CN109037398A - A kind of preparation method of caesium tin iodine film and photovoltaic device based on it - Google Patents
A kind of preparation method of caesium tin iodine film and photovoltaic device based on it Download PDFInfo
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- CN109037398A CN109037398A CN201810830311.9A CN201810830311A CN109037398A CN 109037398 A CN109037398 A CN 109037398A CN 201810830311 A CN201810830311 A CN 201810830311A CN 109037398 A CN109037398 A CN 109037398A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 11
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 11
- PMJHPLYNASCEAT-UHFFFAOYSA-N [Sn].[I] Chemical compound [Sn].[I] PMJHPLYNASCEAT-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 4
- QPBYLOWPSRZOFX-UHFFFAOYSA-J Tin(IV) iodide Inorganic materials I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 6
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000005525 hole transport Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 43
- 239000000463 material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000004528 spin coating Methods 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 229910003953 H3PO2 Inorganic materials 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- -1 diisopropyl titanate esters Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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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
- H01L31/18—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
- H01L31/0248—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
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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
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- 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
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- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of preparation method of caesium tin iodine film and based on its photovoltaic device, which is with SnI4It is that Cs is made in raw material with CsAc2SnI6After powder, then it is deposited in target substrate and obtains through spraying process.Gained Cs of the invention2SnI6Film uniform compact makes photovoltaic device, simple process, pollution-free, abundant raw materials, cheap, particularly suitable preparation high-volume, low-cost solar battery using it as light absorbing layer, thus is conducive to push the development and application of inorganic perovskite solar battery.
Description
Technical field
The present invention relates to a kind of Cs2SnI6The preparation method of film and photovoltaic device based on it belong to thin film solar electricity
The preparation process field of pond photovoltaic device.
Background technique
Perovskite battery is generally represented by using perovskite thin film material as the novel solar battery of light absorbing layer
AMX3, wherein A represents cation, common to narrow (FA) and caesium (Cs) etc. for methylamine (MA), first.In recent years, hybrid inorganic-organic
Perovskite solar battery causes the extensive concern of photovoltaic circle due to its excellent photoelectric characteristic, but it is faced with a sternness
The problem of, i.e., thermal stability is bad, this causes it that can not be applied in actual production.The hybrid inorganic-organic perovskite sun
The thermostabilization difference of energy battery is mainly caused by easy moisture absorption in the heated easily decomposition of organic group, air etc., therefore use is more steady
Fixed inorganic ions Cs replaces organic group to be expected to solve the stability problem of perovskite battery.
Novel inorganic perovskite material CsMX in recent years3(M=Pb, Sn；X=I, Br) due to excellent photoelectric properties
With good thermal stability and cause the extensive concern of researcher, and be expected to solve the stability bottle of the organic perovskite battery of tradition
Neck problem.The Cs of cubic phase2SnI6It is CsSnI3The oxidation state of perovskite structure, due to CsSnI3Perovskite material divalent Sn exists
Oxidizable can not expose at tetravalence Sn of oxygen is met in air to use in air, limits further applying for the material.And
Cs2SnI6Material carrier concentration with higher and mobility, can be stabilized in air.And compared to traditional Pb
Perovskite material, Sn material have the advantages such as nontoxic, green and pollution-free, cheap.Therefore, Cs is developed2SnI6Film material
The technology of preparing that low cost, simple process, the stability of material are good is just particularly important.
Traditional Cs2SnI6Synthetic method be by complicated high-temperature synthesis, under an argon atmosphere by three-necked flask
Middle addition HI, H3PO2With SnI2, HSnI is synthesized first under oil bath at 120 DEG C3, CsI is then added and forms yellow crystal, with third
Ketone dissolution, is placed in ar gas environment and keeps 20-24h, obtains Cs2SnI6, finally again with dehydrated alcohol wash filtering obtain it is available
Cs2SnI6Powder sample.This method complicated and time consumption, and it is more demanding to technique.
Summary of the invention
To avoid above-mentioned existing deficiencies in the technology, the invention discloses a kind of preparation sides of caesium tin iodine film
Method and photovoltaic device based on it.
The present invention is to realize goal of the invention, is adopted the following technical scheme that
The present invention discloses a kind of preparation method of caesium tin iodine film first, it is characterized in that: first by SnI4With CsAc
It is dissolved in ethyl alcohol, lasting to stir, gained reaction solution is centrifuged, is dried in vacuo, and obtains Cs2SnI6Powder；It then will be described
Cs2SnI6Powder is dissolved in DMF solution, is deposited in target substrate by spraying process, i.e. acquisition Cs2SnI6Film.Specifically
Include the following steps:
(1) it takes 1mmol CsAc to be dissolved in 1-5mL dehydrated alcohol, adds the SnI of 1mmol4Powder persistently stirs 1-
3h, after reaction solution is centrifuged, 60 DEG C of vacuum drying 4-8h of gained black precipitate obtain Cs2SnI6Powder；
(2) by the Cs2SnI6Powder is dissolved in DMF, and 2h is stirred at room temperature, and obtains 250mg/mL Cs2SnI6Solution；
(3) target substrate is preheated to 120-140 DEG C, by the Cs2SnI6Solution is added in spray gun, then in target
Even application 20s in substrate forms the film of uniform compact, and the 5-15min that finally anneals under constant temperature again is to get Cs2SnI6Film.
Invention additionally discloses a kind of photovoltaic devices based on caesium tin iodine film, as shown in Figure 1, it is in FTO electro-conductive glass
Surface is sequentially depositing the compacted zone TiO as electron transfer layer2, as the Cs of light absorbing layer2SnI6Film is passed as hole
The Sprio-OMeTAD film (HTM) and positive and negative electrode (Ag) of defeated layer.
The preparation method of above-mentioned photovoltaic device, includes the following steps:
(1) to prevent test battery film is pressed from both sides into perforating when and causes battery short circuit, by FTO conductive glass surface partial etching,
Specifically: FTO conductive glass surface being divided into crystallizing field and non-deposited area, in the upper zinc of local uniform tiling of the crystallizing field
Powder etches 5min then by the HCl drop of 2M on zinc powder；
FTO electro-conductive glass after etching (is successively used into suds, third by the cleaning of FTO electro-conductive glass, the drying after etching
Ketone, EtOH Sonicate clean 20min, then use N2Drying reuses UV-ozone cleaning machine cleaning 20min), obtain cleaning
FTO electro-conductive glass.
(2) in the crystallizing field deposition compact layer TiO of FTO conductive glass surface2As electron transfer layer；
(3) Cs is formed on the electron transport layer with above-mentioned preparation method2SnI6Film, as light absorbing layer；
(4) in the Cs2SnI6Sprio-OMeTAD film is prepared on film as hole transmission layer.
(5) in the non-deposited area of FTO conductive glass surface vapor deposition Ag electrode as negative electrode, in the hole transport
Ag electrode is deposited on layer as positive electrode, negative electrode does not contact with electron transfer layer, light absorbing layer and hole transmission layer to get base
In Cs2SnI6The perovskite photovoltaic device of film.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, Cs of the present invention2SnI6It is the preparation method simple process of film, pollution-free, it is abundant raw materials, cheap, it is particularly suitable for
Preparation high-volume, low-cost solar battery, thus be conducive to push the development and application of inorganic perovskite solar battery.
2, the Cs obtained by the present invention2SnI6Film uniform compact, exposure is stable in the air and is not easy phase transformation.
3, the present invention uses Cs2SnI6Distorted perovskites structure prepares perovskite solar energy film as light absorption layer material
Battery can effectively avoid the numerous of current solar battery preparation compared with common organic inorganic hybridization perovskite solar cell
Trivial glove box operation and expensive vacuum evaporation apparatus investment, high quality can be realized under normal atmospheric conditions, stablize perovskite
The low cost preparation of light absorbing layer film.
4, Cs of the invention2SnI6Thin-film material has nontoxic, environmentally protective nothing compared to traditional Pb perovskite material
The advantages such as pollution, cheap, are more suitable as the solar battery of outdoor utility, are more advantageous to industrialization promotion.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the perovskite solar battery based on caesium tin iodine film；
Fig. 2 is Cs2SnI6The spraying method schematic diagram of film；
Fig. 3 is Cs in embodiment 12SnI6X-ray diffraction (XRD) figure of film；
Fig. 4 is Cs in embodiment 12SnI6The electron scanning micrograph (SEM) of film；
Fig. 5 is that Cs is based in embodiment 12SnI6The Current density-voltage (J-V) of the perovskite solar battery of film is special
Linearity curve；
Fig. 6 is that Cs is based in embodiment 22SnI6The Current density-voltage (J-V) of the perovskite solar battery of film is special
Linearity curve；
Fig. 7 is that Cs is based in embodiment 32SnI6The Current density-voltage (J-V) of the perovskite solar battery of film is special
Linearity curve.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below with reference to embodiment to this hair
Bright specific embodiment is described in detail.The following contents is only to design example of the invention and explanation, institute
Belong to those skilled in the art to make various modifications or additions to the described embodiments or using similar
Mode substitutes, and as long as it does not deviate from the concept of invention or beyond the scope defined by this claim, should belong to the present invention
Protection scope.
Embodiment 1
The present embodiment prepares Cs as follows2SnI6Film and solar battery based on it:
(1) it takes 1mmol CsAc to be dissolved in 2mL dehydrated alcohol, adds the SnI of 1mmol4Powder persistently stirs 2h, right
After reaction solution is centrifuged, 60 DEG C of vacuum drying 6h of gained black precipitate obtain the Cs of black2SnI6Powder；
(2) FTO electro-conductive glass is cut into the fritter of 20 × 15mm, is classified as two of 15mm width and 5mm width
Point, respectively as crystallizing field and non-deposited area.Then the 5mm width using crystallizing field far from non-deposited area is as etched area.Non-
The part of etched area touch adhesive tape, leaks out etched area.Zinc powder is evenly laid out in etched area, the HCl solution drop of 2M is being completed
Zinc powder on, etch 5min.
FTO electro-conductive glass after etching is successively cleaned into 20min with suds, acetone, EtOH Sonicate, then uses N2It blows
It is dry, UV-ozone cleaning machine cleaning 20min is reused, clean FTO electro-conductive glass is obtained.
(3) in the crystallizing field deposition compact layer TiO of FTO conductive glass surface2As electron transfer layer: taking 1g first
75% bis- (levulinic ketone group) diisopropyl titanate esters aqueous isopropanols (wt%), which are added in 10.3g n-butanol, to be formed
The TiO of 0.15mol/L2Precursor liquid takes 2~3 above-mentioned solution of drop to be added drop-wise to the clean non-etched area of FTO conductive glass surface,
Remove substrate after 2000rpm spin coating 40s, 135 DEG C of dry 10min, then 500 DEG C of sintering 30min；After to be sintered, by base
Piece uses 40mmol/L TiCl470 DEG C of processing 30min of aqueous solution, and again with 500 DEG C of sintering 30min to get arrive compacted zone
TiO2(FTO/c-TiO2)。
(3) by Cs2SnI6Powder is dissolved in DMF, and 2h is stirred at room temperature, and obtains 250mg/mL Cs2SnI6Solution；
By step (2) obtained FTO/c-TiO2Substrate is preheated to 130 DEG C, by Cs2SnI6Solution is added in spray gun, so
The even application 20s on substrate afterwards forms the film of uniform compact, and the 10min that finally anneals at 130 DEG C again is to get Cs2SnI6
Film.
(4) in Cs2SnI6Sprio-OMeTAD film is prepared on film as hole transmission layer: taking 72.3mg2,2 ', 7,
7 ',-[N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shell, two fluorenes is dissolved in 1mL chlorobenzene, and 17.5 μ L concentration are added and are
The acetonitrile solution of double trifluoromethanesulfonimide lithiums of 0.52g/mL and 28.8 μ L 4- tert .-butylpyridines are to get Sprio-
OMeTAD film spin coating liquid；In the Cs2SnI6Spin coating Sprio-OMeTAD spin coating liquid on film, spin speed 4000rpm,
Spin-coating time is 30s to get hole transmission layer.
(5) it is deposited on the hole transport layer in the non-deposited area of FTO conductive glass surface vapor deposition Ag electrode as negative electrode
Ag electrode is as positive electrode, and positive and negative electrode thickness~70nm is to get based on Cs2SnI6The perovskite photovoltaic device of film.
Fig. 1 is the structural schematic diagram of the perovskite solar battery based on caesium tin iodine film；Fig. 2 is Cs2SnI6Thin film coatings
Method schematic diagram；Fig. 3 is Cs obtained by the present embodiment2SnI6X-ray diffraction (XRD) figure of film；Fig. 4 is the present embodiment institute
Cs obtained2SnI6The electron scanning micrograph of film.As can be seen that film uniform compact obtained by the present embodiment.
Be tested for the property to perovskite photovoltaic device made by the present embodiment: test temperature is 25 DEG C；Relative humidity
It is 30%；The spectral irradiance of light source is 100mW/m2, and the AM1.5 solar spectrum irradiancy with standard is distributed.After tested,
Current density-voltage (J-V) characteristic curve of battery is as shown in Figure 5.
Embodiment 2
The present embodiment makes Cs by the identical method of embodiment 12SnI6Film and solar battery based on it, difference is only
It is that the annealing temperature in step (3) is 120 DEG C.After tested, film uniform compact made by the present embodiment, corresponding solar energy
The J-V characteristic curve of battery is as shown in Figure 6.
Embodiment 3
The present embodiment makes Cs by the identical method of embodiment 12SnI6Film and solar battery based on it, difference is only
It is that the annealing temperature in step (3) is 140 DEG C.After tested, film uniform compact made by the present embodiment, corresponding solar energy
The J-V characteristic curve of battery is as shown in Figure 7.
The above is only exemplary embodiment of the present invention, are not intended to limit the invention, all in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of preparation method of caesium tin iodine film, it is characterised in that: first by SnI4It is dissolved in ethyl alcohol with CsAc, it is lasting to stir,
Gained reaction solution is centrifuged, is dried in vacuo, and obtains Cs2SnI6Powder；Then by the Cs2SnI6It is molten that powder is dissolved in DMF
It in liquid, is deposited in target substrate by spraying process, i.e. acquisition Cs2SnI6Film.
2. preparation method according to claim 1, which is characterized in that specifically comprise the following steps:
(1) it takes 1mmol CsAc to be dissolved in 1-5mL dehydrated alcohol, adds the SnI of 1mmol4Powder persistently stirs 1-3h, to anti-
After answering liquid to be centrifuged, 60 DEG C of vacuum drying 4-8h of gained black precipitate obtain Cs2SnI6Powder；
(2) by the Cs2SnI6Powder is dissolved in DMF, and 2h is stirred at room temperature, and obtains the Cs of 250mg/mL2SnI6Solution；
(3) target substrate is preheated to 120-140 DEG C, by the Cs2SnI6Solution is added in spray gun, then in target substrate
Upper even application 20s, forms the film of uniform compact, and the 5-15min that finally anneals under constant temperature again is to get Cs2SnI6Film.
3. a kind of photovoltaic device based on caesium tin iodine film, it is characterised in that: the photovoltaic device is in FTO conductive glass surface
It is sequentially depositing the compacted zone TiO as electron transfer layer2, as light absorbing layer with any one of claim 1~2 institute
State Cs obtained by preparation method2SnI6Film, Sprio-OMeTAD film and positive and negative electrode as hole transmission layer.
4. a kind of preparation method of photovoltaic device described in claim 3, which comprises the steps of:
(1) FTO conductive glass surface is divided into crystallizing field and non-deposited area, in the upper zinc of local uniform tiling of the crystallizing field
Powder etches 5min then by the HCl drop of 2M on zinc powder；By the cleaning of FTO electro-conductive glass, the drying after etching；
(2) in the crystallizing field deposition compact layer TiO of FTO conductive glass surface2As electron transfer layer；
(3) Cs is formed on the electron transport layer with preparation method described in any one of claims 1 or 22SnI6Film,
As light absorbing layer；
(4) in the Cs2SnI6Sprio-OMeTAD film is prepared on film as hole transmission layer；
(5) in the non-deposited area of FTO conductive glass surface vapor deposition Ag electrode as negative electrode, on the hole transport layer
Ag electrode is deposited as positive electrode to get based on Cs2SnI6The perovskite photovoltaic device of film.
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| CN115432731A (en) * | 2022-10-12 | 2022-12-06 | 电子科技大学 | Inversion type Cs 8 Sn 3 GaI 24 /Cs 8 Sn 3 InI 24 Hybrid composite material and preparation method thereof |
| CN115975405A (en) * | 2022-12-12 | 2023-04-18 | 合肥工业大学 | Preparation method of Cs2SnI 6-based composite membrane with excellent photoelectric property |
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| CN115975405A (en) * | 2022-12-12 | 2023-04-18 | 合肥工业大学 | Preparation method of Cs2SnI 6-based composite membrane with excellent photoelectric property |
| CN115975405B (en) * | 2022-12-12 | 2024-03-12 | 合肥工业大学 | Preparation method of Cs2SnI 6-based composite film with excellent photoelectric property |
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