CN115966618A - Double-layer stacked sulfur antimony silver-based gradient film and preparation method thereof - Google Patents
Double-layer stacked sulfur antimony silver-based gradient film and preparation method thereof Download PDFInfo
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Abstract
A double-layer stacked S-Sb-Ag based gradient film, which is prepared from S-Sb-Ag (AgSbS) 2 ) AgIn prepared by adding indium (In) to substrate x Sb(S,Se) 2 For the first layer, antimony (Sb) was added to form AgSb 1+y (S,Se) 2 Is a second layer, wherein x =0.1 to 0.5, y =0.1 to 0.5. The double-absorption-layer gradient band gap AgIn of the invention x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The film has high purity, good crystallinity, large grain size, and few defects such as holes and gaps, and the combination of the double absorption layers keeps AgIn x Sb(S,Se) 2 Film heightOn the basis of short-circuit current, passing through the second layer of AgSb 1+y (S,Se) 2 The reduction of open-circuit voltage is reduced, and the efficiency of the whole solar cell is improved to be 3.5 percent at most by AgIn through the matching of the double absorption layers x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 ITO/CdS/AgIn with thin film as absorption layer 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 The Au solar cell has excellent electrical property, and Jsc reaches 17 mA-cm ‑2 Voc reaches 396.5mV and FF is 52.7%.
Description
Technical Field
The invention relates to the technical field of photovoltaic materials, in particular to a double-layer stacked sulfur-antimony-silver-based gradient film and a preparation method thereof.
Background
The sulfur antimony silver (AgSbS 2) is taken as an antimony-based ternary sulfur compound material, has a proper band gap of 1.4-1.7eV under near infrared and visible light, and has an absorption coefficient of 104-105cm under the near infrared and visible light -1 And the material is eco-friendly and nontoxic, and is a promising photovoltaic absorber. In recent years, a great deal of progress has been made in new absorber layer materials represented by antimony sulfide, but there is still a great gap in comparison with CdTe and CIGS, and some potential absorber layer materials such as Cu 2 SnS 3 ，CuSbS 2 ，CuSbSe 2 ，ZnSnN 2 Have also been investigated, but their efficiency is still less than expected. Due to AgSbS 2 First used as a P-type absorber layer, currently AgSbS 2 The solar cell has few reports, and the forbidden band width reported by P.K. Nair et al is 1.68eV, but the crystal grain size of the film is too small, so that the photoconductivity of the film is limited. Since the short circuit current (JSC) of the device was low and there was almost no photoelectric property, then j.o. gonzales et al found that the solution method prepared AgSb (S) x Se 1-x ) 2 The film has better photoelectric property. Based on AgSb (S) x Se 1-x ) 2 The PCE of the device of (3) is 2.7%,9.70mAcm -2 However, it should be noted that, although the photoelectric properties are improved, the thin film preparation process is very complicated and time-consuming. Recently, chengwu Shi et al prepared AgSbS that could be fully covered 2 The film is tightly connected with crystal grains, the size of the crystal grains is increased to about 5 microns, and the solar cell parameters are as follows: voc =440mV, jsc =10.49mA/cm 2 FF =0.45, η =2.09%. Chen Tao et al, spin coatedThe structure made by the chemical heat treatment process is FTO/TiO 2 /AgSbS 2 The solar cell efficiency of/spiro-OMeTAD/Au reaches 2.25 percent, and AgSbS 2 The microstructure of the film is uniform in appearance, the shape of crystal grains is regular, the size is about 3 microns, the short-circuit current is greatly improved, the battery efficiency is improved, and the film is the AgSbS 2 The highest solar cell efficiency of the absorption layer. It can be seen that for pure AgSbS 2 One of the ways to improve the electrical properties of the film is to optimize the preparation process, so that the film has higher crystallinity, larger grain size, uniform overall appearance and reduced defects.
In recent years, the AgSbS prepared by the ultrasonic spray pyrolysis method is adopted 2 The film contains AgSbS after being subjected to selenizing heat treatment 2 、AgSbSe 2 And AgSb (SxSe 1-x) 2 The gradient energy band structure is realized, the light absorption is greatly improved, and the efficiency of the solar cell device is improved from 0.27% to 1.30%. AgIn is prepared by adopting In element In CN113644146A In direct adding mode x SbS (2+3x/2) (Se) to obtain ITO/CdS/AgIn x SbS (2+3x/2) The solar cell efficiency of (Se)/Au is 1.98%, the maximum short-circuit current can reach 20.65mA/cm < 2 > (the maximum value reported so far), and the maximum short-circuit current is not far different from the theoretical maximum short-circuit current, but the device efficiency is not greatly improved due to the reduction of the open-circuit voltage.
Preparation of AgSbS by ultrasonic spray pyrolysis deposition (thermal spray method) 2 The (Se) film is simple to operate and high in preparation efficiency, the sprayed liquid falls on the substrate at a certain speed, and the preparation of the multi-component film is facilitated, but the prepared film has more holes and gaps, the grain size of the film is small, the film structure is damaged due to excessive selenization, the performance of the film is poor, and the efficiency of the (Se) film applied to a solar cell is still not ideal.
Disclosure of Invention
The invention aims to provide a double-layer stacked sulfur antimony silver-based gradient film. The open-circuit voltage is increased while ensuring a high short-circuit current, so that the efficiency is significantly improved.
The second object of the present invention is to provide a method for producing the above film.
The third purpose of the invention is to provide a solar cell taking the double-layer stacked S-Sb-Ag-based gradient 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 double-layer stacked S-Sb-Ag-based gradient film is characterized in that: the film is made of sulfur antimony silver (AgSbS) 2 ) AgIn prepared by adding indium (In) to substrate x Sb(S,Se) 2 AgSb prepared by adding antimony (Sb) as the first layer 1+y (S,Se) 2 Is a second layer, wherein x =0.1 to 0.5, y =0.1 to 0.5.
Further, preferably, the above x =0.5,y =0.25.
Further, the double-layer stacked sulfur-antimony-silver-based gradient film is prepared by preparing a spraying liquid 1 by using silver nitrate, indium nitrate, antimony acetate and thiourea as raw materials and spraying and depositing AgIn x SbS 2 As the first layer of film, preparing a spray solution 2 from silver nitrate, antimony acetate and thiourea in AgIn x SbS 2 Surface spray deposition of AgSb 1+y S 2 As a second thin film, followed by selenization to form AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The sulfur antimony silver-based gradient film is stacked in two layers.
Further, the spray deposition is on N 2 The gas flow is 20-24L/min, the feeding rate of the spraying liquid is 0.3mL/min, the deposition temperature is 330 ℃, the deposition rate is 150nm/min, each deposition time is 2min and is 1 period, and the first layer of film and the second layer of film are respectively sprayed for 2 periods.
Further, the spraying liquid 1 is prepared by dissolving silver nitrate and indium nitrate in ethylene glycol to form a solution 1, dissolving antimony acetate in acetic acid to form a solution 2, mixing the solution 1 and the solution 2, adding concentrated nitric acid with the mass concentration of 68%, and then adding acetic acid and thiourea to mix uniformly.
Further, the spraying liquid 2 is prepared by dissolving silver nitrate in ethylene glycol monomethyl ether to form a solution 3, dissolving antimony acetate in acetic acid to form a solution 4, mixing the solution 3 and the solution 4, adding concentrated nitric acid with the mass concentration of 68%, and then adding acetic acid and thiourea to mix uniformly.
A preparation method of a double-layer stacked S-Sb-Ag gradient film is characterized by comprising the following steps: preparing a spray solution 1 by using silver nitrate, indium nitrate, antimony acetate and thiourea as raw materials, and spraying and depositing AgIn x SbS 2 As the first layer of film, preparing a spray solution 2 from silver nitrate, antimony acetate and thiourea in AgIn x SbS 2 Surface spray deposition of AgSb 1+y S 2 As a second film, and then selenizing to form AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The sulfur antimony silver-based gradient film is stacked in two layers.
Further, the spray deposition is on N 2 The gas flow is 20-24L/min, the feeding rate of the spraying liquid is 0.3mL/min, the deposition temperature is 330 ℃, the deposition rate is 150nm/min, each deposition time is 2min and is 1 period, and the first layer of film and the second layer of film are respectively sprayed for 2 periods.
Further, the spraying solution 1 is prepared by dissolving silver nitrate and indium nitrate in ethylene glycol to form a solution 1, dissolving antimony acetate in acetic acid to form a solution 2, mixing the solution 1 and the solution 2, adding concentrated nitric acid with the mass concentration of 68%, and then adding acetic acid and thiourea to mix uniformly.
According to the invention, silver nitrate and indium nitrate are prepared into a solution 1, antimony acetate is separately dissolved into a solution 2 and then mixed, so that a precursor added with In is ensured to be generated, but not a structure that the In replaces Sb, thiourea is finally added, and a small amount of acetic acid is also 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 distributed, and the uniformity and compactness of a deposited film In the thermal spraying process are improved.
Further, in the spray coating liquid 1, the molar volume ratio of silver nitrate, indium nitrate and ethylene glycol monomethyl ether is 1mmol:0.1-0.5mmol:13 to 15mL.
Preferably, the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:0.5mmol:15mL.
Further, the molar volume ratio of silver nitrate, antimony acetate, thiourea and concentrated nitric acid in the spray solution 1 is 1mmol.
Further, the spraying liquid 2 is prepared by dissolving silver nitrate in ethylene glycol monomethyl ether to form a solution 3, dissolving antimony acetate in acetic acid to form a solution 4, mixing the solution 3 and the solution 4, adding concentrated nitric acid with the mass concentration of 68%, and then adding acetic acid and thiourea to mix uniformly.
Further, the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid in the spray solution 2 is 1mmol.
Preferably, the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid in the spray liquid 2 is 1mmol.
Further, the molar volume concentration of antimony acetate in acetic acid in the above solutions 2 and 4 was 0.29mol/L.
Further, the molar volume ratio of thiourea to acetic acid in the spray liquid 1 and the spray liquid 2 was 7.7 to 8mmol.
Further, the selenization is to place the film in a high temperature area of 380 ℃, place the selenium powder in a low temperature area of 350 ℃ and perform selenization for 6-9 min to form AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The sulfur antimony silver based gradient film is stacked in a two-layer stack.
Preferably, the selenization time is 8min.
Most specifically, the preparation method of the double-side stacked sulfur-antimony-silver-based gradient film is characterized by comprising the following steps of:
(I) preparing spraying liquid
(1) Dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a mixed solution 1, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the solution 1 and the solution 2, adding concentrated sulfuric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to form a spraying solution 1, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:0.1-0.5mmol: 13-15 mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7-8mmol;
(2) Dissolving silver nitrate in ethylene glycol monomethyl ether to form a mixed solution 3, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the mixed solution 3 with the mixed solution 4, adding concentrated nitric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to mix to form a spraying solution 2, wherein the molar volume ratio of the silver nitrate to the ethylene glycol monomethyl ether is 1mmol:15mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7-8mmol;
(II) spray-deposited film double-layer film
(1) In N 2 Under the environment, N 2 The gas flow is 20-24L/min, and AgIn is deposited by ultrasonic spraying pyrolysis x SbS 2 The feeding rate of the spraying liquid 1 is 0.3mL/min, the deposition rate is 150nm/min, each 2min is a period, the films are deposited for 2 periods together, and the deposition temperature is 330 ℃;
(2) Spraying liquid 2 in AgIn x SbS 2 The film is deposited AgSb under the same condition 1+y S 2 Film of AgIn forming a bilayer structure x SbS 2 /AgSb 1+y S 2 A film;
selenization (III)
AgIn is added x SbS 2 /AgSb 1+y S 2 The film is placed in a 380 ℃ high-temperature area of a heat treatment furnace, selenium powder is placed in a 350 ℃ low-temperature area, and selenization is carried out for 6-9 min to form AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The sulfur antimony silver based gradient film is stacked in a two-layer stack.
The research shows that the crystallinity and the phase purity of the film can be improved by adding indium and antimony simultaneously, the band structure of the sulfur antimony silver is changed by adding the sulfur antimony silver into the indium, the open-circuit voltage is reduced while the short-circuit current is improved, so that the efficiency is not greatly improved, so that the main problem of the sulfur antimony silver-based material as the absorption layer at present is how to improve the open-circuit voltage under the condition of keeping high short-circuit current, therefore, double absorption layers are designed, the sulfur antimony silver is taken as the base, the sulfur antimony silver added with the indium is taken as the first layer to ensure high short-circuit current, and the sulfur antimony silver added with the antimony is taken as the second layer to improve the open-circuit voltage.
Compared with the common doping chemical elements, the structure of the double-absorption layer is not changed integrally, and only some elements of a few position points are replaced by the doping elements, the indium element (In) and the antimony element (Sb) In the double-absorption layer are added into an Ag-Sb-S-Se system In a direct adding mode, and the elements are added into AgSbS 2 Under the condition of abundant anions (high thiourea ratio), atoms of the added elements enter the crystal lattice to form a homogeneous-phase compound macroscopically, the arrangement and thickness of two absorption layers can influence the movement of current carriers at an interface and In a film, the performance of the whole absorption layer is changed, in and Se are subjected to site competition In the selenization process, se vapor heat is diffused from the surface of the absorption layer to a CdS layer to form gradient distribution, the energy level distribution of the double absorption layer presents gradient and promotes the position change of the element atoms, the combination of the interface of the double absorption layer is promoted, and due to the fact that the added antimony elements and indium element atoms change the strength of a chemical bond In the crystal lattice, se is prevented from being stronger than pure S-Sb-Ag when substituting for S atoms, damage to the performance of the film caused by too much Se vapor entering the crystal lattice is inhibited, for example, a large amount of Se is diffused into the film, so that Sb elements are lost, the defects of the film are increased, and the generation of heterogeneous phases is increased.
AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The double-layer stacked sulfur-antimony-silver-based gradient film is a solar cell of an absorption layer, and is characterized in that: the solar cell structure is ITO/CdS/AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 /Au。
The above-mentioned material is AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The preparation method of the solar cell with the double-layer stacked sulfur-antimony-silver-based gradient film as the absorption layer is characterized by comprising the following steps of:
s1 cleaning ITO 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 deposited 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 preparation of AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 Absorbing layer
(I) preparing spraying liquid
(1) Dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a mixed solution 1, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the solution 1 and the solution 2, adding concentrated sulfuric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to form a spraying solution 1, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:0.1-0.5mmol: 13-15 mL, wherein the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7-8mmol;
(2) Dissolving silver nitrate in ethylene glycol monomethyl ether to form a mixed solution 3, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the mixed solution 3 with the mixed solution 4, adding concentrated nitric acid with a mass concentration of 68%, and finally adding acetic acid and thiourea to mix to form a spray coating solution 2, wherein the mass-volume ratio of the silver nitrate to the ethylene glycol monomethyl ether is 15mL, the molar volume concentration of the antimony acetate in the acetic acid is 0.29mol/L, the molar volume ratio of the thiourea to the acetic acid is 7.7-8mmol 1mL, and the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea to the concentrated nitric acid is 1mmol;
(II) spray-deposited film double-layer film
(1) In N 2 Under the environment, N 2 The air flow is 20 to 24L/min, and AgIn is deposited by ultrasonic spraying pyrolysis x SbS 2 The feeding rate of the spraying liquid 1 is 0.3mL/min, the deposition rate is 150nm/min, each 2min is a period, the films are deposited for 2 periods together, and the deposition temperature is 330 ℃;
(2) Spraying liquid 2 in AgIn x SbS 2 The film is deposited AgSb under the same conditions 1+y S 2 Film of AgIn forming a bilayer structure x SbS 2 /AgSb 1+y S 2 A film;
selenization (III)
AgIn is added x SbS 2 /AgSb 1+y S 2 The film is placed in a 380 ℃ high-temperature area of a heat treatment furnace, selenium powder is placed in a 350 ℃ low-temperature area, and selenization is carried out for 6-9 min to form AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The antimony sulfide silver based gradient film is stacked in a two-layer stack.
S4 depositing Au electrode layer
AgIn is coated by an ion sputtering coating machine x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 And an Au electrode layer with the thickness of 60nm is sputtered and deposited on the surface of the absorption layer.
The invention has the following technical effects:
the double-absorption-layer gradient band gap AgIn of the invention x Sb(S,Se) 2 /Sb 1+y (S,Se) 2 The film has high purity, good crystallinity, large crystal grain size, and few defects such as holes and gaps, and the combination of the double absorption layers keeps AgIn x Sb(S,Se) 2 On the basis of high short-circuit current of the thin film, passing through the AgSb of the second layer 1+y (S,Se) 2 The reduction of open-circuit voltage is reduced, the efficiency of the whole solar cell is improved to 3.5 percent at most by matching the double absorption layers, and the ITO/CdS/AgIn 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 The Au solar cell has excellent electrical property, and Jsc reaches 17 mA-cm -2 Voc reaches 396.5mV and FF is 52.7%. The method for preparing the double-absorption layer develops a new idea for preparing a solar cell with higher efficiency subsequently by people when the solar cell prepared by taking the sulfur-antimony-silver-based material as the absorption layer has the highest efficiency at present.
Drawings
FIG. 1: agIn with different spraying periods 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 XRD pattern of the film.
FIG. 2: agIn with different spraying periods 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 EQE profile of the film.
FIG. 3: different spraying periodAgIn prepared in preparation 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 Light absorption spectrum of the film.
FIG. 4 is a schematic view of: agIn with different spraying periods 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 Cross-sectional SEM image of thin film.
FIG. 5 is a schematic view of: agIn with different spraying periods 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 Surface SEM images of the films.
FIG. 6: J-V plots of solar cells with absorber layers prepared at different spray cycles.
FIG. 7: agIn prepared in different selenizing times 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 And the absorption layer corresponds to a J-V curve of the solar cell.
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 variations to the present invention based on the above disclosure.
Example 1
A preparation method of a double-side stacked S-Sb-Ag-based gradient film comprises the following steps:
(I) preparing spraying liquid
(1) Dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a mixed solution 1, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the solution 1 and the solution 2, adding concentrated sulfuric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to form a spraying solution 1, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:0.25mmol:13mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7 mmol;
(2) Dissolving silver nitrate in ethylene glycol monomethyl ether to form a mixed solution 3, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the mixed solution 3 with the mixed solution 4, adding concentrated nitric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to mix to form a spraying solution 2, wherein the mass-volume ratio of the silver nitrate to the ethylene glycol monomethyl ether is 1mmol:15mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7 mmol;
(II) spray-deposited film double-layer film
(1) At N 2 Under the environment, N 2 The gas flow is 20L/min, and AgIn is deposited by ultrasonic spraying pyrolysis 0.25 SbS 2 The feeding rate of the spraying liquid 1 is 0.3mL/min, the deposition rate is 150nm/min, each 2min is a period, the films are deposited for 2 periods together, and the deposition temperature is 330 ℃;
(2) Spraying liquid 2 in AgIn 0.25 SbS 2 The film is deposited AgSb under the same conditions 1.1 S 2 Film of AgIn forming a bilayer structure 0.25 SbS 2 /AgSb 1.1 S 2 A film;
selenization (III)
AgIn is added 0.25 SbS 2 /AgSb 1.1 S 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, and selenizing for 9min to obtain AgIn 0.25 Sb(S,Se) 2 /AgSb 1.1 (S,Se) 2 The sulfur antimony silver based gradient film is stacked in a two-layer stack.
Example 2
A preparation method of a double-side stacked S-Sb-Ag-based gradient film comprises the following steps:
preparing spraying liquid
(1) Dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a mixed solution 1, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the solution 1 and the solution 2, adding concentrated sulfuric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to form a spraying solution 1, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:0.4mmol:15mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 8mmol;
(2) Dissolving silver nitrate in ethylene glycol monomethyl ether to form a mixed solution 3, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the mixed solution 3 with the mixed solution 4, adding concentrated nitric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to mix to form a spraying solution 2, wherein the mass-volume ratio of the silver nitrate to the ethylene glycol monomethyl ether is 1mmol:15mL, the molar volume ratio of antimony acetate to acetic acid is 1mmol;
(II) spray-deposited film double-layer film
(1) In N 2 Under the environment, N 2 The air flow is 22L/min, and AgIn is deposited by ultrasonic spraying pyrolysis 0.4 SbS 2 The feeding rate of the spraying liquid 1 is 0.3mL/min, the deposition rate is 150nm/min, each 2min is a period, the films are deposited for 2 periods together, and the deposition temperature is 330 ℃;
(2) Spraying liquid 2 in AgIn 0.4 SbS 2 The film is deposited AgSb under the same condition 1.2 S 2 Film of AgIn forming a bilayer structure 0.4 SbS 2 /AgSb 1.2 S 2 A film;
selenization (III)
AgIn is added 0.4 SbS 2 /AgSb 1.2 S 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, and selenizing for 6min to obtain AgIn 0.4 Sb(S,Se) 2 /AgSb 1.2 (S,Se) 2 The sulfur antimony silver based gradient film is stacked in a two-layer stack.
Example 3
A preparation method of a double-side stacked S-Sb-Ag-based gradient film comprises the following steps:
(I) preparing spraying liquid
(1) Dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a mixed solution 1, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the solution 1 and the solution 2, adding concentrated sulfuric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to form a spraying solution 1, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:0.5mmol:15mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 8mmol;
(2) Dissolving silver nitrate in ethylene glycol monomethyl ether to form a mixed solution 3, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the mixed solution 3 with the mixed solution 4, adding concentrated nitric acid with a mass concentration of 68%, and finally adding acetic acid and thiourea to mix to form a spray coating solution 2, wherein the mass volume ratio of the silver nitrate to the ethylene glycol monomethyl ether is 15mL, the molar volume concentration of the antimony acetate in the acetic acid is 0.29mol/L, the molar volume ratio of the thiourea to the acetic acid is 8mmol;
(II) spray-deposited film double-layer film
(1) In N 2 Under the environment, N 2 The air flow is 24L/min, and AgIn is deposited by ultrasonic spraying pyrolysis 0.5 SbS 2 The feeding rate of the spraying liquid 1 is 0.3mL/min, the deposition rate is 150nm/min, each 2min is a period, the films are deposited for 2 periods together, and the deposition temperature is 330 ℃;
(2) Spraying liquid 2 in AgIn 0.5 SbS 2 The film is deposited AgSb under the same condition 1.25 S 2 Film of AgIn forming a bilayer structure 0.5 SbS 2 /AgSb 1.25 S 2 A film;
selenization (III)
AgIn is added 0.5 SbS 2 /AgSb 1.25 S 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, and selenizing for 8min to obtain AgIn 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 The sulfur antimony silver based gradient film is stacked in a two-layer stack.
Comparative example 1:
different from the embodiment 3By changing AgIn 0.5 SbS 2 Thin film and AgSb 1.25 S 2 Spraying period of film, preparing 4-period AgIn 0.5 SbS 2 Single layer thin film, 1 cycle AgIn 0.5 SbS 2 +3 period AgSb 1.25 S 2 Double-layer thin film, 3-cycle AgIn 0.5 SbS 2 +1 period AgSb 1.25 S 2 Bilayer thin film and 4 cycle AgSb 1.25 S 2 A single layer film.
FIG. 1 shows AgIn prepared in different periods 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 The XRD pattern of the film shows that the double absorption layer is relatively uniform after selenization, and the crystal form is between AgSbS 2 With AgSbSe 2 Between, is the solid solution AgSb (S, se) of the two 2 Multiple additions of indium or antimony atoms did not produce detectable second or hetero-phases, indicating that atoms of both elements have entered AgSb (S, se) 2 A homogeneous phase is formed In crystal lattices, but In the selenization process, in the longitudinal direction, due to the difference of the concentration and the diffusion rate of selenium contacted by a film layer, the longitudinal selenium atoms of the film are In gradient distribution, the distribution of other element atoms is also influenced to be In gradient, such as Sb, S and In elements, the interface of the double-layer absorption layer In the longitudinal direction is not obvious, and due to the thermal diffusion effect In the selenization process, the band gap of the whole film is In gradient distribution In the longitudinal direction, and the movement of current carriers is promoted. Comparative 4 cycles of AgIn 0.5 Sb(S,Se) 2 Monolayer film and AgSb 1.25 (S,Se) 2 The XRD pattern of the monolayer film shows a heterogeneous phase, which indicates that the phase purity is not high, and the single-layer film can be divided into AgSbS 2 With AgSbSe 2 Two phases and other compounds, which degrade the performance of the solar cell.
As is apparent from FIG. 2, agIn 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 Film AgIn with 2 period 0.5 Sb(S,Se) 2 +2 cycle AgSb 1.25 (S,Se) 2 The corresponding EQE value of the formed double-layer film is the highest and reaches more than 70 percent, and the single 4-period AgSb film 1.25 (S,Se) 2 Single layer film EQE lowest, followed by 4 cycles AgIn 0.5 Sb(S,Se) 2 A single layer film. As can be seen from FIG. 3 of the transmission spectrum, 2-cycle AgIn as the absorption layer of the bilayer stack 0.5 SbS 2 +2 cycle AgSb 1.25 S 2 The absorption layer can absorb most of the light, and can absorb light with the wavelength range of 1200nm and the near infrared region. Better light absorption leads to improved efficiency.
In FIG. 4, (a) is 4-cycle AgSb 1.25 (S,Se) 2 A single-layer film, and (b) 1-cycle AgIn 0.5 Sb(S,Se) 2 +3 cycle AgSb 1.25 (S,Se) 2 A bilayer film of (c) 2 cycle AgIn 0.5 Sb(S,Se) 2 +2 cycle AgSb 1.25 (S,Se) 2 A double-layer film of (d) 3-period AgIn 0.5 Sb(S,Se) 2 +1 cycle AgSb 1.25 (S,Se) 2 A double-layer film is formed; (e) 4 cycle AgIn 0.5 Sb(S,Se) 2 A single layer film; (b) The first layer AgIn can be clearly seen 0.5 Sb(S,Se) 2 With the second layer of AgSb 1.25 (S,Se) 2 The film sections are different, but the spraying speed is higher due to the same system, and due to the fact that atoms are diffused again after the selenizing heat treatment, the two layers are combined very tightly, no obvious interface exists, so that the carrier transmission is not greatly hindered, and the short-circuit current of the device is not greatly lost. First layer of AgIn 0.5 Sb(S,Se) 2 The CdS contact with the substrate has a more suitable energy band structure, the crystal material is fine, the crystal grains are transversely longer, the flaky laminating trend and the density are good as can be seen from the graph (e), and the second AgSb layer is AgSb 0.5 (S,Se) 2 The crystal grains are larger and have a certain tendency to be longer in the longitudinal direction, but are inferior to AgIn 0.5 Sb(S,Se) 2 Densification, (c) 2 cycle AgIn 0.5 Sb(S,Se) 2 +2 cycle AgSb 1.25 (S,Se) 2 The device has the highest efficiency, and the section of the device looks better in crystallinity and is tightly combined.
In FIG. 5, (a) is 4-cycle AgSb 1.25 (S,Se) 2 A single layer film; (b) Is 1 cycle AgIn 0.5 Sb(S,Se) 2 +3 cycle AgSb 1.25 (S,Se) 2 A double-layer film is formed; (c) Is 2 cycles of AgIn 0.5 Sb(S,Se) 2 +2 weeksPhase AgSb 1.25 (S,Se) 2 A double-layer film is formed; (d) Is 3 cycles of AgIn 0.5 Sb(S,Se) 2 +1 cycle AgSb 1.25 (S,Se) 2 A double-layer film is formed; (e) Is 4 periods AgIn 0.5 Sb(S,Se) 2 A single layer film; agIn is shown in the removal (e) diagram 0.5 Sb(S,Se) 2 Surface chart, the rest is AgSb 1.25 (S,Se) 2 Because the uppermost layer is AgSb 1.25 (S,Se) 2 The films, which have different thicknesses, have different morphologies after selenization, but are loose as a whole, and the uppermost surface has a tendency of grain dissolution, forming a structure similar to a net, and as can be seen from the cross section, the longitudinally grown morphology has the possibility of forming such morphology on the surface.
Example 4
AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The solar cell with the double-layer stacked S-Sb-Ag-based gradient film as the absorption layer has the structure of ITO/CdS/AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 /Au。
The above-mentioned AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The preparation method of the solar cell with the double-layer stacked sulfur-antimony-silver-based gradient film as the absorption layer comprises the following steps:
s1 cleaning of ITO substrate
Using ITO glass as a substrate, carrying out ultrasonic cleaning by using an alkaline detergent, and then carrying out ultrasonic cleaning by using deionized water;
s2 deposited 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 preparation of AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 Absorbing layer
AgIn was prepared according to the method of example 3 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 An absorbing layer;
s4 depositing Au electrode layer
AgIn is coated by an ion sputtering coating machine x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 And an Au electrode layer with the thickness of 60nm is sputtered and deposited on the surface of the absorption layer.
Comparative example 2
Unlike example 4, agIn 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 The absorption layer was prepared with 4 cycles of AgIn according to the same spraying cycle as in comparative example 1 0.5 Sb(S,Se) 2 Single layer thin film absorber layer, 1 cycle AgIn 0.5 Sb(S,Se) 2 +3 period AgSb 1.25 (S,Se) 2 Double-absorption layer, 3-cycle AgIn 0.5 Sb(S,Se) 2 +1 period AgSb 1.25 (S,Se) 2 Double absorption layer and 4-period AgSb 1.25 (S,Se) 2 And the single absorption layer corresponds to the solar cell.
The solar cell performance parameters of the films prepared by comparing different periods as the absorption layer are shown in table 1.
Table 1:
| period of spraying | Voc(mV) | Jsc(mA/cm 2 ) | FF(％) | PCE(％) |
| 4T(+Sb) | 25 | 2 | 21.23 | 0.009 |
| 1T(+In)+3T(+Sb) | 409 | 10 | 47.37 | 1.87 |
| 2T(+In)+2T(+Sb) | 396.5 | 17 | 52.7 | 3.5 |
| 3T(+In)+1T(+Sb) | 393.7 | 12 | 43.2 | 2.01 |
| 4T(+Sb) | 293.1 | 10 | 23.4 | 0.65 |
As can be seen from the graph of FIG. 6, agIn prepared in different spraying periods 0.5 Sb(S,Se) 2 /AgSb 1.25 (S,Se) 2 Solar cell with thin film as absorbing layer, wherein AgIn of 2 periods 0.5 Sb(S,Se) 2 +2 cycle AgSb 1.25 (S,Se) 2 The corresponding properties of the absorbent layer of the composition are optimal. And gradient change is formed through selenization to adjust the performance of the film in the solar cell.
In previous studies, 2T cycle AgSb alone was used 1.25 S 2 In the solar cell with the film as the absorbing layer, the short-circuit current Voc is more AgSbS 2 The solar cell with the film as the absorption layer is remarkably improvedHigh, so that the PCE also shows a certain improvement; because the Voc is greatly improved and the band gap is large, agSb is theoretically deposited on the surface of CdS firstly 1.25 S 2 The performance of the film is more excellent, so that in the preparation process, agSb is prepared on the surface of CdS in advance 1.25 S 2 Preparing AgIn as the first layer film 0.5 SbS 2 As a second layer film, the prepared solar cell has extremely poor performance, specifically, the prepared solar cell has serious attenuation such as short-circuit current, current density and the like, and AgSb 1.25 S 2 The energy band difference between the film and CdS is large, the interface combination is also poor, and the method is similar to the 4-period AgSb 1.25 (S,Se) 2 Single absorber layer solar cells. Due to AgSbS 2 The Conduction Band Offset (CBO) existing between the base absorption layer and the N-type buffer layer is used for limiting AgSbS 2 An important factor of the photoelectric conversion efficiency of the base thin film solar cell is that the band structure at the interface can be divided into two types: when the conduction band bottom of the P-type absorption layer is higher than the N-type buffer layer and is cliff type, the carrier recombination probability at the heterojunction interface is increased, and the solar cell V is caused oc And a decrease in FF; when the conduction band bottom of the P-type absorption layer is lower than that of the N-type buffer layer, the conduction band bottom is spike-shaped, an electron potential barrier is formed at the heterojunction interface, and the photocurrent is greatly reduced due to the fact that the height of the potential barrier is too large. For AgSbS 2 The N-type buffer layer of the thin-film solar cell mostly uses a CdS buffer layer and AgSbS 2 The position of a conduction band is higher than that of CdS by about 0.95eV, CBO is higher, the efficiency of the device is less ideal, and the energy band matching at a p-n interface is more proper as the sulfur antimony silver added with indium is greatly reduced to 0.16, which shows that the carrier recombination rate at the interface is lower, thereby leading to higher carrier transmission efficiency.
Example 5
Compared with example 4, the difference is that AgIn of a completed double-layer structure is prepared x SbS 2 /AgSb 1+y S 2 When selenization was performed on the thin film, the selenization time was changed to 6min, 7min, 9min and 10min, and the remaining steps were the same as in example 4.
As can be seen from FIG. 7, the performance of the corresponding thin film is the most excellent when selenizing is carried out for 8min.
Claims (10)
1. A double-layer stacked S-Sb-Ag-based gradient film is characterized in that: the film is made of sulfur antimony silver (AgSbS) 2 ) AgIn prepared by adding indium (In) to substrate x Sb(S,Se) 2 For the first layer, antimony (Sb) was added to form AgSb 1+y (S,Se) 2 Is a second layer, wherein x =0.1 to 0.5, y =0.1 to 0.5.
2. A method of making a two-layer stacked gradient film of antimony silver sulfide according to claim 1, wherein: preparing a spray solution 1 by using silver nitrate, indium nitrate, antimony acetate and thiourea as raw materials, and spraying and depositing AgIn x SbS 2 As the first layer of film, preparing a spraying liquid 2 from silver nitrate, antimony acetate and thiourea in AgIn x SbS 2 Surface spray deposition of AgSb 1+y S 2 As a second thin film, agIn was formed x SbS 2 /AgSb 1+y S 2 Double-layer film, and selenizing to obtain AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The sulfur antimony silver-based gradient film is stacked in two layers.
3. The method for preparing a bilayer stacked gradient film of S-Sb-Ag as claimed in claim 2, wherein: the spray deposition is in N 2 The air flow is 20-24L/min, the feeding rate of the spraying liquid is 0.3mL/min, the deposition temperature is 330 ℃, the deposition rate is 150nm/min, each deposition time is 2min and each deposition time is 1 period, and the first layer film and the second layer film are respectively sprayed for 2 periods.
4. The method for preparing a two-layer stacked S-Sb-Ag gradient film according to claim 2 or 3, wherein: the preparation method comprises the steps of dissolving silver nitrate and indium nitrate in ethylene glycol to form a solution 1, dissolving antimony acetate in acetic acid to form a solution 2, mixing the solution 1 and the solution 2, adding concentrated nitric acid with the mass concentration of 68%, adding acetic acid and thiourea, and uniformly mixing.
5. The method for preparing a two-layer stacked S-Sb-Ag gradient film according to claim 4, wherein: in the spraying liquid 1, the mol volume ratio of silver nitrate, indium nitrate and ethylene glycol monomethyl ether is 1mmol:0.1-0.5mmol:13 to 15mL, wherein the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid is 1mmol.
6. The method of any one of claims 2-5, wherein the method comprises the steps of: the preparation of the spraying liquid 2 comprises the steps of dissolving silver nitrate in ethylene glycol monomethyl ether to form a solution 3, dissolving antimony acetate in acetic acid to form a solution 4, mixing the solution 3 and the solution 4, adding concentrated nitric acid with the mass concentration of 68%, and then adding acetic acid and thiourea to be uniformly mixed.
7. The method for preparing a two-layer stacked S-Sb-Ag gradient film according to claim 6, wherein: the molar volume ratio of the silver nitrate, the antimony acetate, the thiourea and the concentrated nitric acid in the spray liquid 2 is 1mmol.
8. The preparation method of the double-side stacked S-Sb-Ag-based gradient film is characterized by comprising the following steps of:
preparing spraying liquid
(1) Dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a mixed solution 1, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the solution 1 and the solution 2, adding concentrated sulfuric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to form a spraying solution 1, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:0.1-0.5mmol:13 to 15mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7 to 8mmol;
(2) Dissolving silver nitrate in ethylene glycol monomethyl ether to form a mixed solution 3, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the mixed solution 3 with the mixed solution 4, adding concentrated nitric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to mix to form a spraying solution 2, wherein the mass-volume ratio of the silver nitrate to the ethylene glycol monomethyl ether is 1mmol:15mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7 to 8 mmol;
(II) spray-deposited film double-layer film
(1) In N 2 Under the environment, N 2 The air flow is 20 to 24L/min, and AgIn is deposited by ultrasonic spray pyrolysis x SbS 2 The feeding rate of the spraying liquid 1 is 0.3mL/min, the deposition rate is 150nm/min, each 2min is a period, the films are deposited for 2 periods together, and the deposition temperature is 330 ℃;
(2) Spraying liquid 2 in AgIn x SbS 2 The film is deposited AgSb under the same condition 1+y S 2 Film of AgIn forming a bilayer structure x SbS 2 /AgSb 1+y S 2 A film;
selenization (III)
AgIn is added x SbS 2 /AgSb 1+y S 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 selenizing for 6 to 9min to form AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The sulfur antimony silver based gradient film is stacked in a two-layer stack.
9. AgIn prepared by the method of claim 8 x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The double-layer stacked sulfur-antimony-silver-based gradient film is a solar cell of an absorption layer, and is characterized in that: the solar cell structure is ITO/CdS/AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 /Au。
10. The above-mentioned AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 The preparation method of the solar cell with the double-layer stacked S-Sb-Ag based gradient film as the absorption layer is characterized in thatThe method comprises the following steps:
s1 cleaning of ITO substrate
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 deposition 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 preparation of AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 Absorbing layer
Preparing spraying liquid
(1) Dissolving silver nitrate and indium nitrate in ethylene glycol monomethyl ether to form a mixed solution 1, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the solution 1 and the solution 2, adding concentrated sulfuric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to form a spraying solution 1, wherein the molar volume ratio of the silver nitrate to the indium nitrate to the ethylene glycol monomethyl ether is 1mmol:0.1 to 0.5mmol:13 to 15mL, wherein the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7 to 8mmol;
(2) Dissolving silver nitrate in ethylene glycol monomethyl ether to form a mixed solution 3, dissolving antimony acetate in acetic acid to form a mixed solution 2, mixing the mixed solution 3 with the mixed solution 4, adding concentrated nitric acid with the mass concentration of 68%, and finally adding acetic acid and thiourea to mix to form a spraying solution 2, wherein the molar volume ratio of the silver nitrate to the ethylene glycol monomethyl ether is 1mmol:15mL, the molar volume concentration of antimony acetate in acetic acid is 0.29mol/L, the molar volume ratio of thiourea to acetic acid is 7.7 to 8mmol, and the molar volume ratio of silver nitrate, antimony acetate, thiourea and concentrated nitric acid is 1mmol;
(II) spray-deposited film double-layer film
(1) In N 2 Under the environment, N 2 The air flow is 20 to 24L/min, and AgIn is deposited by ultrasonic spraying pyrolysis x SbS 2 The feeding speed of the spraying liquid 1 is 0.3mL/min, the deposition speed is 150nm/min, each 2min is a period, the deposition is carried out for 2 periods, and the deposition is carried outThe product temperature is 330 ℃;
(2) Spraying liquid 2 in AgIn x SbS 2 The film is deposited AgSb under the same condition 1+y S 2 Film of AgIn forming a bilayer structure x SbS 2 /AgSb 1+y S 2 A film;
selenization (III)
AgIn is added x SbS 2 /AgSb 1+y S 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 selenizing for 6-9min to form AgIn x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 Stacking the sulfur antimony silver-based gradient film in a double-layer stacking manner;
s4 depositing Au electrode layer
AgIn is coated by an ion sputtering coating machine x Sb(S,Se) 2 /AgSb 1+y (S,Se) 2 And an Au electrode layer with the thickness of 60nm is sputtered and deposited on the surface of the absorption layer.
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