CN110828602B - Antimony selenide thin film solar cell and preparation method thereof - Google Patents
Antimony selenide thin film solar cell and preparation method thereof Download PDFInfo
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- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000010409 thin film Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000010521 absorption reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims description 55
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 27
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 22
- 230000005540 biological transmission Effects 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 9
- 238000002207 thermal evaporation Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- YOXKVLXOLWOQBK-UHFFFAOYSA-N sulfur monoxide zinc Chemical compound [Zn].S=O YOXKVLXOLWOQBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000005092 sublimation method Methods 0.000 claims description 2
- BTWVLFJYEVGKNZ-UHFFFAOYSA-N S=O.[Cd] Chemical compound S=O.[Cd] BTWVLFJYEVGKNZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000004544 sputter deposition Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
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- 230000008022 sublimation Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L Cadmium chloride Inorganic materials Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 4
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 2
- FHKUNGMXAOFZLF-UHFFFAOYSA-L cadmium(2+) methanol dichloride Chemical compound CO.[Cl-].[Cd+2].[Cl-] FHKUNGMXAOFZLF-UHFFFAOYSA-L 0.000 description 2
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- 230000001276 controlling effect Effects 0.000 description 2
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- 239000003599 detergent Substances 0.000 description 2
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- 238000009210 therapy by ultrasound Methods 0.000 description 2
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0272—Selenium or tellurium
- H01L31/02725—Selenium or tellurium characterised by the doping material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/073—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1836—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising a growth substrate not being an AIIBVI compound
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Abstract
The invention relates to an antimony selenide film solar cell and a preparation method thereof, wherein a p-type antimony selenide seed layer is inserted into the antimony selenide thin film solar cell before a p-type antimony selenide absorption layer is grown, and the p-type antimony selenide seed layer and the p-type antimony selenide absorption layer are grown by adopting a single continuous thermal process, so that the crystal grain epitaxy and continuous growth are promoted, and a high-quality antimony selenide thin film with preferred orientation is realized, thereby effectively promoting the extraction and transportation of electrons, and further improving the energy conversion efficiency of an antimony selenide solar cell device.
Description
Technical Field
The invention relates to the field of photovoltaic new energy materials and devices, in particular to an antimony selenide thin-film solar cell and a preparation method thereof.
Background
The thin film solar cell has the advantages of flexibility, light weight, small material consumption, strong environmental adaptability and the like, and is the mainstream development direction of the current solar cell. The compound thin film solar cell mainly comprises a copper indium gallium selenide thin film solar Cell (CIGS) and a cadmium telluride solar cell (CdTe). At present, the latest photoelectric conversion efficiency of the copper indium gallium selenide thin-film solar cell exceeds that of a polycrystalline silicon solar cell. But because the content of indium and gallium in the raw materials of the copper indium gallium selenide thin-film solar cell is rare on the earth. The reserves are limited, the price is high, and due to the quaternary system, the production process is complex, the yield of the product needs to be improved, so the manufacturing cost of the copper indium gallium selenide thin-film solar cell is always high. Cadmium in the cadmium telluride solar cell has toxicity, rare tellurium resources, high production cost, harm to the environment and difficulty in large-scale application.
Compared with the two batteries, the antimony selenide thin-film solar battery has the characteristics of proper forbidden band width, good light absorption coefficient, simple preparation process, low growth temperature, cheap and nontoxic synthetic material and the like, and is an excellent photoelectric conversion material. In addition, the growth orientation of the antimony selenide thin film is found to have a great influence on the performance of the device in application. How to prepare antimony selenide thin films with excellent crystal orientation and solar cells thereof still remains a problem in the art.
In recent years, more and more research work has been directed towards controlling the growth orientation of antimony selenide thin films to achieve optimization of their photovoltaic properties. The patent provides a preparation method of an antimony selenide film with a seed layer assisted single continuous thermal process and a solar cell, and controllable preparation of the antimony selenide film with preferred orientation is realized by introducing and regulating the crystallinity of the seed layer, so that the cell performance is improved.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention mainly aims to provide an antimony selenide thin film solar cell and a preparation method thereof, and based on the aim, the invention at least provides the following technical scheme:
an antimony selenide thin-film solar cell comprises transparent conductive glass, a high-resistance layer, an n-type electron transmission layer, a p-type antimony selenide seed layer, a p-type antimony selenide absorption layer and a back electrode;
the high-resistance layer is positioned on the transparent conductive glass;
the n-type electron transmission layer is positioned on the high-resistance layer;
the p-type antimony selenide seed layer is positioned on the n-type electron transmission layer;
the p-type antimony selenide absorption layer is positioned on the p-type antimony selenide seed layer;
the back electrode is positioned on the p-type antimony selenide absorption layer;
wherein the p-type antimony selenide seed layer has crystallinity.
Furthermore, the thickness of the p-type antimony selenide seed layer is 1-20nm, and the thickness of the p-type antimony selenide absorption layer is 300-1000 nm.
Further, the n-type electron transport layer is an n-type semiconductor thin film, and the thickness of the n-type semiconductor thin film is 40-100 nm.
Further, the n-type semiconductor film is selected from cadmium sulfide, oxygen-doped cadmium sulfide, titanium dioxide, tin dioxide, zinc oxide, zinc sulfide or zinc oxysulfide; the transparent conductive glass consists of a glass substrate and a transparent conductive layer positioned on the glass substrate, wherein the transparent conductive layer is FTO, ITO or AZO, and the thickness of the transparent conductive layer is 200-400 nm.
Further, the high-resistance layer is a high-resistance transparent oxide layer, and the thickness of the high-resistance layer is 5-50 nm; the back electrode is a metal electrode with a high work function, and the thickness of the back electrode is 50-500 nm.
Further, the high-resistance transparent oxide is SnO2(ii) a The high work function metal electrode is gold, nickel or silver.
A preparation method of an antimony selenide thin film solar cell comprises the following steps:
preparing a high-resistance layer on a transparent conductive substrate;
preparing an n-type electron transport layer on the high-resistance layer;
preparing a p-type antimony selenide seed layer on the n-type electron transmission layer;
preparing a p-type antimony selenide absorption layer on the p-type antimony selenide seed layer;
preparing a back electrode on the p-type antimony selenide absorption layer;
the p-type antimony selenide seed layer and the p-type antimony selenide absorption layer are achieved through a single continuous thermal process, after deposition of the p-type antimony selenide seed layer is finished, the temperature of the substrate is reduced to 250-280 ℃, the temperature is kept unchanged for 2-10min, and then the temperature is increased to the deposition temperature of the p-type antimony selenide absorption layer.
Further, in the preparation step of the p-type antimony selenide seed layer, the substrate temperature is 300-330 ℃, and the deposition thickness of the p-type antimony selenide seed layer is 1-20 nm; in the preparation step of the p-type antimony selenide absorption layer, the substrate temperature is 270-370 ℃, and the deposition thickness of the p-type antimony selenide absorption layer is 300-1000 nm.
Further, the n-type electron transmission layer is a n-type CdS electron transmission layer, and after the preparation of the n-type electron transmission layer is finished, and before the preparation of the p-type antimony selenide seed layer, the n-type CdS electron transmission layer is subjected to heat treatment: pulling a layer of CdCl on the surface of the n-type electron transport layer2Then annealed in air, and then the CdCl is removed2。
Further, the preparation method of the antimony selenide seed layer comprises a thermal evaporation method, a magnetron sputtering method, a chemical vapor deposition method, a near space sublimation method and a carrier gas transportation method.
Compared with the prior art, the invention has at least the following beneficial effects:
the p-type antimony selenide seed layer is introduced before the p-type antimony selenide absorption layer grows, the nucleation growth condition on the surface of the substrate is changed, and fundamental influences are exerted on the nucleation density, the lattice orientation and the grain size of the film at the initial growth stage; in addition, the growth process of single continuous heating reduces the repeated nucleation on the crystal grain surface of the seed layer, promotes the crystal grain epitaxy and continuous growth, and improves the film quality, thereby effectively promoting the extraction and transportation of electrons and further improving the energy conversion efficiency of the antimony selenide solar cell device. The antimony selenide thin film solar cell obtained by the solar cell structure and the preparation method thereof has the performances of high photoelectric conversion efficiency, large short-circuit current and the like.
Drawings
Fig. 1 is a schematic structural diagram of an antimony selenide thin film solar cell of the invention.
FIG. 2 shows Sb prepared in example 2 of the present invention and comparative example2Se3Seed layer/Sb2Se3XRD profile of the absorption layer.
FIG. 3 is a J-V plot of antimony selenide solar cells prepared according to example 2 of the invention and a comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other. The present invention will be described in further detail below.
The structure of the antimony selenide thin-film solar cell provided by the invention is shown in fig. 1, and the antimony selenide thin-film solar cell comprises transparent conductive glass 1, a high-resistance layer 2, an n-type electron transmission layer 3, a p-type antimony selenide seed layer 4, a p-type antimony selenide absorption layer 5 and a back electrode 6 which are sequentially stacked. Wherein the p-type antimony selenide seed layer has crystallinity obtained by controlling the crystallization temperature of the seed layer, preferably, the crystallization temperature is 300-330 ℃.
The transparent conductive glass 1 is composed of a glass substrate and a transparent conductive layer positioned on the glass substrate, wherein the transparent conductive layer is FTO, ITO or AZO, and the thickness of the transparent conductive layer is 200-400 nm.
The high resistance layer 2 is in contact with the transparent conductive layer, the high resistance layer is a high-resistance transparent oxide layer, and the thickness of the high-resistance layer is 5-50 nm. In one embodiment, the high-resistance layer is SnO2。
The n-type electron transmission layer 3 is in contact with the high resistance layer 2, and the n-type electron transmission layer 3 is an n-type semiconductor thin film with a thickness of 40-100 nm. The n-type semiconductor film is selected from cadmium sulfide (CdS), oxygen-doped cadmium sulfide (CdS: O), titanium dioxide, tin dioxide, zinc oxide, zinc sulfide or zinc oxysulfide (ZnSO)x). The n-type semiconductor thin film is preferably CdS.
The p-type antimony selenide seed layer 4 is in contact with the n-type electron transmission layer 3, and the thickness of the p-type antimony selenide seed layer 4 is 1-20 nm.
The p-type antimony selenide absorption layer 5 is in contact with the p-type antimony selenide seed layer 4, and the thickness of the p-type antimony selenide absorption layer 5 is 300-1000 nm. The p-type antimony selenide seed layer 4 and the p-type antimony selenide absorption layer 5 are prepared through a single continuous thermal process, the single continuous thermal process means that after the deposition of the seed layer is finished, the temperature of the substrate is reduced to 250-280 ℃, the temperature is kept unchanged for 2-10min, then the temperature of the source is raised to a target temperature, the deposition of the absorption layer is carried out, and in the whole deposition process, the temperature of the substrate is kept above 250 ℃ all the time, so that the single continuous thermal process is guaranteed.
The back electrode 6 is in contact with the p-type antimony selenide absorption layer 5, is made of a high work function metal material, preferably any one of gold, nickel and silver, and has a thickness of 50-500 nm.
The following are specific examples
Example 1
The embodiment provides a preparation method of an antimony selenide thin film solar cell, which comprises the following steps: 1) cleaning FTO conductive glass:
placing the FTO in a solution prepared by the ratio of 3mL of detergent to 3L of deionized water, soaking for 1h, then washing with a large amount of deionized water, and then drying by using nitrogen.
2) Preparation of SnO2A high-resistance layer:
SnO preparation on FTO by radio frequency magnetron sputtering method2Film, the target material used is SnO2The background vacuum degree of the target is better than 5 multiplied by 10-3Pa, the sputtering gas is argon and oxygen, wherein the argon-oxygen ratio is 5%, the sputtering pressure is 0.4Pa, the sputtering power is 90W, and the substrate temperature is 200 ℃. SnO is treated before formal sputtering coating2And pre-sputtering the target for 10min to remove impurities adsorbed on the surface of the target. During sputtering coating, the substrate horizontally rotates along with the substrate to obtain a uniform and flat film, and the sputtering thickness is 35 nm.
3) Preparing a CdS n type electron transport layer:
and preparing the CdS electron transport layer by adopting a chemical water bath method. Firstly, the SnO is sputtered on a beaker measuring cylinder2The substrate is subjected to alcohol ultrasonic treatment for 10min and deionized water ultrasonic treatment for 10min twice, and solution preparation is started after cleaning. 940mL of distilled water is filled in a beaker, cadmium acetate, ammonium acetate and thiourea with the volume of 20mL are sequentially added after that, and ammonia water serving as a complexing agent is dripped in. Then the beaker is put into a water bath kettle with constant temperature, the growth is carried out at constant stirring speed, the precursor is decomposed after a while, and the solution starts to react. As the reaction proceeded, the solution began to appear colloidal, changed color from clear to cyan-yellow, then yellow, and finally the solution began to become cloudy. When the solution is yellow and has high turbidity, the solution is taken out, washed by a large amount of deionized water and dried by nitrogen. Wherein the thickness of the CdS is controlled to be 65-80 nm.
4) CdCl of CdS thin film2And (3) heat treatment:
firstly, the prepared FTO/SnO2The CdS substrate is soaked in a cadmium chloride methanol saturated solution and slowly pulled up at a constant speed in a nitrogen environment, so that a layer of CdCl is covered on the surface of CdS2Then, the substrate was placed in a tube furnace and annealed at 400 ℃ for 10min under air. CdCl2Is very soluble in water, and after the annealing treatment is finished, a large amount of deionized water is adopted to flush the substrateRemoval of CdCl2And then blowing the mixture by using nitrogen. CdCl in this step2The heat treatment of (2) can improve the heat treatment effect of the CdS film.
5) Preparation of Sb2Se3Seed layer:
preparation of Sb by using close-space sublimation equipment2Se3A seed layer. Setting the vacuum degree of the chamber to be less than 1 x 10-1Pa, the source is Sb2Se3Pressing the powder, and fixing CdS substrate tightly to graphite upper substrate, wherein CdS and Sb are2Se3The distance between the sources is about 3-10 mm. Placing the silicon wafer into a cavity of the equipment, vacuumizing, and depositing for 15s, wherein the source temperature is 500 ℃, the substrate temperature is 300 ℃. After the seed layer is deposited, the substrate is naturally cooled to 250-280 ℃ and is stabilized for 2-10 min.
6) Preparation of Sb2Se3An absorption layer:
keeping the temperature of the substrate in the step 5 constant, and continuously carrying out subsequent Sb2Se3And (4) preparing an absorption layer. Using close space sublimation equipment in Sb2Se3Deposition of Sb on seed layers2Se3A film. Vacuum degree lower than 1X 10-1Pa, the source is Sb2Se3Pressing the powder, fixing the CdS substrate close to the graphite upper substrate, setting the source temperature at 500 ℃, setting the substrate temperature at 270 ℃, ending the deposition for 5min, cooling the source and substrate to below 170 ℃, opening the cavity, and naturally cooling to 50-70 ℃ and taking out. Obtained Sb2Se3The thickness of the absorption layer is 470-480 nm.
7) And (3) gold-plated electrode evaporation:
by thermal evaporation in Sb2Se3And depositing a gold electrode on the absorption layer, wherein the thickness of the electrode is 100 nm.
Example 2
The embodiment provides a preparation method of an antimony selenide thin film solar cell, which comprises the following steps: 1) cleaning FTO conductive glass:
placing the FTO in a solution prepared according to the proportion of 3mL of detergent to 3L of deionized water, soaking for 1h, then washing with a large amount of deionized water, and then drying by using nitrogen;
2) preparation of SnO2Buffer layer:
SnO preparation on FTO by radio frequency magnetron sputtering method2Film, the target material used is SnO2The background vacuum degree of the target is better than 5 multiplied by 10-3Below Pa, the sputtering gas is argon and oxygen, wherein the argon-oxygen ratio is 5%, the sputtering pressure is 0.4Pa, the sputtering power is 90W, and the substrate temperature is 200 ℃. SnO is treated before formal sputtering coating2And pre-sputtering the target for 10min to remove impurities adsorbed on the surface of the target. During sputtering coating, the substrate horizontally rotates along with the substrate to obtain a uniform and flat film, and the sputtering thickness is 35 nm.
3) Preparing a CdS n type electron transport layer:
and preparing the CdS electron transport layer by adopting a chemical water bath method. Firstly, the SnO is sputtered on a beaker measuring cylinder2The substrate is ultrasonically cleaned by alcohol and deionized water, and then solution preparation is started. 940mL of distilled water is filled in a beaker, cadmium acetate, ammonium acetate and thiourea with the volume of 20mL are sequentially added after that, and ammonia water serving as a complexing agent is dripped in. Then the beaker is put into a water bath kettle with constant temperature, the growth is carried out at constant stirring speed, the precursor is decomposed after a while, and the solution starts to react. As the reaction proceeded, the solution began to appear colloidal, changed color from clear to cyan-yellow, then yellow, and finally the solution began to become cloudy. Wherein the thickness of the CdS is controlled to be 65-80 nm.
4) CdCl of CdS thin film2And (3) heat treatment:
firstly, the prepared FTO/SnO2The CdS substrate is soaked in a cadmium chloride methanol saturated solution and slowly pulled up at a constant speed in a nitrogen environment, so that a layer of CdCl is covered on the surface of CdS2Then putting the mixture into a tube furnace for annealing treatment at 400 ℃ for 10 min. CdCl2Is very soluble in water, and after the annealing treatment is finished, a large amount of deionized water is adopted to flush the substrate to remove CdCl2And then blowing the mixture by using nitrogen. CdCl in this step2The heat treatment of (2) can improve the heat treatment effect of the CdS film.
5) Preparation of Sb2Se3Seed layer:
by the use of heatPreparation of Sb by using thermal evaporation cavity in evaporation and near-space sublimation double-cavity equipment2Se3A seed layer. Vacuum degree less than 1 × 10-4Pa, regulating the current of the thermal evaporation cavity to 100A, evaporating for 20s, keeping the substrate temperature of 300 ℃ in the whole deposition process, and depositing Sb2Se3The seed layer is 10 nm. And after the deposition is finished, keeping the temperature of the substrate at 250-280 ℃ and keeping the temperature unchanged for 2-10 min.
6) Preparation of Sb2Se3An absorption layer:
vacuum transferring the substrate sample with the seed layer deposited to a near space cavity, and preparing Sb in the near space sublimation cavity2Se3An absorption layer. The source of the close space sublimation cavity is Sb2Se3Pressing the powder, fixing the substrate with the antimony selenide seed layer on the graphite upper substrate, wherein the substrate and Sb2Se3The distance between the sources is about 3-10 mm. And during deposition, the source temperature is 500 ℃, the substrate temperature is 290 ℃, the deposition is finished for 5min, the source and the substrate are cooled to be below 170 ℃, the cavity is opened, and the source and the substrate are naturally cooled to 50-70 ℃ and taken out. Obtained Sb2Se3The thickness of the absorption layer is 470-480 nm.
7) And (3) gold-plated electrode evaporation: by thermal evaporation in Sb2Se3And depositing a gold electrode on the absorption layer, wherein the thickness of the electrode is 100 nm.
Comparative example
Steps 1-4 are the same as in example 2.
5) Preparation of Sb2Se3Seed layer:
sb preparation by adopting thermal evaporation and near-space sublimation double-cavity equipment2Se3A seed layer. Vacuum degree less than 1 × 10-1Pa, regulating the current of the thermal evaporation cavity to 100A, evaporating for 20s, keeping the substrate temperature at 25 ℃ and depositing Sb2Se3Seed layer 15 nm.
6) Preparation of Sb2Se3An absorption layer:
sb preparation by adopting thermal evaporation and near-space sublimation double-cavity equipment2Se3An absorption layer. Will deposit Sb2Se3The substrate of the seed layer is sent into a close space sublimation cavityThe source of the space sublimation cavity is Sb2Se3Pressing the powder, fixing the substrate with the antimony selenide seed layer on the graphite upper substrate, wherein the substrate and Sb2Se3The distance between the sources is about 3-10 mm. And during deposition, the source temperature is 500 ℃, the substrate temperature is 290 ℃, the deposition is finished for 5min, and the chamber is opened when the temperature is reduced to 170 ℃ and is naturally reduced to 50-70 ℃ for taking out. The film thickness is 470-480 nm.
Step 7 is the same as in example 2. Thereby obtaining the antimony selenide thin film solar cell.
FIG. 2 shows Sb prepared in example 2 and comparative example at substrate temperatures of 300 ℃ and 25 ℃ respectively2Se3Seed layer/Sb2Se3XRD test graph of the absorption layer structure. From this figure, it can be seen that Sb obtained by the production method of example 22Se3The absorption layer exhibits (221) a preferred orientation of the lattice direction. Therefore, the introduction of the antimony selenide seed layer under specific growth conditions changes the nucleation growth condition of the substrate surface. In addition, the single continuous heating process reduces the repeated nucleation on the surface of the crystal grains of the seed layer, promotes the crystal grain epitaxy and continuous growth, and improves the quality of the film.
Two kinds of antimony selenide thin film solar cells prepared in example 2 and the comparative example were taken for performance testing. At AM 1.5, 100mW/cm2The J-V performance curve of the cell was tested with a solar simulator under illumination, as shown in fig. 3. The short-circuit current density of the antimony selenide thin-film solar cell prepared in the embodiment 2 is 26.2mA cm-2The open circuit voltage was 394.5mV, the fill factor was 58.8%, and the photoelectric conversion efficiency was 6.11%. The short-circuit current density of the antimony selenide thin film solar cell prepared by the comparative example is 9.9791mA cm-2The open circuit voltage was 359mV, the fill factor was 43.82%, and the photoelectric conversion efficiency was 1.57%. Therefore, the growth method of the single continuous heating process improves the device performance of the solar cell.
The antimony selenide film is prepared by adopting a seed layer assisted single continuous thermal process method, wherein the single continuous thermal process reduces repeated nucleation on the surface of crystal grains of the seed layer, promotes crystal grain epitaxy and continuous growth, improves the film quality and further improves the performance of the antimony selenide film solar cell device.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The antimony selenide thin film solar cell is characterized by comprising transparent conductive glass, a high-resistance layer, an n-type electron transmission layer, a p-type antimony selenide seed layer, a p-type antimony selenide absorption layer and a back electrode;
the high-resistance layer is positioned on the transparent conductive glass;
the n-type electron transmission layer is positioned on the high-resistance layer;
the p-type antimony selenide seed layer is positioned on the n-type electron transmission layer;
the p-type antimony selenide absorption layer is positioned on the p-type antimony selenide seed layer;
the back electrode is positioned on the p-type antimony selenide absorption layer;
wherein the p-type antimony selenide seed layer has crystallinity.
2. The antimony selenide thin film solar cell according to claim 1, wherein the thickness of the p-type antimony selenide seed layer is 1-20nm, and the thickness of the p-type antimony selenide absorption layer is 300-1000 nm.
3. The antimony selenide thin film solar cell according to claim 1 or 2, wherein the n-type electron transport layer is an n-type semiconductor thin film, and the thickness of the n-type semiconductor thin film is 40-100 nm.
4. The antimony selenide thin film solar cell according to claim 3, wherein the n-type semiconductor thin film is selected from cadmium sulfide, cadmium oxysulfide, titanium dioxide, tin dioxide, zinc oxide, zinc sulfide, or zinc oxysulfide; the transparent conductive glass consists of a glass substrate and a transparent conductive layer positioned on the glass substrate, wherein the transparent conductive layer is FTO, ITO or AZO, and the thickness of the transparent conductive layer is 200-400 nm.
5. The antimony selenide thin film solar cell according to claim 1 or 2, wherein the high-resistance layer is a high-resistance transparent oxide layer, and the thickness of the high-resistance layer is 5-50 nm; the back electrode is a metal electrode with a high work function, and the thickness of the back electrode is 50-500 nm.
6. The antimony selenide thin film solar cell according to claim 5, wherein the high-resistance transparent oxide is SnO2(ii) a The high work function metal electrode is gold, nickel or silver.
7. A preparation method of an antimony selenide thin film solar cell is characterized by comprising the following steps:
preparing a high-resistance layer on a transparent conductive substrate;
preparing an n-type electron transport layer on the high-resistance layer;
preparing a p-type antimony selenide seed layer on the n-type electron transmission layer;
preparing a p-type antimony selenide absorption layer on the p-type antimony selenide seed layer;
preparing a back electrode on the p-type antimony selenide absorption layer;
the p-type antimony selenide seed layer and the p-type antimony selenide absorption layer are achieved through a single continuous thermal process, after deposition of the p-type antimony selenide seed layer is finished, the temperature of the substrate is reduced to 250-280 ℃, the temperature is kept unchanged for 2-10min, and then the temperature is increased to the deposition temperature of the p-type antimony selenide absorption layer.
8. The method as claimed in claim 7, wherein in the step of preparing the p-type antimony selenide seed layer, the substrate temperature is 300-330 ℃, and the deposition thickness of the p-type antimony selenide seed layer is 1-20 nm; in the preparation step of the p-type antimony selenide absorption layer, the substrate temperature is 270-370 ℃, and the deposition thickness of the p-type antimony selenide absorption layer is 300-1000 nm.
9. The production method according to claim 7 or 8,
the n-type electron transmission layer is a n-type CdS electron transmission layer, and after the preparation of the n-type electron transmission layer is finished, and before the preparation of the p-type antimony selenide seed layer, the n-type CdS electron transmission layer is subjected to heat treatment: pulling a layer of CdCl on the surface of the n-type electron transport layer2Then annealed in air, and then the CdCl is removed2。
10. The method according to claim 7 or 8, wherein the antimony selenide seed layer is prepared by a method comprising a thermal evaporation method, a magnetron sputtering method, a chemical vapor deposition method, a near space sublimation method and a carrier gas transport method.
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