CN113421969B - Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof - Google Patents

Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof Download PDF

Info

Publication number
CN113421969B
CN113421969B CN202110690401.4A CN202110690401A CN113421969B CN 113421969 B CN113421969 B CN 113421969B CN 202110690401 A CN202110690401 A CN 202110690401A CN 113421969 B CN113421969 B CN 113421969B
Authority
CN
China
Prior art keywords
transport layer
electron transport
perovskite
sno
mapbbr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110690401.4A
Other languages
Chinese (zh)
Other versions
CN113421969A (en
Inventor
刘向阳
赵晓伟
牛晨
梁渺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University
Original Assignee
Henan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan University filed Critical Henan University
Priority to CN202110690401.4A priority Critical patent/CN113421969B/en
Publication of CN113421969A publication Critical patent/CN113421969A/en
Application granted granted Critical
Publication of CN113421969B publication Critical patent/CN113421969B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • H10K30/80—Constructional details
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The application discloses a perovskite solar cell with HF modified tin dioxide as an electron transport layer and a preparation method thereof, wherein the preparation process of the solar cell is as follows: (1) preparation of HF-modified SnO2A hydrosol; (2) deposition of HF-modified SnO on clean ITO electrodes2An electron transport layer; (3) introduction of diblock copolymer into (FAPBI)3)1‑x(MAPbBr3)xIn the system; (4) at SnO2Deposition on electron transport layer (FAPbI)3)1‑x(MAPbBr3)xA photosensitive layer; (5) depositing a Spiro-OMeTAD hole transport layer on the photosensitive layer; (6) and (4) evaporating an Au counter electrode on the Spiro-OMeTAD hole transport layer. The average photoelectric conversion efficiency of the prepared solar cell reaches 22.81%, the maximum photoelectric conversion efficiency exceeds 22.92%, and the prepared solar cell has good stability to moisture, illumination and temperature.

Description

Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell with HF modified tin dioxide as an electron transport layer and a preparation method thereof.
Background
Electric energy is an important guarantee for social development and economic construction, and is closely combined with high technology to create colorful human life, and meanwhile, the wide application of the electric energy also causes the phenomenon of insufficient power supply in the global scope to frequently appear. In the world, thermal power generation is the most important form of power generation at present, but due to the massive combustion of fossil fuels such as petroleum, natural gas and coal, the problem of energy exhaustion is caused, and the problem of environmental pollution, especially air pollution, is increasingly serious. In order to alleviate the contradiction between economic growth, energy shortage and environmental pollution, the problems of energy shortage and environmental pollution can be fundamentally alleviated only by changing the current energy use mode, vigorously developing and popularizing clean energy such as solar energy, wind energy and the like and thoroughly changing the energy structure mainly based on fossil energy.
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 the theoretical efficiency of more than 33%; 2. the novel flexible, light and colorful battery is developed, the complementation with the crystalline silicon battery is realized, and the application requirements of different markets are met; 3. explore new photosensitive materials (simple, non-toxic, low-cost, high abundance and the like) and prepare the novel solar cell. As a new research hotspot in the photovoltaic field, the perovskite material has the characteristics of simplicity, low price 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 breakthrough progress in the aspects of basic structure, working principle, component substitution, morphology optimization, crystallization improvement, interface passivation, electron/hole transport layers, all-inorganic perovskite, lead-free/lead-less perovskite, commercial exploration and the like, the monolithic photoelectric conversion efficiency of the perovskite solar cells is rapidly improved from 3.8% to 25.5%, and good experimental and theoretical bases are laid for deeply exploring the perovskite solar cells and promoting the commercialization of the perovskite solar cells.
However, the existing perovskite solar cell is based on mesoporous TiO mostly2And thin film SnO2Is an electron transport layer, in which SnO2Has obvious advantage over TiO2Conductivity and higher carrier concentration and electron mobility, so that SnO2The perovskite solar cell performance is more potential improved for the electron transport layer. The invention prepares the crystalline SnO by a simple one-step method2Nano sol capable of realizing SnO2The nanocrystalline has higher carrier concentration and electron mobility, and the electron transmission characteristic of the film is improved; simultaneously, proper amount of HF is introduced to modify SnO2Nanocrystalline, passivated SnO2Nanocrystalline defect, surface property improvement, F promotion-1Ions are transferred with perovskite halogen ions, so that interface contact is improved, efficient separation and extraction of photoproduction charges are promoted, and the performance of the perovskite solar cell is further improved; in addition, the large-scale preparation of the perovskite solar cell is explored, and the commercial development of the perovskite solar cell is promoted.
Disclosure of Invention
The invention aims to provide HF modified tin dioxide (SnO)2) Calcium as electron transport layerTitanium ore solar cell and preparation method thereof, HF modified SnO2The hydrosol can be prepared by adopting a one-step method, is simple to prepare, has abundant raw material reserves, is safe and environment-friendly, is used for preparing the perovskite battery device based on a low-temperature solution process, and can be explored for large-scale preparation. The method can not only improve SnO2Carrier concentration and electron transport characteristics, HF modified SnO2Surface property, promotion of F-1The ions are transferred with the perovskite halogen ions, so that the interface contact is improved, the efficient separation and extraction of photo-generated charges are promoted, and the photoelectric conversion efficiency of the perovskite solar cell is improved. In addition, the method can also explore the large-scale preparation of the perovskite solar cell, and provide the best experimental conditions and key experimental techniques for the commercialization of the perovskite solar cell.
Based on the purpose, the invention adopts the following technical scheme:
HF modified SnO2The method for preparing the perovskite solar cell as the electron transport layer comprises the following steps (the electron transport layer is completed in an air environment, and the other preparation processes are completed in a glove box):
(1) dispersing Sn powder into deionized water to obtain a dispersion liquid A, and adding HF and concentrated HNO3Adding the mixed solution into the dispersion liquid A, stirring until the Sn powder is completely dissolved to form HF modified SnO2Precursor solution of HF HNO 31 mol% -10 mol% of mol%, adding SnO2Diluting the precursor solution with deionized water, carrying out hydrothermal reaction at 220-240 ℃ for 20-25 h, adjusting the pH value to 9-10 with ammonia water, and obtaining the HF modified SnO2Hydrosol;
(2) directly depositing the solution obtained in the step (1) on a clean ITO electrode by using a spin coating method, and annealing to obtain HF modified SnO2An electron transport layer;
(3) mixing diblock copolymer (PEO)150-(PPO)20Dissolved in DMF and the diblock copolymer solution is added to (FAPbI)3)1-x(MAPbBr3)xIn the perovskite precursor solution, the value range of x is 0.2-0.5, obtaining the perovskite precursor solution containing the diblock copolymer, and the diblock copolymer is in the perovskite precursor solutionThe concentration of (A) is 1-10 mg/mL;
(4) modification of SnO in HF2Depositing the solution of spin-coating step (3) on the electron transport layer to obtain (FAPBI) containing diblock copolymer3)1-x(MAPbBr3)xA photosensitive layer;
(5) depositing a Spiro-OMeTAD hole transport layer on the photosensitive layer;
(6) and (4) evaporating an Au counter electrode on the Spiro-OMeTAD hole transport layer to obtain the composite material.
The processing process of the clean ITO and the common glass is as follows: selecting a deposited ITO strip electrode glass sheet and a common glass sheet, and repeatedly wiping and washing the glass sheet by using a detergent to remove oil stains on the surface of the glass sheet; dividing ITO conductive glass and common glass into regular small pieces, such as 1 cm multiplied by 1 cm, and sequentially carrying out ultrasonic treatment in deionized water for 30 min, acetone solution for 30 min and isopropanol solution for 30 min; and drying the obtained ITO glass sheet and common glass in an oven at 100 ℃ for 30 min to obtain the ITO glass sheet.
The HF-modified SnO2The hydrosol is obtained by the following method:
(a) directly adding Sn powder and deionized water into the lining of a polytetrafluoroethylene reaction kettle; appropriate amount of HF and concentrated HNO3Adding into the inner liner of another polytetrafluoroethylene reaction kettle, and stirring with lead rod to obtain a uniformly mixed solution of the two, wherein HF is HNO31-10 mol% of the molar weight;
(b) slowly dripping HF and HNO into the mixture of Sn powder and deionized water obtained in the step (a) along the inner lining wall of the polytetrafluoroethylene reaction kettle3Mixing the solution, slightly stirring the solution by using a lead rod, and after the mixed acid solution is dripped, continuously stirring until Sn powder is completely dissolved to obtain a uniform and dispersed solution;
(c) diluting the dissolved Sn powder solution with deionized water, and carrying out hydrothermal reaction at 220-240 ℃ for 20-25 h to obtain HF modified SnO2An aqueous dispersion solution;
(d) modification of SnO in HF2Dropwise adding ammonia water into the aqueous dispersion solution, adjusting the pH value to 9-10, and preventing SnO2The nano particles are agglomerated to obtain stable HF modified SnO2Aqueous solution, can be directly usedSpin-on deposition of HF-modified SnO2An electron transport layer.
Preferably, when the amount of Sn powder is 5 g, 5 mL of deionized water is added in the step (a); 30mL of concentrated HNO3(65-68 wt%) and HNO3Mixing 1-10 mol% of HF (40.0 wt% in mass percentage), and continuously stirring with a lead rod to obtain a uniform mixed solution of the HF and the HF; step (c) was diluted with 30mL of deionized water.
Further, HF-modified SnO2The preparation process of the electron transport layer is as follows: depositing 30-50 mu L HF modified SnO in one step2The hydrosol is annealed on a hot bench to obtain HF modified SnO2An electron transport layer.
Further, the polymer composition contains a diblock copolymer (PEO)150-(PPO)20(FAPBI)3)1-x(MAPbBr3)xThe photosensitive layer was prepared as follows: weighing (1-x) mmol FAI and (1-x) mmol PbI in turn2And 0.35 mmol of MACl, sequentially adding the materials into a mixed solvent of DMF and DMSO (volume ratio of 4:1), and stirring at 60 ℃ until the solid is completely dissolved to obtain a perovskite precursor; weighing x mmol MABr and x mmol PbBr sequentially2Sequentially adding the materials into a mixed solvent of DMF and DMSO (volume ratio of 4:1), and stirring at 60 ℃ until the solid is completely dissolved to obtain another perovskite precursor; mixing the two perovskite precursors, and stirring at room temperature for 60-80 min to obtain a final perovskite precursor solution; addition of a formulated diblock copolymer (PEO)150-(PPO)20The concentration of the diblock copolymer in the perovskite precursor solution is 1-10.0 mg/mL, and the mixture is hermetically stirred at room temperature for 1-2 h to obtain the copolymer-containing (FAPBI)3)1-x(MAPbBr3)xPrecursor solution; will obtain (FAPBI)3)1-x(MAPbBr3)xDeposition of precursor solution to HF-modified SnO2On the electron transport layer, annealing to obtain (FAPBI)3)1-x(MAPbBr3)xA photosensitive layer.
(FAPbI3)1-x(MAPbBr3)xThe photosensitive layer is optimized to(FAPbI3)0.7(MAPbBr3)0.3The preparation method comprises the following specific steps: 0.7 mmol FAI and 0.7 mmol PbI were weighed in turn2And 0.35 mmol of MACl, sequentially adding the materials into a mixed solvent of 480 muL DMF and 120 muL DMSO, and stirring at 60 ℃ until the solid is completely dissolved to obtain a perovskite precursor; 0.3 mmol MABr and 0.3 mmol PbBr were weighed in turn2Sequentially adding the materials into a 206 mu L DMF (dimethyl formamide) and 51 mu L DMSO mixed solvent, and stirring at 60 ℃ until the solid is completely dissolved to obtain another perovskite precursor; mixing the two perovskite precursors, and stirring at room temperature for 60-80 min to obtain a final perovskite precursor solution; addition of a formulated diblock copolymer (PEO)150-(PPO)20The concentration of the diblock copolymer in the perovskite precursor solution is 1-10.0 mg/mL, and the mixture is hermetically stirred at room temperature for 1-2 h to obtain the (FAPBI) containing the diblock copolymer3)0.7(MAPbBr3)0.3Precursor solution; 70 muL (FAPbI)3)0.7(MAPbBr3)0.3Deposition of precursor solution to HF-modified SnO2On the electron transport layer, during spin coating, keeping the first step at 1000 rpm for 40 s, keeping the second step at 5000 rpm for 20 s, depositing 200 mu L chlorobenzene by spin coating 5 s before the second step is finished, and annealing to obtain (FAPBI)3)0.7(MAPbBr3)0.3A photosensitive layer.
Further, the annealing in the step (2) refers to annealing at 120 ℃ for 20 min. The annealing in the preparation process of the photosensitive layer means that annealing is carried out for 10 min at 150 ℃ and annealing is carried out for 10 min at 100 ℃ in sequence.
Further, the specific preparation process of the Spiro-OMeTAD hole transport layer is as follows: adding 72.3 mg of Spiro-OMeTAD into a mixed solution consisting of 1 mL of chlorobenzene, 28.5 muL 4-tert-butylpyridine, 18.5 muL of Li-TFSI and 18.5 muL of Co (III) -TFSI, stirring until the mixture is completely dissolved to obtain a Spiro-OMeTAD solution, and carrying out spin coating to deposit the Spiro-OMeTAD solution to obtain a hole transport layer.
Further, the SnO modified by HF prepared by the method2The perovskite solar cell as an electron transport layer comprises an ITO substrate and a self-descending substrate layerAnd on the surface of the alloy is sequentially HF modified SnO2Electronic transport layer, (FAPBI)3)0.7(MAPbBr3)0.3A photosensitive layer, a cyclone-OMeTAD hole transport layer, and an Au counter electrode layer, wherein HF modified SnO2The thickness of the electron transmission layer is 25-30 nm, (FAPBI)3)0.7(MAPbBr3)0.3The thickness of the photosensitive layer is 570nm, the thickness of the cyclone-OMeTAD hole transport layer is 120 nm, and the thickness of the Au counter electrode layer is 110 nm.
The invention takes Sn powder as raw material and adopts a simple one-step method to prepare HF modified SnO2And spin-coating and depositing the hydrosol to obtain the electron transport layer. SnO prepared by traditional method2The electron transport layer needs to lose part of oxygen in a high-temperature or low-pressure environment, generates more oxygen vacancies and structural defects, and has serious recombination of a photo-generated charge interface, thereby influencing the performance of the device; the invention adopts a simple one-step method to prepare SnO2Hydrosol and HF modified SnO2Surface property, promotion of F-1Ions are transferred with perovskite halogen ions, so that interface contact is improved, and efficient separation and extraction of photoproduction charges are promoted; the resultant SnO2The hydrosol not only can be used for spin coating and depositing a small-area electron transmission layer, but also can be used for preparing large-area HF modified SnO by adopting blade coating, spraying and rolling shaft methods2An electron transport layer; introducing the diblock copolymer into a perovskite precursor to passivate the crystal boundary defects of the perovskite thin film and promote the efficient extraction of photo-generated charges; and a Spiro-OMeTAD hole transport layer is deposited, so that the photovoltaic response and the device performance of the perovskite solar cell are improved.
Compared with the prior art, the invention has the following advantages:
HF modified SnO obtained by the application2/(FAPbI3)0.7(MAPbBr3)0.3The perovskite solar cell has the advantages of simple preparation method, abundant raw material storage and controllable preparation process, can be used for preparing cell devices in a large scale based on a low-temperature solution process, and is explored for commercial development; the average photoelectric conversion efficiency of the prepared solar cell reaches 22.81 percent, and the highest photoelectric conversion efficiency exceeds 22.92 percent; the photoelectric conversion efficiency of the optimized device is still kept above the initial efficiency of 83% after the device is continuously illuminated for 60 hours under the condition of no packaging. Book (I)The invention adopts a one-step method to obtain HF modified SnO2The hydrosol can realize the preparation of the whole perovskite battery device based on a low-temperature solution process. The method can improve interface contact, promote the efficient separation of photo-generated charges and improve the photoelectric conversion efficiency of the device; the preparation method can also adopt blade coating, spraying and roll-to-roll rolling shaft preparation processes to realize batch production and large-scale preparation and reduce the production cost, has wide application prospect, and provides good experimental basis and key technology for promoting the commercialization of the perovskite solar cell.
Drawings
In fig. 1: (a) HF-modified SnO prepared for example 12Surface topography; (b) prepared for example 1 (FAPBI)3)0.7(MAPbBr3)0.3The surface appearance of the film;
in fig. 2: (a) ordinary glass/HF modified SnO prepared for example 12/(FAPbI3)0.7(MAPbBr3)0.3Introducing 3% mole concentration HF corresponding to a steady-state photoluminescence spectrum into the Au composite film; (b) ordinary glass/HF modified SnO prepared for example 12/(FAPbI3)0.7(MAPbBr3)0.3Introducing 3% mole concentration HF corresponding transient photoluminescence spectrum into the Au composite film;
in fig. 3: (a) HF-modified SnO prepared for example 12/(FAPbI3)0.7(MAPbBr3)0.3The battery device being without introduction of HFJ-VA curve; (b) HF modified SnO prepared for example 12/(FAPbI3)0.7(MAPbBr3)0.3Optimized photovoltaic deviceJ-VA curve;
in fig. 4: (a) HF modified SnO prepared for example 22/(FAPbI3)0.7(MAPbBr3)0.3Introducing a mole percent change relation curve of the photoelectric conversion efficiency of the perovskite solar cell along with HF; (b) modification of SnO for HF2/(FAPbI3)0.7(MAPbBr3)0.3The perovskite solar cell incorporates 0% (corresponding to curve (1)), 3% molar concentration HF (corresponding to curve (2)) corresponding to the steady state surface photovoltaic response;
FIG. 5 shows the photoelectric conversion efficiency of perovskite solar cell of example 3 with copolymer (PEO)150-(PPO)20The concentration profile is added.
Detailed Description
The technical solutions of the present invention are described below with specific examples, but the scope of the present invention is not limited thereto.
In the following examples Sn powder was obtained from Fisher Scientific Chemicals Ltd, concentrated nitric acid, hydrofluoric acid and aqueous ammonia were obtained from Amazon Chemicals Ltd, MABr (methylamine hydrobromide), FAI (formamidine hydroiodide), PbI2、PbBr2MACl, DMSO, DMF, chlorobenzene, (PEO)150-(PPO)204-tert-butylpyridine, acetonitrile, Co (III) -TFSI and Li-TFSI were purchased from Sigma Aldrich technology, Inc., Spiro-OMeTAD was purchased from Shenzhen Feizhi, Inc., China.
Example 1
HF modified SnO2The method for preparing the perovskite solar cell as the electron transport layer comprises the following steps:
(1) selecting a deposited ITO strip electrode glass sheet and a common glass sheet, and repeatedly wiping and washing the glass sheet by using a detergent to remove oil stains on the surface of the glass sheet; dividing ITO conductive glass and common glass into regular small pieces, wherein the size of each piece is 1 cm multiplied by 1 cm, and sequentially carrying out ultrasonic treatment in deionized water for 30 min, acetone solution for 30 min and isopropanol solution for 30 min; and drying the obtained ITO glass sheet and common glass in an oven at 100 ℃ for 30 min to obtain a clean ITO electrode and the common glass sheet.
(2) Preparation of HF-modified SnO2Electron transport layer:
adding 5 g of Sn powder and 5 mL of deionized water into the lining of the polytetrafluoroethylene reaction kettle, and stirring by using a lead rod to uniformly disperse the Sn powder into the deionized water. In another polytetrafluoroethylene reactor liner, 30mL of concentrated HNO was added3(65-68 wt percent) is slowly added into a proper amount of HF (the mass percent of HF is 40.0 wt percent, and the HF accounts for HNO)3Mole percent 3mol%) and stirring with a lead rod to obtain a uniformly mixed solution of the two. Mixing the above two solutionsAnd (3) slowly adding the mixed solution into the mixed solution of the Sn powder and the deionized water along the lining wall of the reaction kettle, slightly stirring by using a lead rod, and continuously stirring by using the lead rod after the strong acid mixed solution is added until the Sn powder is completely dissolved to form a transparent solution.
Modification of all HF into SnO2Diluting the precursor solution with 30mL of deionized water, and carrying out hydrothermal reaction at 230 ℃ for 24 h to obtain HF modified SnO with good crystallization2Adding ammonia water (with the concentration of 28 wt%) into the aqueous dispersion solution to adjust the pH value to 9-10. Depositing 50 mu L HF modified SnO by using spin coating method2Aqueous dispersion (HF/HNO)3: 3mol percent) and annealed at 120 ℃ for 20 min on a hot bench to obtain HF modified SnO with the thickness of 30 nm2An electron transport layer, wherein FIG. 1 (a) shows HF-modified SnO2The picture of the surface appearance of the film scanning electron microscope shows that HF modified SnO2The particles are dispersed very uniformly and have an average particle diameter<10 nm。
(3) 368.5 mg of diblock copolymer (PEO)150-(PPO)20Adding the mixture into 1 mL of DMF solution, and stirring the mixture for 1 to 2 hours at room temperature to completely disperse the diblock copolymer into the DMF solution to form a uniform and transparent solution.
(4) Deposition (FAPBI)3)0.7(MAPbBr3)0.3Photosensitive layer: 0.7 mmol FAI and 0.7 mmol PbI are weighed in turn2And 0.35 mmol of MACl, sequentially adding the materials into a 480 muL DMF and 120 muL DMSO mixed solution, and stirring at 60 ℃ until the solid is completely dissolved to obtain a part of perovskite precursor; 0.3 mmol MABr and 0.3 mmol PbBr were weighed in turn2Sequentially adding the materials into a 206 mu L DMF and 51 mu L DMSO mixed solution, and stirring at 60 ℃ until the solid is completely dissolved to obtain another perovskite precursor; mixing the two perovskite precursors, and stirring at room temperature for 60-80 min to obtain a final perovskite precursor solution; addition of a formulated diblock copolymer (PEO)150-(PPO)20The concentration of the diblock copolymer in the perovskite precursor solution is 4 mg/mL, and the mixture is hermetically stirred for 1-2 h at room temperature to obtain (FAPBI) containing the diblock copolymer3)0.7(MAPbBr3)0.3A precursor; 70 muL (FAPbI)3)0.7(MAPbBr3)0.3Deposition of precursors to HF-modified SnO2On the electron transmission layer, during spin coating, the first step of maintaining the 1000 rpm for 40 s, the second step of maintaining the 5000 rpm for 20 s, and when the second step is finished and before 5 s, performing spin coating deposition on 200 mu L chlorobenzene, and annealing at 150 ℃ for 10 min and 100 ℃ for 10 min in sequence to obtain the (FAPbI) with the thickness of 570nm3)0.7(MAPbBr3)0.3A photosensitive layer. FIG. 1 (b) shows the surface morphology (diblock copolymer concentration: 4 mg/mL) of the crystalline perovskite thin film, wherein the perovskite crystal grain size is 1200-2000 nm, which shows that the perovskite crystal is good and the crystal grain size is large.
For a common glass substrate, 50 μ L of HF modified SnO was performed based on the same method as described above2Deposited on a common glass substrate (HF/HNO)3: 3mol%), 70 μ L of the perovskite solution (diblock copolymer concentration: 4 mg/mL) deposited on SnO2Depositing Au electrode on the film after crystallization to obtain HF modified SnO2/(FAPbI3)0.7(MAPbBr3)0.3FIG. 2 (a) shows the steady-state photoluminescence spectrum of the corresponding composite film, which indicates that HF-introduced modified SnO2Surface property, passivating structure defects, reducing charge non-radiative recombination and improving photoluminescence intensity; FIG. 2 (b) is a composite film transient photoluminescence spectrum also showing HF-modifiable SnO2Surface property, passivation structure defects, reduction of charge interface recombination, promotion of photo-generated charge separation and extraction, and improvement of the service life of photo-generated carriers;
(5) preparing a Spiro-OMeTAD hole transport layer: measuring 1 mL of chlorobenzene, 28.5 muL 4-tert-butylpyridine (TBP), 18.5 muL lithium bistrifluoromethanesulfonylimide (Li-TFSI) and 18.5 muL cobalt bistrifluoromethanesulfonylimide (Co (III) -TFSI), mixing, adding 72.3 mg of Spiro-OMeTAD into the solution, continuously stirring for 3-4 h to completely dissolve the solution, depositing 50 muL of Spiro-OMeTAD solution by spin coating, and naturally airing to obtain a Spiro-OMeTAD hole transport layer with the thickness of 120 nm.
(6) Vacuum evaporation of Au counter electrode (110 nm) to obtain HF modified SnO2/(FAPbI3)0.7(MAPbBr3)0.3Perovskite solar cellCan be used as a battery. Without introduction of HF and optimum performance of photovoltaic devicesJ-VThe curves are shown in FIGS. 3(a) and 3(b) (the spin-on volumes of the two electron transport layers are both 50 μ L, the diblock copolymer concentrations in the two perovskite photoactive layers are both 4 mg/mL, HF/HNO for the best performance device33mol%, FIG. 3(a) is the photoelectric response characteristic of a non-HF photovoltaic device, whichJ-VThe curve has a certain hysteresis, which indicates that there is no HF modified SnO2The film surface has more structural defects, resulting inJ-VThe curve has obvious hysteresis; FIG. 3(b) is a view of the preferred deviceJ-VAnd the photovoltaic parameters corresponding to the battery device are as follows: open circuit voltage (V OC= 1.157V), short-circuit current (c: (d)J SC=24.37 mAcm-2) Fill factor (FF =0.813), photoelectric conversion efficiency (PCE =22.92%), indicating that the cell device has significantly improved photovoltaic response characteristics, HF-modifiable SnO2The film property, the defect of a passivation structure, the improvement of interface contact, the promotion of the efficient separation and extraction of photo-generated charges and the elimination ofJ-VCurve hysteresis.
Example 2
SnO for HF modification2Aqueous dispersion of solution, varying mole percent HF (HF vs HNO)3The mol percentages are 0, 1, 3, 5, 7 and 10 mol percent in sequence), and the SnO is tested under different HF mol percentages2The specific results of the electronic conductivity of the thin film are detailed in Table 1, and Table 1 shows that SnO is not obviously reduced after HF with lower molar concentration is introduced2Electron conductivity.
TABLE 1 SnO after introduction of different mole percent HF2Electrical conductivity of electrons
Figure DEST_PATH_IMAGE002
HF-modified SnO with the above-mentioned different HF-introducing amounts2Preparing different HF modified SnO from aqueous solution2Electron transport layer, (HF vs HNO)3Mole percentages of 0, 1, 3, 5, 7, and 10 mol%) in sequence, and the photoelectric conversion efficiency of the perovskite solar cell corresponding to example 1 is determined by HF/HNO3The mol% change relation curve is shown in fig. 4(a), and the photoelectric conversion efficiency of the perovskite solar cell shows a trend of increasing first and then decreasing; shows that proper amount of HF (1-3 mol%) is introduced, and SnO is not obviously reduced2SnO can be passivated under the premise of carrier concentration and mobility2Structural defects, improved interface contact, and promotion of efficient separation and extraction of photo-generated charges. The photoelectric conversion efficiency is increased from 22.19 percent to 22.92 percent of the maximum efficiency, and the best device performance is achieved when the addition amount of HF is 3.0 mol percent in terms of HF molar ratio. When the addition amount of HF is 3.0 mol%, corresponding battery detection parameters are as follows: open circuit voltage of battery: (V OC= 1.157V), short-circuit current (c: (d)J SC=24.37 mAcm-2) Fill factor (FF =0.813), photoelectric conversion efficiency (PCE = 22.92%); FIG. 4(b) is a graph showing the steady-state surface photovoltaic response (optimum performance device, HF addition amount: 3.0 mol%), HF-modified SnO2/(FAPbI3)0.7(MAPbBr3)0.3The solar cell has stronger steady-state surface photovoltaic response, which indicates that HF modified SnO2And the introduction of the diblock copolymer can passivate crystal grain boundaries and interface defects, promote efficient separation and extraction of photo-generated charges and improve the photovoltaic response characteristic.
Example 3
For the incorporated diblock copolymer (PEO)150-(PPO)20The same procedure as in example 1 was repeated, except that the concentration of the copolymer in the perovskite precursor solution was changed (0, 2, 4, 6, 8, 10 mg/mL). The curve of the change of the photoelectric conversion efficiency of the battery device with the introduction of the diblock copolymer is shown in FIG. 5, and the photoelectric conversion efficiency of the battery device shows the trend of increasing first and then decreasing, as can be seen from FIG. 5, the increase of the diblock copolymer (PEO)150-(PPO)20The concentration may be better at passivating perovskite grain boundary defects, but with the introduction of higher concentrations of copolymer, a thicker heterogeneous interfacial layer will form at the perovskite grain boundaries due to the copolymer (PEO)150-(PPO)20The insulating material has excellent insulating property, and can block the transmission and extraction of photo-generated charges, thereby seriously affecting the performance of a battery device; the copolymer has the best photoelectric properties at a concentration of 4 mg/mL in the perovskite precursor (corresponding to photoelectric parameters:V OC=1.157 V、J SC=24.37 mAcm-2FF =0.813, PCE =22.92%), which not only passivates perovskite defects, but also maintains superior electrical properties of the perovskite thin film, improving the photovoltaic response characteristics of the device.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and amendments can be made without departing from the principle of the present invention, and all such modifications and amendments should be considered as the protection scope of the present invention.

Claims (9)

1. HF modified SnO2A method for preparing a perovskite solar cell as an electron transport layer is characterized by comprising the following steps:
(1) dispersing Sn powder into deionized water to obtain a dispersion liquid A, and adding HF and concentrated HNO3Adding the mixed solution into the dispersion liquid A, stirring until the Sn powder is completely dissolved to form HF modified SnO2Precursor solution of HF HNO31 mol% -10 mol% of mol%, adding SnO2Diluting the precursor solution with deionized water, carrying out hydrothermal reaction at 220-240 ℃ for 20-25 h, adjusting the pH value to 9-10 with ammonia water, and obtaining the HF modified SnO2Hydrosol;
(2) directly depositing the solution obtained in the step (1) on a clean ITO electrode by using a spin coating method, and annealing to obtain HF modified SnO2An electron transport layer;
(3) mixing diblock copolymer (PEO)150-(PPO)20Dissolved in DMF and the diblock copolymer solution is added to (FAPbI)3)1-x(MAPbBr3)xIn the perovskite precursor solution, the value range of x is 0.2-0.5, obtaining the perovskite precursor solution containing the diblock copolymer, wherein the concentration of the diblock copolymer in the perovskite precursor solution is 1-10 mg/mL;
(4) modification of SnO in HF2Depositing the solution of spin-coating step (3) on the electron transport layer to obtain (FAPBI) containing diblock copolymer3)1-x(MAPbBr3)xA photosensitive layer;
(5) depositing a Spiro-OMeTAD hole transport layer on the photosensitive layer;
(6) and (4) evaporating an Au counter electrode on the Spiro-OMeTAD hole transport layer to obtain the composite material.
2. HF-modified SnO according to claim 12The method for preparing the perovskite solar cell as the electron transport layer is characterized in that in the step (1), when Sn powder is 5 g in the dispersion liquid A, the using amount of deionized water is 5 mL; 30mL of concentrated HNO3And HNO3Mixing concentrated HF with the mol percentage of 1-10 mol%, and continuously stirring with a glass rod to obtain a uniform mixed solution of the concentrated HF and the glass rod; SnO2The precursor solution was diluted with 30mL of deionized water.
3. HF-modified SnO according to claim 12A method for producing perovskite solar cells as electron transport layers, characterized in that HF-modified SnO2The preparation process of the electron transport layer is as follows: depositing 30-50 mu L HF modified SnO in one step2The hydrosol is annealed on a hot bench to obtain HF modified SnO2An electron transport layer.
4. HF-modified SnO according to claim 12Method for producing perovskite solar cells as electron transport layer, characterized in that said layer comprises a diblock copolymer (PEO)150-(PPO)20(FAPBI)3)1-x(MAPbBr3)xThe photosensitive layer was prepared as follows: weighing (1-x) mmol FAI and (1-x) mmol PbI in turn2And 0.35 mmol of MACl, sequentially adding the materials into a mixed solvent of DMF and DMSO with the volume ratio of 4:1, and stirring at 60 ℃ until the solid is completely dissolved to obtain a perovskite precursor; weighing x mmol MABr and x mmol PbBr in sequence2Sequentially adding the materials into a mixed solvent of DMF and DMSO in a volume ratio of 4:1, and stirring at 60 ℃ until the solid is completely dissolved to obtain another perovskite precursor; mixing the two perovskite precursors, and stirring at room temperature for 60-80 min to obtain a final perovskite precursor solution; addition of a formulated diblock copolymer (PEO)150-(PPO)20The concentration of the diblock copolymer in the perovskite precursor solution is 1-10.0 mg/mL, and the mixture is hermetically stirred at room temperature for 1-2 h to obtain the (FAPBI) containing the block copolymer3)1-x(MAPbBr3)xAnd (3) precursor solution.
5. HF-modified SnO according to claim 42Method for producing perovskite solar cells as electron transport layer, characterized in that (FAPBI)3)1-x(MAPbBr3)xThe photosensitive layer is specifically (FAPBI)3)0.7(MAPbBr3)0.3The preparation method comprises the following specific steps: 0.7 mmol FAI and 0.7 mmol PbI were weighed in turn2And 0.35 mmol of MACl, sequentially adding the materials into a mixed solvent of 480 muL DMF and 120 muL DMSO, and stirring at 60 ℃ until the solid is completely dissolved to obtain a perovskite precursor; 0.3 mmol MABr and 0.3 mmol PbBr were weighed in turn2Sequentially adding the materials into a mixed solvent of 206 mu L DMF and 51 mu L DMSO, and stirring at 60 ℃ until the solid is completely dissolved to obtain another perovskite precursor; mixing the two perovskite precursors, and stirring at room temperature for 60-80 min to obtain a final perovskite precursor solution; addition of a formulated diblock copolymer (PEO)150-(PPO)20The concentration of the diblock copolymer in the perovskite precursor solution is 1-10.0 mg/mL, and the mixture is hermetically stirred at room temperature for 1-2 h to obtain the (FAPBI) containing the diblock copolymer3)0.7(MAPbBr3)0.3And (3) precursor solution.
6. HF-modified SnO according to claim 12A method for preparing a perovskite solar cell as an electron transport layer is characterized in that 70 mu L of (FAPBI) containing diblock copolymer is added in the step (4)3)1-x(MAPbBr3)xDeposition of precursor solution to HF-modified SnO2On the electron transport layer, during spin coating, keeping the first step at 1000 rpm for 40 s, keeping the second step at 5000 rpm for 20 s, depositing 200 mu L chlorobenzene by spin coating 5 s before the second step is finished, and annealing to obtain the diblock copolymer-containing (FAPBI)3)1-x(MAPbBr3)xA photosensitive layer.
7. HF-modified SnO according to claim 12The method for preparing the perovskite solar cell as the electron transport layer is characterized in that the annealing in the step (2) is performed at 120 ℃ for 20 min.
8. HF-modified SnO according to claim 62The method for preparing the perovskite solar cell as the electron transport layer is characterized in that annealing in the preparation process of the photosensitive layer means annealing at 150 ℃ for 10 min and annealing at 100 ℃ for 10 min in sequence.
9. HF-modified SnO produced by the process of any one of claims 1 to 82The perovskite solar cell as the electron transport layer is characterized by comprising an ITO substrate, wherein HF modified SnO is sequentially arranged on the substrate from bottom to top2Electronic transport layer, (FAPBI)3)1-x(MAPbBr3)xA photosensitive layer, a cyclone-OMeTAD hole transport layer, and an Au counter electrode layer, wherein HF modified SnO2The thickness of the electron transmission layer is 25-30 nm, (FAPbI)3)1-x(MAPbBr3)xThe thickness of the photosensitive layer is 570nm, the thickness of the Spiro-OMeTAD hole transport layer is 120 nm, and the thickness of the Au counter electrode layer is 110 nm.
CN202110690401.4A 2021-06-22 2021-06-22 Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof Active CN113421969B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110690401.4A CN113421969B (en) 2021-06-22 2021-06-22 Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110690401.4A CN113421969B (en) 2021-06-22 2021-06-22 Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113421969A CN113421969A (en) 2021-09-21
CN113421969B true CN113421969B (en) 2022-05-31

Family

ID=77789744

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110690401.4A Active CN113421969B (en) 2021-06-22 2021-06-22 Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113421969B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114551723B (en) * 2021-12-30 2023-08-04 苏州科技大学 Perovskite battery based on acid treatment of tin oxide and preparation thereof
KR20240117212A (en) 2023-01-25 2024-08-01 연세대학교 산학협력단 Electron transporting layer for perovskite solar cell and perovskite solar cell comprising the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111668378A (en) * 2020-06-08 2020-09-15 河南大学 Perovskite solar cell with V-tin dioxide as electron transport layer and preparation method thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4497999B2 (en) * 2004-04-23 2010-07-07 シャープ株式会社 Dye-sensitized solar cell
KR101489209B1 (en) * 2013-08-26 2015-02-04 에스에프씨 주식회사 An organic light emitting diode and the method for preparation of the same
WO2016102401A1 (en) * 2014-12-23 2016-06-30 Agc Glass Europe Translucent conductive substrate for an organic light emitting device and method for its production
EP3065189A1 (en) * 2015-03-05 2016-09-07 Solaronix Sa Novel hole transport materials and optoelectronic devices containing the same
EP3279960A1 (en) * 2016-08-02 2018-02-07 Aalto University Foundation Method for inkjet printing an organic-inorganic perovskite
CN108011045B (en) * 2017-12-01 2020-11-03 江西钛创新能源科技有限公司 Silicon micro-column array organic-inorganic hybrid solar cell and preparation method thereof
CN109119614A (en) * 2018-08-28 2019-01-01 湖北文理学院 Lithium ion battery ternary positive electrode active material and preparation method thereof, positive electrode, lithium ion battery and products thereof
CN109216557B (en) * 2018-09-03 2022-04-01 陕西师范大学 Based on citric acid/SnO2Perovskite solar cell of electron transport layer and preparation method thereof
CN111668377B (en) * 2020-06-08 2022-02-18 河南大学 Perovskite solar cell with Mo-tin dioxide as electron transport layer and preparation method thereof
CN112071992A (en) * 2020-09-11 2020-12-11 中国计量大学 Phosphorus alkene/stannic oxide compound perovskite solar cell electron transport layer and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111668378A (en) * 2020-06-08 2020-09-15 河南大学 Perovskite solar cell with V-tin dioxide as electron transport layer and preparation method thereof

Also Published As

Publication number Publication date
CN113421969A (en) 2021-09-21

Similar Documents

Publication Publication Date Title
CN105226187B (en) Film crystal silicon perovskite heterojunction solar battery and preparation method thereof
CN109524548B (en) Perovskite solar cell and preparation method thereof
CN111668377B (en) Perovskite solar cell with Mo-tin dioxide as electron transport layer and preparation method thereof
CN107482122B (en) perovskite solar cell and preparation method
CN113421969B (en) Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof
CN110311039B (en) Nb-tin dioxide nano precursor and method for preparing perovskite solar cell by using Nb-tin dioxide nano precursor as electron transport layer
CN103296211B (en) Heterojunction solar battery device of organic-two dimensional crystal-inorganic hybridization and preparation method thereof
CN110335945B (en) Double-electron-transport-layer inorganic perovskite solar cell and manufacturing method and application thereof
CN109065724B (en) Mo-titanium dioxide-AgNWs flexible perovskite solar cell and preparation method thereof
CN107154460A (en) A kind of complete carbon-based perovskite solar cell and its preparation technology
CN111430544A (en) Perovskite solar cell based on organic material mixed doping and preparation method thereof
CN115440893B (en) Tin-lead perovskite solar cell based on 4-hydroxyphenylethyl ammonium halide modified layer and preparation method thereof
CN114649480B (en) Perfluoroorganic compound-doped perovskite type solar cell and preparation method thereof
CN105470399A (en) Perovskite solar cell based on undoped organic hole transport layer and preparation method
CN111261783B (en) Novel electron transport layer perovskite solar cell and preparation method thereof
CN111668378B (en) Perovskite solar cell with V-tin dioxide as electron transport layer and preparation method thereof
CN114678472A (en) FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same
CN113421970B (en) Perovskite solar cell with HCl modified tin dioxide as electron transport layer and preparation method thereof
CN110311043B (en) Sb-tin dioxide nano precursor and method for preparing perovskite solar cell by using Sb-tin dioxide nano precursor as electron transport layer
CN112687808A (en) High-stability perovskite solar cell based on sulfate doping
CN113328040B (en) Preparation method of organic solar cell with ZnO doped Fe2O3 as cathode interface layer material
CN109786558B (en) Perovskite type solar cell and preparation method thereof
CN109065649B (en) ZTO-AgNWs/CBS-GNs flexible thin-film solar cell and preparation method thereof
CN107369729B (en) A kind of nano ordered interpenetrating total oxygen compound hetero-junction thin-film solar cell and preparation method thereof
CN114937743B (en) Organic/inorganic perovskite solar cell based on formamidino and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant