阅读说明：本技术 一种x射线多层膜反射镜的制备方法 (Preparation method of X-ray multilayer film reflecting mirror ) 是由 李艳丽 孔祥东 韩立 姚广宇 董增雅 于 2020-05-21 设计创作，主要内容包括：本发明提供了一种X射线多层膜反射镜的制备方法,属于多层膜反射镜技术领域。本发明首先根据X射线的波长和入射角,确定X射线多层膜的周期厚度；然后确定多层膜的厚度和周期数；再利用原子层沉积法在基底表面交替沉积制备X射线多层膜反射镜。本发明制备的X射线多层膜的周期厚度小,可制备适用于波长更短的X射线多层膜反射镜；此外,制备的多层膜的粗糙度小(≤基底的粗糙度),膜间的界面清晰,多层膜反射镜的反射率高。(The invention provides a preparation method of an X-ray multilayer film reflecting mirror, and belongs to the technical field of multilayer film reflecting mirrors. Firstly, determining the period thickness of an X-ray multilayer film according to the wavelength and the incident angle of an X-ray; then determining the thickness and the periodicity of the multilayer film; and preparing the X-ray multilayer film reflecting mirror on the surface of the substrate by utilizing an atomic layer deposition method through alternate deposition. The X-ray multilayer film prepared by the invention has small cycle thickness, and can be used for preparing an X-ray multilayer film reflecting mirror suitable for shorter wavelength; in addition, the roughness of the prepared multilayer film is small (less than or equal to that of the substrate), the interface between the films is clear, and the reflectivity of the multilayer film reflecting mirror is high.)

1. A method for manufacturing an X-ray multilayer film reflecting mirror is characterized by comprising the following steps:

(1) determining the period thickness of the multilayer film reflecting mirror according to the wavelength and the incident angle of the X-ray; the period of the multilayer film reflecting mirror is counted by the period of a double-layer film, wherein the double-layer film is a spacing layer thin film and an absorption layer thin film; the period thickness is the thickness of the double-layer film;

(2) determining the thickness ratio of the spacer layer film and the absorption layer film and the cycle number of the double-layer film according to the maximization of the X-ray reflectivity;

(3) obtaining the thickness of the spacer layer film and the thickness of the absorption layer film according to the thickness ratio determined in the step (2) and the period thickness determined in the step (1), then determining the reaction period number of the spacer layer film according to the thickness of the spacer layer film and the deposition rate, and determining the reaction period number of the absorption layer film according to the thickness of the absorption layer film and the deposition rate;

(4) taking a precursor corresponding to the material of the absorption layer film as a raw material, performing first atomic layer deposition on the surface of a substrate to finish a reaction period, and repeating the first atomic layer deposition until the reaction period number of the absorption layer film is reached to form the absorption layer film;

(5) taking a precursor corresponding to the material of the spacer layer thin film as a raw material, performing second atomic layer deposition on the surface of the absorption layer thin film to finish a reaction period, and repeating the second atomic layer deposition until the reaction period number of the spacer layer thin film is reached to form the spacer layer thin film;

and (5) finishing a double-layer film period after the step (4) and the step (5), and then repeatedly and alternately performing the step (4) and the step (5) until the double-layer film period is reached to obtain the X-ray multilayer film reflecting mirror.

2. The manufacturing method according to claim 1, wherein in the step (1), the formula for determining the periodic thickness of the multilayer film mirror is d ═ n λ/(2cos θ), where λ is a wavelength of the X-ray, n is a diffraction order and n is a positive integer, θ is an incident angle, and d is the periodic thickness.

3. The method according to claim 1, wherein the material of the absorber layer film comprises Co, Cu, Ta, W, Ge, Pt, Ru, Ni, Fe, TaN, ZrN, HfN, WN, HfO₂、ZnO、ZrO₂、La₂O₃Or SnO₂。

4. The production method according to claim 1, wherein the material of the spacer layer film comprises TiN, AlN, TiO₂、SiO₂Or Al₂O₃。

5. The method according to claim 1, wherein in the step (3), the number of reaction cycles of the absorber layer film is equal to the thickness of the absorber layer film/the deposition rate of the absorber layer film, and the deposition rate of the absorber layer film is 1 angstrom/reaction cycle.

6. The method according to claim 1, wherein in the step (3), the number of reaction cycles of the spacer layer film is 1 angstrom/reaction cycle, which is the thickness of the spacer layer film/deposition rate of the spacer layer film.

7. The method according to claim 1, wherein in the step (4), the vacuum degree of the first atomic layer deposition is less than 20Pa, and the temperature is 150-300 ℃.

8. The method according to claim 3, wherein in the step (4), the first atomic layer deposition is performed on the substrate surface, and the step of completing one reaction cycle comprises: carrying out surface chemical adsorption on a main precursor A corresponding to the material of the absorption layer film and a substrate, carrying out surface chemical reaction on a secondary precursor B corresponding to the material of the absorption layer film and the main precursor A after first purification, and carrying out second purification to finish a reaction period;

the main precursor A contains metal elements required by an absorption layer film, and is a metal salt compound;

when the material of the absorption layer film is a metal simple substance, the secondary precursor B is silane, oxygen or ozone;

when the material of the absorption layer film is metal oxide, the secondary precursor B is deionized water;

when the material of the absorption layer film is nitride, the secondary precursor B is nitrogen-containing gas.

9. The method according to claim 1, wherein in the step (5), the vacuum degree of the second atomic layer deposition is less than 20Pa, and the temperature is 150-300 ℃.

10. The method according to claim 4, wherein in the step (5), a second atomic layer deposition is performed on the surface of the absorption layer film, and the step of completing one reaction cycle comprises the following steps: carrying out surface chemical adsorption on a main precursor C corresponding to the material of the spacer layer film and the surface of the absorption layer film, carrying out surface chemical reaction on a secondary precursor D corresponding to the material of the spacer layer film and the main precursor C after third purification, and carrying out fourth purification to complete a reaction period;

the main precursor C contains metal elements or silicon elements required by a spacer layer film; the main precursor C is a silicon-containing compound or a metal salt compound;

when the main precursor C contains the metal elements required for the spacer layer thin film:

when the material of the spacer layer film is metal oxide, the secondary precursor D is deionized water or hydrogen peroxide;

when the material of the spacer layer film is metal nitride, the secondary precursor D is nitrogen-containing gas;

when the main precursor C contains silicon elements required by the spacer layer thin film: when the material of the spacer layer film is silicon oxide, the secondary precursor D is deionized water.

Technical Field

The invention relates to the technical field of multilayer film reflectors, in particular to a preparation method of an X-ray multilayer film reflector.

Background

Since its discovery in 1895, X-rays have been widely used due to their unique properties, such as X-ray astronomical telescope, synchrotron X-ray diffraction, X-ray imaging, and the like. The X-ray multilayer film reflecting mirror is an important X-ray optical element, can greatly improve the reflectivity of X-rays under the non-grazing incidence condition, and has important significance for reducing the size of an optical system, reducing the difficulty of installation and adjustment, improving the imaging quality and the like.

At present, the preparation method of the X-ray multilayer film reflecting mirror mainly adopts magnetron sputtering and electron beam thermal evaporation methods, the control difficulty of the thickness and the roughness of the film is high, the diffusion among the films is difficult to control, and the period thickness of the multilayer film reflecting mirror is large (more than 2 nm). In the case of the X-ray multilayer mirror, the roughness of the thin films and the diffusion between the thin films are important factors affecting the reflectance of the X-ray multilayer mirror. Therefore, the actual reflectance of the X-ray multilayer film mirror prepared by the above method is much lower than the theoretical reflectance. In addition, since the wavelength of the X-ray is short, the periodic thickness of the thin film is small, and in general, the shorter the X-wavelength, the smaller the periodic thickness of the thin film, in a few nanometers or even below 1 nm. The period thickness of the film prepared at present is several nanometers, so the prepared multilayer film reflecting mirror is mainly applied to a soft X-ray wave band with longer wavelength, and for the X-ray wave band with shorter wavelength, the existing method is difficult to prepare the multilayer film reflecting mirror with smaller period thickness. Therefore, it is necessary to further improve the reflectance of the soft X-ray band multilayer film mirror and to produce an X-ray multilayer film mirror suitable for use in shorter wavelengths.

Disclosure of Invention

The invention aims to provide a method for preparing an X-ray multilayer film reflecting mirror, which has high reflectivity and can be suitable for an X-ray waveband with shorter wavelength.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of an X-ray multilayer film reflecting mirror, which comprises the following steps:

(1) determining the period thickness of the multilayer film reflecting mirror according to the wavelength and the incident angle of the X-ray; the period of the multilayer film reflecting mirror is counted by the period of a double-layer film, wherein the double-layer film is a spacing layer thin film and an absorption layer thin film; the period thickness is the thickness of the double-layer film;

(2) determining the thickness ratio of the spacer layer film and the absorption layer film and the cycle number of the double-layer film according to the maximization of the X-ray reflectivity;

(3) obtaining the thickness of the spacer layer film and the thickness of the absorption layer film according to the thickness ratio determined in the step (2) and the period thickness determined in the step (1), then determining the reaction period number of the spacer layer film according to the thickness of the spacer layer film and the deposition rate, and determining the reaction period number of the absorption layer film according to the thickness of the absorption layer film and the deposition rate;

(4) taking a precursor corresponding to the material of the absorption layer film as a raw material, performing first atomic layer deposition on the surface of a substrate to finish a reaction period, and repeating the first atomic layer deposition until the reaction period number of the absorption layer film is reached to form the absorption layer film;

(5) taking a precursor corresponding to the material of the spacer layer thin film as a raw material, performing second atomic layer deposition on the surface of the absorption layer thin film to finish a reaction period, and repeating the second atomic layer deposition until the reaction period number of the spacer layer thin film is reached to form the spacer layer thin film;

and (5) finishing a double-layer film period after the step (4) and the step (5), and then repeatedly and alternately performing the step (4) and the step (5) until the double-layer film period is reached to obtain the X-ray multilayer film reflecting mirror.

Preferably, in the step (1), the formula for determining the periodic thickness of the multilayer film mirror is d ═ n λ/(2cos θ), where λ is the wavelength of the X-ray, n is the diffraction order and n is a positive integer, θ is the angle of incidence, and d is the periodic thickness.

Preferably, the material of the absorption layer film includes Co, Cu, Ta, W, Ge, Pt, Ru,Ni、Fe、TaN、ZrN、HfN、WN、HfO₂、ZnO、ZrO₂、La₂O₃Or SnO₂。

Preferably, the material of the spacer layer film comprises TiN, AlN and TiO₂、SiO₂Or Al₂O₃。

Preferably, in the step (3), the number of reaction cycles of the absorber layer film is equal to the thickness of the absorber layer film/the deposition rate of the absorber layer film, and the deposition rate of the absorber layer film is 1 angstrom/reaction cycle.

Preferably, in the step (3), the number of reaction cycles of the spacer layer film is equal to the thickness of the spacer layer film/the deposition rate of the spacer layer film, and the deposition rate of the spacer layer film is 1 angstrom/reaction cycle.

Preferably, in the step (4), the vacuum degree of the first atomic layer deposition is less than 20Pa, and the temperature is 150-300 ℃.

Preferably, in step (4), the performing of the first atomic layer deposition on the substrate surface, and the completing of one reaction cycle includes: carrying out surface chemical adsorption on a main precursor A corresponding to the material of the absorption layer film and a substrate, carrying out surface chemical reaction on a secondary precursor B corresponding to the material of the absorption layer film and the main precursor A after first purification, and carrying out second purification to finish a reaction period;

the main precursor A contains metal elements required by an absorption layer film, and is a metal salt compound;

when the material of the absorption layer film is a metal simple substance, the secondary precursor B is silane, oxygen or ozone;

when the material of the absorption layer film is metal oxide, the secondary precursor B is deionized water;

when the material of the absorption layer film is nitride, the secondary precursor B is nitrogen-containing gas.

Preferably, in the step (5), the vacuum degree of the second atomic layer deposition is less than 20Pa, and the temperature is 150-300 ℃.

Preferably, in the step (5), performing second atomic layer deposition on the surface of the absorption layer film, and completing a reaction cycle includes: carrying out surface chemical adsorption on a main precursor C corresponding to the material of the spacer layer film and the surface of the absorption layer film, carrying out surface chemical reaction on a secondary precursor D corresponding to the material of the spacer layer film and the main precursor C after third purification, and carrying out fourth purification to complete a reaction period;

the main precursor C contains metal elements or silicon elements required by a spacer layer film; the main precursor C is a silicon-containing compound or a metal salt compound;

when the main precursor C contains the metal elements required for the spacer layer thin film:

when the material of the spacer layer film is metal oxide, the secondary precursor D is deionized water or hydrogen peroxide;

when the material of the spacer layer film is metal nitride, the secondary precursor D is nitrogen-containing gas;

when the main precursor C contains silicon elements required by the spacer layer thin film:

when the material of the spacer layer film is silicon oxide, the secondary precursor D is deionized water.

The invention provides a preparation method of an X-ray multilayer film reflecting mirror, which comprises the following steps: (1) determining the period thickness of the multilayer film reflecting mirror according to the wavelength and the incident angle of the X-ray; the period of the multilayer film reflecting mirror is counted by the period of a double-layer film, wherein the double-layer film is a spacing layer thin film and an absorption layer thin film; the period thickness is the thickness of the double-layer film; (2) determining the thickness ratio of the spacer layer film and the absorption layer film and the cycle number of the double-layer film according to the maximization of the X-ray reflectivity; (3) obtaining the thickness of the spacer layer film and the thickness of the absorption layer film according to the thickness ratio determined in the step (2) and the period thickness determined in the step (1), then determining the reaction period number of the spacer layer film according to the thickness of the spacer layer film and the deposition rate, and determining the reaction period number of the absorption layer film according to the thickness of the absorption layer film and the deposition rate; (4) taking a precursor corresponding to the material of the absorption layer film as a raw material, performing first atomic layer deposition on the surface of a substrate to finish a reaction period, and repeating the first atomic layer deposition until the reaction period number of the absorption layer film is reached to form the absorption layer film; (5) taking a precursor corresponding to the material of the spacer layer thin film as a raw material, performing second atomic layer deposition on the surface of the absorption layer thin film to finish a reaction period, and repeating the second atomic layer deposition until the reaction period number of the spacer layer thin film is reached to form the spacer layer thin film; and (5) finishing a double-layer film period after the step (4) and the step (5), and then repeatedly and alternately performing the step (4) and the step (5) until the double-layer film period is reached to obtain the X-ray multilayer film reflecting mirror.

Firstly, determining the period thickness of an X-ray multilayer film according to the wavelength and the incident angle of an X-ray; then determining the thickness and the periodicity of the multilayer film; and preparing the X-ray multilayer film reflecting mirror on the surface of the substrate by utilizing an atomic layer deposition method through alternate deposition. The invention utilizes the atomic layer deposition method to prepare the multilayer film structure, can obtain the multilayer film reflecting mirror with high reflectivity by adjusting the film material combination, and the atomic layer deposition method is a self-limiting saturation type growth method, only grows the thickness of a single atomic layer in each reaction period, has high thickness control precision of the film, can prepare the film with the period thickness smaller than 1nm, and can be suitable for X rays with shorter wavelength when the X rays are incident at a smaller incident angle. In addition, the atomic layer deposition has self-limiting property and high conformality, the prepared films can keep the same small roughness as the substrate, the growth processes among the films are mutually independent, the interfaces among the films are clear, and the diffusion is less, so that the multilayer film reflecting mirror prepared by the method has high quality, and the reflectivity is closer to the theoretical reflectivity.

The X-ray multilayer film prepared by the method has small period thickness (2 angstroms-3 nm), and can be used for preparing an X-ray multilayer film reflecting mirror with shorter wavelength; in addition, the roughness of the prepared multilayer film is small (less than or equal to that of the substrate), the interface between the films is clear, and the reflectivity of the multilayer film reflecting mirror is high.

Drawings

FIG. 1 is a schematic diagram of a process for growing a thin film by atomic layer deposition according to the present invention;

FIG. 2 is a schematic view of the structure of the multi-layer X-ray mirror of the present invention.

Detailed Description

The invention provides a preparation method of an X-ray multilayer film reflecting mirror, which comprises the following steps:

(1) determining the period thickness of the multilayer film reflecting mirror according to the wavelength and the incident angle of the X-ray; the period of the multilayer film reflecting mirror is counted by the period of a double-layer film, wherein the double-layer film is a spacing layer thin film and an absorption layer thin film; the period thickness is the thickness of the double-layer film;

(2) determining the thickness ratio of the spacer layer film and the absorption layer film and the cycle number of the double-layer film according to the maximization of the X-ray reflectivity;

(3) obtaining the thickness of the spacer layer film and the thickness of the absorption layer film according to the thickness ratio determined in the step (2) and the period thickness determined in the step (1), then determining the reaction period number of the spacer layer film according to the thickness of the spacer layer film and the deposition rate, and determining the reaction period number of the absorption layer film according to the thickness of the absorption layer film and the deposition rate;

(4) taking a precursor corresponding to the material of the absorption layer film as a raw material, performing first atomic layer deposition on the surface of a substrate to finish a reaction period, and repeating the first atomic layer deposition until the reaction period number of the absorption layer film is reached to form the absorption layer film;

(5) taking a precursor corresponding to the material of the spacer layer thin film as a raw material, performing second atomic layer deposition on the surface of the absorption layer thin film to finish a reaction period, and repeating the second atomic layer deposition until the reaction period number of the spacer layer thin film is reached to form the spacer layer thin film;

and (5) finishing a double-layer film period after the step (4) and the step (5), and then repeatedly and alternately performing the step (4) and the step (5) until the double-layer film period is reached to obtain the X-ray multilayer film reflecting mirror.

In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.

The invention determines the period thickness of the multilayer film reflecting mirror according to the wavelength and the incident angle of the X-ray; the period of the multilayer film reflecting mirror is counted by the period of a double-layer film, wherein the double-layer film is a spacing layer thin film and an absorption layer thin film; the period thickness is the thickness of the double-layer film. In the present invention, the formula for determining the periodic thickness of the multilayer film mirror is preferably d ═ n λ/(2cos θ), where λ is the wavelength of the X-ray, n is the diffraction order and n is a positive integer, θ is the angle of incidence, and d is the periodic thickness. In the invention, the value range of the lambda is preferably 0.5-20 nm, more preferably 2-15 nm, further preferably 3-10 nm, and the value range of the theta is preferably 0-85 degrees, more preferably 60-80 degrees. The value range of n is preferably determined according to actual requirements, and in the embodiment of the present invention, the value range of n is specifically 1 or 2. In the present invention, the periodic thickness of the multilayer film mirror is preferably 2 angstroms to 5nm, and more preferably 1 to 3 nm.

The invention determines the thickness ratio of the spacer layer film and the absorption layer film and the cycle number of the double-layer film according to the maximization of X-ray reflectivity. The thickness ratio of the spacer layer film and the absorption layer film and the periodicity of the double-layer film are preferably determined according to the maximization of the reflectivity by the conventional method in the field, specifically, the thickness of the film with larger beta is set as a smaller thickness according to the difference of the optical constants beta of the absorption layer and the spacer layer, and the periodicity when the reflectivity does not change obviously along with the increase of the periodicity is determined as the periodicity of the double-layer film. In the invention, the thickness ratio of the spacing layer film to the absorption layer film is preferably (1-4): 1, more preferably 3:2 or 4:1, and the number of cycles of the bilayer membrane is preferably equal to or greater than 70, more preferably 80, 90, 100.

After the thickness ratio and the period thickness of the spacing layer thin film and the absorption layer thin film are obtained, the thickness of the spacing layer thin film and the thickness of the absorption layer thin film are obtained according to the thickness ratio of the spacing layer thin film and the absorption layer thin film and the period thickness of the multilayer film reflecting mirror, then the reaction period number of the spacing layer thin film is determined according to the thickness and the deposition rate of the spacing layer thin film, and meanwhile, the reaction period number of the absorption layer thin film is determined according to the thickness and the deposition rate of the absorption layer thin film.

In the present invention, the period thickness is a thickness of the double-layer film, that is, the period thickness of the multilayer film mirror is a sum of thicknesses of the spacer layer film and the absorption layer film. The thickness of the spacer layer thin film and the thickness of the absorption layer thin film are preferably calculated respectively through the thickness ratio of the spacer layer thin film and the absorption layer thin film and the period thickness of the multilayer film reflecting mirror. In the present invention, the thickness of the spacer layer film is preferably 1 angstrom to 4nm, more preferably 1 to 3nm, and even more preferably 1.5 to 2.5nm, and the thickness of the absorption layer film is preferably 1 angstrom to 2.5nm, and more preferably 1.0 to 1.5 nm. In the atomic layer deposition method, the minimum value of the thickness of the prepared absorption layer film or the spacing layer film is 1 angstrom, and when the thickness of the spacing layer film and the thickness of the absorption layer film are respectively calculated according to the thickness ratio of the spacing layer film to the absorption layer film and the period thickness of the multilayer film reflecting mirror, the thickness ratio is (1-4): 1, the thickness of the thin film of the absorption layer is preferably 1 angstrom to 2.5nm, which is determined in consideration of practical circumstances.

In the present invention, the number of reaction cycles of the absorber layer film is preferably equal to the thickness of the absorber layer film/the deposition rate of the absorber layer film, and the deposition rate of the absorber layer film is preferably 1 angstrom/reaction cycle. In the present invention, the number of reaction cycles of the spacer layer film is preferably equal to the thickness of the spacer layer film/the deposition rate of the spacer layer film, and the deposition rate of the spacer layer film is preferably 1 angstrom/reaction cycle. In the present invention, the deposition rate preferably refers to the thickness/reaction period of one atomic layer, and the thickness of the one atomic layer is preferably 1 angstrom for different thin film materials.

After the reaction period number of the absorption layer film is obtained, the method takes a precursor corresponding to the material of the absorption layer film as a raw material, carries out first atomic layer deposition on the surface of a substrate, completes a reaction period, and repeatedly carries out the first atomic layer deposition until the reaction period number of the absorption layer film is reached, so as to form the absorption layer film. In the present invention, the material of the absorption layer filmPreferably comprising Co, Cu, Ta, W, Ge, Pt, Ru, Ni, Fe, TaN, ZrN, HfN, WN, HfO₂、ZnO、ZrO₂、La₂O₃Or SnO₂. In the invention, the precursor corresponding to the material of the absorption layer film is a precursor required for synthesizing the material of each absorption layer film, the specific type of the precursor corresponding to the material of the absorption layer film is not particularly limited, and the precursor can be selected according to the conventional synthesis raw materials in the field; in an embodiment of the invention, HfO is synthesized₂The precursor of (a) is specifically tetrakis (dimethylamino) hafnium and deionized water.

In the present invention, the substrate preferably includes a high-precision Si substrate, a SiC substrate, or an optical glass substrate; the surface roughness of the substrate is preferably < 1 nm.

In the invention, the vacuum degree of the first atomic layer deposition is preferably less than 20Pa, and the temperature is preferably 150-300 ℃, more preferably 180-270 ℃, and further preferably 200-240 ℃. In the present invention, the performing of the first atomic layer deposition on the substrate surface preferably includes: carrying out surface chemical adsorption on a main precursor A corresponding to the material of the absorption layer film and a substrate, carrying out surface chemical reaction on a secondary precursor B corresponding to the material of the absorption layer film and the main precursor A after first purification, and carrying out second purification to finish a reaction period; the main precursor A contains metal elements required by an absorption layer film, and is a metal salt compound; when the material of the absorption layer film is a metal simple substance, the secondary precursor B is silane, oxygen or ozone; when the material of the absorption layer film is metal oxide, the secondary precursor B is deionized water; when the material of the absorption layer film is nitride, the secondary precursor B is nitrogen-containing gas. In the present invention, the specific process of the one reaction cycle is preferably: introducing a main precursor A corresponding to the material of the absorption layer film into a reaction chamber of atomic layer deposition equipment for 100 ms-50 s, wherein the main precursor A is subjected to saturated chemical adsorption on the surface of a substrate; then using inert gas N₂Purging for 40-120 s, performing first purification, and removing reaction productsRaw by-products and excess primary precursor a; then introducing a secondary precursor B corresponding to the material of the absorption layer film into the reaction chamber for 15 ms-60 s, and carrying out surface chemical reaction with the primary precursor A on the surface of the substrate until the primary precursor A is saturated to synthesize the material of the absorption layer film; using inert gas N₂Purging for 35-120 s, and removing by-products and excessive secondary precursors B generated in the reaction; this is one reaction cycle. The flow rate in the introducing process is not specially limited, and the flow rate can be controlled through introducing time according to the control of an air valve inherent to the atomic layer deposition equipment.

In the present invention, the main precursor a preferably contains a metal element required for the absorber layer film, and the main precursor a is preferably a metal salt compound; when the material of the absorption layer film is a metal simple substance, the secondary precursor B is preferably silane, oxygen or ozone; when the material of the absorption layer film is metal oxide, the secondary precursor B is preferably deionized water; when the material of the absorption layer thin film is a nitride, the sub-precursor B is preferably a nitrogen-containing gas. In the present invention, the metal salt compound is preferably tetrakis (dimethylamino) hafnium, tungsten hexafluoride, (acetylacetonato) iridium, ethylruthenocene, trimethyl (methylcyclopentadienyl) platinum, or (acetylacetonato) iridium.

After a reaction period is finished, the method repeats the first atomic layer deposition until the reaction period number of the absorption layer film is reached, and the absorption layer film is formed. The atomic layer deposition method adopted by the invention controls the thickness of the film through the number of reaction cycles, and the deposition rate of the film of the absorption layer is 1 angstrom/reaction cycle, namely, the film with the thickness of 1 angstrom grows in each reaction cycle. Thus, after one reaction cycle was completed, an absorber layer thin film of 1 angstrom thickness was prepared from the main precursor A and the sub-precursor B. Therefore, in order to deposit a thin film with a certain thickness, a plurality of reaction cycles (the number of reaction cycles is equal to the thickness of the thin film/deposition rate) are required. In the present invention, the number of reaction cycles of the absorption layer film is preferably 2 to 30, and more preferably 4 to 12.

Obtaining the number of reaction cycles of the spacer layer filmAfter the absorption layer thin film is formed, the precursor corresponding to the material of the spacing layer thin film is used as a raw material, second atomic layer deposition is carried out on the surface of the absorption layer thin film, a reaction period is completed, and the second atomic layer deposition is repeatedly carried out until the reaction period number of the spacing layer thin film is reached, so that the spacing layer thin film is formed. In the present invention, the material of the spacer layer film preferably includes TiN, AlN, TiO₂、SiO₂Or Al₂O₃. In the invention, the precursor corresponding to the material of the spacer layer film is a precursor required for synthesizing the material of each spacer layer film, the specific type of the precursor corresponding to the material of the spacer layer film is not particularly limited, and the precursor can be selected according to the conventional synthesis raw materials in the field; in the examples of the present invention, Al was synthesized₂O₃The precursor of (1) is specifically trimethylaluminum and deionized water.

In the invention, the vacuum degree of the second atomic layer deposition is preferably less than 20Pa, and the temperature is preferably 150-300 ℃, more preferably 180-270 ℃, and further preferably 200-240 ℃.

In the present invention, the second atomic layer deposition is performed on the surface of the absorption layer film, and the process of completing one reaction cycle preferably includes: carrying out surface chemical adsorption on a main precursor C corresponding to the material of the spacer layer film and the surface of the absorption layer film, carrying out surface chemical reaction on a secondary precursor D corresponding to the material of the spacer layer film and the main precursor C after third purification, and carrying out fourth purification to complete a reaction period; the main precursor C contains metal elements or silicon elements required by a spacer layer film; the main precursor C is a silicon-containing compound or a metal salt compound; when the main precursor C contains the metal elements required for the spacer layer thin film: when the material of the spacer layer film is metal oxide, the secondary precursor D is deionized water or hydrogen peroxide; when the material of the spacer layer film is metal nitride, the secondary precursor D is nitrogen-containing gas; when the main precursor C contains silicon elements required by the spacer layer thin film: when the material of the spacer layer film is silicon oxide, the secondary precursor D is deionized water. In the present inventionIn the invention, the specific process of the one reaction cycle is preferably as follows: introducing a main precursor C corresponding to the material of the spacer layer film into a reaction chamber of atomic layer deposition equipment for 100 ms-50 s, wherein the main precursor C is subjected to saturated chemical adsorption on the surface of the absorption layer film; then using inert gas N₂Purging for 40-120 s, performing third purification, and removing by-products and excessive main precursors C generated in the reaction; then introducing a secondary precursor D corresponding to the material of the spacer layer film into the reaction chamber for 15 ms-60 s, and carrying out surface chemical reaction with the primary precursor C on the surface of the absorption layer film until saturation to synthesize the material of the spacer layer film; using inert gas N₂Purging for 35-120 s, and removing by-products and excessive secondary precursors D generated in the reaction; this is one reaction cycle.

In the invention, the main precursor C contains metal elements or silicon elements required by a spacer layer film; the main precursor C is a silicon-containing compound or a metal salt compound. In the present invention, the silicon-containing compound is preferably tris (dimethylamino) silicon, tris (dimethylamino) silicon or silicon tetrachloride; the metal salt compound is preferably trimethylaluminum, titanium isopropoxide, trimethylaluminum, titanium tetrachloride or trimethylaluminum.

After a reaction period is finished, the second atomic layer deposition is repeatedly carried out until the reaction period number of the spacing layer thin film is reached, and the spacing layer thin film is formed on the surface of the absorption layer thin film. The atomic layer deposition method adopted by the invention controls the thickness of the film through the number of reaction cycles, and the deposition rate of the spacing layer film is 1 angstrom/reaction cycle, namely, the film with the thickness of 1 angstrom grows in each reaction cycle. Thus, after one reaction cycle was completed, a spacer layer thin film of 1 angstrom thickness was prepared from the main precursor C and the sub-precursor D. Therefore, in order to deposit a thin film with a certain thickness, a plurality of reaction cycles (the number of reaction cycles is equal to the thickness of the thin film/deposition rate) are required. In the present invention, the number of reaction cycles of the spacer layer film is preferably 2 to 50, and more preferably 6 to 18.

The equipment used for the first atomic layer deposition and the second atomic layer deposition is not particularly limited, and well-known atomic layer deposition equipment can be selected.

FIG. 1 is a schematic diagram of a process of growing a thin film by an atomic layer deposition method according to the present invention, where as shown in FIG. 1, a main precursor A corresponding to a material of an absorption layer thin film or a main precursor C corresponding to a material of a spacer layer thin film chemically adsorbs to a substrate surface, and passes through N₂After purging, adding a secondary precursor B corresponding to the material of the absorption layer film or a secondary precursor D corresponding to the material of the spacing layer film, respectively carrying out surface chemical reaction with the primary precursor A or C, and carrying out N-step surface chemical reaction₂And after purging, obtaining the material of the absorption layer film or the material of the spacing layer film, and then carrying out an Atomic Layer Deposition (ALD) cyclic process, thereby forming the absorption layer film or the spacing layer film.

After the absorbing layer thin film and the spacing layer thin film are formed, a period of a double-layer film is completed. The outermost layer of the X-ray multilayer film reflecting mirror is not particularly limited to be an absorption layer thin film or a spacing layer thin film, and the periodicity of the double-layer film is met.

FIG. 2 is a schematic structural diagram of the X-ray multilayer film mirror of the present invention, as shown in FIG. 2, the present invention adopts atomic layer deposition method, and forms the absorption layer thin film and the spacer layer thin film which are alternately arranged in sequence on the substrate surface by repeating the above steps of alternately forming the absorption layer thin film and forming the spacer layer thin film until the number of cycles of the double-layer film is reached, wherein d₁Represents the thickness of the spacer layer film, d₂Representing the thickness of the thin film of the absorbing layer and d representing the thickness of the double-layer film, namely the period thickness, the X-ray multilayer film reflecting mirror prepared by the method has high reflectivity and can be suitable for the X-ray wave band with shorter wavelength.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.