阅读说明：本技术 一种全锑基薄膜太阳电池及其制备方法 (All-antimony-based thin film solar cell and preparation method thereof ) 是由 曹宇 刘超颖 周静 祝新运 蒋家豪 凌同 曲鹏 于 2020-12-22 设计创作，主要内容包括：一种全锑基薄膜太阳电池及其制备方法,包括：前电极、顶电池、背电极,其特点是,前电极为透明导电玻璃层,顶电池由依次层叠设置的Sb-2O-3薄膜作为第一电子传输层、Sb-2S-3薄膜作为第一吸光层、CuSbS-2薄膜作为第一空穴传输层组成；还包括在顶电池与背电极之间依次层叠设置中间电池、底电池,中间电池由依次层叠设置的Sb-2O-3薄膜作为第二电子传输层、Sb-2(S,Se)-3薄膜作为第二吸光层、CuSbS-2薄膜作为第二空穴传输层组成；底电池由依次层叠设置的Sb-2O-3薄膜作为第三电子传输层、Sb-2Se-3薄膜作为第三吸光层、CuSbS-2薄膜作为第三空穴传输层；背电极为金属电极层。其结构简单,成本低且性能稳定。(An all-antimony-based thin film solar cell and a preparation method thereof comprise the following steps: the front electrode is a transparent conductive glass layer, and the top cell is formed by sequentially stacking Sb 2 O 3 Film as first electron transport layer, Sb 2 S 3 Film as first light-absorbing layer, CuSbS 2 The film is composed of a first hole transport layer; the battery also comprises a middle battery and a bottom battery which are sequentially stacked between the top battery and the back electrode, wherein the middle battery is formed by sequentially stacking Sb 2 O 3 Film as second electron transport layer, Sb 2 (S,Se) 3 Film as second light-absorbing layer, CuSbS 2 Film as a second hole transportLayer composition; the bottom cell is composed of Sb arranged in a stacked manner 2 O 3 Film as third electron transport layer, Sb 2 Se 3 Film as third light-absorbing layer, CuSbS 2 The film is used as a third hole transport layer; the back electrode is a metal electrode layer. The structure is simple, the cost is low and the performance is stable.)

1. An all-antimony-based thin film solar cell, comprising: a front electrode, a top cell, a back electrode,the battery is characterized in that the front electrode is a transparent conductive glass layer, and the top battery is formed by sequentially stacking Sb from top to bottom₂O₃Film as first electron transport layer, Sb₂S₃Film as first light-absorbing layer, CuSbS₂The film is composed of a first hole transport layer; the battery structure also comprises a middle battery and a bottom battery which are sequentially stacked from top to bottom between the top battery and the back electrode, wherein the middle battery is formed by sequentially stacking Sb from top to bottom₂O₃Film as second electron transport layer, Sb₂(S,Se)₃Film as second light-absorbing layer, CuSbS₂The film is used as a second hole transport layer; the bottom battery is composed of Sb stacked from top to bottom₂O₃Film as third electron transport layer, Sb₂Se₃Film as third light-absorbing layer, CuSbS₂The film is used as a third hole transport layer; the back electrode is a metal electrode layer.

2. The all-antimony-based thin film solar cell according to claim 1, wherein the transparent conductive glass layer is at least one of a boron, aluminum and gallium doped zinc oxide thin film, a fluorine doped tin dioxide thin film and an indium tin oxide thin film.

3. The all-antimony-based thin film solar cell according to claim 1, wherein: the metal electrode layer is a gold, silver, copper or aluminum film.

4. The all-antimony-based thin film solar cell according to claim 1, wherein the preparation method comprises the following steps:

1) preparing a transparent conductive glass layer: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

2) first electron transport layer Sb₂O₃Preparing a film: 0.3-0.6g (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1, mixing the solution to prepare 0.005-0.01MM of Sb (Ac)₃The solution is repeatedly coated on the surface of the FTO conductive glass layer obtained in the step 1) for 3-5 times by a spin coating method at the rotation speed of 1500r.p.m and the time of 30s, then the FTO conductive glass layer is put into a drying oven at 150 ℃ for 10min for oxidation, and annealing is carried out under the Ar gas atmosphere at 300 ℃ to obtain Sb with the thickness of 50-100nm₂O₃A film;

3) first light-absorbing layer Sb₂S₃Preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 1.5-2h at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treatment is carried out for 2min on a heating plate at 100 ℃, annealing is carried out for 5min at 350 ℃ under Ar gas atmosphere after cooling, and Sb with the thickness of 250-350nm is prepared₂S₃A film;

4) first hole transport layer CuSbS₂Preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5-4.5:6, spraying for 20min by a spraying method, controlling the distance between a nozzle and a heating table to be 27cm, the temperature of the heating table to be 125 ℃, the liquid inlet speed to be 1mL/min, and then annealing under the Ar atmosphere, wherein the annealing temperature is 270 ℃ to form uniform and flat CuSbS₂A thin film having a thickness of 50 to 100 nm;

5) second electron transport layer Sb₂O₃Preparing a film: 0.3-0.6g (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005-0.01M Sb (Ac)₃The solution is coated on the surface of FTO conductive glass layer by spin coating at 1500r.p.m for 30s for 3-5 times, oxidized in 150 deg.C oven for 10min, and annealed at 300 deg.C in Ar gas atmosphere to obtain Sb with thickness of 50-100nm₂O₃A film;

6) second light-absorbing layer Sb₂(S,Se)₃Preparing a film: taking 10mmol seleniumAdding 10mmol Sb into the powder₂O₃、5mLDMF、3mLCS₂And stirring, and adding 5mL of n-butylamine solution to complete the preparation of the Sb-Se-S precursor solution. Sucking 50-100 μ L of the filtered precursor solution with a liquid-transferring gun, dripping on a substrate at 9000r/min for 30-45s, pre-annealing the precursor film on a heating plate at 200 deg.C for 1min, heating the heating plate to 220 deg.C for 2min, heating the film on a heating plate at 320 deg.C for 5min to obtain Sb with a particle size of 600-₂(S,Se)₃A film;

7) second hole transport layer CuSbS₂Preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5-4.5:6, spraying for 20min by a spraying method, controlling the distance between a nozzle and a heating table to be 27cm, the temperature of the heating table to be 125 ℃, the liquid inlet speed to be 1mL/min, and then annealing under the Ar atmosphere, wherein the annealing temperature is 270 ℃ to form uniform and flat CuSbS₂A thin film having a thickness of 50 to 100 nm;

8) third electron transport layer Sb₂O₃Preparing a film: 0.3-0.6g (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005-0.01M Sb (Ac)₃The solution is coated on the surface of FTO conductive glass layer by spin coating at 1500r.p.m for 30s for 3-5 times, oxidized in 150 deg.C oven for 10min, and annealed at 300 deg.C in Ar gas atmosphere to obtain Sb with thickness of 50-100nm₂O₃A film;

9) third light-absorbing layer Sb₂Se₃Preparing a film; weighing 0.6gSb₂Se₃Powder, in a vacuum environment of 1pa, adjusting the evaporation distance to 7mm, setting the substrate temperature to 300 ℃, raising the temperature of the evaporation source to 350 ℃ and keeping the temperature for 20min, then raising the temperature of the evaporation source to 465 ℃, controlling the heating time to 55-75s, and preparing Sb with the thickness of 1500-2000nm by using a near space sublimation method₂Se₃A film;

10) third hole transport layer CuSbS₂Preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5-4.5:6, spraying for 20min by a spraying method, controlling the distance between a nozzle and a heating table to be 27cm, the temperature of the heating table to be 125 ℃, the liquid inlet speed to be 1mL/min, and then annealing under the Ar atmosphere, wherein the annealing temperature is 270 ℃ to form uniform and flat CuSbS₂A thin film having a thickness of 50 to 100 nm;

11) preparing the metal electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4And (4) starting evaporation at Pa, wherein the deposition speed is 1nm/s, and evaporating and depositing a metal electrode layer with the thickness of 50-100 nm.

Technical Field

The invention belongs to the technical field of photoelectric materials and thin film solar cells, and particularly relates to an all-antimony-based thin film solar cell and a preparation method thereof.

Background

With industry development and population growth, global energy demand is increasing, and in particular reliance on traditional energy sources, such as oil, coal, and natural gas, continues. Fossil fuels are non-renewable energy sources and will be exhausted in the future, while the development of modern society requires more low-pollution, sustainable energy sources. The solar cell has attracted a high degree of attention in the art because it can convert light energy into electric energy and has great potential for development. The antimony-based thin film solar cell has the characteristics of low cost, simple process, greenness, no toxicity, easiness in large-scale production and the like, and becomes a hotspot of research in recent years.

In the structure of the thin film solar cell, the electron transport layer is one of important components, and the quality of the material selected for the electron transport layer not only affects the extraction and transportation of carriers, but also has a great influence on the growth of the light absorption layer. The electron transport layer commonly used at present is zinc oxide (ZnO) and titanium dioxide (TiO)₂) Tin dioxide (SnO)₂) Cadmium sulfide (CdS), a problem with these materials is: the method has the advantages of certain ion diffusion, high energy level matching degree, complex preparation method, insufficient film uniformity and flatness, low light transmittance, relatively high cost and poor photoelectric property.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide an all-antimony-based thin film solar cell which is simple in structure, low in cost and stable in performance; and the preparation method of the all-antimony-based thin film solar cell is scientific and reasonable, simple in preparation flow, strong in practicability, suitable for industrial production and high in efficiency.

The technical scheme adopted for realizing one of the purposes of the invention is as follows: an all-antimony-based thin film solar cell, comprising: the solar cell comprises a front electrode, a top cell and a back electrode and is characterized in that the front electrode is a transparent conductive glass layer, and the top cell is formed by sequentially stacking Sb from top to bottom₂O₃Film as first electron transport layer, Sb₂S₃Film as first light-absorbing layer, CuSbS₂The film is composed of a first hole transport layer; the battery structure also comprises a middle battery and a bottom battery which are sequentially stacked from top to bottom between the top battery and the back electrode, wherein the middle battery is formed by sequentially stacking Sb from top to bottom₂O₃Film as second electron transport layer, Sb₂(S,Se)₃Film as second light-absorbing layer, CuSbS₂The film is used as a second hole transport layer; the bottom battery is composed of Sb stacked from top to bottom₂O₃Film as third electron transport layer, Sb₂Se₃Film as third light-absorbing layer, CuSbS₂The film is used as a third hole transport layer; the back electrode is a metal electrode layer.

Further, the transparent conductive glass layer is at least one of a boron, aluminum and gallium doped zinc oxide film, a fluorine doped tin dioxide film and an indium tin oxide film.

Further, the metal electrode layer is a gold, silver, copper or aluminum film, and the thickness is 50-100 nm.

The second technical scheme adopted for achieving the purpose of the invention is as follows: the all-antimony-based thin film solar cell according to claim 1, wherein the preparation method comprises the following steps:

1) preparing a transparent conductive glass layer: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

2) first electron transport layer Sb₂O₃Production of filmsPreparing: 0.3-0.6g (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005-0.01M Sb (Ac)₃The solution is repeatedly coated on the surface of the FTO conductive glass layer obtained in the step 1) for 3-5 times by a spin coating method at the rotating speed of 1500r.p.m and the time of 30s, then the FTO conductive glass layer is put into a drying oven at 150 ℃ for 10min for oxidation, and annealing is carried out at 300 ℃ in Ar atmosphere to obtain Sb with the thickness of 50-100nm₂O₃A film;

3) first light-absorbing layer Sb₂S₃Preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 1.5-2h at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treatment is carried out for 2min on a heating plate at 100 ℃, annealing is carried out for 5min at 350 ℃ in Ar gas atmosphere after cooling, and Sb with thickness of 250-350nm is prepared₂S₃A film;

4) first hole transport layer CuSbS₂Preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5-4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet rate to be 1mL/min, spraying for 20min, and then annealing in an Ar atmosphere at the annealing temperature of 270 ℃ to form uniform and flat CuSbS₂A thin film having a thickness of 50 to 100 nm;

5) second electron transport layer Sb₂O₃Preparing a film: 0.3-0.6g (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005-0.01M Sb (Ac)₃The solution is coated on the surface of FTO conductive glass layer by spin coating at 1500r.p.m for 30s for 3-5 times, oxidized in 150 deg.C oven for 10min, and annealed at 300 deg.C in Ar atmosphere to obtain Sb with thickness of 50-100nm₂O₃A film;

6) second light-absorbing layer Sb₂(S,Se)₃Preparing a film: 10mmol of selenium powder is taken and 10mmol of Sb is added₂O₃、5mLDMF、3mLCS₂And stirring, and adding 5mL of n-butylamine solution to complete the preparation of the Sb-Se-S precursor solution. Sucking 50-100 μ L of the filtered precursor solution with a liquid-transferring gun, dripping on a substrate at 9000r/min for 30-45s, pre-annealing the precursor film on a heating plate at 200 deg.C for 1min, heating the heating plate to 220 deg.C for 2min, heating the film on a heating plate at 320 deg.C for 5min to obtain Sb with a particle size of 600-₂(S,Se)₃A film;

7) second hole transport layer CuSbS₂Preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5-4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet rate to be 1mL/min, spraying for 20min, and then annealing in an Ar atmosphere at the annealing temperature of 270 ℃ to form uniform and flat CuSbS₂A thin film having a thickness of 50 to 100 nm;

8) third electron transport layer Sb₂O₃Preparing a film: 0.3-0.6g (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005-0.01M Sb (Ac)₃The solution is coated on the surface of FTO conductive glass layer by spin coating at 1500r.p.m for 30s for 3-5 times, oxidized in 150 deg.C oven for 10min, and annealed at 300 deg.C in Ar atmosphere to obtain Sb with thickness of 50-100nm₂O₃A film;

9) third light-absorbing layer Sb₂Se₃Preparing a film; weighing 0.6gSb₂Se₃Adjusting evaporation distance to 7mm, setting substrate temperature to 300 deg.C, heating to 350 deg.C for 20min, increasing evaporation source temperature to 465 deg.C, heating for 55-75s, and sublimating in near space to obtain 150-mm thick powder0-2000nm Sb₂Se₃A film;

10) third hole transport layer CuSbS₂Preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5-4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet rate to be 1mL/min, spraying for 20min, and then annealing in an Ar atmosphere at the annealing temperature of 270 ℃ to form uniform and flat CuSbS₂A thin film having a thickness of 50 to 100 nm;

11) preparing the metal electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^{- 4}And (4) starting evaporation at Pa, wherein the deposition speed is 1nm/s, and evaporating and depositing a metal electrode layer with the thickness of 50-100 nm.

According to the all-antimony-based thin-film solar cell, all functional layers of the solar cell are all antimony-based materials, and the first electron transport layer material, the second electron transport layer material and the third electron transport layer material are all antimony oxide (Sb)₂O₃) The first light-absorbing layer is made of antimony sulfide (Sb)₂S₃) The thin film and the second light absorption layer are made of antimony selenide sulfide (Sb)₂(S,Se)₃) The material of the film and the third light absorption layer is antimony selenide (Sb)₂Se₃) A film; the first, second and third hole transport layer materials are all copper antimony sulfide (CuSbS)₂) Thin films, especially Sb₂O₃The film is used as an electron transport layer material, the application range of the electron transport layer material in the solar cell is expanded, and Sb₂O₃The film is used as an electron transmission layer of the thin film solar cell, is uniform and flat, and has high light transmittance and electric conductivity; the full-antimony-based solar cell can adjust the spectral response range through the change of the selenium-antimony ratio of the light absorption layer, thereby constructing a full-antimony-based double-junction and full-antimony-based triple-junction laminated solar cell structure, improving the photoelectric conversion efficiency of the solar cell, having rich raw materials, similar material structures, more matched energy band arrangement, effectively improving the device performance of the solar cell, having simple structure,low cost and stable chemical property; the preparation method is scientific and reasonable, simple in preparation process, strong in practicability, suitable for industrial production and high in efficiency.

Drawings

FIG. 1 is a schematic diagram of the basic structure of a single-junction all-antimony-based solar cell;

FIG. 2 is a schematic diagram of the basic structure of a double-junction all-antimony-based solar cell;

fig. 3 is a schematic diagram of the basic structure of a three-layer-stack all-antimony-based solar cell.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

Referring to fig. 1, the method for preparing an all-antimony-based single junction solar cell of the present invention comprises the following steps:

step S1: using transparent conductive glass as a substrate and cleaning;

step S2: preparation of Sb Using spin coating method₂O₃The film is used as a first electron transport layer;

step S3: preparation of Sb Using a hydrothermal Process₂S₃The film is used as a first light absorption layer;

step S4: preparation of CuSbS by spray pyrolysis method₂The film is used as a first hole transport layer;

step S5: and evaporating the metal electrode layer to be used as a back electrode.

Referring to fig. 2, the preparation method of the all-antimony-based double-junction solar cell of the invention comprises the following steps:

step S1: using transparent conductive glass as a substrate and cleaning;

step S2: preparation of Sb Using spin coating method₂O₃The film is used as a first electron transport layer;

step S3: preparation of Sb Using a hydrothermal Process₂S₃The film is used as a first light absorption layer;

step S4: preparation of CuSbS by spray pyrolysis method₂The film is used as a first hole transport layer;

step S5: preparation of Sb Using spin coating method₂O₃The film is used as a second electron transport layer;

step S6: preparation of Sb Using close space sublimation₂Se₃The film is used as a second light absorption layer;

step S7: preparation of CuSbS by spray pyrolysis method₂The film is used as a second hole transport layer;

step S8: and evaporating the metal electrode layer to be used as a back electrode.

Referring to fig. 3, the method for preparing an all-antimony-based tri-stack solar cell of the present invention comprises the following steps:

step S1: using transparent conductive glass as a substrate and cleaning;

step S2: preparation of Sb Using spin coating method₂O₃The film is used as a first electron transport layer;

step S3: preparation of Sb Using a hydrothermal Process₂S₃The film is used as a second light absorption layer;

step S4: preparation of CuSbS by spray pyrolysis method₂The film is used as a second hole transport layer;

step S5: preparation of Sb Using spin coating method₂O₃The film is used as a second electron transport layer;

step S6: preparation of Sb Using solution Process₂(S,Se)₃The film is used as a second light absorption layer;

step S7: preparation of CuSbS by spray pyrolysis method₂The film is used as a second hole transport layer;

step S8: preparation of Sb Using spin coating method₂O₃The film is used as a third electron transport layer;

step S9: preparation of Sb Using close space sublimation₂Se₃The film is used as a third light absorption layer;

step S10: by sprayingPreparation of CuSbS by fog pyrolysis method₂The film is used as a third hole transport layer;

step S11: and evaporating the metal electrode layer to be used as a back electrode.

The specific embodiment is as follows:

example 1: the preparation process of the single-junction all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: 0.3g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating the surface of the FTO conductive glass. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare Sb with the thickness of 50nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 4.8h at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 800nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 50 nm;

(5) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4Starting evaporation at Pa, wherein the deposition speed is 1nm/s, and a gold electrode with the thickness of 50nm is evaporated and deposited to be used as a metal electrode layer; the structure of the prepared single-junction all-antimony-based thin-film solar cell is shown in figure 1.

Example 2: the preparation process of the single-junction all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: 0.45g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.0075M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at the temperature of 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 75nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 6 hours at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 1000nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:3.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and flat surfaces are formedWhole CuSbS₂A thin film having a thickness of 75 nm;

(5) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4Starting evaporation at Pa, wherein the deposition speed is 1nm/s, and a gold electrode with the thickness of 75nm is evaporated and deposited to be used as a metal electrode layer; the structure of the single-junction all-antimony-based thin-film solar cell is shown in figure 1.

Example 3: the preparation process of the single-junction all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: 0.6g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 in the mixed solution, 0.01M Sb (Ac) was prepared₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 100nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 7.2h at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 1200nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then at AAnnealing at 270 ℃ in the atmosphere of r to form uniform and flat CuSbS₂A thin film having a thickness of 100 nm;

(5) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4Starting evaporation at Pa, wherein the deposition speed is 1nm/s, and a gold electrode with the thickness of 100nm is evaporated and deposited to be used as a metal electrode layer; the structure of the single-junction all-antimony-based thin-film solar cell is shown in figure 1.

Example 4: the preparation process of the double-junction all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: 0.3g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 50nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 2.4h at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 400nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5:6, and controlling the distance between a nozzle and a heating table to be 27cm and the temperature of the heating table by a spraying methodThe temperature is 125 ℃, the liquid inlet speed is 1mL/min, and the spraying time is 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 50 nm;

(5)Sb₂O₃preparing a film: 0.3g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare Sb with the thickness of 50nm₂O₃A film;

(6)Sb₂Se₃preparing a film; weighing 0.6gSb₂Se₃Powder, the evaporation distance was adjusted to 7mm under a vacuum atmosphere of 1pa, and the substrate temperature was set to 300 ℃. Raising the temperature of the evaporation source to 350 ℃ for 20min, then raising the temperature of the evaporation source to 465 ℃ and controlling the heating time to be 40 s. Sb with the thickness of 800nm is prepared by using a close space sublimation method₂Se₃A film;

(7)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 50 nm;

(8) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4Starting evaporation at Pa, wherein the deposition speed is 1nm/s, and a gold electrode with the thickness of 50nm is evaporated and deposited to be used as a metal electrode layer; the structure of the double-laminated all-antimony-based device is shown in figure 2.

Example 5: the preparation process of the double-junction all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: 0.45g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.0075M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at the temperature of 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 75nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 3 hours at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 500nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:3.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 75 nm;

(5)Sb₂O₃preparing a film: 0.45g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.0075M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare the alloySb with a thickness of 75nm was obtained₂O₃A film;

(6)Sb₂Se₃preparing a film; weighing 0.6gSb₂Se₃Powder, the evaporation distance was adjusted to 7mm under a vacuum atmosphere of 1pa, and the substrate temperature was set to 300 ℃. Raising the temperature of the evaporation source to 350 ℃ for 20min, then raising the temperature of the evaporation source to 465 ℃ and controlling the heating time to be 50 s. Sb with the thickness of 1000nm is prepared by using a close space sublimation method₂Se₃A film;

(7)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:3.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 75 nm;

(8) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4Starting evaporation at Pa, wherein the deposition speed is 1nm/s, and a gold electrode with the thickness of 75nm is evaporated and deposited to be used as a metal electrode layer; the structure of the prepared double-laminated all-antimony-based thin-film solar cell is shown in figure 2.

Example 6: the preparation process of the double-junction all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: 0.6g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 in the mixed solution, 0.01M Sb (Ac) was prepared₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare Sb with the thickness of 100nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 3.6h at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 600nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 100 nm;

(5)Sb₂O₃preparing a film: 0.6g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 in the mixed solution, 0.01M Sb (Ac) was prepared₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 100nm₂O₃A film;

(6)Sb₂Se₃preparing a film; weighing 0.6gSb₂Se₃Powder, the evaporation distance was adjusted to 7mm under a vacuum atmosphere of 1pa, and the substrate temperature was set to 300 ℃. Raising the temperature of the evaporation source to 350 ℃ for 20min, then raising the temperature of the evaporation source to 465 ℃ and controlling the heating time to be 60 s. Sb with the thickness of 1200nm is prepared by using a near space sublimation method₂Se₃A film;

(7)CuSbS₂preparing a film: adding CuCl₂·2H₂O, purity of99% (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 100 nm;

(8) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4Starting evaporation at Pa, wherein the deposition speed is 1nm/s, and a gold electrode with the thickness of 100nm is evaporated and deposited to be used as a metal electrode layer; the structure of the prepared double-laminated all-antimony-based thin-film solar cell is shown in figure 2.

Example 7: the preparation process of the three-laminated all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: 0.3g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare Sb with the thickness of 50nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 1.5h at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 250nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 50 nm;

(5)Sb₂O₃preparing a film: 0.3g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare Sb with the thickness of 50nm₂O₃A film;

(6)Sb₂(S,Se)₃preparing a film: 10mmol of selenium powder is taken and 10mmol of Sb is added₂O₃、5mLDMF、3mLCS₂And stirring, and adding 5mL of n-butylamine solution to complete the preparation of the Sb-Se-S precursor solution. Sucking 50 μ L of the filtered precursor solution with a liquid-transfering gun, dripping on a substrate at 9000r/min for 30s, pre-annealing the precursor film on a 200 deg.C heating plate for 1min, heating the heating plate to 220 deg.C for 2min, and heating the film on a 320 deg.C heating plate for 5min to obtain 600nm Sb₂(S,Se)₃A film;

(7)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 50 nm;

(8)Sb₂O₃preparing a film: 0.3g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.005M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare Sb with the thickness of 50nm₂O₃A film;

(9)Sb₂Se₃preparing a film; weighing 0.6gSb₂Se₃Powder, the evaporation distance was adjusted to 7mm under a vacuum atmosphere of 1pa, and the substrate temperature was set to 300 ℃. Raising the temperature of the evaporation source to 350 ℃ for 20min, then raising the temperature of the evaporation source to 465 ℃ and controlling the heating time to 55 s. Sb with the thickness of 1500nm is prepared by using a close space sublimation method₂Se₃A film;

(10)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:2.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 50 nm;

(11) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4Starting evaporation at Pa, wherein the deposition speed is 1nm/s, and a gold electrode with the thickness of 50nm is evaporated and deposited to be used as a metal electrode layer; the three-layer-stacked all-antimony-based thin film solar cell is prepared as shown in fig. 3.

Example 8: the preparation process of the three-laminated all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: will be 0.45g(CH₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.0075M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at the temperature of 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 75nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 1.8h at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 300nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:3.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 75 nm;

(5)Sb₂O₃preparing a film: 0.45g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.0075M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at the temperature of 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 75nm₂O₃A film;

(6)Sb₂(S,Se)₃preparing a film: 10mmol of selenium powder is taken and 10mmol of Sb is added₂O₃、5mLDMF、3mLCS₂And stirring, and adding 5mL of n-butylamine solution to complete the preparation of the Sb-Se-S precursor solution. Sucking 75 μ L of the filtered precursor solution with a liquid-transfering gun, dripping on a substrate at 9000r/min for 40s, pre-annealing the precursor film on a 200 deg.C heating plate for 1min, heating the heating plate to 220 deg.C for 2min, and heating the film on a 320 deg.C heating plate for 5min to obtain 750nm Sb₂(S,Se)₃A film;

(7)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:3.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 75 nm;

(8)Sb₂O₃preparing a film: 0.45g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 to prepare 0.0075M Sb (Ac)₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at the temperature of 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 75nm₂O₃A film;

(9)Sb₂Se₃preparing a film; weighing 0.6gSb₂Se₃Powder, the evaporation distance was adjusted to 7mm under a vacuum atmosphere of 1pa, and the substrate temperature was set to 300 ℃. Raising the temperature of the evaporation source to 350 ℃ for 20min, then raising the temperature of the evaporation source to 465 ℃ and controlling the heating time to 65 s. Using a close space sublimation method to prepare Sb with the thickness of 1750nm₂Se₃A film;

(10)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂The proportion of the three is 1:3.5:6, preparing a precursor solution, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 75 nm;

(11) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4Starting evaporation at Pa, wherein the deposition speed is 1nm/s, and a gold electrode with the thickness of 75nm is evaporated and deposited to be used as a metal electrode layer; the three-layer-stacked all-antimony-based thin film solar cell is prepared as shown in fig. 3.

Example 9: the preparation process of the three-laminated all-antimony-based thin film solar cell comprises the following steps:

(1) cleaning FTO conductive glass: sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 40min by using deionized water, acetone, isopropanol and absolute ethyl alcohol respectively, and drying by using nitrogen for later use;

(2)Sb₂O₃preparing a film: 0.6g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 in the mixed solution, 0.01M Sb (Ac) was prepared₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture at 300 ℃ in Ar atmosphere to prepare Sb with the thickness of 100nm₂O₃A film;

(3)Sb₂S₃preparing a film: weighing 2g of antimony potassium tartrate hemihydrate to dissolve in 200ml of ultrapure water, adding 0.9g of thioacetamide into the ultrapure water, and fully stirring to complete preparation of a precursor solution; then putting the substrate into a hydrothermal reaction kettle, pouring a precursor solution, and reacting for 2 hours at 135 ℃; after the hydrothermal process is finished, sequentially washing the mixture by using ultrapure water and absolute ethyl alcohol; finally, heat treating on a heating plate at 100 ℃ for 2min, cooling, and annealing at 350 ℃ in Ar gas atmosphere for 5min to obtain Sb with the thickness of 350nm₂S₃A film;

(4)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, purityIs 99% of H₂NCSNH₂Preparing a precursor solution according to the ratio of 1:4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 100 nm;

(5)Sb₂O₃preparing a film: 0.6g of (CH)₃COO)₃Dissolving Sb in a proper amount of glycol absolute ethyl alcohol 1: 1 in the mixed solution, 0.01M Sb (Ac) was prepared₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare Sb with the thickness of 100nm₂O₃A film;

(6)Sb₂(S,Se)₃preparing a film: 10mmol of selenium powder is taken and 10mmol of Sb is added₂O₃、5mLDMF、3mLCS₂And stirring, and adding 5mL of n-butylamine solution to complete the preparation of the Sb-Se-S precursor solution. Sucking 100 μ L of filtered precursor solution with a liquid-transfering gun, dripping on a substrate at 9000r/min for 45s, pre-annealing the precursor film on a 200 deg.C heating plate for 1min, heating the heating plate to 220 deg.C for 2min, heating the film on a 320 deg.C heating plate for 5min to obtain 900nm Sb₂(S,Se)₃A film;

(7)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 100 nm;

(8)Sb₂O₃preparing a film: 0.6g of (CH)₃COO)₃Sb is dissolved in proper amount of glycolAbsolute ethyl alcohol 1: 1 in the mixed solution, 0.01M Sb (Ac) was prepared₃And (3) solution. And (3) repeating the steps for 3-5 times by a spin coating method at a rotating speed of 1500r.p.m for 30s, and spin-coating on the surface of the FTO. Then putting the mixture into a 150 ℃ oven for 10min for oxidation, and annealing the mixture in an Ar atmosphere at 300 ℃ to prepare Sb with the thickness of 100nm₂O₃A film;

(9)Sb₂Se₃preparing a film; weighing 0.6gSb₂Se₃Powder, the evaporation distance was adjusted to 7mm under a vacuum atmosphere of 1pa, and the substrate temperature was set to 300 ℃. Raising the temperature of the evaporation source to 350 ℃ for 20min, then raising the temperature of the evaporation source to 465 ℃ and controlling the heating time to be 75 s. Sb with the thickness of 2000nm is prepared by using a close space sublimation method₂Se₃A film;

(10)CuSbS₂preparing a film: adding CuCl₂·2H₂O, 99% pure (CH)₃COO)₃Sb, H with purity of 99%₂NCSNH₂Preparing a precursor solution according to the ratio of 1:4.5:6, controlling the distance from a nozzle to a heating table to be 27cm by a spraying method, controlling the temperature of the heating table to be 125 ℃, controlling the liquid inlet speed to be 1mL/min, and spraying for 20 min. Then annealing is carried out in Ar atmosphere, the annealing temperature is 270 ℃, and uniform and smooth CuSbS is formed₂A thin film having a thickness of 100 nm;

(11) preparing an Au electrode; putting the sample into evaporation equipment, adopting a gold evaporation source, and vacuumizing to 10 DEG^-4And (3) starting evaporation at Pa, enabling the deposition speed to be 1nm/s, carrying out evaporation deposition on a 100 nm-thick gold electrode as a metal electrode layer, and carrying out steps 1) -11) to obtain the three-lamination all-antimony-based thin film solar cell shown in the figure 3.

It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.