阅读说明：本技术 一种多层膜合金化制备太阳能电池吸收层材料硒化锑/硫硒化锑的方法 (Method for preparing solar cell absorbing layer material antimony selenide/antimony selenide sulfide by multi-layer film alloying ) 是由 蒋立峰 陈超 陈涛 朱长飞 江国顺 于 2019-09-16 设计创作，主要内容包括：本发明提供了一种多层膜扩散合金化制备太阳能电池吸收层材料硒化锑/硫硒化锑的方法,包括以下步骤：A)在太阳能电池的电子传输层表面沉积金属锑膜；B)在金属锑膜表面沉积硒薄膜或二硫化硒薄膜,得到复合薄膜；C)在所述复合薄膜表面覆盖衬底后,在保护气氛条件下,在垂直于复合薄膜的方向施加压力并进行热处理,得到太阳能电池吸收层。本发明提供的方法简单,得到的吸收层材料具有组分可控的优势,并且无杂相、结晶性好。(The invention provides a method for preparing a solar cell absorbing layer material antimony selenide/antimony selenide sulfide by diffusion alloying of a multilayer film, which comprises the following steps: A) depositing a metal antimony film on the surface of an electron transport layer of the solar cell; B) depositing a selenium film or a selenium disulfide film on the surface of the metal antimony film to obtain a composite film; C) and after the surface of the composite film is covered with the substrate, applying pressure in a direction vertical to the composite film under the condition of protective atmosphere and carrying out heat treatment to obtain the solar cell absorbing layer. The method provided by the invention is simple, and the obtained absorbing layer material has the advantage of controllable components, no impurity phase and good crystallinity.)

1. a method for preparing a solar cell absorbing layer material antimony selenide/antimony selenide sulfide by multi-layer film diffusion alloying is characterized by comprising the following steps:

A) depositing a metal antimony film on the surface of an electron transport layer of the solar cell;

B) Depositing a selenium film or a selenium disulfide film on the surface of the metal antimony film to obtain a composite film;

C) And after the surface of the composite film is covered with the substrate, applying pressure in a direction vertical to the composite film under the condition of protective atmosphere and carrying out heat treatment to obtain the solar cell absorbing layer.

2. a method for preparing a solar cell absorbing layer material antimony selenide/antimony selenide sulfide by multi-layer film diffusion alloying is characterized by comprising the following steps:

a) Depositing a metal antimony film on the surface of an electron transport layer of the solar cell;

b) depositing a selenium film or a selenium disulfide film on the surface of the substrate;

c) Relatively superposing the metal antimony film and the selenium film, or relatively superposing the metal antimony film and the selenium disulfide film to obtain a superposed film;

d) And applying pressure in the direction vertical to the superposed film, and carrying out heat treatment under the protective atmosphere condition to obtain the solar cell absorbing layer.

3. The method of claim 1 or 2, wherein the electron transport layer is one of a titanium dioxide electron transport layer, a cadmium sulfide electron transport layer, or a titanium dioxide/cadmium sulfide dual electron transport layer.

4. The method according to claim 1 or 2, wherein the method for depositing the metallic antimony film is vacuum deposition, the vacuum deposition is selected from molecular beam epitaxy or thermal evaporation, and the deposition thickness of the metallic antimony film is 30-90 nm.

5. The method of claim 1 or 2, wherein the means for depositing the selenium film or the selenium sulfide film comprises a vacuum method or a spin coating method, and the vacuum method comprises molecular beam epitaxy or a thermal evaporation method.

6. The method of claim 5, wherein the selenium film or the selenium disulfide film is deposited to a thickness of 45 to 180 nm.

7. The method according to claim 1 or 2, characterized in that the protective atmosphere conditions are selected from nitrogen or argon.

8. The method according to claim 1 or 2, characterized in that the heat treatment is carried out by: heating to 100-150 ℃, preserving heat for 20-40 min, heating to 300-350 ℃, annealing for 2-10 min, and naturally cooling.

9. The method of claim 1 or 2, wherein the substrate is a glass substrate.

10. The method of claim 1 or 2, wherein the method of applying pressure is by applying pressure with a clamp.

Technical Field

The invention belongs to the technical field of solar cells, and particularly relates to a method for preparing a material antimony selenide/antimony selenide sulfide selenide of a solar cell absorbing layer by multi-layer film alloying.

Background

With the continuous progress of technological productivity, the demand of human society for energy is continuously expanding. A large number of scientific researchers are eagerly seeking renewable energy sources or clean energy sources to replace and supplement traditional disposable energy sources such as coal, petroleum and the like. Solar energy is used as a clean renewable energy source, is inexhaustible, and is one of the most effective ways to solve energy crisis and relieve environmental stress by exploring and utilizing solar energy. Therefore, the development of efficient and stable solar cells has become an struggle for researchers. Nowadays, the types of solar cells are various, and among them, antimony-based (antimony selenide, antimony sulfide, antimony selenide sulfide) thin-film solar cells are considered to have great potential due to high theoretical conversion efficiency, low cost, good stability and no toxicity.

There are many methods for preparing antimony-based solar cells, such as spin coating, hydrothermal method, thermal evaporation, water bath deposition, etc. In the vacuum method, the obtained absorption layer film has the advantages of good crystallinity, pure phase and the like, but the film components are difficult to control because elements such as sulfur, selenium and the like are easy to lose.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a solar cell absorption layer material antimony selenide/antimony selenide sulfide through multilayer film alloying.

the invention provides a method for preparing a solar cell absorbing layer material antimony selenide/antimony selenide sulfide by diffusion alloying of a multilayer film, which comprises the following steps:

A) Depositing a metal antimony film on the surface of an electron transport layer of the solar cell;

B) Depositing a selenium film or a selenium disulfide film on the surface of the metal antimony film to obtain a composite film;

C) And after the surface of the composite film is covered with the substrate, applying pressure in a direction vertical to the composite film under the condition of protective atmosphere and carrying out heat treatment to obtain the solar cell absorbing layer.

The invention also provides a method for preparing the material antimony selenide/antimony selenide sulfide by diffusion alloying of the multilayer film, which comprises the following steps:

a) depositing a metal antimony film on the surface of an electron transport layer of the solar cell;

b) Depositing a selenium film or a selenium disulfide film on the surface of the substrate;

c) relatively superposing the metal antimony film and the selenium film, or relatively superposing the metal antimony film and the selenium disulfide film to obtain a superposed film;

d) and applying pressure in the direction vertical to the superposed film, and carrying out heat treatment under the protective atmosphere condition to obtain the solar cell absorbing layer.

Preferably, the electron transport layer is one of a titanium dioxide electron transport layer, a cadmium sulfide electron transport layer or a titanium dioxide/cadmium sulfide double electron transport layer.

Preferably, the method for depositing the metal antimony film is vacuum deposition, the vacuum deposition is selected from a molecular beam epitaxy method or a thermal evaporation method, and the deposition thickness of the metal antimony film is 30-90 nm.

Preferably, the method for depositing the selenium film or the selenium disulfide film comprises a vacuum method or a spin coating method, and the vacuum method comprises molecular beam epitaxy or a thermal evaporation method.

Preferably, the deposition thickness of the selenium film or the selenium disulfide film is 45-180 nm.

Preferably, the protective atmosphere conditions are selected from nitrogen or argon.

Preferably, the heat treatment method comprises the following steps: heating to 100-150 ℃, preserving heat for 20-40 min, heating to 300-350 ℃, annealing for 2-10 min, and naturally cooling.

preferably, the substrate is a glass substrate.

Preferably, the method for applying pressure is to apply pressure by using a clamp.

Compared with the prior art, the invention provides a method for preparing a solar cell absorbing layer material antimony selenide/antimony selenide sulfide by multilayer film diffusion alloying, which comprises the following steps: A) depositing a metal antimony film on the surface of an electron transport layer of the solar cell; B) depositing a selenium film or a selenium disulfide film on the surface of the metal antimony film to obtain a composite film; C) and after the surface of the composite film is covered with the substrate, applying pressure in a direction vertical to the composite film under the condition of protective atmosphere and carrying out heat treatment to obtain the solar cell absorbing layer.

The invention adopts a multilayer film diffusion alloy mode to prepare the antimony selenide/antimony selenide sulfide absorption layer material. In the invention, the antimony film (selenium film) is evaporated by adopting a vacuum evaporation mode, the problems of decomposition and component control do not exist for simple substances, and the problem does not exist for a non-metallic element layer which is spin-coated by a solution method, so that the film components are controlled by controlling the thickness of the precursor film in the method. And from the related XRD and SEM images, the prepared film maintains the better crystallinity possessed by the vacuum method and simultaneously maintains the purity of the phase. The invention adopts a multilayer film diffusion alloy mode to prepare the antimony selenide/antimony selenide sulfide absorption layer material, and has the advantage of controllable components compared with a direct vacuum method vapor plating compound. Compared with the traditional solution method, the film prepared by the method has the advantages of no impurity phase and good crystallinity.

Drawings

FIG. 1 is a schematic view of an antimony film deposited on the surface of an electron transport layer;

FIG. 2 is a schematic structural diagram of deposition of a selenium film on the surface of an antimony film;

FIG. 3 is a schematic view of two substrate positions placed in a tube furnace;

Fig. 4 is a schematic process flow diagram of a method for preparing solar cell absorbing layer material antimony selenide/antimony selenide sulfide by diffusion alloying of a multilayer film provided by the invention;

FIG. 5 is an SEM photograph of the antimony selenide thin film obtained in example 1;

Fig. 6 is an XRD pattern of the antimony selenide thin film obtained in example 1.

Detailed Description

The invention provides a method for preparing a solar cell absorbing layer material antimony selenide/antimony selenide sulfide by diffusion alloying of a multilayer film, which comprises the following steps:

A) depositing a metal antimony film on the surface of an electron transport layer of the solar cell;

B) Depositing a selenium film or a selenium disulfide film on the surface of the metal antimony film to obtain a composite film;

C) And after the surface of the composite film is covered with the substrate, applying pressure in a direction vertical to the composite film under the condition of protective atmosphere and carrying out heat treatment to obtain the solar cell absorbing layer.

The method comprises the step of depositing a metal antimony film on the surface of an electron transport layer of the solar cell. A structure of conductive glass/electron transport layer/antimony film was formed. The electron transport layer of the solar cell is one of a titanium dioxide electron transport layer, a cadmium sulfide electron transport layer or a titanium dioxide/cadmium sulfide double electron transport layer. The surface of the electron transport layer is cleaned prior to deposition. The cleaning mode is not particularly limited, and the cleaning can be carried out by using a nitrogen gun.

In the invention, the metallic antimony film is deposited by adopting a vacuum deposition method. The vacuum deposition is selected from a molecular beam epitaxy method or a thermal evaporation method, and the deposition thickness of the metal antimony film is 30-90 nm, preferably 40-80 nm, and further preferably 50-70 nm.

Referring to fig. 1, fig. 1 is a schematic view of depositing an antimony film on the surface of an electron transport layer.

And then, depositing a selenium film or a selenium disulfide film on the surface of the metal antimony film to obtain a composite film.

The mode of depositing the selenium film or the selenium disulfide film comprises a vacuum method or a spin-coating method, and the vacuum method comprises a molecular beam epitaxy method or a thermal evaporation method.

And preparing a selenium or selenium disulfide solution during the spin-coating process, wherein the solvent is selected from carbon disulfide, and the concentration of the carbon disulfide is 0.01-0.05M, preferably 0.02-0.04M. The spin coating is performed for 5-10 times at 2000-4000 rpm for 20-40 s.

The deposition thickness of the obtained selenium film or selenium disulfide film is 45-180 nm, preferably 50-160 nm, and further preferably 70-140 nm.

Referring to fig. 2, fig. 2 is a schematic structural view of depositing a selenium film on the surface of an antimony film.

And covering a substrate on the surface of the composite film, wherein the substrate is a glass substrate. Forming a composite structure of conductive glass/electron transport layer/antimony film/selenium film (or selenium disulfide film)/glass substrate.

Then, applying pressure in a direction perpendicular to the composite film under a protective atmosphere condition, wherein the protective atmosphere condition is selected from nitrogen or argon. The method of applying pressure is not particularly limited, and the film clamping may be achieved using a jig.

Subsequently, heat treatment is performed. The heat treatment method comprises the following steps: firstly heating to 100-150 ℃, preferably 110-140 ℃, and keeping the temperature for 20-40 min, preferably 25-35 min; then heating to 300-350 ℃, preferably 310-340 ℃, annealing for 2-10 min, preferably 4-8 min, and then naturally cooling.

Referring to fig. 3, fig. 3 is a schematic view of two substrate positions placed in a tube furnace.

the surface of the absorption layer is cleaned by carbon disulfide, and the method specifically comprises the steps of spin-coating the carbon disulfide solution for more than 3 times or soaking the carbon disulfide solution for 3 times in the carbon disulfide solution for 5-10 s each time by using parameters of the rotating speed of 2000-6000 rpm and the time of 20-40 s, and naturally drying the carbon disulfide solution.

The invention also provides a method for preparing the material antimony selenide/antimony selenide sulfide by diffusion alloying of the multilayer film, which comprises the following steps:

a) Depositing a metal antimony film on the surface of an electron transport layer of the solar cell;

b) Depositing a selenium film or a selenium disulfide film on the surface of the substrate;

c) Relatively superposing the metal antimony film and the selenium film, or relatively superposing the metal antimony film and the selenium disulfide to obtain a superposed film;

d) and applying pressure in the direction vertical to the superposed film, and carrying out heat treatment under the protective atmosphere condition to obtain the solar cell absorbing layer.

The invention deposits the metal antimony film on the surface of the electron transport layer of the solar cell. A structure of conductive glass/electron transport layer/antimony film was formed. The electron transport layer of the solar cell is one of a titanium dioxide electron transport layer, a cadmium sulfide electron transport layer or a titanium dioxide/cadmium sulfide double electron transport layer. The surface of the electron transport layer is cleaned prior to deposition. The cleaning mode is not particularly limited, and the cleaning can be carried out by using a nitrogen gun.

In the invention, the metallic antimony film is deposited by adopting a vacuum deposition method. The vacuum deposition is selected from a molecular beam epitaxy method or a thermal evaporation method, and the deposition thickness of the metal antimony film is 30-90 nm, preferably 40-80 nm, and further preferably 50-70 nm.

The invention also deposits a selenium film or a selenium disulfide film on the surface of the substrate. Wherein the substrate is preferably a glass substrate.

the mode of depositing the selenium film or the selenium disulfide film comprises a vacuum method or a spin-coating method, and the vacuum method comprises a molecular beam epitaxy method or a thermal evaporation method.

And preparing a selenium or selenium disulfide solution during the spin-coating process, wherein the solvent is selected from carbon disulfide, and the concentration of the carbon disulfide is 0.01-0.05M, preferably 0.02-0.04M. The spin coating is performed for 5-10 times at 2000-4000 rpm for 20-40 s.

The deposition thickness of the obtained selenium film or selenium disulfide film is 45-180 nm, preferably 50-160 nm, and further preferably 70-140 nm.

In the present invention, there is no particular limitation on the order of preparation of step a) and step b).

and then, relatively superposing the metal antimony film and the selenium film, or relatively superposing the metal antimony film and the selenium disulfide film to obtain a superposed film. Forming a composite structure of conductive glass/electron transport layer/antimony film/selenium film (or selenium disulfide film)/glass substrate.

and then applying pressure in the direction perpendicular to the superposed film and carrying out heat treatment under the condition of protective atmosphere to obtain the solar cell absorbing layer.

wherein the protective atmosphere condition is selected from nitrogen or argon. The method of applying pressure is not particularly limited, and the film clamping may be achieved using a jig.

Subsequently, heat treatment is performed. The heat treatment method comprises the following steps: firstly heating to 100-150 ℃, preferably 110-140 ℃, and keeping the temperature for 20-40 min, preferably 25-35 min; then heating to 300-350 ℃, preferably 310-340 ℃, annealing for 2-10 min, preferably 4-8 min, and then naturally cooling.

the surface of the absorption layer is cleaned by carbon disulfide, and the method specifically comprises the steps of spin-coating the carbon disulfide solution for more than 3 times or soaking the carbon disulfide solution for 3 times in the carbon disulfide solution for 5-10 s each time by using parameters of the rotating speed of 2000-6000 rpm and the time of 20-40 s, and naturally drying the carbon disulfide solution.

referring to fig. 4, fig. 4 is a schematic process flow diagram of a method for preparing a solar cell absorbing layer material antimony selenide/antimony selenide sulfide by diffusion alloying of a multilayer film provided by the invention.

The invention utilizes a vacuum method and a spin coating method to deposit two layers of films on the same substrate or different substrates, and the two layers of films are subjected to heat treatment under the condition of applying certain pressure on the upper substrate and the lower substrate, so that the two layers of films are subjected to thermal diffusion and mutual reaction, and the corresponding antimony selenide or antimony selenide sulfide films are obtained.

The invention adopts a multilayer film diffusion alloy mode to prepare the antimony selenide/antimony selenide sulfide absorption layer material. In the invention, the antimony film (selenium film) is evaporated by adopting a vacuum evaporation mode, the problems of decomposition and component control do not exist for simple substances, and the problem does not exist for a non-metallic element layer which is spin-coated by a solution method, so that the film components are controlled by controlling the thickness of the precursor film in the method. From the related XRD and SEM images, the prepared film maintains the better crystallinity possessed by the evaporation method and simultaneously maintains the purity of the phase. The invention adopts a multilayer film diffusion alloy mode to prepare the antimony selenide/antimony selenide sulfide absorption layer material, and has the advantage of controllable components compared with a direct vacuum method vapor plating compound. Compared with the traditional solution method, the film prepared by the method has the advantages of no impurity phase and good crystallinity.

For further understanding of the present invention, the method for preparing the solar cell absorption layer material antimony selenide/antimony selenide sulfide by alloying the multilayer film provided by the present invention is described below with reference to the following examples, and the scope of the present invention is not limited by the following examples.

In the following examples, the processes are conventional unless otherwise specified, and the starting materials are commercially available from the public unless otherwise specified. The FTO glass is purchased from the optimized technology company Limited, and the related medicines are purchased from the chemical reagent company Limited of the national medicine group.