CN116963511A - Perovskite solar cell modified by phenylphosphoric acid and preparation method thereof - Google Patents
Perovskite solar cell modified by phenylphosphoric acid and preparation method thereof Download PDFInfo
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- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 71
- 230000005525 hole transport Effects 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- -1 phenylphosphoric acid modified tin dioxide Chemical class 0.000 claims abstract description 17
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 238000004528 spin coating Methods 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- JKSIBASBWOCEBD-UHFFFAOYSA-N N,N-bis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-1-amine Chemical compound COc1ccc(cc1)N(c1ccc(OC)cc1)c1cccc2-c3ccccc3C3(c4ccccc4-c4ccccc34)c12 JKSIBASBWOCEBD-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- VJVNWXUZZOBHRZ-UHFFFAOYSA-N benzene phosphoric acid Chemical compound P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.C1=CC=CC=C1 VJVNWXUZZOBHRZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 abstract 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 239000010408 film Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000007547 defect Effects 0.000 description 9
- 230000001133 acceleration Effects 0.000 description 8
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 238000012876 topography Methods 0.000 description 6
- 238000013112 stability test Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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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
- Y02E10/549—Organic PV cells
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- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The application belongs to the technical field of solar cells, and discloses a perovskite solar cell modified by phenylphosphoric acid and a preparation method thereof. The perovskite solar cell consists of an FTO conductive substrate, a tin dioxide electron transport layer, a perovskite photosensitive layer, a hole transport layer and a metal counter electrode, wherein the photoelectric conversion efficiency reaches 22.81%, and the perovskite solar cell has good stability. The preparation method comprises the following steps: depositing a phenylphosphoric acid modified tin dioxide electron transport layer on the clean FTO conductive substrate; deposition on tin dioxide electron transport layer (FAPbI 3 ) 1‑x (MAPbBr 3 ) x A perovskite photoactive layer; deposition of 2, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] on perovskite photoactive layer]-a 9, 9-spirobifluorene hole transport layer; and evaporating a metal counter electrode on the hole transport layer. Simple process, mild production condition, low cost and high repeatability, and is beneficial to the commercial application of perovskite solar cells.
Description
Technical Field
The application belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell modified by phenylphosphoric acid and a preparation method thereof.
Background
Solar energy is a renewable energy source, and under the condition that fossil fuels are gradually reduced, solar cells have good development prospects as important renewable clean energy sources and are continuously developed. Solar energy is utilized in two modes of photo-thermal conversion and photoelectric conversion, wherein solar power generation is an emerging renewable energy source. Currently, solar energy development has been widely paid attention to, and applications of solar cells have been brought into industries, businesses, agriculture, communications, home appliances, utilities, and the like from the military field and the aerospace field. Since the society advocates environmental protection and energy saving all the time, pollution resources such as coal, petroleum, natural gas and the like are gradually replaced by solar energy, many countries are trying to study the natural resource of solar energy, and are listed as important study plans.
Currently, solar cell research presents several new directions: 1. developing a top battery or a bottom battery matched with the crystalline silicon battery, and constructing a laminated battery with theoretical efficiency exceeding 33%; 2. developing novel batteries with flexibility, light weight, colorful and the like, realizing complementation with the crystalline silicon battery and meeting the application requirements of different markets; 3. explore new photoactive materials (simple, non-toxic, low cost, high abundance, etc.), and prepare new solar cells. As a new research point in the photovoltaic field, the perovskite material has the characteristics of simplicity, low cost and solution processability, and the thin film solar cell technology can replace the existing photovoltaic technology and realize low-cost development. In recent years, perovskite solar cells have made breakthrough progress in basic structure, working principle, component substitution, morphology optimization, crystallization improvement, interface passivation, electron/hole transport layer, all-inorganic perovskite, lead-free/lead-free perovskite, commercialized exploration and the like, and the single-chip photoelectric conversion efficiency of the perovskite solar cells is rapidly improved from 3.8% to 25.5%, so that good experiment and theoretical foundation are laid for deep exploration of the perovskite solar cells and promotion of commercialization of the perovskite solar cells.
The preparation method of the tin dioxide electron transport material has various advantages, but the solution method is still the preferred method for preparing the tin dioxide electron transport layer from the aspects of operation conditions, cost and device efficiency. Nevertheless, the sol-gel method for preparing tin dioxide film crystallization is still not ideal, and Sn vacancies and O vacancy defects exist in the interior and the surface, and the defects not only capture carriers to generate non-radiative recombination, but also influence interface energy level matching. In addition, a large number of oxygen vacancy defects on the tin dioxide surface become H in the air 2 O and O 2 And then induce perovskite decomposition, the device efficiency and stability are significantly reduced. Therefore, improving the conductivity through tin dioxide doping and passivation of surface defects of tin dioxide to improve the charge transmission of interfaces becomes an effective way for improving the efficiency and stability of perovskite solar cell devices. The common method is metal ion doping, for example, the device performance is improved by reducing the defect state density of the tin dioxide film, increasing the carrier mobility and improving the interface energy level matching; however, considering the solubility of doped metal ions in a tin dioxide precursor solution and the influence on tin dioxide crystallization, the doping amount of the metal ions is relatively small (the tin dioxide structure collapses due to heavy doping, high-resistance conversion is generated), so that the internal defects of the tin dioxide film can be reduced to a certain extent, and the effect of optimizing the performance is still not ideal. In addition, a large number of Sn dangling bonds exist on the surface of the tin dioxide film, and the Sn dangling bonds are potential factors for limiting the efficiency and the stability of the device. Therefore, passivating tin dioxide surface defects is an important way to further enhance device performance.
Disclosure of Invention
Aiming at the problem of interface defects of a perovskite photosensitive layer and a tin dioxide electron transport layer in the prior art, the application aims to provide a perovskite solar cell modified by benzene phosphoric acid and a preparation method thereof, and the perovskite solar cell has higher photoelectric conversion efficiency.
The perovskite solar cell with the phenylphosphoric acid modified electron transport layer is characterized by comprising an FTO conductive substrate, a tin dioxide electron transport layer, a perovskite photosensitive layer, a hole transport layer and a metal counter electrode.
The application provides a perovskite solar cell modified by phenylphosphoric acid, which comprises an FTO conductive substrate, a phenylphosphoric acid modified tin dioxide electron transport layer, a perovskite photosensitive layer, a hole transport layer and a metal counter electrode which are sequentially distributed in a layered mode.
Further, the perovskite photoactive layer is (FAPbI 3 ) 1-x (MAPbBr 3 ) x The hole transport layer is 2, 7-tetra [ N, N-di (4-methoxyphenyl) amino group]-9, 9-spirobifluorene (Spiro-ome tad), the metal counter electrode being gold, silver or copper.
Further, the thickness of the tin dioxide electron transport layer is 30-80 nm, the thickness of the perovskite photosensitive layer is 500-800 nm, the thickness of the hole transport layer is 150-250 nm, the thickness of the metal counter electrode is 80nm, and the area is 0.09-1.00 cm 2 。
The application also provides a preparation method of the perovskite solar cell modified by the phenylphosphoric acid, which comprises the following steps:
s1, adding benzene phosphoric acid into tin dioxide dispersion liquid, and performing ultrasonic dispersion to obtain benzene phosphoric acid modified tin dioxide aqueous solution;
s2, spin-coating the benzene phosphoric acid modified tin dioxide aqueous solution on the FTO conductive substrate subjected to the cleaning treatment, annealing and cooling to room temperature to form a benzene phosphoric acid modified tin dioxide electron transport layer on the FTO conductive substrate;
preferably, in step S2, the spin-coating conditions are as follows: the rotating speed is 3000-5000 rpm, the rotating acceleration is 1000-2000 rpm/s, and the spin coating time is 30s.
Preferably, in step S2, the annealing conditions are as follows: the annealing temperature is 150 ℃ and the annealing time is 20-40 min.
S3, pbI is processed 2 Solution spin coating on benzene phosphoric acid modified tin dioxide electron transport layerCooling to room temperature after annealing to obtain PbI 2 A film;
preferably, in step S3, the spin-coating conditions are as follows: the spin coating rotating speed is 1500-3000 rpm, the rotating acceleration is 1000-2000 rpm/s, and the spin coating time is 30s.
Preferably, in step S3, the annealing conditions are as follows: the annealing temperature is 70 ℃ and the annealing time is 1min.
S4, spin-coating the mixed solution of FAI/MABr/MACl on the PbI 2 Rapidly transferring to 30% -40% humidity air atmosphere on the film, annealing, cooling to room temperature to obtain (FAPbI) 3 ) 1-x (MAPbBr 3 ) x A perovskite photoactive layer;
preferably, in step S4, the spin-coating conditions are as follows: the spin coating rotating speed is 2000-3000 rpm, the rotating acceleration is 1000-2000 rpm/s, and the spin coating time is 30s.
Preferably, in step S4, the annealing conditions are as follows: the annealing temperature is 150 ℃ and the annealing time is 15min.
S5, dissolving 2, 7-tetra [ N, N-di (4-methoxyphenyl) amino ] -9, 9-spirobifluorene, lithium bistrifluoro methylsulfonylimide and tert-butylpyridine in a chlorobenzene solvent, and stirring to obtain a Spiro-OMeTAD solution;
s6 spin coating the Spiro-OMeTAD solution on the (FAPbI 3 ) 1-x (MAPbBr 3 ) x Obtaining a Spiro-OMeTAD hole transport layer on the surface of the perovskite photosensitive layer;
preferably, in step S6, the spin-coating conditions are as follows: the rotating speed is 3000-5000 rpm, the rotating acceleration is 1000-2000 rpm/s, and the spin coating time is 30s.
S7, depositing a metal layer on the Spiro-OMeTAD hole transport layer to obtain the perovskite solar cell, wherein the metal layer is a metal counter electrode.
Further, in step S1, the ratio of the phenylphosphoric acid to the tin dioxide dispersion was (1-8) mg/1 mL.
Further, in step S2, the cleaning process specifically includes: and sequentially ultrasonically cleaning the FTO conductive substrate in a detergent, alcohol, acetone and isopropanol for 30min, and then drying by using an air spray gun to obtain the clean FTO conductive substrate.
Further, pbI 2 The preparation method of the solution comprises the following steps: pbI is prepared 2 Dissolving the powder in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, and stirring overnight on a 70deg.C heating plate to obtain PbI with a concentration of 1.4M 2 And in the mixed solvent of the N, N-dimethylformamide and the dimethyl sulfoxide, the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 9:1.
Further, the preparation method of the FAI/MABr/MACl mixed solution comprises the following steps: FAI, MABr and MACl were dissolved in isopropanol and stirred at room temperature for 2h to give a mixed solution of FAI/MABr/MACl, wherein the ratio of FAI, MABr, MACl to isopropanol was 110mg:11mg:12mg:1.5mL.
Further, in step S5, the amount of 2, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene, lithium bistrifluoromethylsulfonylimide, tert-butylpyridine and chlorobenzene solvent was 72.3 mg/17.5. Mu.L/28.8. Mu.L/1 mL.
Compared with the prior art, the method mainly has the following technical advantages:
(1) According to the application, the electron transport layer is improved by introducing the phenylphosphoric acid, so that the roughness of the surface of the film is reduced, and the conductivity of the electron transport layer is effectively improved; meanwhile, the chemical combination of the interface is enhanced, the defect state of the interface is reduced, and the service life and the transmission efficiency of carriers are enhanced; the benzene phosphoric acid modification obviously reduces the work function of the electron transport layer, enhances the interface electron transport capacity, has lower energy loss and greatly increases the device efficiency. The average photoelectric conversion efficiency of the prepared solar cell reaches 22.75%, and the highest photoelectric conversion efficiency exceeds 22.86%, which shows that the solar cell has higher performance.
(2) The stability is also obviously improved, the device is tested for long-term stability in a room temperature environment filled with nitrogen, darkness and relative air humidity of 20% -25% and in a room temperature environment filled with nitrogen, natural light, and the stability test result shows that after the device is stored for 600 hours, the photoelectric conversion efficiency of the device modified by phenylphosphoric acid is still maintained to be more than 82% of the initial efficiency, and the hole and electron recombination behavior in the device after treatment is greatly delayed, so that the photoelectron recombination is further inhibited.
(3) The preparation method disclosed by the application is simple in preparation process, mild in production condition, low in cost and high in repeatability, and is beneficial to the commercial application of perovskite solar cells.
Drawings
Fig. 1 is a schematic structural diagram of a perovskite solar cell prepared in example 1 of the present application;
FIG. 2 is an atomic force microscope topography of perovskite solar cells prepared according to the prior art and obtained according to example 1; wherein, the left graph is an atomic force microscope topography of the perovskite solar cell obtained in the comparative example, and the right graph is an atomic force microscope topography of the perovskite solar cell obtained in the example 1;
FIG. 3 is a graph of current density versus voltage characteristics of perovskite solar cells prepared according to comparative example and example 1 prepared based on the prior art;
FIG. 4 is a scanning electron microscope topography of the electron transport layer of the perovskite solar cell produced according to the comparative example and example 1 prepared based on the prior art;
FIG. 5 is a graph of current density versus voltage characteristics of the electron transport layers of perovskite solar cell prepared according to the prior art and obtained as example 1;
FIG. 6 is a graph showing a test of the stability of the electron transport layer of the perovskite solar cell prepared according to the prior art and obtained in example 1; the upper graph is a room temperature environment stability test graph filled with nitrogen, dark and with the relative air humidity of 20% -25%, and the lower graph is a room temperature environment stability test graph filled with nitrogen, natural light;
fig. 7 is a table of PSC photoelectric property parameters of the electron transport layers of perovskite solar cells prepared based on the prior art comparative examples and examples.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application. In addition, the technical features of the embodiments of the present application described below may be combined with each other as long as they do not collide with each other.
Example 1
The preparation method of the perovskite solar cell modified by the phenylphosphoric acid comprises the following steps:
CAS:1571-33-1 english name: phenylphosphonic acid packaging: 1kg purity specification: 99%, available from Tesco chemical (Hubei) Co.
Step 1, pretreatment of an FTO conductive substrate: dividing the FTO conductive substrate into regular small pieces with the length of 1cm multiplied by 1cm, sequentially ultrasonically cleaning the regular small pieces in detergent, alcohol, acetone and isopropanol for 30min, and blow-drying the finally obtained FTO conductive substrate by using an air spray gun to obtain a clean FTO conductive substrate;
step 2, preparing a phenylphosphoric acid modified tin dioxide electron transport layer:
step 2.1: adding phenylphosphoric acid into the tin dioxide dispersion liquid, and performing ultrasonic dispersion for 30min to obtain a benzene phosphoric acid modified tin dioxide aqueous solution with the concentration of 3.0 mg/mL.
Step 2.2: sucking 50 mu L of benzene phosphoric acid modified tin dioxide aqueous solution by a pipette gun, and spin-coating the tin dioxide aqueous solution on the FTO conductive substrate obtained in the step 1; the spin coating conditions were: the rotating speed is 3000-5000 rpm, the rotating acceleration is 1000-2000 rpm/s, and the spin coating time is 30s; and then annealing for 20-40 min on a heating plate at 150 ℃ to obtain a tin dioxide electron transport layer modified by phenylphosphoric acid, wherein the thickness is about 40nm, and transferring the tin dioxide electron transport layer into a glove box for standby.
Step 3: preparation (FAPbI) 3 ) 1-x (MAPbBr 3 ) x Perovskite photoactive layer:
step 3.1: 645.4mg of PbI was weighed by an electronic balance 2 The powder was dissolved in 1mL of a mixed solvent of N, N-Dimethylformamide (DMF) and Dimethylsulfoxide (DMSO) in a volume ratio of 9:1, and then stirred overnight on a hot plate at 70℃to give 1.4M PbI 2 Solution A.
Step 3.2: 110mg of FAI, 11mg of MABr and 12mg of MACl were weighed by an electronic balance and dissolved in 1.5mL of isopropyl alcohol (IPA), and stirred at room temperature for 2 hours to obtain a mixed solution B of FAI/MABr/MACl.
Step 3.3: sucking 50 mu L of solution A by a pipette, spin-coating on electron transport of phenylphosphoric acid modified tin dioxide, annealing at 70 ℃ for 1min, and cooling to room temperature to obtain PbI 2 A film. Wherein the spin coating rotating speed is 1500-3000 rpm, the rotating acceleration is 1000-2000 rpm/s, and the spin coating time is 30s.
Step 3.4: mu.L of solution B was spun onto PbI using a pipette 2 The spin coating speed is 2000-3000 rpm, the spin acceleration is 1000-2000 rpm/s, and the spin coating time is 30s.
Step 3.5: rapidly transferring the film obtained in the step 3.4 to 30% -40% humidity air atmosphere, and annealing at 150 ℃ for 15min to obtain (FAPbI) 3 ) 1-x (MAPbBr 3 ) x Perovskite photoactive layer.
Step 4: preparation of a Spiro-ome tad hole transport layer:
72.3mg of 2, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino]9, 9-spirobifluorene (Spiro-OMeTAD), 17.5. Mu.L of lithium bistrifluoromethylsulfonylimide (LiTFSI) and 28.8. Mu.L of t-butylpyridine (TBP) were dissolved in 1mL of chlorobenzene solvent and stirred for 30min to obtain solution C. Subsequently 30. Mu.L of solution C was spin-coated onto (FAPbI 3 ) 1-x (MAPbBr 3 ) x The surface of the perovskite photosensitive layer is provided with a Spiro-OMeTAD hole transport layer, the rotating speed is 3000rpm, the rotating acceleration is 2000rpm/s, and the time is 30s.
Step 5: depositing a metal counter electrode:
in the embodiment, gold with the thickness of 80nm is evaporated on the hole transport layer obtained in the step 4 through a mask plate by adopting a vacuum thermal evaporation method as a metal counter electrode, and the area of the metal counter electrode is 0.09-1 cm 2 And finally obtaining the complete perovskite solar cell device.
Example 2
Compared with example 1, the difference in this embodiment is that the concentration of phenylphosphoric acid is adjusted to 1.5mg/mL in the process of preparing the tin dioxide solution in the step 2.1, and other steps are unchanged.
Example 3
Compared with example 1, the difference in this embodiment is that the concentration of phenylphosphoric acid is adjusted to 5.0mg/mL in the process of preparing the tin dioxide solution in the step 2.1, and other steps are unchanged.
Example 4
Compared with example 1, the implementation differs from the preparation of the tin dioxide solution in the step 2.1 only in that the concentration of the phenylphosphoric acid is adjusted to be 8.0mg/mL, and other steps are unchanged.
Comparative example
In this example, a tin dioxide electron transport layer without added phenylphosphoric acid was prepared according to the procedure of example 1 and applied to perovskite solar energy, and compared with example 1, the difference in this implementation was only that during the preparation of the aqueous tin dioxide solution in step 2.1, the process was adjusted so that the phenylphosphoric acid was not added to the aqueous tin dioxide solution, and the other steps were unchanged.
Analytical tests were performed on the above examples and comparative examples as follows:
as shown in the atomic force microscope topography of the perovskite solar cell prepared based on the prior art in fig. 2 and the perovskite solar cell obtained in example 1, the roughness of the thin film modified by the phenylphosphoric acid is significantly reduced, the thin film has finer granularity, the surface is smoother, the interface stress can be reduced, and the distribution of the nuclei for perovskite growth is uniform.
As shown in fig. 3, which is a graph of current density versus voltage characteristics of the perovskite solar cell prepared according to the comparative example and example 1 prepared based on the prior art, it was calculated that the conductivity of the tin dioxide film modified with phenylphosphoric acid was much higher than that of the general tin dioxide film. This indicates that the electron transport in the tin dioxide film modified by the phenylphosphoric acid is more rapid, the charge accumulation of the electron transport layer and the charge accumulation of the peroxide interface are obviously reduced, and a better photovoltaic effect is shown.
Fig. 4 is a scanning electron microscope topography of the perovskite solar cell electron transport layer obtained in the comparative example and example 1 prepared based on the prior art, wherein the crystal grain size of the phenylphosphoric acid modified composite film is obviously increased, the film is more uniform and flat, the crystallization performance of the sample film is gradually improved, the inter-grain hole density is also reduced to a certain extent, and the contact problem between the electron transport layer and the perovskite interface is improved. The method has the optimal morphological characteristics, so that the recombination centers are directly reduced, the charge transmission is promoted, the occurrence probability of interface recombination is reduced, and the stability of the device is improved.
Fig. 5 is a graph showing current density versus voltage characteristics of the electron transport layer of the perovskite solar cell prepared according to the prior art and example 1, and it can be seen that the effect of phenylphosphoric acid on the hysteresis of the cell is slight.
FIG. 6 is a graph showing a test of the stability of the electron transport layer of the perovskite solar cell prepared according to the prior art and obtained in example 1; the device is placed in a room temperature environment filled with nitrogen, dark and with relative air humidity of 20% -25% and is subjected to long-term stability test in the environment filled with nitrogen, natural light and room temperature, the stability test result shows that after 600 hours of storage, the photoelectric conversion efficiency of the device modified by phenylphosphoric acid is still maintained at more than 82% of the initial efficiency, which indicates that the recombination behavior of holes and electrons in the optimized device is greatly delayed and the photoelectron recombination is further inhibited, and the device has good stability.
As can be seen from the PSC photoelectric property parameter tables of the perovskite solar cell electron transport layers obtained based on the comparative example and the example prepared in the prior art of FIG. 7, the addition of phenylphosphoric acid has a significant effect on the efficiency of perovskite, while the cell efficiency gradually increases as the concentration of phenylphosphoric acid increases, and when the concentration of phenylphosphoric acid is 3mg/mL, the photoelectric conversion efficiency of the device is highest, reaching 22.81%, the open circuit voltage is 1.16V, and the short circuit current density is 24.11mA/cm 2 The fill factor was 81.57%. In addition, when the concentration of the phenylphosphoric acid is 3mg/mL, the open-circuit voltage of the solar cell is the largest, because the modification of the phenylphosphoric acid reduces the work function of the electron transport layer, so that the energy levels of the electron transport layer and the perovskite layer are more matched, the energy loss of the final carrier in the transport process is reduced, the interface electron transport capacity is enhanced, the open-circuit voltage is improved, and the device efficiency is greatly increased
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the application and is not intended to limit the application, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (9)
1. The perovskite solar cell modified by the phenylphosphoric acid is characterized by comprising an FTO conductive substrate, a phenylphosphoric acid modified tin dioxide electron transport layer, a perovskite photosensitive layer, a hole transport layer and a metal counter electrode which are sequentially distributed in a layered mode.
2. The perovskite solar cell of claim 1, wherein the perovskite photoactive layer is (FAPbI 3 ) 1-x (MAPbBr 3 ) x The hole transport layer is 2, 7-tetra [ N, N-di (4-methoxyphenyl) amino group]-9, 9-spirobifluorene (Spiro-ome tad), the metal counter electrode being gold, silver or copper.
3. The perovskite solar cell according to claim 2, wherein the thickness of the tin dioxide electron transport layer is 30-80 nm, the thickness of the perovskite photoactive layer is 500-800 nm, the thickness of the hole transport layer is 150-250 nm, the thickness of the metal counter electrode is 80nm, and the area is 0.09-1.00 cm 2 。
4. The preparation method of the perovskite solar cell modified by the phenylphosphoric acid is characterized by comprising the following steps of:
s1, adding benzene phosphoric acid into tin dioxide dispersion liquid, and performing ultrasonic dispersion to obtain benzene phosphoric acid modified tin dioxide aqueous solution;
s2, spin-coating the benzene phosphoric acid modified tin dioxide aqueous solution on the FTO conductive substrate subjected to the cleaning treatment, annealing and cooling to room temperature to form a benzene phosphoric acid modified tin dioxide electron transport layer on the FTO conductive substrate;
s3, pbI is processed 2 Spin-coating the solution on a phenylphosphoric acid modified tin dioxide electron transport layer, annealing and cooling to room temperature to obtain PbI 2 A film;
s4, mixing the FAI/MABr/MACl solutionSpin-coating on the PbI 2 Cooling the film to room temperature after annealing, rapidly transferring the film to 30-40% humidity air atmosphere, annealing and cooling the film to room temperature to obtain (FAPbI) 3 ) 1-x (MAPbBr 3 ) x A perovskite photoactive layer;
s5, dissolving 2, 7-tetra [ N, N-di (4-methoxyphenyl) amino ] -9, 9-spirobifluorene, lithium bistrifluoro methylsulfonylimide and tert-butylpyridine in a chlorobenzene solvent, and stirring to obtain a Spiro-OMeTAD solution;
s6, spin-coating the Spiro-OMeTAD solution on the (FAPbI) 3 ) 1-x (MAPbBr 3 ) x Obtaining a Spiro-OMeTAD hole transport layer on the surface of the perovskite photosensitive layer;
s7, depositing a metal layer on the Spiro-OMeTAD hole transport layer to obtain the perovskite solar cell, wherein the metal layer is a metal counter electrode.
5. The method according to claim 4, wherein the ratio of the phenylphosphoric acid to the tin dioxide dispersion in step S1 is (1-8) mg/1 mL.
6. The method according to claim 4, wherein in step S2, the cleaning process specifically comprises: and sequentially ultrasonically cleaning the FTO conductive substrate in a detergent, alcohol, acetone and isopropanol for 30min, and then drying by using an air spray gun to obtain the clean FTO conductive substrate.
7. The method of claim 4, wherein PbI 2 The preparation method of the solution comprises the following steps: pbI is prepared 2 Dissolving the powder in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, and stirring overnight on a 70deg.C heating plate to obtain PbI with a concentration of 1.4M 2 And in the mixed solvent of the N, N-dimethylformamide and the dimethyl sulfoxide, the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 9:1.
8. The preparation method of the FAI/MABr/MACl mixed solution according to claim 4, wherein the preparation method comprises the following steps: FAI, MABr and MACl were dissolved in isopropanol and stirred at room temperature for 2h to give a mixed solution of FAI/MABr/MACl, wherein the ratio of FAI, MABr, MACl to isopropanol was 110mg:11mg:12mg:1.5mL.
9. The process according to claim 4, wherein in step S5, the ratio of the amount of 2, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene, lithium bistrifluoromethylsulfonylimide, tert-butylpyridine and chlorobenzene solvent is 72.3mg:17.5 mu L, 28.8 mu L and 1mL.
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