CN110518081A - A kind of solar battery obsorbing layer and preparation method thereof and application - Google Patents
A kind of solar battery obsorbing layer and preparation method thereof and application Download PDFInfo
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- CN110518081A CN110518081A CN201910823846.8A CN201910823846A CN110518081A CN 110518081 A CN110518081 A CN 110518081A CN 201910823846 A CN201910823846 A CN 201910823846A CN 110518081 A CN110518081 A CN 110518081A
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- Prior art keywords
- film
- sodium thiosulfate
- preparation
- selenizing
- solar battery
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000005864 Sulphur Substances 0.000 claims abstract description 60
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 60
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 230000008021 deposition Effects 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 39
- 238000000137 annealing Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims description 40
- 239000011669 selenium Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- AUJJPYKPIQVRDH-UHFFFAOYSA-N antimony potassium Chemical compound [K].[Sb] AUJJPYKPIQVRDH-UHFFFAOYSA-N 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 87
- 238000000034 method Methods 0.000 abstract description 20
- 239000010409 thin film Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000000280 densification Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- MUYUEDVRJJRNOO-UHFFFAOYSA-N selanylidene(sulfanylidene)antimony Chemical compound S=[Sb]=[Se] MUYUEDVRJJRNOO-UHFFFAOYSA-N 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 229940007424 antimony trisulfide Drugs 0.000 description 2
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 2
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- GNZJTRGEKSBAAS-UHFFFAOYSA-N selanylideneantimony;selenium Chemical compound [Se].[Sb]=[Se].[Sb]=[Se] GNZJTRGEKSBAAS-UHFFFAOYSA-N 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 thio Sodium sulfate Chemical compound 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- 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
- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
-
- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of preparation methods of solar battery obsorbing layer, comprising the following steps: A) potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water, obtain deposition liquid；B) the deposition liquid carries out hydro-thermal reaction in substrate surface, obtains the sulphur selenizing Sb film for being compound in substrate surface；C) obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery obsorbing layer.The present invention goes out sulphur selenizing Sb film using hydro-thermal method Direct precipitation, is not necessarily to subsequent selenizing, solves the problems, such as that solwution method needs subsequent selenizing mostly.By changing the concentration of sodium thiosulfate and sodium thiosulfate in deposition liquid, adjusts the band gap of film with can be convenient, obtain the adjustable sulphur selenizing Sb film of band gap.It is compared with other methods, Preparation equipment of the present invention and simple process, crystalline property be good, thin film composition and thickness are easy to control, and film has good uniformity.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to a kind of solar battery obsorbing layer and preparation method thereof
And application.
Background technique
As a kind of inorganic light absorbing material, it is more and more that the application of sulphur antimony selenide in solar cells causes people
Concern.The storage of element contained by this kind of material is very rich, nontoxic, has biggish absorption coefficient (≈ 105cm-1) and suitable light
It learns band gap (1.03~1.8eV).Particular, it is important that the compound has good water, oxidative stability.Due to antimony trisulfide and selenium
Change antimony crystal structure having the same, the flexible tune of material band gap can be realized by adjusting the ratio of two kinds of elements of sulphur and selenium
Section, to obtain the light absorbing material with perfect optics band gap.Therefore, this kind of material has huge application prospect.
Currently, the method for preparing antimony trisulfide and selenizing Sb film mainly has vacuum method and solwution method.Vacuum method is to equipment
More demanding, obtained film composition may be uneven.Traditional solwution method is easy to operate, but crystalline property is poor, and big
Need subsequent selenizing, it is difficult to which a step prepares sulphur selenizing Sb film, complex process more.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of solar battery obsorbing layer and its preparation side
Method and application, the present invention prepare sulphur selenizing Sb film using one step of hydro-thermal method, have Preparation equipment and simple process, film
The advantages that good crystallinity, thin film composition and thickness are easy to control.
The present invention provides a kind of preparation methods of solar battery obsorbing layer, comprising the following steps:
A potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water), obtain deposition liquid；
B) the deposition liquid carries out hydro-thermal reaction in substrate surface, obtains the sulphur selenizing Sb film for being compound in substrate surface；
C) obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery absorption
Layer.
Preferably, step A) specifically:
Potassium antimony tartrate and sodium thiosulfate are dissolved in water, obtain mixed solution；
Sodium thiosulfate aqueous solution is added into the mixed solution, obtains depositing liquid needed for deposition sulphur selenizing Sb film.
Preferably, the sodium thiosulfate aqueous solution is flowed back at 90~98 DEG C by sodium sulfite solution and selenium powder and is obtained；
The concentration of the sodium thiosulfate aqueous solution is 0.1M~0.4M.
Preferably, the concentration of the deposition liquid mesotartaric acid antimony potassium is 0.015~0.04M, and concentration of sodium thiosulfate is
0.06~0.16M, the concentration of sodium thiosulfate are 0.00025~0.002M.
Preferably, the temperature of the hydro-thermal reaction is 110~180 DEG C, and the time is 1~5h.
Preferably, the substrate is selected from one of FTO, transparent electro-conductive glass；The substrate surface is also deposited with
CdS film.
Preferably, the temperature of the annealing is 300~380 DEG C, and the time of annealing is 5~30min.
The present invention also provides a kind of solar battery obsorbing layer that above-mentioned preparation method is prepared, chemical formula Sb2
(SxSe1-x)3, wherein 0 < x < 1.
The present invention also provides a kind of solar batteries, absorb including the solar battery that above-mentioned preparation method is prepared
Layer.
Compared with prior art, the present invention provides a kind of preparation methods of solar battery obsorbing layer, including following step
It is rapid: A) potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water, obtain deposition liquid；B) the deposition liquid is serving as a contrast
Bottom surface carries out hydro-thermal reaction, obtains the sulphur selenizing Sb film for being compound in substrate surface；C it) will obtain in an inert atmosphere
Sulphur selenizing Sb film made annealing treatment, obtain solar battery obsorbing layer.The present invention goes out sulphur using hydro-thermal method Direct precipitation
Selenizing Sb film is not necessarily to subsequent selenizing, solves the problems, such as that solwution method needs subsequent selenizing mostly.By changing sulphur in deposition liquid
The concentration of sodium thiosulfate and sodium thiosulfate adjusts the band gap of film in which can be convenient, and it is thin to obtain the adjustable sulphur antimony selenide of band gap
Film.It is compared with other methods, Preparation equipment of the present invention and simple process, crystalline property be good, thin film composition and thickness are easy control
System, and film has good uniformity.
Detailed description of the invention
Fig. 1 is the uv-visible absorption spectra of sulphur selenizing Sb film and the forbidden bandwidth of fitting in embodiment 1；
Fig. 2 is the scanning electron microscope diagram piece of sulphur selenizing Sb film in embodiment 1；
Fig. 3 is the XRD spectrum of sulphur selenizing Sb film in embodiment 1；
Fig. 4 is the uv-visible absorption spectra of sulphur selenizing Sb film and the forbidden bandwidth of fitting in embodiment 2；
Fig. 5 is the scanning electron microscope diagram piece of sulphur selenizing Sb film in embodiment 2；
Fig. 6 is the XRD spectrum of sulphur selenizing Sb film in embodiment 2；
Fig. 7 is the uv-visible absorption spectra of sulphur selenizing Sb film and the forbidden bandwidth of fitting in embodiment 3；
Fig. 8 is the scanning electron microscope diagram piece of sulphur selenizing Sb film in embodiment 3；
Fig. 9 is the XRD spectrum of sulphur selenizing Sb film in embodiment 3；
Figure 10 is the corresponding profile scanning electron microscope of embodiment 4；
Figure 11 is the corresponding profile scanning electron microscope of embodiment 5.
Specific embodiment
The present invention provides a kind of preparation methods of solar battery obsorbing layer, comprising the following steps:
A potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water), obtain deposition liquid；
B) the deposition liquid carries out hydro-thermal reaction in substrate surface, obtains the sulphur selenizing Sb film for being compound in substrate surface；
C) obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery absorption
Layer.
The method comprises the steps of firstly, preparing deposition liquid to obtain mixing molten specifically, potassium antimony tartrate and sodium thiosulfate are dissolved in water
Liquid；
Sodium thiosulfate aqueous solution is added into the mixed solution, obtains depositing liquid needed for deposition sulphur selenizing Sb film.
The sodium thiosulfate aqueous solution is flowed back at 90~98 DEG C by sodium sulfite solution and selenium powder and is obtained；
The concentration of the sodium thiosulfate aqueous solution is 0.1~0.4M, preferably 0.2~0.3M.
In the deposition liquid, the concentration of potassium antimony tartrate is 0.015~0.04M, preferably 0.02~0.035M；It is thio
Sodium sulfate concentration is 0.06~0.16M, and preferably 0.08~0.13M, the concentration of sodium thiosulfate is 0.00025~0.002M,
Preferably 0.001~0.0015M.
Then, the deposition liquid carries out hydro-thermal reaction in substrate surface, and the sulphur antimony selenide for obtaining being compound in substrate surface is thin
Film.
The substrate is selected from one of FTO, transparent electro-conductive glass；The substrate surface is also deposited with CdS film.
Specifically, first carrying out pre-treatment to substrate, wherein the substrate is one of FTO, transparent electro-conductive glass.
Substrate ultrapure water, ethyl alcohol, isopropanol, acetone are successively cleaned by ultrasonic 10~60min, oxygen plasma cleaning 10
~30min.
Then in substrate surface CdS thin films.
Then, the deposition liquid is poured into hydrothermal reaction kettle, the substrate for being deposited with CdS film is put into hydrothermal reaction kettle
In, control temperature is at 110~180 DEG C, and preferably 120~160 DEG C；Time is 1~5h, preferably 2~4h, obtains sulphur antimony selenide
Film.It carries out in hydrothermal reaction process, substrate is completely immersed in deposition liquid, and the angle of substrate surface and deposition liquid level is 0~90
Degree.Substrate is horizontally or diagonally or to be disposed vertically in hydrothermal reaction kettle.
Then, substrate is taken out with being dried with nitrogen.
Obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery absorption
Layer.
The inert gas environment is preferably nitrogen or argon gas.
The temperature of the annealing is 300~380 DEG C, and preferably 340~360 DEG C, the time of annealing is 5~30min, preferably
For 10~20min.
The annealing is selected from heating plate annealing or tube annealing.
The present invention also provides a kind of solar battery obsorbing layer that above-mentioned preparation method is prepared, chemical formula Sb2
(SxSe1-x)3, wherein 0 < x < 1.
The present invention also provides a kind of solar batteries, absorb including the solar battery that above-mentioned preparation method is prepared
Layer.The present invention is not particularly limited the structure and preparation method of solar battery, and well known to a person skilled in the art the sun
It can battery structure and preparation method.
The principle of the present invention is:
It 1) the use of potassium antimony tartrate is antimony source, sodium thiosulfate is sulphur source, and sodium thiosulfate is selenium source, takes water as a solvent and matches
System deposition liquid, the high quality sulphur selenizing Sb film of smooth densification is obtained using hydro-thermal reaction on substrate.
2) by changing the concentration of sodium thiosulfate and sodium thiosulfate, to control sulphur member in hydro-thermal reaction institute deposition film
The content of element and selenium element obtains the adjustable sulphur selenizing Sb film of band gap to adjust the band gap of film.
The invention has the following advantages:
1) there is patent report to cross and obtain precursor thin-film using solwution method, obtain the side of selenizing Sb film through high temperature selenizing
Method.The present invention directly obtains sulphur selenizing Sb film using hydro-thermal method, and manufacturing process is simpler, and preparation cost is low, is suitble to industry
Change large-scale production.
2) it is found through patent retrieval, this patent directly prepares sulphur selenizing Sb film using hydro-thermal method for the first time.
3) compared with the method reported, the sulphur antimony selenide crystalline property that the present invention obtains is good, the smooth cause of surface topography
Close, uniformity is good, can be used for preparing the photoelectric device of high quality.
4) by adjusting the dosage of sodium thiosulfate and sodium thiosulfate, the element of sulphur and selenium in film can flexibly be controlled
Ratio obtains the continuously adjustable sulphur selenizing Sb film of band gap.It, can be easily by adjusting dosage and the reaction time of each raw material
Control the ingredient and thickness of film.
For a further understanding of the present invention, below with reference to embodiment to solar battery obsorbing layer provided by the invention and its
Preparation method and application are illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
1) clean to FTO Conducting Glass: by substrate ultrapure water, ethyl alcohol, isopropanol, acetone, successively ultrasound is clear
15min is washed, oxygen plasma cleans 15min.One layer of CdS film is deposited on cleaning substrate.
2) by substrate slant setting in hydrothermal reaction kettle.It prepares deposition liquid: taking 50mL beaker, 40mL deionization is first added
Water is being added 0.2671g potassium antimony tartrate, is being stirred using stirrer to dissolution.Then 0.7936g sodium thiosulfate is added, stirs
The sodium thiosulfate solution that 100 μ L concentration are 0.1M is added after mixing 60s, continues to stir 120s, obtains deposition liquid.Liquid is deposited at this time
The concentration of mesotartaric acid antimony potassium is 0.02M, and the concentration of sodium thiosulfate is 0.08M, and the concentration of sodium thiosulfate is 0.00025M.
3) the deposition liquid that step 2) obtains is poured into hydrothermal reaction kettle, make substrate surface and deposits the angle 75 of liquid level
Degree, is put into baking oven for hydrothermal reaction kettle, 120 DEG C of heating 3h is arranged.After heating, taken out after hydrothermal reaction kettle natural cooling
It is deposited with the substrate of sulphur selenizing Sb film, is rinsed, is dried with nitrogen with deionized water and ethyl alcohol.
4) the sulphur selenizing Sb film that step 3) obtains is made annealing treatment in a nitrogen atmosphere.Selection is moved back using heating plate
Fire, annealing temperature is 350 DEG C, time 10min, to obtain the sulphur selenizing Sb film of smooth densification.
5) uv-visible absorption spectra of the sulphur selenizing Sb film obtained is as shown in Figure 1, to obtain its forbidden band by fitting wide
Degree is about 1.69eV.Surface topography picture that scanning electron microscope obtains as shown in Fig. 2, it can be seen that the smooth densification of film,
Crystallinity is fine.XRD spectrum is as shown in Figure 3 (peak marked in figure is substrate peak).
Embodiment 2
1) clean to FTO Conducting Glass: by substrate ultrapure water, ethyl alcohol, isopropanol, acetone, successively ultrasound is clear
15min is washed, oxygen plasma cleans 15min.One layer of CdS film is deposited on cleaning substrate.
2) by substrate slant setting in hydrothermal reaction kettle.It prepares deposition liquid: taking 50mL beaker, 40mL deionization is first added
Water is being added 0.2671g potassium antimony tartrate, is being stirred using stirrer to dissolution.Then 0.7936g sodium thiosulfate is added, stirs
The sodium thiosulfate solution that 200 μ L concentration are 0.1M is added after mixing 60s, continues to stir 120s, obtains deposition liquid.Liquid is deposited at this time
The concentration of mesotartaric acid antimony potassium is 0.02M, and the concentration of sodium thiosulfate is 0.08M, and the concentration of sodium thiosulfate is 0.0005M.
3) the deposition liquid that step 2) obtains is poured into hydrothermal reaction kettle, make substrate surface and deposits the angle 75 of liquid level
Degree, is put into baking oven for hydrothermal reaction kettle, 120 DEG C of heating 3h is arranged.After heating, taken out after hydrothermal reaction kettle natural cooling
It is deposited with the substrate of sulphur selenizing Sb film, is rinsed, is dried with nitrogen with deionized water and ethyl alcohol.
4) the sulphur selenizing Sb film that step 3) obtains is made annealing treatment in a nitrogen atmosphere.Selection is moved back using heating plate
Fire, annealing temperature is 350 DEG C, time 10min, to obtain the sulphur selenizing Sb film of smooth densification.
5) uv-visible absorption spectra of the sulphur selenizing Sb film obtained is as shown in figure 4, to obtain its forbidden band by fitting wide
Degree is about 1.58eV.Surface topography picture that scanning electron microscope obtains as shown in figure 5, it can be seen that the smooth densification of film,
Crystallinity is fine.XRD spectrum is as shown in Figure 6 (peak marked in figure is substrate peak).
Embodiment 3
1) clean to FTO Conducting Glass: by substrate ultrapure water, ethyl alcohol, isopropanol, acetone, successively ultrasound is clear
15min is washed, oxygen plasma cleans 15min.One layer of CdS film is deposited on cleaning substrate.
2) by substrate slant setting in hydrothermal reaction kettle.It prepares deposition liquid: taking 50mL beaker, 40mL deionization is first added
Water is being added 0.2671g potassium antimony tartrate, is being stirred using stirrer to dissolution.Then 0.7936g sodium thiosulfate is added, stirs
The sodium thiosulfate solution that 300 μ L concentration are 0.1M is added after mixing 60s, continues to stir 120s, obtains deposition liquid.Liquid is deposited at this time
The concentration of mesotartaric acid antimony potassium is 0.02M, and the concentration of sodium thiosulfate is 0.08M, and the concentration of sodium thiosulfate is 0.00075M.
3) the deposition liquid that step 2) obtains is poured into hydrothermal reaction kettle, make substrate surface and deposits the angle 75 of liquid level
Degree, is put into baking oven for hydrothermal reaction kettle, 120 DEG C of heating 3h is arranged.After heating, taken out after hydrothermal reaction kettle natural cooling
It is deposited with the substrate of sulphur selenizing Sb film, is rinsed, is dried with nitrogen with deionized water and ethyl alcohol.
4) the sulphur selenizing Sb film that step 3) obtains is made annealing treatment in a nitrogen atmosphere.Selection is moved back using heating plate
Fire, annealing temperature is 350 DEG C, time 10min, to obtain the sulphur selenizing Sb film of smooth densification.
5) uv-visible absorption spectra of the sulphur selenizing Sb film obtained is as shown in fig. 7, to obtain its forbidden band by fitting wide
Degree is about 1.40eV.Surface topography picture that scanning electron microscope obtains as shown in figure 8, it can be seen that the smooth densification of film,
Crystallinity is fine.XRD spectrum is as shown in Figure 9 (peak marked in figure is substrate peak).
Embodiment 4
1) clean to FTO Conducting Glass: by substrate ultrapure water, ethyl alcohol, isopropanol, acetone, successively ultrasound is clear
15min is washed, oxygen plasma cleans 15min.One layer of CdS film is deposited on cleaning substrate.
2) by substrate slant setting in hydrothermal reaction kettle.It prepares deposition liquid: taking 50mL beaker, 40mL deionization is first added
Water is being added 0.2671g potassium antimony tartrate, is being stirred using stirrer to dissolution.Then 0.7936g sodium thiosulfate is added, stirs
The sodium thiosulfate solution that 300 μ L concentration are 0.1M is added after mixing 60s, continues to stir 120s, obtains deposition liquid.Liquid is deposited at this time
The concentration of mesotartaric acid antimony potassium is 0.02M, and the concentration of sodium thiosulfate is 0.08M, and the concentration of sodium thiosulfate is 0.00075M.
3) the deposition liquid that step 2) obtains is poured into hydrothermal reaction kettle, make substrate surface and deposits the angle 75 of liquid level
Degree, is put into baking oven for hydrothermal reaction kettle, 135 DEG C of heating 3h is arranged.After heating, taken out after hydrothermal reaction kettle natural cooling
It is deposited with the substrate of sulphur selenizing Sb film, is rinsed, is dried with nitrogen with deionized water and ethyl alcohol.
4) the sulphur selenizing Sb film that step 3) obtains is made annealing treatment in a nitrogen atmosphere.Selection is moved back using heating plate
Fire, annealing temperature is 350 DEG C, time 10min, to obtain the sulphur selenizing Sb film of smooth densification.
5) the profile scanning electron microscope for obtaining film is as shown in Figure 10, and the thickness indicated in figure is successively right from top to bottom
Answer: sulphur selenizing Sb film, cadmium sulphide membrane, fluorine-doped tin dioxide thin film (FTO), wherein sulphur selenizing Sb film with a thickness of
138nm。
Embodiment 5
1) clean to FTO Conducting Glass: by substrate ultrapure water, ethyl alcohol, isopropanol, acetone, successively ultrasound is clear
15min is washed, oxygen plasma cleans 15min.One layer of CdS film is deposited on cleaning substrate.
2) by substrate slant setting in hydrothermal reaction kettle.It prepares deposition liquid: taking 50mL beaker, 40mL deionization is first added
Water is being added 0.4006g potassium antimony tartrate, is being stirred using stirrer to dissolution.Then 1.1904g sodium thiosulfate is added, stirs
The sodium thiosulfate solution that 300 μ L concentration are 0.1M is added after mixing 60s, continues to stir 120s, obtains deposition liquid.Liquid is deposited at this time
The concentration of mesotartaric acid antimony potassium is 0.03M, and the concentration of sodium thiosulfate is 0.12M, and the concentration of sodium thiosulfate is 0.00075M.
3) the deposition liquid that step 2) obtains is poured into hydrothermal reaction kettle, make substrate surface and deposits the angle 75 of liquid level
Degree, is put into baking oven for hydrothermal reaction kettle, 135 DEG C of heating 5h is arranged.After heating, taken out after hydrothermal reaction kettle natural cooling
It is deposited with the substrate of sulphur selenizing Sb film, is rinsed, is dried with nitrogen with deionized water and ethyl alcohol.
4) the sulphur selenizing Sb film that step 3) obtains is made annealing treatment in a nitrogen atmosphere.Selection is moved back using heating plate
Fire, annealing temperature is 350 DEG C, time 10min, to obtain the sulphur selenizing Sb film of smooth densification.
5) the profile scanning electron microscope for obtaining film is as shown in figure 11, and the thickness indicated in figure is successively right from top to bottom
Answer: sulphur selenizing Sb film, cadmium sulphide membrane, fluorine-doped tin dioxide thin film (FTO), wherein sulphur selenizing Sb film with a thickness of
243nm。
1, larger, the smooth densification, it was demonstrated that crystallinity and uniformity that can be seen that film crystal grain from the electromicroscopic photograph of embodiment
It is good；
2, embodiment 1-3 has adjusted the ratio that sodium thiosulfate and sodium thiosulfate is added, and obtains containing different sulphur selenium ratios
Film.The variation of thin film composition is embodied in the band gap that uv-visible absorption spectra obtains.Theoretically speaking due to vulcanization
Antimony (Sb2S3) band gap be 1.8eV, antimony selenide (Sb2Se3) band gap be 1.03eV, so for sulphur antimony selenide Sb2(SxSe1-x)
For 3, with the increase of Se content, band gap can reduce, and variation range is between 1.03-1.8eV.The selenium that embodiment 1-3 is added
The amount of sodium thiosulfate gradually increases, and obtained film band gap is gradually reduced, and illustrates that Se content gradually increases in film.Therefore, may be used
To prove, the ingredient of the amount regulation film of raw material is added by changing.
3, film can be made by a certain range, improving hydrothermal temperature, extend the hydro-thermal time or increasing raw material dosage
Thickness increases, and obtains the controllable film of thickness.The film Electronic Speculum cross-section diagram of embodiment 4,5 can prove this point.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of solar battery obsorbing layer, which comprises the following steps:
A potassium antimony tartrate, sodium thiosulfate and sodium thiosulfate are mixed with water), obtain deposition liquid；
B) the deposition liquid carries out hydro-thermal reaction in substrate surface, obtains the sulphur selenizing Sb film for being compound in substrate surface；
C) obtained sulphur selenizing Sb film is made annealing treatment in an inert atmosphere, obtains solar battery obsorbing layer.
2. preparation method according to claim 1, which is characterized in that step A) specifically:
Potassium antimony tartrate and sodium thiosulfate are dissolved in water, obtain mixed solution；
Sodium thiosulfate aqueous solution is added into the mixed solution, obtains depositing liquid needed for deposition sulphur selenizing Sb film.
3. preparation method according to claim 2, which is characterized in that the sodium thiosulfate aqueous solution is molten by sodium sulfite
Liquid and selenium powder flow back at 90~98 DEG C to be obtained；
The concentration of the sodium thiosulfate aqueous solution is 0.1M~0.4M.
4. preparation method according to claim 1, which is characterized in that it is described deposition liquid mesotartaric acid antimony potassium concentration be
0.015~0.04M, concentration of sodium thiosulfate are 0.06~0.16M, and the concentration of sodium thiosulfate is 0.00025~0.002M.
5. preparation method according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 110~180 DEG C,
Time is 1~5h.
6. preparation method according to claim 1, which is characterized in that the substrate is selected from FTO, transparent electro-conductive glass
One of；The substrate surface is also deposited with CdS film.
7. preparation method according to claim 1, which is characterized in that the temperature of the annealing is 300~380 DEG C, annealing
Time be 5~30min.
8. a kind of solar battery obsorbing layer that the preparation method as described in claim 1~7 any one is prepared, special
Sign is, chemical formula Sb2(SxSe1-x)3, wherein 0 < x < 1.
9. a kind of solar battery, which is characterized in that including the preparation method preparation as described in claim 1~7 any one
Obtained solar battery obsorbing layer.
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|---|---|---|---|---|
| CN111320395A (en) * | 2020-03-03 | 2020-06-23 | 中国科学技术大学 | Preparation method and application of selenium antimony sulfide film |
| CN111876809A (en) * | 2020-08-07 | 2020-11-03 | 中国科学技术大学 | Preparation method and application of antimony selenide film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861284A (en) * | 2007-09-14 | 2010-10-13 | 丰田自动车株式会社 | Single-crystal fine powder of sulfide or sulfide complex and method for preparing the same |
| CN105932114A (en) * | 2016-07-19 | 2016-09-07 | 福建师范大学 | Method for preparing solar cell absorbing layer film based on water bath and post-selenization |
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2019
- 2019-09-02 CN CN201910823846.8A patent/CN110518081B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861284A (en) * | 2007-09-14 | 2010-10-13 | 丰田自动车株式会社 | Single-crystal fine powder of sulfide or sulfide complex and method for preparing the same |
| CN105932114A (en) * | 2016-07-19 | 2016-09-07 | 福建师范大学 | Method for preparing solar cell absorbing layer film based on water bath and post-selenization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320395A (en) * | 2020-03-03 | 2020-06-23 | 中国科学技术大学 | Preparation method and application of selenium antimony sulfide film |
| CN111876809A (en) * | 2020-08-07 | 2020-11-03 | 中国科学技术大学 | Preparation method and application of antimony selenide film |
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