrate on which the alloy film was prepared was taken out, thereby obtaining an amorphous high-entropy alloy thick film.

Preferably, the diameter of the target material is equal to or greater than the diameter of the low temperature target stage, and the target material composition includes all metals of the high-entropy alloy prepared by the target.

Preferably, the working gas is nitrogen or argon.

Preferably, the substrate is any one of silicon wafer, silicon nitride, glass wafer, silicon carbide wafer and metal wafer.

Preferably, the thickness of the amorphous high-entropy alloy thick film prepared by the method of the present invention is at least 30 mm.

Preferably, the prepared amorphous high-entropy alloy includes Fe, Mn, Co, Ni, Cr, Mo, W, V, Al, Ti, Zr, Li, Mg, Sc, Hf, Nb, Ta, Si, at least two elements in B.

The preparation process of the amorphous high-entropy alloy thick film provided by the invention is to bombard the target material with an ion beam under high vacuum, and deposit the target components on the low-temperature substrate, and finally obtain an amorphous high-entropy alloy with a thickness of not less than 15 μm. alloy, and even obtain a thick film of amorphous high-entropy alloy of not less than 100 μm.

Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:

1. The preparation equipment and process of the amorphous high-entropy alloy thick film of the present invention is to bombard the target material with an ion beam, so that a cascade collision effect occurs in several atomic layers on the surface of the target material, thereby sputtering a large number of high-energy particles; When deposited on a low-temperature substrate, it solidifies before it can nucleate, which greatly improves the glass-forming ability of single-phase high-entropy alloys. The film is densified, the coating quality is improved, and the amorphous high-entropy alloy thick film is finally obtained. ;

2. The thickness of the metal film prepared by the present invention can even reach more than 100m;

3. The high deposition rate and low temperature substrate of the present invention enable high-entropy alloys with small glass forming ability to obtain amorphous structures, so the preparation of amorphous high-entropy alloy thick films with more composition systems is important for basic scientific problems such as glass nature and glass transition. Research and engineering applications have strong practical value.

Description of drawings

FIG. 1 is a schematic diagram of the apparatus used for the preparation of amorphous high-entropy alloy thick films. Among them: 1- vacuum chamber, 2- low temperature substrate stage, 3- baffle plate, 4- substrate, 5- rotating target stage, 6- target material, 7- auxiliary ion source, 8- main ion source, 9- Molecular Pumps, 10-Mechanical Pumps.

2 is a scanning electron microscope picture of a cross section of a 30 μm thick CoCrFeMnNi amorphous high-entropy alloy thick film prepared in Example 1 of the present invention.

3 is the XRD of the FeSiBAlNi amorphous high-entropy alloy thick film prepared in Example 2 of the present invention.

4 is a high-resolution picture and a selected area electron diffraction pattern of the TiZrHfNbTa amorphous high-entropy alloy thick film prepared in Example 3 of the present invention.

Detailed ways

In this embodiment, referring to FIG. 1, an amorphous high-entropy alloy thick film preparation equipment includes a vacuum chamber 1 and a vacuum pumping system; a low-temperature substrate stage 2, a baffle 3, The rotating target table 5 , the main ion source 8 , the auxiliary ion source 7 , the low temperature substrate table 2 , the baffle 3 , the fixing part of the rotating target table 5 , the main ion source 8 , and the auxiliary ion source 7 are fixed on the wall surface of the vacuum chamber 1 ; The substrate 4 is arranged on the low temperature substrate table 2, and the target material 6 is arranged on the rotating target table 5;

The vacuum chamber 1 is provided with an observation window;

The low-temperature substrate stage 2 can be installed with various types of substrates, and the low-temperature substrate stage 2 has a built-in circulating cooling liquid to take away the heat generated during the preparation of the amorphous high-entropy alloy thick film, so that the low-temperature substrate stage 2 has a built-in circulating cooling liquid. 2 Keep the temperature within the set range;

The rotating target platform 5 is provided with a circulating cooling water system;

The emission port of the main ion source 8 is aligned with the rotating target platform 5, and the ion beam generated by the main ion source 8 is emitted toward the rotating target platform 5;

The emission port of the auxiliary ion source 7 is aligned with the low-temperature substrate table 2, and the ion beam generated by the auxiliary ion source 7 is emitted toward the low-temperature substrate table 2;

The baffle 3 is installed between the target stage 5 and the cryogenic substrate stage 2;

The vacuum pumping system includes a mechanical pump 10 and a molecular pump 9. The mechanical pump 10 is used for first-level vacuuming of the vacuum chamber 1. The air inlet of the mechanical pump 10 is connected to the air outlet of the molecular pump 9. The pump 9 is used for secondary vacuuming of the vacuum chamber 1, and the air inlet of the molecular pump 9 is connected to the air outlet of the vacuum chamber 1;

A gas cylinder is set up, and the gas cylinder provides working gas to the vacuum chamber 1 to complete the preparation of the amorphous high-entropy alloy thick film.

The preparation process and method of the amorphous high-entropy alloy thick film provided by the present invention is to realize rapid solidification through rapid deposition and low-temperature substrate, and utilize the bombardment effect of the auxiliary ion source on the alloy film during the deposition process to realize the densification of the film, thereby realizing The preparation of the thick film specifically includes the following steps:

1) Prepare a target with uniform composition and thickness, which can be obtained by traditional metallurgical methods, such as induction melting, arc melting or powder metallurgy, etc. The target composition is a single-phase solid solution high-entropy alloy, such as CrCoFeMnNi, TiZrHfNbTa, etc.; The material is installed on the target table, and the diameter of the target material is larger than or close to the diameter of the ion beam of the sputtering ion source;

2) Install the substrate on the substrate stage; choose a variety of substrates, such as SiN, Si, glass sheets, etc.; after closing the chamber, open the baffle, and the vacuum system will pump the air pressure to less than 1×10 ^-3 Pa;

3) Pour in the working gas to keep the air pressure stable; open the substrate table cooling system, set the substrate temperature, and wait for the temperature to be constant; open the auxiliary ion source to generate; The ion beam current of 100mA carries out a short-term bombardment cleaning on the substrate on the substrate table, thereby changing the surface activity of the substrate, improving the bonding force between the prepared substrate and the film and the purity of the coating; after cleaning the substrate, open the shutter plate, turn off the auxiliary ion source; turn on the main ion source, bombard the target with an energy of 150-1500eV and an ion beam current of 0-100mA to remove oxides or other impurities on the surface of the target;

4) After the target is cleaned, turn on the auxiliary ion source to generate 50-150eV energy and 0-50mA beam; close the baffle, formally coat the film, and deposit the sputtered target atoms or molecules on the low-temperature substrate;

5) Open the baffle to stop the coating; turn off the substrate table cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system in turn; after a period of time, the gas is introduced into the vacuum chamber to atmospheric pressure, and the alloy film is removed from the vacuum. removed from the cavity.

The above scheme will be further described below in conjunction with specific embodiments, and preferred embodiments of the present invention are described in detail as follows:

Example 1

In this embodiment, a method for preparing an amorphous high-entropy alloy thick film, preparing a CrMnFeCoNi amorphous high-entropy alloy thick film, includes the following steps:

1) Wipe the vacuum chamber clean with sandpaper and gauze. A circular CoCrFeMnNi alloy target with a thickness of 5 mm and a diameter of 10 cm was mounted on the target stage. A Si wafer was used as a substrate to mount on a substrate stage.

2) Open the baffle to avoid the airflow directly hitting the substrate. The vacuum chamber was evacuated to 5 Pa with a mechanical pump, and the pressure of the stainless steel vacuum chamber was evacuated to 8′10 ^-4 Pa by turning on the molecular pump. High-purity argon gas was introduced to maintain the pressure at 2.6′10 ^-2 Pa.

3) Turn on the cooling system of the substrate table, set the temperature of the substrate table to -120°C, and turn on the auxiliary ion source after the substrate temperature is constant to generate an energy of 500eV and a beam current of 50mA. The shutter was closed, and the auxiliary ion source performed bombardment cleaning on the substrate for 5 minutes. After the cleaning of the substrate, the shutter was opened, the auxiliary ion source was closed, and the main ion source was opened to bombard the CoCrFeMnNi high-entropy alloy target with an energy of 700 eV and a beam of 70 mA for 30 minutes. After the target is cleaned, the auxiliary ion source is turned on to generate an energy of 100 eV and a beam current of 20 mA. The shutter is closed, the sputtered target particles are deposited on the substrate, and the coating begins.

4) After 60h of continuous deposition, open the shutter and stop the coating. The substrate table cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system are closed in sequence. After 16 hours of deposition, the chamber was filled with nitrogen to atmospheric pressure, and the CoCrFeMnNi amorphous thick film was taken out.

The cross-section of the CoCrFeMnNi amorphous thick film prepared in this example is shown in Figure 2. In the scanning electron microscope picture, it can be seen that the metal film has a dense and uniform structure with a thickness of about 30 mm.

Example 2

This embodiment is basically the same as Embodiment 1, and the special features are:

In this embodiment, a method for preparing an amorphous high-entropy alloy thick film to prepare a FeSiBAlNi amorphous high-entropy alloy thick film includes the following steps:

1) Wipe the vacuum chamber clean with sandpaper and gauze. In the apparatus as in Example 1, a silicon wafer is mounted on a substrate table as a substrate. A FeSiBAlNi circular target with a thickness of 4 mm and a diameter of 10 cm was mounted on the target stage. Open the baffle to prevent the airflow directly hitting the substrate. The air pressure was evacuated to 6'10 ^-4 Pa using a vacuum system, and high-purity argon gas was introduced as the working gas to maintain the air pressure at 2.5'10 ^-2 Pa.

2) Turn on the substrate table cooling system, set the substrate table temperature to -120°C, and after the substrate temperature is stable, turn on the auxiliary ion source to generate an energy of 500eV and a beam current of 50mA. The shutter was closed, and the auxiliary ion source performed bombardment cleaning on the substrate for 10 minutes.

3) After cleaning the substrate, open the shutter and close the auxiliary ion source. Turn on the main ion source, blast the FeSiBAlNi high-entropy alloy target with an energy of 700 eV and a beam of 70 mA for 1 h to remove surface oxides and other impurities.

4) After cleaning the target, turn on the auxiliary ion source to generate an energy of 85 eV and a beam current of 15 mA. Close the shutter and start coating.

5) After continuous coating for 80h, open the baffle and stop coating. The substrate cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system are closed in sequence. After the coating was stopped for 12 h, nitrogen was charged into the vacuum chamber to atmospheric pressure, and a thick film of FeSiBAlNi amorphous high-entropy alloy with a thickness of 40 mm was taken out.

The X-ray diffraction of the FeSiBAlNi amorphous high-entropy alloy thick film prepared in this example is shown in the curve in Figure 3. It can be seen that there is no sharp Bragg corresponding to the crystal on the XRD pattern except for the broad diffuse scattering peak. peak. Therefore, the FeSiBAlNi metal thick film prepared by the present invention under the condition of low temperature substrate and high deposition rate is a single amorphous phase.

Example 3

This embodiment is basically the same as the above-mentioned embodiment, and the special features are:

In this embodiment, a method for preparing an amorphous high-entropy alloy thick film, preparing a TiZrHfNbTa amorphous high-entropy alloy thick film, includes the following steps:

1) Wipe the vacuum chamber clean with sandpaper and gauze, and install a circular TiZrHfNbTa high-entropy alloy target with a thickness of 7 mm and a diameter of 10 cm on the target table. Mounted on a substrate stage using silicon nitride as the substrate.

2), open the baffle to prevent the airflow from directly impacting the substrate. Open the vacuum system to pump the air pressure to 4'10 ^-4 Pa, pass high-purity argon gas as the working gas, and keep the air pressure at 2.6'10 ^-2 Pa.

3) Turn on the cooling system of the substrate table, set the temperature of the substrate table to -130°C, and turn on the auxiliary ion source after the substrate temperature is stabilized to generate an energy of 700eV and a beam current of 70mA. The shutter was closed, and the auxiliary ion source performed bombardment cleaning on the substrate for 3 minutes. After the cleaning of the substrate, the baffle was opened, the auxiliary ion source was closed, and the main ion source was opened to bombard the TiZrHfNbTa high-entropy alloy target with an energy of 900eV and a beam of 90mA for 30min to remove surface oxides or impurities.

4) After cleaning the target, turn on the auxiliary ion source to generate an energy of 90 eV and a beam current of 20 mA. Close the shutter and start coating.

5) After 100h of continuous deposition, open the shutter and stop the coating. Turn off the substrate table cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system in sequence. After 5 hours, nitrogen gas was introduced into the vacuum chamber to atmospheric pressure, and a 60 mm thick amorphous thick film of TiZrHfNbTa was taken out.

As shown in FIG. 4 , no crystalline phase is found in the high-resolution picture of the TiZrHfNbTa amorphous thick film prepared in this example, and diffused amorphous rings are obtained by selective area diffraction.

Example 4

This embodiment is basically the same as the above-mentioned embodiment, and the special features are:

In this embodiment, a method for preparing an amorphous high-entropy alloy thick film, preparing a CoCrNi amorphous high-entropy alloy thick film, includes the following steps:

1) Wipe the vacuum chamber with sandpaper and gauze, and install a CoCrNi circular target with a thickness of 5mm and a diameter of 10cm on the target table. A silicon wafer is used as the substrate to mount on the substrate stage.

2) Open the baffle to prevent the airflow from directly hitting the substrate. The air pressure was evacuated to 6'10 ^-4 Pa using a vacuum system, and high-purity argon gas was introduced as the working gas to maintain the air pressure at 2.7'10 ^-2 Pa.

3) Turn on the cooling system of the substrate table, set the temperature of the substrate table to -120°C, and turn on the auxiliary ion source after the substrate temperature is stabilized to generate an energy of 700eV and a beam current of 70mA. The shutter was closed, and the auxiliary ion source performed bombardment cleaning on the substrate for 7 minutes.

4) After cleaning the substrate, open the baffle, close the auxiliary ion source, open the main ion source, bombard the CoCrNi high-entropy alloy target with 700eV energy and 70mA beam current for 3 minutes to remove surface oxides or other impurities. After the target is cleaned, the auxiliary ion source is turned on to generate a beam of 80 eV and an energy of 20 mA. Close the shutter and start coating.

5) Coating continuously for 30h, open the baffle, and stop the coating. Turn off the substrate table cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system in sequence. After the coating was stopped for 12 h, nitrogen gas was introduced into the vacuum chamber to atmospheric pressure, and a thick film of CoCrNi amorphous high-entropy alloy with a thickness of 15 mm was taken out.

Example 5

This embodiment is basically the same as the above-mentioned embodiment, and the special features are:

In this embodiment, a method for preparing an amorphous high-entropy alloy thick film, preparing a NbMoTaW amorphous high-entropy alloy thick film, includes the following steps:

1) Wipe the vacuum chamber with sandpaper and gauze, and install a NbMoTaW circular target with a thickness of 7 mm and a diameter of 10 cm on the target table. Mounted on a substrate stage using silicon nitride as the substrate.

2) Open the baffle to prevent the airflow from directly hitting the substrate. The air pressure was evacuated to 6'10 ^-4 Pa using a vacuum system, and high-purity argon was introduced as the working gas to maintain the air pressure at 2.6'10 ^-2 Pa.

3) Turn on the substrate stage cooling system, set the substrate stage temperature to -140°C, and turn on the auxiliary ion source to generate 400eV energy and 40mA beam current after the substrate temperature is stable. The shutter was closed, and the auxiliary ion source performed bombardment cleaning on the substrate for 10 minutes. After the substrate was cleaned, the shutter was opened, the auxiliary ion source was turned off, and the main ion source was turned on to bombard the NbMoTaW high-entropy alloy target with an energy of 500 eV and a beam of 50 mA for 45 minutes to remove surface oxides or other impurities.

4) After cleaning the target, turn on the auxiliary ion source to generate an energy of 100eV and a beam current of 20mA, and close the shutter to start the coating.

5) After 70h of continuous deposition, open the baffle to stop the coating. Turn off the substrate table cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system in sequence. After the coating was stopped for 10 h, nitrogen was charged into the vacuum chamber to atmospheric pressure, and a 35 mm thick NbMoTaW amorphous high-entropy alloy thick film was taken out.

Example 6

This embodiment is basically the same as the above-mentioned embodiment, and the special features are:

In this embodiment, a method for preparing an amorphous high-entropy alloy thick film to prepare an Al ₂₀ Li ₂₀ Mg ₁₀ Sc ₂₀ Ti ₃₀ amorphous high-entropy alloy thick film includes the following steps:

1) Wipe the vacuum chamber clean with sandpaper and gauze, and install an Al ₂₀ Li ₂₀ Mg ₁₀ Sc ₂₀ Ti ₃₀ circular target with a thickness of 4 mm and a diameter of 10 cm on the target table. A silicon wafer is used as the substrate to mount on the substrate stage.

2) Open the baffle to prevent the airflow from directly hitting the substrate. The chamber pressure was pumped to 5.2′10 ^-4 Pa using a vacuum system, and high-purity argon was introduced as the working gas to maintain the pressure at 2.9′10 ^-2 Pa.

3) Turn on the substrate stage cooling system, set the substrate stage temperature to -175°C, and turn on the auxiliary ion source to generate 300eV energy and 30mA beam current after the substrate temperature is stable. The shutter was closed, and the auxiliary ion source performed bombardment cleaning on the substrate for 10 minutes. After the substrate cleaning, the shutter was opened, the auxiliary ion source was closed, and the main ion source was turned on to bombard the Al ₂₀ Li ₂₀ Mg ₁₀ Sc ₂₀ Ti ₃₀ high-entropy alloy target with a beam of 600 eV and 60 mA for 30 minutes to remove surface oxidation. substances or other impurities.

4) After cleaning the target, turn on the auxiliary ion source to generate an energy of 100 eV and a beam current of 20 mA. Close the shutter and start coating.

5) After 100h of continuous deposition, open the baffle to stop the coating. Turn off the substrate table cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system in sequence. After the coating was stopped for 10 h, nitrogen was charged into the vacuum chamber to atmospheric pressure, and a 40 mm thick Al ₂₀ Li ₂₀ Mg ₁₀ Sc ₂₀ Ti ₃₀ amorphous high-entropy alloy thick film was taken out.

Example 7

This embodiment is basically the same as the above-mentioned embodiment, and the special features are:

In this embodiment, a method for preparing an amorphous high-entropy alloy thick film to prepare an AlCoCrNiFe amorphous high-entropy alloy thick film includes the following steps:

1) Wipe the vacuum chamber with sandpaper and gauze, and install the AlCoCrNiFe circular target with a thickness of 6mm and a diameter of 10cm on the target table. A silicon wafer is used as the substrate to mount on the substrate stage.

2) Open the baffle to prevent the airflow from directly hitting the substrate. The air pressure was pumped to 2'10 ^-4 Pa using a vacuum system, and high-purity argon was introduced as the working gas to maintain the air pressure at 2.9'10 ^-2 Pa.

3) Turn on the substrate stage cooling system, set the substrate stage temperature to -170°C, and turn on the auxiliary ion source to generate 500eV energy and 50mA beam current after the substrate temperature is stable. The shutter was closed, and the auxiliary ion source performed bombardment cleaning on the substrate for 5 minutes. After cleaning, the baffle was opened, the auxiliary ion source was closed, the main ion source was opened, and the AlCoCrNiFe high-entropy alloy target was bombarded and cleaned with a beam of 1200 eV and 100 mA for 20 min to remove surface oxides or other impurities.

4) After cleaning the target, turn on the auxiliary ion source to generate an energy of 150 eV and a beam current of 30 mA. Close the shutter and start coating.

5) After 100h of continuous deposition, open the baffle to stop the coating. Turn off the substrate table cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system in sequence. After the coating was stopped for 16 h, nitrogen gas was introduced into the vacuum chamber to atmospheric pressure, and a 100 mm thick AlCoCrNiFe amorphous high-entropy alloy thick film was taken out. The alloy film has a dense structure and a uniform thickness.

Example 8

This embodiment is basically the same as the above-mentioned embodiment, and the special features are:

In this embodiment, a method for preparing an amorphous high-entropy alloy thick film, preparing a NbMoTaWV amorphous high-entropy alloy thick film, includes the following steps:

1) Wipe the vacuum chamber with sandpaper and gauze, and install a NbMoTaWV circular target with a thickness of 3 mm and a diameter of 10 cm on the target table. A silicon wafer is used as the substrate to mount on the substrate stage.

2) Open the baffle to prevent the airflow from directly hitting the substrate. The air pressure was evacuated to 8'10 ^-4 Pa using a vacuum system, and high-purity argon was introduced as the working gas to maintain the air pressure at 2.4'10 ^-2 Pa.

3) Turn on the cooling system of the substrate table, set the temperature of the substrate table to -100°C, and turn on the auxiliary ion source after the substrate temperature is stable to generate an energy of 500eV and a beam current of 50mA. The shutter was closed, and the auxiliary ion source performed bombardment cleaning on the substrate for 5 minutes. After cleaning, the baffle was opened, the auxiliary ion source was closed, the main ion source was opened, and the NbMoTaWV high-entropy alloy target was bombarded and cleaned with a beam of 400 eV and 50 mA for 40 min to remove surface oxides or other impurities.

4) After the target is cleaned, the auxiliary ion source is turned on to generate an energy of 70 eV and a beam current of 15 mA. Close the shutter and start coating.

5) After 60h of continuous deposition, open the baffle to stop the coating. Turn off the substrate table cooling system, the main ion source, the auxiliary ion source, the working gas valve and the vacuum system in sequence. After the coating was stopped for 10 h, the vacuum chamber was filled with nitrogen to atmospheric pressure, and a 20 mm thick NbMoTaW amorphous high-entropy alloy thick film was taken out.

The equipment and process for preparing the amorphous high-entropy alloy thick film in the above embodiment is to bombard the target with an ion beam, so that a cascade collision effect occurs in several atomic layers on the surface of the target, thereby sputtering a large number of high-energy particles. The high-energy particles are rapidly deposited on the low-temperature substrate and solidify before nucleation, which greatly improves the glass-forming ability of single-phase high-entropy alloys. At the same time, the auxiliary ion source carries out low-energy bombardment on the surface of the substrate, which enhances the diffusion and migration of the deposited atoms, densifies the metal film, and improves the quality of the coating. Finally, a thick amorphous high-entropy alloy film with a thickness of even more than 100 μm is obtained.

The embodiments of the present invention have been described above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and various changes can also be made according to the purpose of the invention and creation of the present invention. Changes, modifications, substitutions, combinations or simplifications should be equivalent substitution methods, as long as they meet the purpose of the present invention, as long as they do not deviate from the technical principles and inventive concepts of the present invention, all belong to the protection scope of the present invention.

Claims (10)

1. A device for preparing an amorphous high-entropy alloy thick film, comprising a vacuum chamber (1) and an evacuation system; it is characterized in that: a low-temperature substrate stage (2), a baffle plate are arranged in the vacuum chamber (1) (3), a rotating target table (5), a main ion source (8), an auxiliary ion source (7), a low temperature substrate table (2), a baffle plate (3), the fixed part of the rotating target table (5), the main The ion source (8) and the auxiliary ion source (7) are fixed on the wall surface of the vacuum chamber (1); the substrate (4) is arranged on the low temperature substrate stage (2), and the target material (6) is arranged on the rotating target stage ( 5) on; The vacuum chamber (1) is provided with an observation window; The low-temperature substrate stage (2) can be installed with various types of substrates, and the low-temperature substrate stage (2) has a built-in circulating cooling liquid to take away the heat generated during the preparation of the amorphous high-entropy alloy thick film, so that the The temperature of the low temperature substrate stage (2) is kept within the set range; The rotating target platform (5) is provided with a circulating cooling water system; The emission port of the main ion source (8) is aligned with the rotating target platform (5), and the ion beam generated by the main ion source (8) is emitted toward the rotating target platform (5); The emission port of the auxiliary ion source (7) is aligned with the low-temperature substrate table (2), and the ion beam generated by the auxiliary ion source (7) is emitted toward the low-temperature substrate table (2); The baffle plate (3) is installed between the target stage (5) and the low temperature substrate stage (2); The vacuum evacuation system includes a mechanical pump (10) and a molecular pump (9), the mechanical pump (10) is used for first-stage evacuation of the vacuum chamber (1), and the mechanical pump (10) has an air inlet The air outlet of the molecular pump (9) is communicated with, the molecular pump (9) is used to carry out the secondary vacuuming of the vacuum chamber (1), and the air inlet of the molecular pump (9) is communicated with the vacuum chamber (1). air outlet; A gas cylinder is provided, and the gas cylinder provides working gas to the vacuum chamber (1) to complete the preparation of the amorphous high-entropy alloy thick film. 2 . The device for preparing thick films of amorphous high-entropy alloys according to claim 1 , wherein the temperature range provided by the low-temperature substrate stage ( 2 ) is -271° C. to room temperature. 3 . 3 . The device for preparing amorphous high-entropy alloy thick films according to claim 1 , wherein the vacuum degree provided by the vacuum chamber ( 1 ) is not higher than 1′10 ⁻³ Pa. 4 . 4. The device for preparing amorphous high-entropy alloy thick films according to claim 1, characterized in that: the energy range of the ion beam provided by the main ion source (8) during coating is 150-1500 eV, and the beam current range is 150-1500 eV. It is 0 to 100 mA. 5 . The device for preparing amorphous high-entropy alloy thick films according to claim 1 , wherein the auxiliary ion source ( 7 ) provides an energy range of ion beams in the range of 150-1000 eV during coating, and a beam current range It is 0 to 100 mA. 6. The amorphous high-entropy alloy thick film preparation device according to claim 1, wherein the main ion source (8) and the auxiliary ion source (7) are selected from Kaufman type ion source, radio frequency type ion source or ERC type ion source. 7. a preparation method of amorphous high-entropy alloy thick film, utilizes the amorphous high-entropy alloy thick film preparation equipment of claim 1 to carry out sputtering coating, it is characterized in that, comprise the steps: 1) Clean the surface of the target material, remove oxide scale or other impurities, and install the target material on the rotating target table; 2) Install the clean substrate on the low-temperature substrate stage in the vacuum chamber, open the baffle; start the vacuum system, and pump the air pressure in the vacuum chamber to no higher than 1×10 ^-3 Pa; 3) Pour the working gas into the vacuum chamber, keep the air pressure stable, open the cooling system of the low-temperature substrate stage, regulate and set the substrate temperature, and wait for the temperature to be constant; 4) Turn on the auxiliary ion source to generate an energy of 150-1000 eV and a beam current of 0-100 mA; then, close the baffle to bombard and clean the substrate with the auxiliary ion source; after the cleaning of the substrate, open the baffle and close the Auxiliary ion source, turn on the main ion source, bombard and clean the target with 150-1500eV energy and 0-100mA beam current to remove oxides or other impurities on the surface of the target; 5) After cleaning the target, turn on the auxiliary ion source to generate an energy of 50-150 eV and a beam current of 0-50 mA; close the baffle to start coating; 6) After deposition for a period of time, that is, after coating is completed, stop coating, and turn off the cooling system, main ion source, auxiliary ion source, working gas valve and vacuum system of the low-temperature substrate table in turn; wait at least 2 hours after stopping coating , the vacuum chamber is inflated to atmospheric pressure, and then the substrate on which the alloy film is prepared is taken out, thereby obtaining an amorphous high-entropy alloy thick film. 8. The method for preparing an amorphous high-entropy alloy thick film according to claim 7, wherein the diameter of the target material is equal to or greater than the diameter of the low-temperature target platform, and the target material composition includes all metals of the high-entropy alloy prepared by the target. . 9 . The method for preparing an amorphous high-entropy alloy thick film according to claim 7 , wherein the working gas is nitrogen or argon. 10 . 10. The method for preparing an amorphous high-entropy alloy thick film according to claim 7, wherein the substrate is selected from any one of silicon wafer, silicon nitride, glass wafer, silicon carbide wafer and metal wafer substrate.

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