CN110137272A - A kind of preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film - Google Patents

A kind of preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film Download PDF

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CN110137272A
CN110137272A CN201910398353.4A CN201910398353A CN110137272A CN 110137272 A CN110137272 A CN 110137272A CN 201910398353 A CN201910398353 A CN 201910398353A CN 110137272 A CN110137272 A CN 110137272A
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antimony
film
annealing
alcohol
trisulfide
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CN110137272B (en
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李炫华
韩剑
王双洁
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Northwestern Polytechnical University
Shenzhen Institute of Northwestern Polytechnical University
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Northwestern Polytechnical University
Shenzhen Institute of Northwestern Polytechnical University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/02Details
    • H01L31/0216Coatings
    • H01L31/02161Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/0248Semiconductor devices sensitive to infra-red 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
    • H01L31/0256Semiconductor devices sensitive to infra-red 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
    • H01L31/0264Inorganic materials
    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1864Annealing
    • YGENERAL 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
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a kind of preparation methods of the solar battery of alcohol steam after annealing processing antimony trisulfide base film, and antimony trisulfide light absorbing layer is handled using alcohol steam after annealing: the precursor solution of antimony is spin-coated on TiO2On electron transfer layer, after preparation vulcanization Sb film, after annealing processing is carried out to vulcanization Sb film using " alcohol steam after annealing processing method ".Compared with traditional preparation methods, it is more smooth that the invention enables film surfaces, meanwhile, in alcohol molecule, hydroxyl hydrogen and Sb in alcohol2S3The lone pair electrons of end S interact, and alcohol steam can be partly dissolved the crystal boundary of film, cause film grain growth, improve crystalline quality." alcohol steam after annealing processing method " significantly improves the short (V of open-circuit voltage of antimony trisulfide based thin film solar cellOC) road current density (JSC), fill factor (FF) and energy conversion efficiency (PCE).Compared with conventional anneal processing method, it is increased to 5.27% from 4.01% using antimony trisulfide based thin film solar cell incident photon-to-electron conversion efficiency prepared by this method, increases by 31.42% on a year-on-year basis.

Description

A kind of preparation of the solar battery of alcohol steam after annealing processing antimony trisulfide base film Method
Technical field
The invention belongs to solar cell device field, it is related to a kind of alcohol steam after annealing processing antimony trisulfide base film too The preparation method of positive energy battery.
Background technique
Environmental pollution and shortage of energy are the principal elements for restricting today's society economic development, to renewable, sustainable energy Source increasing need has become the power of Low-cost, stabilization, high performance solar batteries.Therefore, as copper-zinc-tin-selenium, A variety of semiconductors such as copper indium gallium selenide, vulcanized lead, hybrid inorganic-organic perovskite and antimony trisulfide are used as absorbed layer, obtain Excellent device transfer efficiency.In these materials, antimony trisulfide (Sb2S3) it is V-VI stable race's direct band gap of a kind of property half Conductor material is the main component of stibnite, and earth's crust rich content, the cost of material is low and nontoxic, absorption coefficient with higher (α=105cm-1), band gap width is moderate, is easy to regulate and control (1.5-2.2eV), covers most of visible light, therefore regarded To be most hopeful one of solar cell material being applied.
However, during preparing antimony trisulfide based thin film solar cell, vulcanization Sb film crystallite dimension is small and crystallinity Difference greatly affected the photoelectric properties of antimony trisulfide based thin film solar cell.For antimony trisulfide photoactive layer, annealing Be regulate and control crystalline property and crystallite dimension important means therefore suitable annealing method is selected to help to improve The photoelectric characteristic of battery.Currently, the annealing way used mainly has traditional type and program mode, but both methods cannot have Effect ground solves the problems, such as that vulcanization Sb film crystallite dimension is small and crystallinity is poor, and which has limited antimony trisulfide based thin film solar cell light The promotion and large-scale industrial application of electrotransformation efficiency.Therefore, we have developed one kind to be applied to antimony trisulfide based thin film solar The processing method of battery photoactive layer is completed at the same time to vulcanization Sb film crystallite dimension and crystalline improvement, to obtain height The antimony trisulfide based thin film solar cell of efficiency.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of alcohol steam after annealing processing antimony trisulfide base film Solar battery preparation method, with " alcohol steam after annealing processing method ", by select opposed polarity alcohol (isopropanol, Ethyl alcohol and methanol), and applied in vulcanization Sb film post anneal.
Technical solution
A kind of preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film, it is characterised in that step It is as follows:
The processing of step 1, FTO glass: conventional pretreatment is carried out to FTO glass;
The preparation of step 2, electron transfer layer: TiO is used2As electron transport material, electronics biography is prepared on FTO glass Defeated layer;
The alcohol steam after annealing processing of step 3, antimony trisulfide light absorbing layer: the precursor solution of antimony is spin-coated on TiO2Electronics In transport layer, after preparation vulcanization Sb film, vulcanization Sb film is carried out at after annealing using " alcohol steam after annealing processing method " Reason: the substrate of the precursor solution of spin coating antimony is placed on the warm table of small crucible, by the isopropanol, ethyl alcohol and first of 10-200 μ l Alcohol is respectively dropped into crucible, while being covered with culture dish rapidly, 100-400 DEG C of annealing 1-5min, to vulcanization Sb film into Row is solvent-free to be made annealing treatment to get antimony trisulfide light-absorption layer is arrived;
The preparation of step 4, hole transmission layer: by Spiro-OMeTAD solution vulcanization Sb film on Spiro-OMeTAD Layer;
Step 5, electrode vapor deposition: using hot evaporation instrument, and the Au that one layer of 100-120nm thickness is deposited on the hole transport layer carries on the back electricity Pole to get arrive antimony trisulfide based thin film solar cell.
The conventional pretreatment of the step 1: FTO glass is cleaned using cleanser, then it is used to deionized water, third respectively Ketone and dehydrated alcohol carry out ultrasonic treatment 5-15min, with being dried with nitrogen, are finally carried out UV processing 5-20min.
The step 2 prepares TiO on FTO glass2Electron transfer layer: with the rate of 1000-5000rpm/min, spin coating TiO2Solution makes annealing treatment 10-60min at 100-500 DEG C in air, then cools to room temperature, and obtains fine and close TiO2Electronics Transport layer.
The precursor solution of the antimony of the step 3 are as follows: the Sb of 1.0-2.0mmol2O3Powder, in the ethyl alcohol of 1.0-3.0mL The CS of diluted 1.0-2.5mL2It is mixed with the n- butylamine of 1.0-2.5mL, obtains the precursor solution of antimony.
The preparation of the step 3 vulcanizes Sb film: the processed FTO substrate of glass immigration of step 2 is had nitrogen protection In glove box, the precursor solution solution of antimony is added dropwise in TiO2On layer, with the rate spin coating 20- of 3000-9000rpm/min Then 80s heats 1-10min at 100-400 DEG C, obtain vulcanization Sb film.
The Spiro-OMeTAD solution of the step 4 are as follows: by the 4- tert .-butylpyridine 4-tert-butyl of 28 μ l Double trifluoromethanesulfonimide lithium Li-TFSI of pyridine and 17 μ l are added in 1mL chlorobenzene, and it is molten to obtain Spiro-OMeTAD Liquid;Double trifluoromethanesulfonimide lithium Li-TFSI are dissolved in 1ml acetonitrile with 520mg Li-TFSI;The component content For every part of metering.
The step 4 vulcanization Sb film on Spiro-OMeTAD layers: Spiro-OMeTAD solution is thin in antimony trisulfide With the rate spin coating 20-80s of 3000-9000rpm/min on film, 10- finally is made annealing treatment at 50-200 DEG C in air 30min is to get to Spiro-OMeTAD layers.
The Sb2O3Powder, CS2It is pure using analyzing with n- butylamine.
The ethyl alcohol uses excellent pure grade.
Beneficial effect
A kind of preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film proposed by the present invention, mentions A kind of entitled " alcohol steam after annealing processing method " is supplied.This method be by select opposed polarity alcohol (isopropanol, ethyl alcohol and Methanol), and applied in vulcanization Sb film post anneal, for " the alcohol steam after annealing processing method ", on the one hand, Grain boundaries lattice distortion is big, and there are crystal boundary energy, atom energy with higher vulcanizes crystal boundary in Sb film at a certain temperature Atom active is strong, is conducive to the migration of crystal boundary, and growing up for crystal grain is carried out by the migration of crystal boundary, so as to cause crystal grain It grows up.On the other hand, it since the alkyl on carbon atom in alcohol molecule, being connected directly with hydroxyl is fewer, pushes away electronic action and gets over Weak, hydrogen-oxygen bond polarity is stronger, and the activity of hydroxyl hydrogen is stronger, so hydroxyl hydrogen and Sb in methanol2S3The effect of medial end portions S Most strong, ethyl alcohol is secondly, isopropanol is most weak.In conclusion hydroxyl hydrogen and Sb in alcohol2S3The lone pair electrons of end S interact, and one Determine at temperature, alcohol steam is allowed to be partly dissolved the crystal boundary of film, to form liquid phase or quasi- liquid phase, the liquid phase or quasi- liquid Mutually play the role of " suture adhesive ", causes film grain growth, improve crystalline quality, to effectively improve antimony trisulfide base The photoelectric properties of thin-film solar cells.
Compared with traditional preparation methods, " alcohol steam after annealing processing method " provided by the invention uses the alcohol of opposed polarity (isopropanol, ethyl alcohol and methanol) carries out after annealing processing to vulcanization Sb film, so that film surface is more smooth, meanwhile, in alcohol In molecule, hydroxyl hydrogen and Sb in alcohol2S3The lone pair electrons of end S interact, and under certain temperature, alcohol steam can be partly dissolved The crystal boundary of film finally causes film grain growth, improves crystalline quality." alcohol steam after annealing processing method " significantly improves Short (the V of the open-circuit voltage of antimony trisulfide based thin film solar cellOC) road current density (JSC), fill factor (FF) and energy conversion Efficiency (PCE).Compared with conventional anneal processing method, the antimony trisulfide based thin film solar cell photoelectricity using this method preparation turns Change efficiency and be increased to 5.27% from 4.01%, increases by 31.42% on a year-on-year basis.
Detailed description of the invention
Fig. 1 is the antimony trisulfide based thin film solar cell structural representation of " alcohol steam after annealing processing method " of the invention preparation Figure.
Fig. 2 (a) is tender antimony trisulfide film scanning Electronic Speculum top view, and Fig. 2 (b), (c) and (d) are " alcohol steam after annealing The antimony trisulfide base film scanning electron microscope top view of processing method " preparation, wherein figure (b), (c) and (d) is respectively IPA vapor The antimony trisulfide film scanning Electronic Speculum top view of after annealing processing, the processing of alcohol vapour after annealing and the processing of methanol steam after annealing. Fig. 2 (e), (f), (g) and (h) are the statistics of the antimony trisulfide base film crystallite dimension of " alcohol steam after annealing processing method " preparation Distribution map, wherein figure (e), (f), (g) and (h) are respectively tender, the processing of IPA vapor after annealing, at alcohol vapour after annealing The statistical Butut of reason and the vulcanization Sb film crystallite dimension of methanol steam after annealing processing.
Fig. 3 is the present invention in solar energy spectrum energy AM 1.5G, 100mW/cm2Under illumination, antimony trisulfide based thin film solar Current density-voltage (J-V) performance diagram of battery.
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
A kind of antimony trisulfide based thin film solar cell, structure is by the fin oxide condutire glass (FTO) of fluorine doped, electron-transport Layer, antimony trisulfide light absorbing layer, hole transmission layer and back electrode are sequentially overlapped composition.
Using the preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film, it is characterised in that step It is as follows:
1) processing of FTO glass: FTO glass is cleaned using cleanser first, then it is used to deionized water, acetone respectively Ultrasonic treatment 5-15min is carried out with dehydrated alcohol, with being dried with nitrogen, is finally carried out UV processing 5-20min;
2) preparation of electron transfer layer: the present invention uses TiO2As electron transport material, which is being passed through into step 1) with the rate spin coating 20-80s of 1000-5000rpm/min on processed FTO glass, then in air at 100-500 DEG C 10-60min is made annealing treatment, is then slowly cooled to room temperature to get fine and close TiO is arrived2Layer;
3) preparation of antimony trisulfide light absorbing layer: the processed substrate of step 2) is moved into the glove box for having nitrogen protection. By Sb2O3Diluted CS in powder (1.0-2.0mmol, AR analysis are pure), ethyl alcohol (1.0-3.0mL, excellent pure grade GR)2(1.0- 2.5mL, AR) and n- butylamine (1.0-2.5mL, AR) be sufficiently mixed stirring, obtain the precursor solution of antimony.Then by the presoma Solution is added dropwise in TiO2On layer, with the rate spin coating 20-80s of 3000-9000rpm/min, 1- then is heated at 100-400 DEG C 10min then carries out after annealing processing to vulcanization Sb film using " alcohol steam after annealing processing method ", which is moved on to and is put Have on the warm table of small crucible, the isopropanol, ethyl alcohol and methanol of 10-200 μ l are respectively dropped into crucible, while rapidly with culture Ware lid is lived, 100-400 DEG C of annealing 1-5min, and tender vulcanizes Sb film and carries out solvent-free annealing to get antimony trisulfide is arrived Light-absorption layer.
4) preparation of hole transmission layer: 28 μ l 4- tert .-butylpyridines (4-tert-butyl pyridine) and 17 μ l are bis- Trifluoromethanesulfonimide lithium (Li-TFSI) (520mg Li-TFSI is dissolved in 1ml acetonitrile) is added in 1mL chlorobenzene, obtains Spiro-OMeTAD solution revolves the solution on step 3) vulcanization Sb film obtained with the rate of 3000-9000rpm/min Apply 20-80s, finally in air at 50-200 DEG C annealing 10-30min to get arriving Spiro-OMeTAD layers.
5) electrode is deposited: hot evaporation instrument is used, the Au back electrode of one layer of 100-120nm thickness is deposited on the hole transport layer, Obtain antimony trisulfide based thin film solar cell.
In order to make it easy to understand, being described further with exemplary embodiments and comparative example to technical solution of the present invention as follows:
Comparative example one: comparative example is using " no alcohol steam after annealing processing method " to vulcanization Sb film compared to the examples, After annealing processing is carried out, concrete operations are as follows,
1) processing of FTO glass: being first 15mm × 15mm by size, impedance is 14 Ω/sq FTO glass cleanser Cleaning, then carries out ultrasonic treatment 10min with deionized water, acetone and dehydrated alcohol respectively for it, with being dried with nitrogen, finally will It carries out UV and handles 15min;
2) preparation of electron transfer layer: the TiO that will be prepared2Solution by the processed FTO glass of step 1) with The rate spin coating 60s of 4000rpm/min then makes annealing treatment 40min at 400 DEG C in air, is then slowly cooled to room temperature, Obtain fine and close TiO2Layer;
3) preparation of antimony trisulfide light-absorption layer: the processed substrate of step 2) is moved into the glove box for having nitrogen protection.It will Sb2O3Diluted CS in powder (1.0mmol, AR), ethyl alcohol (2mL, GR)2(2mL, AR) and n- butylamine (1.5mL, AR) are sufficiently mixed Stirring is closed, the precursor solution of antimony is obtained, which is added dropwise in TiO2On layer, revolved with the rate of 8000rpm/min Apply 40s, 3min is then heated at 250 DEG C, finally the substrate is carried out at 300 DEG C solvent-free annealing 3min to get To antimony trisulfide light-absorption layer;
4) preparation of hole transmission layer: 28 μ l 4- tert .-butylpyridines (4-tert-butyl pyridine) and 17 μ l are bis- Trifluoromethanesulfonimide lithium (Li-TFSI) (520mg Li-TFSI is dissolved in 1ml acetonitrile) is added in 1mL chlorobenzene, obtains Spiro-OMeTAD solution, by the solution with the rate spin coating of 6000rpm/min on step 3) vulcanization Sb film obtained 60s, finally in air at 120 DEG C annealing 20min to get arriving Spiro-OMeTAD layers;
5) electrode be deposited: use hot evaporation instrument, on the hole transport layer be deposited one layer of 110nm thickness Au back electrode to get To antimony trisulfide based thin film solar cell.
The photoelectric properties test result of the battery: VOC、JSC, FF and PCE be respectively 0.57V ± 0.01,14.45mA/cm2± 0.25,48.67% ± 0.49,4.01% ± 0.14.
Using the embodiment of the method for the present invention:
Embodiment one:
1) processing of FTO glass: being first 15mm × 15mm by size, impedance is 14 Ω/sq FTO glass cleanser Cleaning, then carries out ultrasonic treatment 10min with deionized water, acetone and dehydrated alcohol respectively for it, with being dried with nitrogen, finally will It carries out UV and handles 15min;
2) preparation of electron transfer layer: the TiO that will be prepared2Solution by the processed FTO glass of step 1) with The rate spin coating 60s of 4000rpm/min then makes annealing treatment 40min at 400 DEG C in air, is then slowly cooled to room temperature, Obtain fine and close TiO2Layer;
3) preparation of antimony trisulfide light-absorption layer: the processed substrate of step 2) is moved into the glove box for having nitrogen protection.It will Sb2O3Diluted CS in powder (1.0mmol, AR), ethyl alcohol (2mL, GR)2(2mL, AR) and n- butylamine (1.5mL, AR) are sufficiently mixed Stirring is closed, the precursor solution of antimony is obtained, which is added dropwise in TiO2On layer, revolved with the rate of 8000rpm/min 40s is applied, heats 3min at 250 DEG C then to get antimony trisulfide light-absorption layer is arrived.Then " alcohol steam after annealing processing method " is used After annealing processing is carried out to vulcanization Sb film, which is moved on on the warm table for being placed with small crucible, the isopropanol of 81 μ l is dripped Enter in crucible, while being covered with culture dish rapidly, 300 DEG C of annealing 3min are handled to get to through IPA vapor after annealing Antimony trisulfide light-absorption layer.
4) preparation of hole transmission layer: 28 μ l 4- tert .-butylpyridines (4-tert-butyl pyridine) and 17 μ l are bis- Trifluoromethanesulfonimide lithium (Li-TFSI) (520mg Li-TFSI is dissolved in 1ml acetonitrile) is added in 1mL chlorobenzene, obtains Spiro-OMeTAD solution, by the solution with the rate spin coating of 6000rpm/min on step 3) vulcanization Sb film obtained 60s, finally in air at 120 DEG C annealing 20min to get arriving Spiro-OMeTAD layers;
5) electrode be deposited: use hot evaporation instrument, on the hole transport layer be deposited one layer of 110nm thickness Au back electrode to get To the antimony trisulfide based thin film solar cell through IPA vapor after annealing.
The photoelectric properties test result of the battery are as follows: VOC、JSC, FF and PCE be respectively 0.58V ± 0.03,15.72mA/cm2 ± 0.28,50.08% ± 0.50,4.57% ± 0.13;
Embodiment two:
1) processing of FTO glass: being first 15mm × 15mm by size, impedance is 14 Ω/sq FTO glass cleanser Cleaning, then carries out ultrasonic treatment 10min with deionized water, acetone and dehydrated alcohol respectively for it, with being dried with nitrogen, finally will It carries out UV and handles 15min;
2) preparation of electron transfer layer: the TiO that will be prepared2Solution by the processed FTO glass of step 1) with The rate spin coating 60s of 4000rpm/min then makes annealing treatment 40min at 400 DEG C in air, is then slowly cooled to room temperature, Obtain fine and close TiO2Layer;
3) preparation of antimony trisulfide light-absorption layer: the processed substrate of step 2) is moved into the glove box for having nitrogen protection.It will Sb2O3Diluted CS in powder (1.0mmol, AR), ethyl alcohol (2mL, GR)2(2mL, AR) and n- butylamine (1.5mL, AR) are sufficiently mixed Stirring is closed, the precursor solution of antimony is obtained, which is added dropwise in TiO2On layer, revolved with the rate of 8000rpm/min 40s is applied, heats 3min at 250 DEG C then to get antimony trisulfide light-absorption layer is arrived.Then " alcohol steam after annealing processing method " is used After annealing processing is carried out to vulcanization Sb film, which is moved on on the warm table for being placed with small crucible, the ethyl alcohol of 40 μ l is instilled It in crucible, while being covered with culture dish rapidly, 300 DEG C of annealing 3min are to get to the sulphur handled through alcohol vapour after annealing Change antimony light-absorption layer.
4) preparation of hole transmission layer: 28 μ l 4- tert .-butylpyridines (4-tert-butyl pyridine) and 17 μ l are bis- Trifluoromethanesulfonimide lithium (Li-TFSI) (520mg Li-TFSI is dissolved in 1ml acetonitrile) is added in 1mL chlorobenzene, obtains Spiro-OMeTAD solution, by the solution with the rate spin coating of 6000rpm/min on step 3) vulcanization Sb film obtained 60s, finally in air at 120 DEG C annealing 20min to get arriving Spiro-OMeTAD layers;
5) electrode is deposited: electrode vapor deposition: using hot evaporation instrument, and the Au back of one layer of 110nm thickness is deposited on the hole transport layer Electrode to get arrive the antimony trisulfide based thin film solar cell through alcohol vapour after annealing.
The photoelectric properties test result of the battery are as follows: VOC、JSC, FF and PCE be respectively 0.59V ± 0.02,16.03mA/cm2 ± 0.26,51.63% ± 0.52,4.88% ± 0.12.
Embodiment three:
1) processing of FTO glass: being first 15mm × 15mm by size, impedance is 14 Ω/sq FTO glass cleanser Cleaning, then carries out ultrasonic treatment 10min with deionized water, acetone and dehydrated alcohol respectively for it, with being dried with nitrogen, finally will It carries out UV and handles 15min;
2) preparation of electron transfer layer: the TiO that will be prepared2Solution by the processed FTO glass of step 1) with The rate spin coating 60s of 4000rpm/min then makes annealing treatment 40min at 400 DEG C in air, is then slowly cooled to room temperature, Obtain fine and close TiO2Layer;
3) preparation of antimony trisulfide light-absorption layer: the processed substrate of step 2) is moved into the glove box for having nitrogen protection.It will Sb2O3Diluted CS in powder (1.0mmol, AR), ethyl alcohol (2mL, GR)2(2mL, AR) and n- butylamine (1.5mL, AR) are sufficiently mixed Stirring is closed, the precursor solution of antimony is obtained, which is added dropwise in TiO2On layer, revolved with the rate of 8000rpm/min 40s is applied, heats 3min at 250 DEG C then to get antimony trisulfide light-absorption layer is arrived.Then " alcohol steam after annealing processing method " is used After annealing processing is carried out to vulcanization Sb film, which is moved on on the warm table for being placed with small crucible, the methanol of 42 μ l is instilled It in crucible, while being covered with culture dish rapidly, 300 DEG C of annealing 3min are to get to the sulphur handled through methanol steam after annealing Change antimony light-absorption layer;
4) preparation of hole transmission layer: 28 μ l 4- tert .-butylpyridines (4-tert-butyl pyridine) and 17 μ l are bis- Trifluoromethanesulfonimide lithium (Li-TFSI) (520mg Li-TFSI is dissolved in 1ml acetonitrile) is added in 1mL chlorobenzene, obtains Spiro-OMeTAD solution, by the solution with the rate spin coating of 6000rpm/min on step 3) vulcanization Sb film obtained 60s, finally in air at 120 DEG C annealing 20min to get arriving Spiro-OMeTAD layers;
5) electrode be deposited: use hot evaporation instrument, on the hole transport layer be deposited one layer of 110nm thickness Au back electrode to get To the antimony trisulfide based thin film solar cell through IPA vapor after annealing.
The photoelectric properties test result of the battery are as follows: VOC、JSC, FF and PCE be respectively 0.60V ± 0.02,16.61mA/cm2 ± 0.28,52.86% ± 0.65,5.27% ± 0.14.

Claims (9)

1. a kind of preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film, it is characterised in that step is such as Under:
The processing of step 1, FTO glass: conventional pretreatment is carried out to FTO glass;
The preparation of step 2, electron transfer layer: TiO is used2As electron transport material, electron transfer layer is prepared on FTO glass;
The alcohol steam after annealing processing of step 3, antimony trisulfide light absorbing layer: the precursor solution of antimony is spin-coated on TiO2Electron-transport On layer, after preparation vulcanization Sb film, after annealing processing is carried out to vulcanization Sb film using " alcohol steam after annealing processing method ": will The substrate of the precursor solution of spin coating antimony is placed on the warm table of small crucible, by the isopropanol, ethyl alcohol and methanol of 10-200 μ l point Di Ru not be in crucible, while being covered with culture dish rapidly, 100-400 DEG C of annealing 1-5min, nothing is carried out to vulcanization Sb film Solvent anneal handles to arrive antimony trisulfide light-absorption layer;
The preparation of step 4, hole transmission layer: by Spiro-OMeTAD solution Spiro-OMeTAD layers on vulcanization Sb film;
Step 5, electrode vapor deposition: using hot evaporation instrument, the Au back electrode of one layer of 100-120nm thickness be deposited on the hole transport layer, Obtain antimony trisulfide based thin film solar cell.
2. the preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film according to claim 1, Be characterized in that: the conventional pretreatment of the step 1: cleaning FTO glass using cleanser, then it is used respectively deionized water, Acetone and dehydrated alcohol carry out ultrasonic treatment 5-15min, with being dried with nitrogen, are finally carried out UV processing 5-20min.
3. the preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film according to claim 1, Be characterized in that: the step 2 prepares TiO on FTO glass2Electron transfer layer: with the rate of 1000-5000rpm/min, spin coating TiO2Solution makes annealing treatment 10-60min at 100-500 DEG C in air, then cools to room temperature, and obtains fine and close TiO2Electronics Transport layer.
4. the preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film according to claim 1, It is characterized in that: the precursor solution of the antimony of the step 3 are as follows: the Sb of 1.0-2.0mmol2O3Powder, the ethyl alcohol in 1.0-3.0mL In diluted 1.0-2.5mL CS2It is mixed with the n- butylamine of 1.0-2.5mL, obtains the precursor solution of antimony.
5. according to claim 1 or the preparation method of the solar battery of 4 alcohol steam after annealings processing antimony trisulfide base films, It is characterized by: the preparation of the step 3 vulcanizes Sb film: the processed FTO substrate of glass immigration of step 2 is had nitrogen protection Glove box in, the precursor solution solution of antimony is added dropwise in TiO2On layer, with the rate spin coating 20- of 3000-9000rpm/min Then 80s heats 1-10min at 100-400 DEG C, obtain vulcanization Sb film.
6. the preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film according to claim 1, It is characterized in that: the Spiro-OMeTAD solution of the step 4 are as follows: by the 4- tert .-butylpyridine 4-tert-butyl of 28 μ l Double trifluoromethanesulfonimide lithium Li-TFSI of pyridine and 17 μ l are added in 1mL chlorobenzene, and it is molten to obtain Spiro-OMeTAD Liquid;Double trifluoromethanesulfonimide lithium Li-TFSI are dissolved in 1ml acetonitrile with 520mgLi-TFSI;The component content For every part of metering.
7. the preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film according to claim 1 or 6, It is characterized by: the step 4 vulcanization Sb film on Spiro-OMeTAD layers: by Spiro-OMeTAD solution in antimony trisulfide With the rate spin coating 20-80s of 3000-9000rpm/min on film, 10- finally is made annealing treatment at 50-200 DEG C in air 30min is to get to Spiro-OMeTAD layers.
8. the preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film according to claim 4, It is characterized in that: the Sb2O3Powder, CS2It is pure using analyzing with n- butylamine.
9. the preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film according to claim 4, Be characterized in that: the ethyl alcohol uses excellent pure grade.
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