Nano multilayer film material based on high-entropy alloy material as well as preparation method and application of nano multilayer film material

Abstract

The invention relates to a nano multilayer film material based on a high-entropy alloy material, the nano multilayer film material comprises high-entropy alloy layers and low atomic number layers which are alternately arranged on a substrate, and the high-entropy alloy layers are selected from at least five of the following simple substance metal materials: Ni, Co, Fe, Nb, W, Mo, Ta, Ti, V, Cr, V, Si, Al and the like, and nitrides and carbides of the elements. Compared with the prior art, the high-entropy alloy material which is high in melting point, stable in phase state and slow in diffusion is adopted as the absorbing layer and the reflecting layer of the multilayer film, the prepared multilayer film has good interface quality and optical performance, and meanwhile, compared with a traditional material multilayer film, the prepared multilayer film is better in thermal stability and radiation resistance; the device is suitable for X-ray wave band application in high-temperature and high-irradiation working environments such as synchrotron radiation light sources, X-ray space observation, plasma diagnosis and the like.

Description

Technical Field

[0001] The present invention belongs to the field of X-ray optics, and in particular relates to a nano multilayer film material based on a high entropy alloy material, a preparation method thereof, and an application thereof. Background Art

[0002] In the X-ray band, on the one hand, the strong absorption of light by the material makes this type of transmissive refractive optical element unusable; on the other hand, the refractive index of almost all materials is close to 1, and the normal incidence reflectivity of a single interface is low, which limits the application of reflective optical elements.

[0003] Researchers have invented nanoscale periodic multilayer film structures composed of alternating materials, one with a high atomic number and one with a low atomic number. In such multilayer films, light reflected from different interfaces constructively interferes with each other, significantly increasing reflectivity and providing a certain degree of spectral resolution. Multilayer film fabrication technology is maturing, and multilayer film reflective elements have found widespread application in fields such as extreme ultraviolet lithography, biology, life sciences and medicine, astrophysics, X-ray lasers, synchrotron radiation, and plasma physics, becoming important reflective and monochromating optical elements in the X-ray band. For X-ray multilayer films above 1 keV, high-atomic-number materials are typically W, Ru, Pt, Mo, and the like, while low-atomic-number materials are typically B4C, Si, C, SiC, and the like.

[0004] With advances in preparation and testing technologies, the performance of these multilayer films has improved to a certain extent but has now approached the intrinsic limit of the material. Multilayer films are often exposed to high-energy radiation environments for long periods of time, such as in synchrotron radiation and space applications, which result in high thermal loads and radiation damage. Newly prepared multilayer films may be in a non-equilibrium state, which can lead to instability in chemical composition and physical structure during application. The interface and structure of multilayer films that have undergone thermal treatment may change, typically with periodic expansion and contraction, further diffusion, film crystallization, and so on. Diffusion can form compounds or interfacial layers at the interface, and a two-layer period may become a three- or four-layer structure. These changes will ultimately affect the reflectivity and reflection peak position of the multilayer film, and may even completely damage the multilayer film structure. Summary of the Invention

[0005] The purpose of the present invention is to provide a nano multilayer film material based on high entropy alloy material and its preparation method and application in order to solve the above problems.

[0006] The present invention is achieved through the following technical solutions:

[0007] A nano multilayer film material based on high entropy alloy material, comprising high entropy alloy layers and low atomic number layers alternately arranged on a substrate,

[0008] The high entropy alloy layer is selected from at least five of the following raw materials: Ni, Co, Fe, Nb, W, Mo, Ta, Ti, V, Cr, V, Si, Al, and nitrides and carbides of the above elements.

[0009] The high-entropy alloys and their compounds of the present invention exhibit optical constants similar to those of conventional materials such as W and Pt in the high-energy X-ray band. When combined with low-atomic-number materials, they can achieve relatively good reflectivity and bandwidth, demonstrating excellent optical properties. Furthermore, the high-entropy alloys and their compounds are stable, and their interfaces with low-atomic-number materials remain stable under high-temperature and high-irradiation conditions, without chemical reactions or severe diffusion, maintaining their performance at room temperature and low-irradiation conditions.

[0010] The high entropy alloy layer is selected from a combination of at least five elements selected from Ni, Co, Fe, Nb, W, Mo, Ta, Ti, V, Cr, V, Si, and Al, and preferably, is selected from a combination of at least five elements selected from W, Mo, Ta, Ti, V, Cr, Nb, Si, and Al. As a preferred technical solution of the present invention, the high entropy alloy layer is selected from the following elements: Cr, V, Ta, Ti, W; or Cr, V, Ta, W, Mo; or Mo, Ta, W, Nb, V; or Cr, Mo, W, Ta, Ti; or Al, Ti, Cr, Mo, Si, etc.

[0011] As a further preferred technical solution of the present invention, the high entropy alloy layer is composed of the following elements: Cr, V, Ta, Ti, and W.

[0012] As a preferred technical solution of the present invention, the low atomic number layer is selected from at least one of the following raw materials: Si, C, SiC, and B4C.

[0013] As a preferred technical solution of the present invention, the high entropy alloy layer and the low atomic number layer are alternately arranged in 10-200 cycles, which is specifically determined according to the wavelength band of X-ray application.

[0014] As a preferred technical solution of the present invention, the thickness of the high entropy alloy layer and the low atomic number layer is 1-10 nm, which is specifically determined according to the wavelength band of the X-ray application.

[0015] As a preferred technical solution of the present invention, the substrate is a smooth substrate with a roughness of less than 0.5 nanometers, and the substrate includes silicon or quartz.

[0016] As a preferred technical solution of the present invention, a primer layer is provided between the substrate, the high entropy alloy layer and the low atomic number layer, the primer layer comprises a metal layer of 5-10 nm, and the metal layer comprises Cr or Ti.

[0017] A method for preparing a nano multilayer film material based on a high entropy alloy material, wherein the high entropy alloy layer and the low atomic number layer are alternately prepared on a substrate by magnetron sputtering or ion beam sputtering.

[0018] The above-mentioned application of a nano multilayer film material based on a high entropy alloy material is used to make an X-ray reflector or a monochromator.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention provides an X-ray multilayer film reflector based on a high entropy alloy material, in which a high entropy alloy and its compound materials are used as the absorption layer and the reflection layer of the X-ray multilayer film, and are combined with a low atomic number material. The multilayer film reflector utilizes the excellent properties of the high entropy alloy. Due to its high entropy effect, slow diffusion effect and the composite effect of multiple principal elements, it has excellent mechanical properties, corrosion resistance, thermal stability and radiation resistance. While having good interface quality and optical properties, it also has thermal stability and radiation resistance that exceed those of traditional multilayer film materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a schematic structural diagram of a nano multilayer film material based on a high entropy alloy material of the present invention;

[0022] Figure 2 is the X-ray grazing incidence reflectivity curve of the multilayer film of Example 1;

[0023] Figure 3 This is the XRR curve of the Cr / B4C multilayer film of comparative example 1. DETAILED DESCRIPTION

[0024] The present invention will be described in detail below with reference to specific embodiments, but the present invention is by no means limited thereto.

[0025] like Figure 1 As shown, a nano-multilayer film material based on a high-entropy alloy material includes a high-entropy alloy layer 2 and a low-atomic-number layer 3 alternately arranged on a substrate 1. The high-entropy alloy layer is selected from at least five of the following raw materials: W, Mo, Ta, Ti, V, Cr, Nb, Si, Al, and nitrides and carbides of the above elements. The alloying elements of the high-entropy alloy layer are combined in an equal molar ratio or a nearly equal molar ratio, and the proportion of each element is 5% to 35%.

[0026] Preferably, the high entropy alloy layer is composed of the following elements: Cr, V, Ta, Ti, W; or Cr, V, Ta, W, Mo; or Mo, Ta, W, Nb, V; or Cr, Mo, W, Ta, Ti; or Al, Ti, Cr, Mo, Si, etc.

[0027] Preferably, the low atomic number layer is selected from at least one of the following materials: Si, C, SiC, and B4C.

[0028] Preferably, the high entropy alloy layer and the low atomic number layer are alternately arranged for 10-200 cycles.

[0029] Preferably, the thickness of the high entropy alloy layer and the low atomic number layer is 1-10 nm.

[0030] Preferably, the substrate is a smooth substrate with a roughness of less than 0.5 nanometers, and the substrate comprises silicon or quartz.

[0031] Preferably, a primer layer is provided between the substrate and the high entropy alloy layer and the low atomic number layer, the primer layer comprising a metal layer of 5-10 nm, and the metal layer comprises Cr or Ti.

[0032] A method for preparing a nano-multilayer film material based on a high entropy alloy material, wherein high entropy alloy layers and low atomic number layers are alternately prepared on a substrate by magnetron sputtering or ion beam sputtering.

[0033] Based on the application of nano multilayer film materials of high entropy alloy materials, nano multilayer film materials are used to make X-ray reflectors or monochromators.

[0034] Example 1

[0035] like Figure 1 As shown, a nano-multilayer film material based on a high-entropy alloy material comprises a high-entropy alloy layer 2 and a low-atomic-number layer 3 alternately arranged on an ultra-smooth quartz substrate, wherein the high-entropy alloy layer is composed of the following elements: Cr, V, Ta, Ti, W, combined in an equal molar ratio, the low-atomic-number layer is B4C, the high-entropy alloy layer and the low-atomic-number layer are alternately arranged for 40 periods, the thickness of the high-entropy alloy layer and the low-atomic-number layer is about 4.6 nm, and is prepared by magnetron sputtering.

[0036] Figure 2 : This is the X-ray grazing incidence reflectivity curve of the multilayer film in Example 1, where the abscissa is the grazing incidence angle and the ordinate is the reflection intensity. Figure 1 The upper panel shows data before heat treatment, while the lower panel shows data after heat treatment at 800°C in vacuum for one hour. The data show that after heat treatment, the intensity of the first-order reflection peak at a grazing incidence angle of 0.96 degrees does not decrease significantly, and the thickness change caused by the peak shift is only 0.15 nm. This demonstrates that the CrVTaTiW / B4C multilayer film has excellent interface quality and thermal stability.

[0037] Comparative Example 1

[0038] The same method as in the example was used to prepare a nano-multilayer Cr / C film with a period thickness of 4 nm and a period number of 30. Figure 3The XRR curves before and after annealing at 600℃ show that after annealing at 600℃ for 1 hour, the Bragg peak value and peak position in the XRR curve of the Cr / C multilayer film drop significantly and shift, indicating that the interface quality and periodic thickness have changed significantly, and the interface quality and thermal stability are poor.

[0039] Example 2

[0040] Reference Figure 1 , a nano-multilayer film material based on high-entropy alloy material, a high-entropy alloy layer 2 and a low-atomic-number layer 3 are alternately arranged on an ultra-smooth silicon substrate, wherein the high-entropy alloy layer is composed of the following elements: Cr, V, Ta, W, Mo, combined in an equal molar ratio, the low-atomic-number layer is B4C, the high-entropy alloy layer and the low-atomic-number layer are alternately arranged for 40 periods, the thickness of the high-entropy alloy layer and the low-atomic-number layer is about 5nm, and they are prepared by magnetron sputtering.

[0041] Example 3

[0042] Reference Figure 1 , a nano-multilayer film material based on high-entropy alloy material, a high-entropy alloy layer 2 and a low-atomic-number layer 3 are alternately arranged on an ultra-smooth quartz substrate, wherein the high-entropy alloy layer is composed of the following elements: Mo, Ta, W, Nb, V, combined in an equal molar ratio, the low-atomic-number layer is SiC, the high-entropy alloy layer and the low-atomic-number layer are alternately arranged in 35 periods, the period of the high-entropy alloy layer and the low-atomic-number layer is about 8nm, and is prepared by ion beam sputtering.

[0043] Example 4

[0044] Reference Figure 1 , a nano-multilayer film material based on high-entropy alloy material, a high-entropy alloy layer 2 and a low-atomic-number layer 3 are alternately arranged on an ultra-smooth quartz substrate, wherein the high-entropy alloy layer is composed of the following elements: Cr, Mo, W, Ta, Ti, combined in an equal molar ratio, the low-atomic-number layer is SiC, the high-entropy alloy layer and the low-atomic-number layer are alternately arranged for 30 cycles, the thickness of the high-entropy alloy layer and the low-atomic-number layer is about 10nm, and they are prepared by magnetron sputtering.

[0045] Example 5

[0046] Reference Figure 1 , a nano-multilayer film material based on high-entropy alloy material, a high-entropy alloy layer 2 and a low-atomic-number layer 3 are alternately arranged on an ultra-smooth quartz substrate, wherein the high-entropy alloy layer is composed of the following elements: Al, Ti, Cr, Mo, Si, combined in an equal molar ratio, the low-atomic-number layer is C, the high-entropy alloy layer and the low-atomic-number layer are alternately arranged 45 periods, the thickness of the high-entropy alloy layer and the low-atomic-number layer is about 10nm, and they are prepared by ion beam sputtering.

[0047] The multilayer films obtained in Examples 2 to 5 above all have good interface quality and thermal stability.

[0048] The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. Improvements and modifications made by those skilled in the art based on the disclosure of the present invention, without departing from the scope of the present invention, should be within the scope of protection of the present invention.

Claims

1. A nano multilayer film material based on high entropy alloy material, characterized in that: comprising high entropy alloy layers and low atomic number layers alternately arranged on a substrate, The high entropy alloy layer is selected from at least five of the following raw materials: Ni, Co, Fe, Nb, W, Mo, Ta, Ti, V, Cr, Si, Al, and nitrides and carbides of the above elements.

2. The nano multilayer film material based on high entropy alloy material according to claim 1, characterized in that: The high entropy alloy layer is selected from the following elements: Cr, V, Ta, Ti, W; or Cr, V, Ta, W, Mo; Or Mo, Ta, W, Nb, V; or Cr, Mo, W, Ta, Ti; Or Al, Ti, Cr, Mo, Si.

3. The nano multilayer film material based on high entropy alloy material according to claim 1, characterized in that: The high entropy alloy layer is composed of the following elements: Cr, V, Ta, Ti, and W.

4. The nano multilayer film material based on high entropy alloy material according to claim 1, characterized in that: The low atomic number layer is selected from at least one of the following raw materials: Si, C, SiC, and B4C.

5. The nano multilayer film material based on high entropy alloy material according to claim 1, characterized in that: The high entropy alloy layer and the low atomic number layer are alternately arranged for 10-200 cycles.

6. The nano multilayer film material based on high entropy alloy material according to claim 1, characterized in that: The thickness of the high entropy alloy layer and the low atomic number layer is 1-10 nm.

7. The nano multilayer film material based on high entropy alloy material according to claim 1, characterized in that: The substrate is a smooth substrate, and the substrate comprises silicon or quartz.

8. The nano multilayer film material based on high entropy alloy material according to claim 1, characterized in that: A primer layer is provided between the substrate, the high entropy alloy layer and the low atomic number layer. The primer layer comprises a metal layer having a thickness of 5-10 nm. The metal layer comprises Cr or Ti.

9. A method for preparing a nano multilayer film material based on a high entropy alloy material according to any one of claims 1 to 8, characterized in that: The high entropy alloy layer and the low atomic number layer are alternately prepared on the substrate by magnetron sputtering or ion beam sputtering.

10. The use of a nano multilayer film material based on a high entropy alloy material according to any one of claims 1 to 8, characterized in that: The nano multilayer film material is used for making an X-ray reflector or a monochromator.

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