阅读说明：本技术 一种用于太阳能电池的薄膜、太阳能电池及其制备方法 (Thin film for solar cell, solar cell and preparation method of thin film ) 是由 唐华 唐明睿 程江 李璐 于 2021-08-09 设计创作，主要内容包括：一种用于太阳能电池的薄膜,其成分的化学表达为AgIn-(x)SbS-((2+3x/2))(Se),其中x=0.25～1.0；本发明中AgIn-(x)SbS-((2+3x/2))(Se)薄膜纯度高,结晶度好、晶粒尺寸大,孔洞、缝隙等缺陷少,本发明方法降低了Se对薄膜结构损害,制备的薄膜致密性、均匀性优异,以该薄膜作为吸收层的ITO/CdS/AgIn-(x)SbS-((2+3x/2))(Se)/Au太阳能电池具有优异的电性能,Jsc达到20.65mA cm～(-2),FF达到42.8%,PEC达到最大值为1.98%,EQE达到70%；均有优异的稳定性。(A thin film for solar cell comprises AgIn as chemical expression x SbS (2+3x/2) (Se), wherein x = 0.25-1.0; AgIn in the invention x SbS (2+3x/2) The (Se) film has high purity, good crystallinity, large crystal grain size and few defects such as holes, gaps and the like, the method reduces the damage of Se to the film structure, the prepared film has excellent compactness and uniformity, and the ITO/CdS/AgIn film taking the film as an absorption layer x SbS (2+3x/2) The (Se)/Au solar cell has excellent electrical property, and the Jsc reaches 20.65mA cm ‑2 FF toTo 42.8%, PEC reaches a maximum of 1.98%, EQE reaches 70%; all have excellent stability.)

1. A film for a solar cell, characterized by: the chemical expression of the composition of the film is AgIn_xSbS _(2+3x/2)(Se), wherein x = 0.25-1.0.

2. A film for a solar cell according to claim 1, wherein: the film is prepared by preparing a spraying liquid by taking silver nitrate, indium nitrate, antimony acetate and thiourea as raw materials and preparing AgIn through thermal spraying deposition_xSbS₂And (3) selenizing the film in a selenium steam environment to obtain the film.

3. A method for preparing a thin film for a solar cell according to claim 1, wherein: dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, dissolving antimony acetate in acetic acid to form a solution B, mixing the solution A and the solution B, adding concentrated nitric acid, finally adding acetic acid and thiourea to form a spraying liquid, and adding N₂Under the environment, the AgIn is deposited by ultrasonic spraying pyrolysis_xSbS_(2+3x/2)Thin film, then AgIn_xSbS_(2+3x/2)And placing the film in a 380 ℃ high-temperature area, placing the selenium powder in a 350 ℃ low-temperature area, and performing selenization for 6-9 min.

4. A method of manufacturing a thin film for a solar cell according to claim 3, wherein: the molar volume ratio of the thiourea to the acetic acid is 7.7-8 mmol:1 mL.

5. The method of manufacturing a thin film for a solar cell according to claim 3 or 4, wherein: the molar volume ratio of silver nitrate to indium nitrate to ethylene glycol monomethyl ether in the solution A is 1mmol: 0.25-1 mmol: 13-15 mL.

6. The method of producing a thin film for a solar cell according to any one of claims 3 to 5, wherein: the molar volume ratio of the antimony acetate to the acetic acid in the solution B is 1mmol: 3.5-4 mL.

7. The method of producing a thin film for a solar cell according to any one of claims 3 to 6, wherein: the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid in the spraying liquid is 1mmol to 4mmol to 80 mu L.

8. The method of claim 7, wherein the method comprises: said N is₂The gas flow is 20-24L/min, the feeding rate of the spraying liquid is 0.3mL/min, the deposition rate is 150nm/min, and the deposition temperature is 330 ℃.

9. A solar cell based on the thin film of claim 1, wherein: the solar cell takes ITO as a base material and CdS as a buffer layer, the thickness of the solar cell is about 150nm, and the AgIn is_xSbS _(2+3x/2)The (Se) film is used as an absorption layer of the solar cell, the Au layer is an electrode layer, the thickness is about 60nm, and the structure of the solar cell is ITO/CdS/AgIn_xSbS_(2+3x/2)(Se) /Au。

10. A method of manufacturing a solar cell according to claim 9, comprising the steps of:

s1, cleaning the base material: using ITO glass as a base material, carrying out ultrasonic cleaning by using an alkaline detergent, and then carrying out ultrasonic cleaning by using deionized water;

s2, depositing a CdS buffer layer: depositing a CdS buffer layer with the thickness of about 150nm on an ITO substrate by adopting a chemical plating method, and then annealing for 5min at 400 ℃;

s3, depositing AgIn_xSbS _(2+3x/2)(Se) absorption layer:

preparing a spraying liquid:

(1) dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol: 0.25-1 mmol: 13-15 mL;

(2) dissolving antimony acetate in acetic acid to form a solution B, wherein the molar volume ratio of the antimony acetate to the acetic acid is 1mmol: 3.5-4 mL;

(3) mixing the solution A and the solution B, adding concentrated nitric acid with the mass concentration of 68%, finally adding acetic acid and thiourea, and mixing to form a spraying liquid, wherein the molar volume ratio of the thiourea to the acetic acid is 7.7-8 mmol:1mL, and the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid is 1mmol:1mmol:4mmol:80 mu L;

(II) depositing AgIn_xSbS_(2+3x/2)Film(s)

In N₂Under the environment, N₂The gas flow is 20-24L/min, and AgIn is deposited by ultrasonic spraying pyrolysis_xSbS_(2+3x/2)The feeding rate of the spraying liquid is 0.3mL/min, the deposition rate is 150nm/min, the deposition temperature is 330 ℃, and the deposition thickness is about 600 nm;

selenization (III)

AgIn is added_xSbS_(2+3x/2)Placing the film in a 380 ℃ high-temperature region of a heat treatment furnace, placing selenium powder in a 350 ℃ low-temperature region, and performing selenization for 6-9 min to obtain AgIn with the thickness of about 950nm_xSbS_(2+3x/2)(Se) thin films;

s4, depositing an Au electrode layer: au of about 60nm thickness was sputtered to AgIn with an ion sputter coater_xSbS _(2+3x/2)(Se) surface.

Technical Field

The invention relates to the technical field of photovoltaic materials, in particular to a thin film for a solar cell, the solar cell and a preparation method thereof.

Background

Compared with the traditional silicon-based solar cell, the multi-composite thin film solar cell is concerned by the advantages of low demand of raw materials, various preparation methods, light weight and the like. In recent years, the Power Conversion Efficiency (PCE) of cadmium telluride (CdTe) and Copper Indium Gallium Selenide (CIGS) thin film solar cells has reached extremely high levels, but these cells have not been suitable for further commercialization due to high cost and large amount of harmful waste. Therefore, many researchers are still looking for photovoltaic absorber materials that are low in production cost and environmentally friendly. In recent years, a great deal of progress has been made in new absorbers represented by antimony sulfide, but there is still a large gap compared with CdTe and CIGS, and some potential absorber layer materials such as Cu₂SnS₃,CuSbS₂,CuSbSe₂ ZnSnN₂Have also been investigated, but their efficiency is still less than expected. At present, novel inorganic photovoltaic films with excellent photoelectric properties and suitable preparation methods are yet to be discovered.

Sulfur antimony silver (AgSbS)₂) As an antimony-based ternary sulfur compound material, the material has a proper band gap of 1.4-1.7eV under near infrared and visible light, and the absorption coefficient under the near infrared and visible light is as high as 10⁴-10⁵cm^-1And the material is eco-friendly and nontoxic, and is a promising photovoltaic absorber. Due to AgSbS₂Is used as a P-type absorption layer for the first time, and is currently paired with AgSbS₂There are few studies on solar cells. The forbidden band width reported by p.k.nair et al is 1.68eV, but the grain size of the film is too small, limiting the photoconductivity of the film. Short-circuit current (J) due to device_SC) Lower, with little photovoltaic performance, then j.o. gonzales et al found that the solution process produced AgSb (S)_xSe_1-x)₂The film has better photoelectric property. Based on AgSb (S)_xSe_1-x)₂The PCE of the device of (1) is 2.7%, 9.70mA cm^-2However, it should be noted that, although the photoelectric properties are improved, the thin film preparation process is very complicated and time-consuming.

Preparation of AgSbS by ultrasonic spray pyrolysis deposition (thermal spray method)₂(Se) film, simple operation, high preparation efficiency, but preparedThe film has many holes and gaps, the crystal grain size of the film is small, Se after selenization has certain damage to the film structure, the performance of the film is poor, and the efficiency of the Se-Se film is low when the Se-Se thin film is applied to solar cells.

Disclosure of Invention

In view of the above problems, the present invention aims to provide a thin film for a solar cell.

The second purpose of the invention is to provide a preparation method of the film.

The third purpose of the invention is to provide a solar cell using the film as an absorption layer.

The fourth purpose of the invention is to provide a preparation method of the solar cell.

The purpose of the invention is realized by the following technical scheme:

a film for a solar cell, characterized by: the chemical expression of the composition of the film is AgIn_xSbS_(2+3x/2)(Se), wherein x is 0.25-1.0.

Preferably, x is 0.55.

Further, the film is prepared by preparing a spraying liquid by taking silver nitrate, indium nitrate, antimony acetate and thiourea as raw materials and preparing AgIn through thermal spraying deposition_xSbS₂And (3) selenizing the film in a selenium steam environment to obtain the film.

Wherein after selenization, part of S is replaced by (Se) representing Se.

Further, the spraying liquid is formed by dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, dissolving antimony acetate in acetic acid to form a solution B, mixing the solution A and the solution B, adding concentrated nitric acid, and finally adding acetic acid and thiourea.

Further, the molar volume ratio of the thiourea to the acetic acid is 7.7-8 mmol:1 mL.

Further, the molar volume ratio of silver nitrate, indium nitrate and ethylene glycol monomethyl ether in the solution A is 1mmol: 0.25-1 mmol: 13-15 mL.

Furthermore, the molar volume ratio of the antimony acetate to the acetic acid in the solution B is 1mmol: 3.5-4 mL.

Further, the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid in the spraying liquid is 1mmol to 4mmol to 80 mu L.

The method is different from the common doping chemical elements that the original structure is not changed integrally, but some elements of a few position points are replaced by doping elements or particles, In element (In) is added into an Ag-Sb-S-Se system In a direct adding mode, and the In is added into AgSbS₂Is filled in the lattice gaps of the AgSbS₂The middle element generates extrusion to change the positions of Ag and Sb In crystal lattices, thereby changing the final performance of the film, and a large amount of In is filled In AgSbS₂In the selenization process, In and Se generate site competition, and Se steam is blocked during thermal diffusion, so that Se steam is inhibited from entering crystal lattice gaps, and the damage of Se embedded crystal lattices to the film is reduced; in addition, substitution of Se for S results in reduced Sb-S bond, damaged thin film, and increased defects, as compared to AgSbS without indium addition₂And (Se) and indium are added to adjust the substitution degree of Se to S, so that Sb is more tightly connected to S, and the structural defects of the film are reduced. In addition, the valence band of the film is adjusted by adding In.

The above AgIn_xSbS_(2+3x/2)A method for producing a (Se) thin film, comprising: dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, dissolving antimony acetate in acetic acid to form a solution B, mixing the solution A and the solution B, adding concentrated nitric acid, finally adding acetic acid and thiourea to form a spraying liquid, and adding N₂Under the environment, the AgIn is deposited by ultrasonic spraying pyrolysis_xSbS_(2+3x/2)Thin film, then AgIn_xSbS_(2+3x/2)And placing the film in a 380 ℃ high-temperature area, placing the selenium powder in a 350 ℃ low-temperature area, and performing selenization for 6-9 min.

According to the invention, silver nitrate and indium nitrate are prepared into a solution A, antimony acetate is separately dissolved into a solution B and then mixed, so that a precursor added with In is ensured to be generated, instead of a structure that the In replaces Sb, thiourea is finally added, and a small amount of acetic acid is added to play a role In pH buffering, so that a regulating effect is formed on the generation of the precursor In the spraying liquid, the In is promoted to be more uniformly and fully embedded into a crystal lattice gap, and the uniformity and compactness of a deposited film In the thermal spraying process are improved.

Preferably, the selenization time is 8 min.

Further, the above-mentioned N₂The gas flow is 20-24L/min, the feeding rate of the spraying liquid is 0.3mL/min, the deposition rate is 150nm/min, and the deposition temperature is 330 ℃.

Further, the molar volume ratio of the thiourea to the acetic acid is 7.7-8 mmol:1 mL.

Further, the molar volume ratio of silver nitrate, indium nitrate and ethylene glycol monomethyl ether in the solution A is 1mmol: 0.25-1 mmol: 13-15 mL.

Furthermore, the molar volume ratio of the antimony acetate to the acetic acid in the solution B is 1mmol: 3.5-4 mL.

Further, the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid in the spraying liquid is 1mmol to 4mmol to 80 mu L.

Most specifically, AgIn_xSbS_(2+3x/2)The preparation method of the (Se) thin film is characterized by comprising the following steps:

preparing a spraying liquid:

(1) dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol: 0.25-1 mmol: 13-15 mL;

(2) dissolving antimony acetate in acetic acid to form a solution B, wherein the molar volume ratio of the antimony acetate to the acetic acid is 1mmol: 3.5-4 mL;

(3) mixing the solution A and the solution B, adding concentrated nitric acid with the mass concentration of 68%, finally adding acetic acid and thiourea, and mixing to form a spraying liquid, wherein the molar volume ratio of the thiourea to the acetic acid is 7.7-8 mmol:1mL, and the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid is 1mmol:1mmol:4mmol:80 mu L;

(II) depositing AgIn_xSbS_(2+3x/2)Film(s)

In N₂Under the environment, N₂The gas flow is 20-24L/min, and AgIn is deposited by ultrasonic spraying pyrolysis_xSbS_(2+3x/2)Film, spray coating feed rate 0.3mL/min, the deposition rate is 150nm/min, and the deposition temperature is 330 ℃;

selenization (III)

AgIn is added_xSbS_(2+3x/2)And placing the film in a 380 ℃ high-temperature area of a heat treatment furnace, placing selenium powder in a 350 ℃ low-temperature area, and performing selenization for 6-9 min.

Based on above-mentioned AgIn_xSbS_(2+3x/2)A solar cell of (Se) thin film, characterized in that: the solar cell takes ITO as a base material and CdS as a buffer layer, and the AgIn_xSbS_(2+3x/2)The (Se) film is used as an absorption layer of the solar cell, the Au layer is an electrode layer, and the solar cell has the structure of ITO/CdS/AgIn_xSbS_(2+3x/2)(Se)/Au。

The above AgIn-based_xSbS_(2+3x/2)A method for manufacturing a (Se) thin film solar cell, comprising the steps of:

s1, cleaning the base material: using ITO glass as a base material, carrying out ultrasonic cleaning by using an alkaline detergent, and then carrying out ultrasonic cleaning by using deionized water;

s2, depositing a CdS buffer layer: depositing a CdS buffer layer with the thickness of about 150nm on an ITO substrate by adopting a chemical plating method, and then annealing for 5min at 400 ℃;

s3, depositing AgIn_xSbS_(2+3x/2)(Se) absorption layer:

preparing a spraying liquid:

(1) dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol: 0.25-1 mmol: 13-15 mL;

(2) dissolving antimony acetate in acetic acid to form a solution B, wherein the molar volume ratio of the antimony acetate to the acetic acid is 1mmol: 3.5-4 mL;

(3) mixing the solution A and the solution B, adding concentrated nitric acid with the mass concentration of 68%, finally adding acetic acid and thiourea, and mixing to form a spraying liquid, wherein the molar volume ratio of the thiourea to the acetic acid is 7.7-8 mmol:1mL, and the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid is 1mmol:1mmol:4mmol:80 mu L;

(II) depositing AgIn_xSbS_(2+3x/2)Film(s)

In N₂Under the environment, N₂The gas flow is 20-24L/min, and AgIn is deposited by ultrasonic spraying pyrolysis_xSbS_(2+3x/2)The feeding rate of the spraying liquid is 0.3mL/min, the deposition rate is 150nm/min, the deposition temperature is 330 ℃, and the deposition thickness is about 600 nm;

selenization (III)

AgIn is added_xSbS_(2+3x/2)Placing the film in a 380 ℃ high-temperature region of a heat treatment furnace, placing selenium powder in a 350 ℃ low-temperature region, and performing selenization for 6-9 min to obtain AgIn with the thickness of about 950nm_xSbS_(2+3x/2)(Se) thin films;

s4, depositing an Au electrode layer: au of about 60nm thickness was sputtered to AgIn with an ion sputter coater_xSbS_(2+3x/2)(Se) surface.

The invention has the following technical effects:

AgIn in the invention_xSbS_(2+3x/2)The (Se) film has high purity, good crystallinity, large crystal grain size and few defects such as holes, gaps and the like, the method reduces the damage of Se to the film structure, the prepared film has excellent compactness and uniformity, and the ITO/CdS/AgIn film taking the film as an absorption layer_xSbS_(2+3x/2)The (Se)/Au solar cell has excellent electrical property, and the Jsc reaches 20.65mA cm^-2FF reaches 42.8%, PEC reaches the maximum value of 1.98%, and EQE reaches 70%; the PCE has excellent stability, after being placed in an air environment for 7 weeks, the PCE is slightly reduced to 1.85% from 1.92% after being placed in a damp-heat environment for 7 days, and the severe environment hardly damages the performance of equipment, so that the foundation is laid for the subsequent research of people.

Drawings

FIG. 1: AgSbS₂Comparison of X-ray diffraction patterns before and after In addition.

FIG. 2: elemental profile prepared in inventive example 1.

FIG. 3: AgIn prepared by the invention_xSbS_(2+3x/2)SEM image of (Se) thin film.

FIG. 4: AgIn prepared by the invention_xSbS_(2+3x/2)(Se) film as absorbing layerJ-V curve of solar cell.

FIG. 5: AgIn prepared by the invention_xSbS_(2+3x/2)EQE profile of solar cell with (Se) thin film as absorber layer.

FIG. 6: AgIn prepared by the invention_xSbS_(2+3x/2)AC impedance diagram of solar cell with (Se) thin film as absorption layer

FIG. 7: AgIn prepared by the invention_xSbS_(2+3x/2)Stability profile of solar cells with (Se) thin films as absorber layers.

Detailed Description

The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.

Chemicals used in the present invention: silver nitrate (AgNO) produced by Aladdin chemical industry (Shanghai)₃Purity 99.95%), indium nitrate (InN)₃O₉Purity 99.99%), antimony acetate (C)₆H₉O₆Sb, purity 99.99%), thiourea (N)₂H₄CS, purity 99%), ethylene glycol monomethyl ether (C)₃H₈O₂99.7% mass concentration), acetic acid (C)₂H₄O₂99.7% mass concentration) and nitric acid (HNO)₃Mass concentration 68%).

Example 1

AgIn_xSbS_(2+3x/2)The preparation method of the (Se) thin film comprises the following steps:

preparing a spraying liquid:

(1) dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:1mmol: 15 mL;

(2) dissolving antimony acetate in acetic acid to form a solution B, wherein the molar volume ratio of the antimony acetate to the acetic acid is 1mmol:3.8 mL;

(3) mixing the solution A and the solution B, adding concentrated nitric acid with the mass concentration of 68%, finally adding acetic acid and thiourea, and mixing to form a spraying liquid, wherein the molar volume ratio of the thiourea to the acetic acid is 7.8mmol:1mL, and the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid is 1mmol:1mmol:4mmol:80 mu L;

(II) depositing AgIn_xSbS_(2+3x/2)Film(s)

In N₂Under the environment, N₂The gas flow is 24L/min, and AgIn is deposited by ultrasonic spraying pyrolysis_xSbS_(2+3x/2)The feeding rate of the spraying liquid is 0.3mL/min, the deposition rate is 150nm/min, and the deposition temperature is 330 ℃;

selenization (III)

AgIn is added_xSbS_(2+3x/2)The film is placed in a 380 ℃ high-temperature area of a heat treatment furnace, and selenium powder is placed in a 350 ℃ low-temperature area for selenization for 6 min.

Example 2

AgIn_xSbS_(2+3x/2)The preparation method of the (Se) thin film comprises the following steps:

preparing a spraying liquid:

(1) dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol: 0.25 mmol: 13 mL;

(2) dissolving antimony acetate in acetic acid to form a solution B, wherein the molar volume ratio of the antimony acetate to the acetic acid is 1mmol:3.5 mL;

(3) mixing the solution A and the solution B, adding concentrated nitric acid with the mass concentration of 68%, finally adding acetic acid and thiourea, and mixing to form a spraying liquid, wherein the molar volume ratio of the thiourea to the acetic acid is 8mmol:1mL, and the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid is 1mmol:1mmol:4mmol:80 mu L;

(II) depositing AgIn_xSbS_(2+3x/2)Film(s)

In N₂Under the environment, N₂The gas flow is 20L/min, and AgIn is deposited by ultrasonic spraying pyrolysis_xSbS_(2+3x/2)The feeding rate of the spraying liquid is 0.3mL/min, the deposition rate is 150nm/min, and the film is depositedThe temperature is 330 ℃;

selenization (III)

AgIn is added_xSbS_(2+3x/2)And placing the film in a 380 ℃ high-temperature area of a heat treatment furnace, placing selenium powder in a 350 ℃ low-temperature area, and performing selenization for 6-9 min.

Example 3

AgIn_xSbS_(2+3x/2)The preparation method of the (Se) thin film comprises the following steps:

preparing a spraying liquid:

(1) dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a solution A, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol: 0.55 mmol: 14 mL;

(2) dissolving antimony acetate in acetic acid to form a solution B, wherein the molar volume ratio of the antimony acetate to the acetic acid is 1mmol:4 mL;

(3) mixing the solution A and the solution B, adding concentrated nitric acid with the mass concentration of 68%, finally adding acetic acid and thiourea, and mixing to form a spraying liquid, wherein the molar volume ratio of the thiourea to the acetic acid is 7.7mmol:1mL, and the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid is 1mmol:1mmol:4mmol:80 mu L;

(II) depositing AgIn_xSbS_(2+3x/2)Film(s)

In N₂Under the environment, N₂The gas flow is 22L/min, and AgIn is deposited by ultrasonic spraying pyrolysis_xSbS_(2+3x/2)The film is formed by AgIn deposited at the feeding rate of 0.3mL/min, the deposition rate of 150nm/min and the deposition temperature of 330 DEG C_xSbS_(2+3x/2)The thickness of the film is 600 nm;

selenization (III)

AgIn is added_xSbS_(2+3x/2)Placing the film in 380 deg.C high temperature region of heat treatment furnace, placing selenium powder in 350 deg.C low temperature region, selenizing for 8min to obtain AgIn with thickness of 950nm_xSbS_(2+3x/2)(Se) thin film.

As can be seen from the XRD diffractogram of FIG. 1, the SRD patterns showed the same crystal structure before and after the addition of In, comparing AgSbS without In addition₂The purity of the film is not high, and the number of the film is threeThe splitting of the diffraction peak occurred, but after the addition of In, the splitting of the diffraction peak disappeared, the film showed a high-purity phase, and the intensity of the diffraction peak was higher, and the (200) diffraction peak was narrower, indicating that it had a lower full width at half maximum (FWHM), the grain size was increased, and the crystallinity became good.

FIG. 2 is a chemical composition distribution diagram (EDS), from which it can be seen that the composition of the thin film contains Ag, In, Sb, S and Se, which is AgIn by comparative analysis of the energy spectrum data_0.55SbS_2.825(Se), consistent with XRD results.

In FIG. 3, (a) and (b) are AgSbS without In addition In the order named₂(Se) thin film, and AgIn with x equal to 0.55_0.55SbS_2.825SEM image of (Se) thin film, (c) AgIn deposited on ITO/CdS surface_0.55SbS_2.825SEM image of cross section of (Se). It can be seen that, when In was not added, the surface gap was large and the densification was poor, and that, after In was added, the densification was improved and the film uniformity was excellent.

Example 4

Based on AgIn_xSbS_(2+3x/2)A method for manufacturing a (Se) thin film solar cell, comprising the steps of:

s1, cleaning the base material: using ITO glass as a base material, carrying out ultrasonic cleaning by using an alkaline detergent, and then carrying out ultrasonic cleaning by using deionized water;

s2, depositing a CdS buffer layer: depositing a CdS buffer layer with the thickness of about 150nm on an ITO substrate by adopting a chemical plating method, and then annealing for 5min at 400 ℃;

s3, depositing AgIn_xSbS_(2+3x/2)(Se) absorption layer:

AgIn with a total thickness of 950nm was prepared as in example 3_0.55SbS_2.825(Se)；

S4, depositing an Au electrode layer: au of about 60nm thickness was sputtered to AgIn with an ion sputter coater_xSbS_(2+3x/2)(Se) surface.

Table 1: AgIn with different In addition amounts_xSbS_(2+3x/2)Atomic percent of each element in (Se) thin film

As can be seen from Table 1, AgIn increased with In_xSbS_(2+3x/2)The atomic proportion of Se In the (Se) film is reduced, and the atomic proportion of S is gradually increased, which shows that with the addition of In, lattice gaps are filled, the permeation of Se into the lattice gaps is hindered, meanwhile, the substitution of Se for S is reduced, the damage effect of Se on the film is reduced, and the performance is improved, which is consistent with the performance of an SEM chart.

To study the In addition to AgSbS₂Effect of electrical properties of (Se) thin films hall effect measurements were performed at room temperature and the results are shown in table 2 below.

Table 2: AgIn_xSbS_(2+3x/2)Electrical parameter of (Se) (x ═ 0, 0.25, 0.40, 0.55, 0.70, 1.0)

After In addition, the Carrier concentration (Carrier concentration) of all thin films increased, wherein AgIn_0.55SbS_2.825The carrier concentration of (Se) thin film is increased by two orders of magnitude from 2.41X 10¹⁶cm^-3To 9.61X 10¹⁸cm^-3The Resistivity (Resistivity) of the film was reduced to 4.75X 10 as compared with that of the film to which In was not added³Omega, series resistance (Rs) from 15.86 omega cm as shown in Table 3²Reduced to 3.32. omega. cm²Jsc and photovoltaic performance of the device can be greatly improved.

Table 3: AgIn_xSbS_(2+3x/2)Solar cell device performance data with (Se) as absorber layer

Cell(ratio)	VOC(V)	JSC(mA cm-2)	FF	PCE(％)	RS(Ωcm2)
						AgSbS2(Se)	0.36±0.01	6.37±0.53	0.30±0.01	0.71±0.03	13.22±2.64
AgIn0.25SbS2(Se)	0.23±0.01	14.22±0.31	0.39±0.01	1.25±0.06	8.68±0.84
						AgIn0.40SbS2(Se)	0.22±0.01	17.16±0.21	0.35±0.01	1.32±0.11	8.90±0.57
AgIn0.55SbS2(Se)	0.22±0.01	19.95±0.70	0.42±0.06	1.85±0.13	4.62±1.30
						AgIn0.70SbS2(Se)	0.21±0.01	16.96±0.09	0.34±0.01	1.20±0.10	9.44±0.52
AgInSbS2(Se)	0.26±0.01	10.93±0.21	0.40±0.01	1.13±0.01	12.78±1.69

As shown In Table 3 and FIG. 4, AgSbs to which In was not added₂The open-circuit voltage (Voc) of the solar cell device having the absorbing layer (Se) was 0.37V, and the short-circuit current density (Jsc) was 6.9mA cm^-2The Fill Factor (FF) was 0.29, resulting In a photoelectric conversion efficiency PEC of 0.74%, while AgIn with In added_xSbS_(2+3x/2)(Se), with increasing In content, Voc decreases slightly, when x is 0.55, Jsc reaches 20.65mA cm^-2FF reached 42.8% and PEC reached a maximum of 1.98%. The photoresponse and the carrier transport performance can be proved by an EQE (photon absorption rate) spectrum, as shown In FIG. 5, the solar cell device without adding In has a narrower photoresponse wavelength range (350-The recombination rate is low, and the addition of In reduces the recombination loss and improves the interface quality. In order to research the influence of In on carrier transport, impedance analysis was performed on the material at a scanning frequency of 1Hz to 1MHz, as shown In FIG. 6, as In increases, the actual impedance Z' of the device showed a consistent trend, which indicates that the conductivity of the device is improved by adding indium, wherein AgIn_0.55SbS_2.825The highest conductivity of the device with (Se) as the absorption layer indicates that the addition of In increases the carrier concentration resulting In improved film performance.

And AgSbs₂Solar cell devices with (Se) thin films as absorber layers for comparison, AgIn_xSbS_(2+3x/2)The efficiency of the solar cell device with the (Se) film as the absorption layer is improved, the stability of the solar cell device is also improved, the prepared solar cell is stored for 7 weeks in a normal-temperature air environment, and then the solar cell device is transferred to a damp-heat condition (the temperature is 85 ℃ and the humidity is 85%) and placed for 7 days. AgIn prepared by the invention_0.55SbS₂The change in efficiency PCE of a solar cell device with (Se) as absorber layer as a function of storage time is shown in the figure, AgIn_0.55SbS₂After the (Se) device is placed in an air environment for 7 weeks and is placed in a damp-heat environment for 7 days, the PCE is slightly reduced from 1.92% to 1.85%, and the severe environment hardly damages the performance of equipment. In contrast, AgSbS₂PCE of solar cell devices with (Se) as an absorber layer is severely degraded after being stored for the same time in the same environment. It is clear that AgIn was prepared_xSbS_(2+3x/2)Solar cell ratio AgSbS with (Se) as absorption layer₂(Se) has better stability as an absorption layer, which is benefited by AgIn_xSbS_(2+3x/2)The (Se) thin film has better micro-morphology and crystallinity. We respectively try to adopt metals Ga (gallium), Sn (tin) and the like with similar chemical properties with In to replace In to participate In the preparation of the film, but the performance of the prepared film is still poor, the crystal grain size of the film is not changed greatly when the film is not added, the defect is not obviously improved, and the performance of the solar cell prepared as an absorption layer is AgSbS with no addition₂The (Se) increase is not significant.