CN110819958A - Method for changing electrical properties of antimony selenide film and antimony selenide solar cell - Google Patents
Method for changing electrical properties of antimony selenide film and antimony selenide solar cell Download PDFInfo
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- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000000956 alloy Substances 0.000 claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 10
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000005457 optimization Methods 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005092 sublimation method Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 25
- 238000002202 sandwich sublimation Methods 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 10
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000011669 selenium Substances 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 238000004544 sputter deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000013077 target material Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 thio compound Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention provides a method for changing the electrical property of an antimony selenide film and an antimony selenide solar cell, wherein the method comprises the steps of depositing a metal layer on a substrate by a magnetron sputtering method or a thermal evaporation coating method, then depositing antimony selenide on the metal layer by a close-space sublimation method, and regulating the temperature of the substrate to be 250-450 ℃ when depositing antimony selenide, so that metal elements in the metal layer are diffused to the antimony selenide layer, thereby forming an antimony selenide alloy film and realizing the optimization of the electrical property of the antimony selenide film. In the film deposition process, the antimony selenide alloy film with better crystallization condition, smaller defect density and high carrier concentration is prepared by regulating and controlling the substrate temperature, and the process method has the advantages of simple operation, controllable conditions and adjustable electrical properties, and is suitable for further popularization and application.
Description
Technical Field
The invention relates to the technical field of semiconductor film preparation, in particular to a method for changing the electrical property of an antimony selenide film and an antimony selenide solar cell.
Background
Antimony selenide (Sb)2Se3) Due to the appropriate band gap (1.1-1.3 eV), high absorption coefficient (10)5cm-1) Low cost, no toxicity and the like, and is considered to be a promising absorption material of the thio compound photovoltaic device. Antimony selenide has a one-dimensional crystal structure and anisotropic optoelectronic properties that are of great interest.
The film forming quality of the absorption layer of the solar cell device based on the antimony selenide thin film is crucial to the performance of the device, and determines the highest efficiency which can be achieved by the device. One way to obtain a high quality antimony selenide absorber layer is to reduce the intrinsic point defects in antimony selenide and extend the lifetime of the electron carriers (antimony selenide carrier concentration of 10)13-1014cm-3). At present, the preparation process of the high-efficiency antimony selenide solar cell in each laboratory mainly comprises three steps: 1) by carrying out post-selenization treatment on antimony selenide, the selenium vacancy defect of an antimony selenide absorption layer in the thermal evaporation process is compensated, and the recombination loss in the device is reduced; 2) the antimony selenide film is deposited in a selenium-rich environment, so that a long carrier life and low interface defect and bulk defect films can be obtained; 3) the vapor deposition (VTD) technology is adopted to prepare the antimony selenide absorption layer, so that the density of main defects can be reduced by 1 order of magnitude. However, the open circuit voltage (Voc) of these high efficiency antimony selenide solar cells is in the range of 350-420mV, with low Voc still limiting Sb2Se3The main impediment to device performance. In addition, calculation by the first principle shows that Sb2Se3The intrinsic point defects of (a) are forced by their low symmetry, and it is difficult to suppress the formation of these deep complex defects merely by controlling the growth environment. Therefore, a method for changing the electrical property of antimony selenide is soughtAnd further, the solar cell device with high open-circuit voltage and high efficiency has important research significance.
Disclosure of Invention
The invention aims to provide a method for changing the electrical property of an antimony selenide film and an antimony selenide solar cell, and aims to solve the problems that the current carrier concentration of the existing antimony selenide solar cell is low, and the existing method is difficult to inhibit the formation of the deep recombination defect of the antimony selenide film.
The purpose of the invention is realized by the following technical scheme: a method for changing the electrical properties of an antimony selenide film comprises the steps of depositing a metal layer on a substrate through a magnetron sputtering method or a thermal evaporation coating method, then depositing antimony selenide on the metal layer through a near space sublimation method, regulating the temperature of the substrate to be 250-450 ℃ when depositing antimony selenide, and enabling metal elements in the metal layer to diffuse towards the antimony selenide layer, so that an antimony selenide alloy film is formed, and optimization of the electrical properties of the antimony selenide film is achieved.
The antimony selenide alloy thin film is (Sb)2Se3)x(ASbSe2)1-xWherein A represents Cu or Ag, and 0 < x < 1.
The substrate is glass or FTO deposited with a molybdenum back electrode.
The near-space sublimation method is characterized in that high-purity solid antimony selenide particles are ground into powder to prepare an evaporation source, and the temperature of the evaporation source is 400-550 ℃.
The thickness of the metal layer deposited on the substrate by the magnetron sputtering method or the thermal evaporation coating method is 1-10 nm.
An antimony selenide solar cell comprises the antimony selenide alloy thin film prepared by the method.
The solar cell sequentially comprises a glass substrate, a molybdenum electrode layer, an antimony selenide alloy film layer, a cadmium sulfide layer, a zinc oxide layer, an aluminum-doped zinc oxide layer and a gold electrode layer from bottom to top.
In the film deposition process, the antimony selenide alloy film with better crystallization condition, smaller defect density and high carrier concentration is prepared by regulating and controlling the substrate temperature, and the process method has the advantages of simple operation, controllable conditions and adjustable electrical properties, and is suitable for further popularization and application.
The low carrier concentration is one of the key factors for limiting the open-circuit voltage of an antimony selenide device, namely the antimony-based ternary compound (CuSbSe) of the invention2、AgSbSe2) Has rock salt crystal structure, and its electric properties are influenced by atom arrangement, so that its carrier concentration can be up to 1018-19cm-3. Compared with the prior art, the invention has the advantages that:
1) the preparation method is simple, and the substrate temperature can be accurately regulated and controlled in the preparation process; 2) the preparation process is pollution-free, and no toxic product is generated; 3) the antimony selenide film is prepared by adopting Close Space Sublimation (CSS), the adopted source is antimony selenide powder, the deposition rate is adjustable, and the material is saved; 4) the thickness of the deposited metal layer and the diffusion amount of the metal layer to the antimony selenide layer can be accurately controlled through the substrate temperature and the deposition time, and further the electrical property of the antimony selenide can be optimized and regulated.
Drawings
FIG. 1 shows (Sb)2Se3)x(AgSbSe2)1-xXRD test pattern of the alloy film.
FIG. 2 shows (Sb)2Se3)x(AgSbSe2)1-xHall test pattern of the alloy film.
FIG. 3 is (Sb)2Se3)x(CuSbSe2)1-xXRD test pattern of the alloy film.
Fig. 4 is a schematic structural diagram of the prepared alloy thin film solar cell. In the figure, 1 is a glass substrate, 2 is a molybdenum electrode layer, 3 is an antimony selenide alloy thin film layer, 4 is a cadmium sulfide layer, 5 is a zinc oxide layer, 6 is an aluminum-doped zinc oxide layer, and 7 is a silver electrode layer.
FIG. 5 is an I-V diagram of the prepared alloy thin film solar cell.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
Invention (Sb)2Se3)x(AgSbSe2)1-xThe preparation method of the film comprises the following steps:
a. the glass deposited with the molybdenum back electrode is used as a substrate, and the area of the substrate is 5 multiplied by 5cm2Fixing the substrate on a substrate table of a cavity of a magnetron sputtering device by taking high-purity silver as a target material, and vacuumizing the cavity to 10 DEG-4Pa, introducing Ar with the flow of 15sccm into the cavity, adjusting the interface valve to maintain the pressure in the cavity at 0.5Pa, turning on a radio frequency source for controlling the brightness of the silver target material, adjusting the power of the radio frequency source to 90W to enable the silver target material to be bright, and pre-sputtering for 3 min; and then formally sputtering for 15s to form a metal silver layer with the thickness of 10nm on the substrate.
b. Taking out the substrate with the deposited metal silver layer, fixing the substrate in a graphite box of Close Space Sublimation (CSS), setting the temperature of the substrate at 280 ℃, grinding high-purity solid antimony selenide particles into powder in advance and using the powder as an evaporation source, setting the temperature of an antimony selenide source at 510 ℃, vacuumizing for 10min by using a mechanical pump, and vacuumizing a cavity at 10 DEG-1Pa below, opening the temperature controllers of the substrate and the source simultaneously to start deposition, and taking out the substrate when the temperature is reduced to 160 ℃ after the deposition is finished, wherein the thickness of the prepared antimony selenide alloy film is about 1000 nm.
The prepared antimony selenide alloy thin film was subjected to electrical property (XRD, hall) tests, and the results are shown in fig. 1 and 2, respectively.
Examples 2 to 4
The temperature of the substrate during the deposition of antimony selenide by the Close Space Sublimation (CSS) process (see fig. 1 and 2 in particular) was changed, and the electrical properties (XRD, hall) of the prepared antimony selenide alloy thin film were measured by the same process parameters as in example 1, and the results are shown in fig. 1 and 2. As can be seen from the figure, when the substrate temperature is 280 ℃, the carrier concentration of the antimony selenide alloy thin film is 4.61 multiplied by 1017cm-3Much higher than the carrier concentration of pure antimony selenide film (10)13-1014cm-3) When the substrate temperature is 320 ℃, the carrier concentration is reduced to 3.87 multiplied by 10 due to the enhanced anisotropic electrical property in the antimony selenide16cm-1When the temperature of the substrate rises to 420 ℃, the AgSbSe is generated2Formation of a phase ofThe carrier concentration reaches 1.45 multiplied by 1018cm-1。
Example 5
Invention (Sb)2Se3)x(CuSbSe2)1-xThe preparation method of the film comprises the following steps:
high-purity copper particles are used as an evaporation source, a thermal evaporation mode is adopted to deposit a copper film of about 10nm on a glass or FTO substrate deposited with a Mo film with the thickness of 700nm, the temperature of a copper source is 1080 ℃, and the temperature of the substrate is normal temperature; and then depositing a layer of antimony selenide on the copper film by adopting a Close Space Sublimation (CSS) process, wherein the temperature of an antimony selenide source is 510 ℃, the temperature of a substrate is 320 ℃, and the thickness of the prepared antimony selenide alloy film is about 1000 nm. XRD test was carried out on the prepared antimony selenide alloy thin film, and the result is shown in FIG. 3.
Example 6
The invention selects silver target material, and the invention is applied to prepare the antimony selenide solar cell by changing the electrical property of antimony selenide, the cell comprises a glass substrate, a molybdenum electrode layer, an antimony selenide alloy film layer, a cadmium sulfide layer, a zinc oxide layer, an aluminum-doped zinc oxide layer and a gold electrode layer from bottom to top, and the structure is shown in figure 4.
The preparation process comprises the following steps:
(1) preparation of the substrate
Glass was used as a substrate, and the size was 5X 5cm2Firstly, soaking the glass in an electronic cleaning agent solution for 12 hours, then taking out the glass, then washing the glass with deionized water, and finally drying the glass with nitrogen.
(2) Deposited molybdenum back electrode
The Mo back electrode is prepared by adopting a magnetron sputtering technology, Ar gas is adopted as reaction gas, the sputtering pressure is 0.4 Pa, and the sputtering power density is about 4W/cm2The thickness of the prepared film is about 700nm, and the resistivity of the prepared film is about 3 multiplied by 10-5Ω•cm。
(3) Deposition of silver layer
And depositing a silver layer by adopting a magnetron sputtering technology. The glass deposited with the molybdenum back electrode is selected as a substrate, a high-purity silver target material is adopted as a source, Ar gas is adopted as a reaction gas, the sputtering pressure is 0.3 Pa, and the thickness of the prepared film is about 10 nm.
(3) Deposition of antimony selenide layer
And depositing the antimony selenide layer by adopting a Close Space Sublimation (CSS) process. Selecting a sample deposited with a silver layer as a substrate, setting the substrate temperature to be 280 ℃, 320 ℃, 350 ℃ and 420 ℃, respectively, grinding high-purity solid antimony selenide particles into powder to be used as an evaporation source, and setting the antimony selenide source temperature to be 510 ℃. At a vacuum degree of 10-1The deposition was started under Pa for 1min47s, and the thickness of the alloy film prepared was about 1000 nm.
(4) Deposition of cadmium sulfide layer
Depositing cadmium sulfide layer by chemical water bath method, putting the sample into solution prepared from cadmium salt, thiourea, ammonia water and buffer agent according to a certain proportion, placing the solution in constant temperature water bath, keeping the temperature at 70 deg.C, and stirring uniformly to obtain the final product with thickness of about 80 nm.
(5) Depositing an intrinsic ZnO layer
Depositing an intrinsic ZnO layer by magnetron sputtering with a sputtering power density of 1W/cm2The sputtering target material is an intrinsic ZnO target material with the purity of 4N, Ar gas is selected as sputtering gas, the sputtering pressure is about 0.5Pa, the substrate temperature is normal temperature, and the thickness is about 50 nm.
(6) Depositing an aluminum-doped zinc oxide layer
And depositing the aluminum-doped zinc oxide layer by adopting a magnetron sputtering technology, wherein the sputtering power density is 1W/cm 2, the sputtering target material is an aluminum-doped ZnO target material with the purity of 4N, Ar gas is selected as sputtering gas, the sputtering pressure is about 0.2Pa, the substrate temperature is normal temperature, and the thickness is about 300 nm.
(7) Depositing Au top electrode layer
Depositing Au top electrode layer by thermal evaporation technology, and vacuum cavity to 5 × 10-4After Pa, gold wire with a purity of 4N was used as a gold source and had a thickness of about 60 nm. As shown in fig. 5, the results of measuring the I-V curve of the solar cell show that the cell efficiency of the antimony selenide alloy thin film at 320 ℃ is the best as shown in fig. 5.
Claims (7)
1. A method for changing the electrical properties of an antimony selenide film is characterized in that a metal layer is deposited on a substrate through a magnetron sputtering method or a thermal evaporation coating method, then antimony selenide is deposited on the metal layer through a near space sublimation method, and when antimony selenide is deposited, the temperature of the substrate is regulated to 250-450 ℃, so that metal elements in the metal layer diffuse to the antimony selenide layer, the antimony selenide alloy film is formed, and the optimization of the electrical properties of the antimony selenide film is realized.
2. The method of claim 1, wherein the antimony selenide thin film comprises (Sb)2Se3)x(ASbSe2)1-xWherein A represents Cu or Ag, and 0 < x < 1.
3. The method of claim 1, wherein the substrate is a glass or FTO with a molybdenum back electrode deposited thereon.
4. The method for changing the electrical properties of the antimony selenide film as claimed in claim 1, wherein the near space sublimation method is carried out under the condition that the high-purity solid antimony selenide particles are ground into powder to prepare an evaporation source, and the temperature of the evaporation source is 400-550 ℃.
5. The method of claim 1, wherein the thickness of the metal layer deposited on the substrate by magnetron sputtering or thermal evaporation coating is 1-10 nm.
6. An antimony selenide solar cell, comprising the antimony selenide alloy thin film prepared by the method of any one of claims 1 to 5.
7. The antimony selenide solar cell according to claim 6, wherein the solar cell sequentially comprises a glass substrate, a molybdenum electrode layer, an antimony selenide alloy thin film layer, a cadmium sulfide layer, a zinc oxide layer, an aluminum-doped zinc oxide layer and a gold electrode layer from bottom to top.
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