CN111668377A - Perovskite solar cell with Mo-tin dioxide as electron transport layer and preparation method thereof - Google Patents

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

Info

Publication number
CN111668377A
CN111668377A CN202010510530.6A CN202010510530A CN111668377A CN 111668377 A CN111668377 A CN 111668377A CN 202010510530 A CN202010510530 A CN 202010510530A CN 111668377 A CN111668377 A CN 111668377A
Authority
CN
China
Prior art keywords
sno
transport layer
layer
electron transport
solar cell
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.)
Pending
Application number
CN202010510530.6A
Other languages
Chinese (zh)
Inventor
刘向阳
赵晓伟
牛晨
丁恒川
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 CN202010510530.6A priority Critical patent/CN111668377A/en
Publication of CN111668377A publication Critical patent/CN111668377A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/4213Comprising organic semiconductor-inorganic semiconductor hetero-junctions
    • H01L51/422Majority carrier devices using sensitisation of widebandgap semiconductors, e.g. TiO2
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • H01L51/0002Deposition of organic semiconductor materials on a substrate
    • H01L51/0003Deposition of organic semiconductor materials on a substrate using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • H01L51/0026Thermal treatment of the active layer, e.g. annealing
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2251/00Indexing scheme relating to organic semiconductor devices covered by group H01L51/00
    • H01L2251/30Materials
    • H01L2251/301Inorganic materials
    • H01L2251/303Oxides, e.g. metal oxides
    • H01L2251/305Transparent conductive oxides [TCO]
    • H01L2251/306Transparent conductive oxides [TCO] composed of tin oxides, e.g. F doped SnO2
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Abstract

The application discloses a Mo-SnO2The perovskite solar cell as an electron transport layer and the preparation method thereof are as follows: (1) deposition of Mo-SnO on clean ITO electrodes2An electron transport layer; (2) in Mo-SnO2Deposition of NH on the electron transport layer4A Cl/KCl interface modification layer; (3) introducing the P123 copolymer into a (FAMA) CsPbIBr system; (4) at NH4Depositing a (FAMA) CsPbIBr photosensitive layer on the Cl/KCl interface modification 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 22.83 percent, the highest photoelectric conversion efficiency exceeds 22.97 percent, and the solar cell has good illumination stability.

Description

Perovskite solar cell with Mo-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 Mo-tin dioxide as an electron transport layer and a preparation method thereof.
Background
Solar cells are an important technical basis for converting solar energy into electric energy in a large scale, and the development of solar cells is a new green technology for relieving the contradiction between economic development and energy and environment, wherein the crystal silicon solar cells have remarkable progress in the aspects of conversion efficiency, preparation cost and the like and occupy most of application markets. 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. For a new research hotspot in the photovoltaic field, the performance of the organic-inorganic hybrid perovskite solar cell is remarkably improved and exceeds the highest efficiency of a semiconductor compound solar cell (such as CdTe, CuInGaSn and the like). 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 photoelectric conversion efficiency of the perovskite solar cells is rapidly improved from 3.8% to 25.2%, and the researches lay a good experimental and theoretical foundation 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 TiO2And nano SnO2Being an electron-transporting layer, TiO2And SnO2Poor conductivity and low electron mobility, seriously affectPerovskite solar cell performance. The novel electron transport layer material is prepared by a low-temperature solution method, the electron transport property of the film is improved, the efficient extraction of photoproduction charges is promoted, the performance of the perovskite solar cell is improved, the large-scale preparation of the perovskite solar cell is realized, and the rapid commercialization of the perovskite solar cell is promoted.
Disclosure of Invention
The invention aims to provide a perovskite solar cell taking Mo-tin dioxide as an electron transport layer and a preparation method thereof. The method can improve the electron transmission characteristic of the electron transmission layer and the photoelectric conversion efficiency of the perovskite solar cell, can explore the large-scale preparation of the perovskite solar cell, and provides experimental conditions and key technologies for the rapid commercial exploration of the perovskite solar cell.
Based on the purpose, the invention adopts the following technical scheme:
Mo-SnO2The preparation method of 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) deposition of Mo-SnO on clean ITO electrodes2The electron transport layer comprises the following specific processes: Mo-SnO2Diluting the water dispersion solution with deionized water, adding ammonia water to adjust the pH value to 9-10, and carrying out spin coating on the Mo-SnO with the pH value adjusted2Depositing the aqueous dispersion solution on a clean ITO electrode, and annealing at 120 ℃ for 30min to obtain Mo-SnO2An electron transport layer;
(2) in Mo-SnO2Deposition of NH on the electron transport layer4Cl/KCl is used as an interface modification layer;
(3) at NH4Deposition of P123-containing (FA) on Cl/KCl interface modification layer0.85MA0.15)1-xCsxPb(I1-yBry)3The value range of x is 0.01-0.1, and the value range of y is 0.1-0.5;
(4) depositing a Spiro-OMeTAD hole transport layer on the photosensitive layer;
(5) and (4) evaporating an Au counter electrode on the Spiro-OMeTAD hole transport layer to obtain the composite material.
The Mo-SnO2The aqueous dispersion solution was obtained by the following method:
(a) mixing Sn powder and MoO3Mixing the powders, putting the mixture into the bottom of a round-bottom flask, and adding deionized water; stirring in an ice water bath, wherein the molar weight of Mo accounts for 1-8% of that of Sn;
(b) dropwise adding acetic acid into the product obtained in the step (a), and stirring the mixture at the temperature of below 50 ℃ until Sn powder and MoO3Completely dissolving;
(c) adding H dropwise to the solution of step (b)2O2
(d) Dropwise adding the solution obtained in the step (c) into an ammonia water solution, and stirring to obtain a precipitate; aging the precipitate for 12-24 h under the stirring state, repeatedly carrying out suction filtration and washing until the conductivity of the filtrate is less than or equal to 250 mu S cm-1To obtain Mo-SnO2Precursor solution;
(e) the obtained Mo-SnO2Diluting the precursor solution with deionized water, adjusting the pH value to 9-10 with ammonia water, and carrying out hydrothermal reaction at 120-230 ℃ for 12-24 h to obtain Mo-SnO2An aqueous dispersion solution.
Preferably, when the amount of Sn powder is 10 g, 55-65 mL of acetic acid with the concentration of 15-20 wt% is added in the step (b), and 3-5 mL of H with the concentration of 10-20 wt% is added in the step (c)2O2And (d) adding 55-65 mL of 10-15 wt% ammonia water.
The preparation process of the clean ITO electrode is as follows: selecting a glass sheet with deposited ITO strip electrodes, and repeatedly wiping and washing the glass sheet by using a detergent to remove oil stains on the surface of the glass sheet; dividing the ITO conductive glass into regular small pieces, such as 1 cm multiplied by 1 cm, and sequentially carrying out ultrasonic treatment in deionized water for 30min, acetone solution for 30min and isopropanol solution for 30 min; and drying the obtained ITO glass sheet in an oven at 100 ℃ for 30min to obtain a clean ITO electrode.
Further, the NH4The preparation process of the Cl/KCl interface modification layer is as follows: reacting NH4Cl and KCl are added according to the molar ratio of 1:1Stirring the two in ionized water to fully dissolve the two to obtain NH4The total concentration of Cl and KCl is 0.5 mg mL-1Mixing the solution, and depositing 60 mu L NH at one time4Cl/KCl solution to Mo-SnO2And annealing the electron transport layer to obtain the final product.
Further, said (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3The photosensitive layer was prepared by weighing 0.85 × (1-x) mmol of FAI, 0.15 × (1-x) mmol of MAI, and (3(1-y) -1)/2 mmol of PbI in that order2、3y/2 mmolPbBr2X mmol CsI and 9.12 mg Pb (SCN)2Mixing, adding a mixed solvent of DMSO and DMF in a volume ratio of 1:4, placing on a hot table at 60 ℃ in a glove box for 12 hours until the solid is completely dissolved, adding a triblock copolymer P123, wherein the concentration of the triblock copolymer P123 in the solution is 2.5 mg/mL-10.0 mg/mL, and stirring at room temperature for 1-2 hours in a sealing manner to obtain (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3A precursor; will obtain (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3Deposition of precursor to NH4Annealing the Cl/KCl interface modification layer to obtain (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3A photosensitive layer.
(FA0.85MA0.15)1-xCsxPb(I1-yBry)3The photosensitive layer is specifically (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3The preparation method comprises the following specific steps: 0.8075 mmol of FAI, 0.1425 mmol of MAI and 0.85 mmol of PbI are weighed in sequence2、0.15mmol PbBr20.05 mmol CsI and 9.12 mg Pb (SCN)2Mixing, adding 600 muL DMF and 150 muL DMSO, and placing the solution on a 60 ℃ hot table in a glove box for 12h until the solid is completely dissolved; 72 muL (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3Deposition of precursor solution to NH4On the Cl/KCl interface modification layer, when spin-coating,maintaining 1000 rpm for 10 s in the first step, maintaining 5000 rpm for 30 s in the second step, spin-coating and depositing 200 mu L chlorobenzene by using a solvent-resistant method 10 s before the second step is finished, and annealing at 100 ℃ for 30min to obtain (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3A photosensitive layer.
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 of 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 performing spin coating to deposit the Spiro-OMeTAD solution to obtain a hole transport layer.
Further, Mo-SnO obtained by the preparation method2The perovskite solar cell of the electron transmission layer comprises an ITO substrate, and Mo-SnO is sequentially arranged on the ITO substrate from bottom to top2Electron transport layer, NH4Cl/KCl interface modification layer and (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3A photosensitive layer, a cyclone-OMeTAD hole transport layer, and an Au counter electrode layer, wherein Mo-SnO2Thickness of electron transport layer is 25nm, NH4The thickness of the Cl/KCl interface modification layer is 3-5 nm, (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3The thickness of the photosensitive layer is 580 nm, the thickness of the Spiro-OMeTAD hole transport layer is 120nm, and the thickness of the Au counter electrode layer is 80 nm.
For glass flake/Mo-SnO2/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3The substrate of the/Au perovskite composite film is clean common glass.
The invention adopts non-chloride as raw material to prepare Mo-SnO2And spin-coating and depositing the precursor and the corresponding nano particles to obtain the electron transport layer. SnO prepared by traditional method2Electron transport layer, SnO needs to lose part of oxygen under high temperature or low pressure environment2The conductive material has certain conductivity, and the corresponding carrier concentration and the electron mobility are lower and the conductivity is poorer; the invention dopes proper amount of Mo into SnO2In the nano-particles, the particles are,increase carrier concentration and electron transport characteristics, improve SnO2Crystallinity, can be coated to deposit small-area electron transmission layer, and can also be used for preparing large-area Mo-SnO by blade coating, spraying and rolling method2An electron transport layer; deposition of NH4Cl/KCl passivates the interface defects of the electron transport layer and the perovskite layer, and promotes efficient separation and extraction of photo-generated charges; introducing the P123 copolymer into a perovskite precursor, passivating crystal grain boundaries and interface defects, and promoting 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:
Mo-SnO prepared by the application2/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3The perovskite solar cell has the advantages of simple preparation method, abundant raw material storage, wide application range, safety and environmental protection, and is based on a full low-temperature solution process, can be prepared in a large scale; the average photoelectric conversion efficiency of the prepared solar cell reaches 22.83%, and the highest photoelectric conversion efficiency exceeds 22.97% by optimizing the device preparation process; under the condition of no packaging, the prepared optimized device is continuously illuminated for 50 hours, and the photoelectric conversion efficiency of the optimized device is still kept above 80 percent of the initial efficiency. The preparation method can realize the preparation of the perovskite solar cell based on the full low-temperature solution process, not only can obtain higher photoelectric conversion efficiency, but also can realize batch production and large-scale preparation by adopting blade coating, spraying and roll-to-roll rolling shaft preparation processes, reduces the production cost, has wide application prospect, and lays a good experimental foundation for promoting the commercialization of the perovskite solar cell.
Drawings
In fig. 1: (a) Mo-SnO prepared for example 12Surface topography; (b) Mo-SnO prepared for example 12/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3A sectional structure morphology graph of the solar cell;
in fig. 2: (a) glass sheet/Mo-SnO prepared for example 12/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3J-V curve of Au composite film in dark state; (b) Mo-SnO prepared for example 12/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3Perovskite solar cell impedance spectroscopy;
in fig. 3: (a) Mo-SnO prepared for example 12/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3A perovskite solar cell J-V curve; (b) Mo-SnO prepared for example 12/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3Perovskite solar cell external quantum efficiency spectroscopy (EQE);
in fig. 4: (a) is Mo-SnO2/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3The photoelectric conversion efficiency of the perovskite solar cell changes along with the Mo doping mole percentage; (b) is Mo-SnO2/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3The perovskite solar cell time-resolved surface photovoltaic response;
FIG. 5 is a curve showing the change of the photoelectric conversion efficiency of the perovskite solar cell with the addition concentration of the copolymer P123.
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.
Sn powder and MoO in the following examples3The powder was obtained from Fisher Scientific Chemicals, Inc., the concentrated acetic acid, hydrogen peroxide and aqueous ammonia were obtained from Amazon Chemicals, Inc., MAI (methylamine hydroiodide), FAI (formamidine hydroiodide), PbI2、PbBr2、CsI、DMSO、DMF、Pb(SCN)2Chlorobenzene, P123, NH4Cl, KCl, Spiro-OMeTAD, 4-tert-butylpyridine, acetonitrile, Co (III) -TFSI, and Li-TFSI were purchased from Sigma Aldrich scientific Co.
Example 1
Mo-SnO2The preparation method of the perovskite solar cell as the electron transport layer comprises the following steps:
(1) selecting a deposited ITO strip electrode and a common glass sheet, and repeatedly wiping and washing the deposited ITO strip electrode and the common glass sheet by using a detergent to remove oil stains on the surface of the glass sheet; dividing the two into regular small pieces, such as 1 cm × 1 cm, and sequentially performing ultrasonic treatment in deionized water for 30min, acetone solution for 30min, and isopropanol solution for 30 min; and drying the obtained ITO electrode and the common glass sheet in an oven at 100 ℃ for 30min to obtain a clean ITO electrode and a common glass sheet.
(2) Preparation of Mo-SnO2Electron transport layer: 10 g of Sn powder and 0.485 g of MoO are weighed in sequence3Powder (Mo in 4 mol% relative to Sn) was added to a two-necked round bottom flask, 30 mL of deionized water was added, and stirring was continued (due to the presence of Sn powder and MoO)3The powder dissolution can generate more heat, and the whole experiment process is carried out in an ice-water bath in order to avoid the solution overflowing the flask); weighing 30 mL of concentrated acetic acid (36-38 wt%) and diluting the concentrated acetic acid with deionized water according to the volume ratio of 1:1, slowly dripping the diluted acetic acid into the aqueous solution, and continuously stirring at the temperature of below 50 ℃ to ensure that Sn powder and MoO powder3Completely dissolving to form a transparent solution; 2 mL of H was measured2O2(30 wt%) diluted with deionized water according to the volume ratio of 1:1, and slowly added into the transparent solution dropwise without stirring to ensure that Mo is ensured6+Is not reduced to Mo4+(ii) a Slowly dripping 60 mL of ammonia water (the ammonia water with the concentration of 28 wt% and deionized water are diluted according to the volume ratio of 1: 1) into the solution, and continuously stirring to ensure that the atomic-level uniform coprecipitation is formed; aging the precipitate overnight under the condition of continuous stirring, repeatedly performing suction filtration and washing by using deionized water until the conductance is less than or equal to 250 mu S cm-1Thus obtaining Mo-SnO2And (3) precursor solution. FIG. 1 (a) shows Mo-SnO2Scanning electron microscope pictures after hydrothermal reaction crystallization show that Mo-SnO2The particles are dispersed very uniformly and have an average particle diameter<10 nm。
100 mL of Mo-SnO was weighed2Diluting the precursor solution with 30 mL of deionized water, and carrying out hydrothermal reaction at 230 ℃ for 18 h to obtain Mo-SnO with good crystallization2An aqueous dispersion solution of a water-soluble polymer,adjusting the pH value to 9-10 by using ammonia water (the concentration is 28 wt%), and depositing 60 mu L of Mo-SnO by using a spin coating method2Dispersing the solution in water, and annealing at 120 deg.C for 30min on a hot bench to obtain Mo-SnO with a thickness of 25nm2An electron transport layer.
(3) Deposition of NH4Cl/KCl interface modification layer: adding 5.35 mg of NH4Dissolving Cl and 7.45 mg KCl into 25.6 mL deionized water, stirring for 10 min to fully dissolve the Cl and the KCl to obtain NH4The total concentration of Cl/KCl is 0.5 mg mL-1Mixing the solution in Mo-SnO2Depositing 60 mu L NH by one-time spin coating4Annealing the Cl/KCl solution for 10 min at 100 ℃ to obtain NH with the thickness of 2-4 nm4And a Cl/KCl interface modification layer.
(4) Deposition (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3Photosensitive layer: 0.8075 mmol of FAI, 0.1425 mmol of MAI and 0.85 mmol of PbI are weighed in sequence2、0.15 mmol PbBr20.05 mmol CsI and 9.12 mg Pb (SCN)2Mixing, adding 600 muL DMF and 150 muL DMSO, and placing the solution on a 60 ℃ hot table in a glove box for 12h until the solid is completely dissolved; adding the P123 copolymer solution according to the volume of P123 (molecular weight: 5750) in the perovskite precursor solution with the concentration of 5.0 mg/mL, sealing and stirring for 1-2 h in a glove box at room temperature, and dispersing and uniformly mixing; obtained from 72 μ L (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3Deposition of precursor solution to NH4Keeping the first step at 1000 rpm for 10 s and the second step at 5000 rpm for 30 s on the Cl/KCl interface modification layer, carrying out spin-coating deposition on 200 mu L chlorobenzene by using an anti-solvent method 10 s before the second step is finished, and carrying out annealing treatment to obtain the chlorobenzene layer (FA/KCl interface modification layer) with the thickness of 580 nm0.85MA0.15)0.95Cs0.05PbI2.7Br0.3A photosensitive layer.
For a common glass substrate, depositing a perovskite layer and evaporating an Au electrode to obtain a glass sheet/Mo-SnO based on the same method2/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3The composite film, FIG. 2 (a) is the composite film in the dark stateJ-V curve shows that the composite film has very low dark state current, and also shows that after P123 is introduced and KCl is deposited for modification, the crystal grain boundary and interface defects can be passivated, and the dark state current caused by the defect state is reduced;
(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 120nm thick Spiro-OMeTAD hole transport layer.
(6) Vacuum evaporating Au counter electrode (thickness is 80 nm) to obtain Mo-SnO2/(FA0.85MA0.15)0.95Cs0.05PbI2.7Br0.3Perovskite solar cell. FIG. 1 (b) is a cross-sectional morphology of the perovskite battery, which shows that the distribution of each component is clear, and the perovskite crystal particles are 800 nm-1500 nm, which shows that the perovskite crystal is good, the crystal grain size is large, and the perovskite battery has good morphology. Fig. 2 (b) is an electrochemical impedance spectrum of the perovskite cell, which shows that the solar cell has very large interface charge recombination impedance in a low-frequency region, and after crystal grain boundary and interface modification is performed by adopting P123 and KCl, the interface defect state concentration can be remarkably reduced, and the interface charge recombination impedance can be remarkably improved. It is composed ofJ-VThe curve and the External Quantum Efficiency (EQE) are shown in FIGS. 3(a) and 3(b), and it can be seen from FIG. 3(a) that the open-circuit voltage of the cell is: (V oc= 1.162V), short-circuit current: (J sc=24.26 mAcm-2) Fill factor (FF =0.81), photoelectric conversion efficiency (PCE =22.83%), indicating its superior photoelectric properties; as can be seen from fig. 3(b), the quantum efficiency (EQE) outside the visible light region of 420 to 790 nm is greater than 85.5%, which indicates that the perovskite solar cell has high photoelectric conversion efficiency in the entire visible light region.
Example 2
For Mo-SnO2The Mo mol percentage content of the aqueous dispersion is gradually increased (the mol percentage of Mo relative to Sn is 0, 2, 4, 6 and 8 mol percent in sequence), and different Mo doping mol percentages are testedMo-SnO2The specific results of the electronic conductivity are shown in table 1, and table 1 shows that the electronic conductivity of the doped Mo can be obviously improved.
TABLE 1 Mo-SnO after introduction of different Mo mol percents2Electrical conductivity of electrons
Mo-SnO with different Mo doping amounts2Preparation of Mo-SnO with different doping amounts by using aqueous dispersion2The electron transmission layer (mol percent of Mo relative to Sn is 0, 2, 4, 6, 8 mol%) and the corresponding perovskite solar cell photoelectric conversion efficiency shows a trend of increasing first and then decreasing, other is the same as example 1; perovskite solar cell photoelectric conversion efficiency along with Mo-SnO2The Mo/Sn mol% variation curve in the electron transport layer is shown in FIG. 4 (a); the method shows that Mo-SnO can be obviously improved by introducing a proper amount (2-4 mol%) of Mo under the premise of not obviously improving the carrier concentration2The electron transfer characteristic is that the photoelectric conversion efficiency is increased from 18.85% to 22.83% of the maximum efficiency (calculated by Sn molar ratio, Mo addition is 4.0 mol%), the photo-generated charge extraction is promoted, and the performance of a photovoltaic device is improved; when the addition amount of Mo is 4.0 mol%, the battery detection parameters are as follows: open circuit voltage (V oc= 1.162V), short-circuit current: (J sc=24.26 mAcm-2) Fill factor (FF =0.81), photoelectric conversion efficiency (PCE = 22.83%); FIG. 4(b) is a Mo-SnO time resolved surface photovoltaic response of a solar cell2/FA0.8Cs0.2Pb(I0.7Br0.3)3The solar cell has stronger transient surface photovoltaic response, and shows that after P123 and KCl deposition are introduced, crystal grain boundary and interface defects can be passivated, and efficient separation and extraction of photo-generated charges are promoted.
Example 3
For the introduced P123 copolymer, the concentration of the copolymer in the perovskite precursor solution is gradually increased (2.5 mg/mL, 5.0 mg/mL, 7.5 mg/mL, 10.0 mg/mL), and the photoelectric conversion efficiency of the corresponding perovskite solar cell also shows a trend of increasing and then decreasing, and the rest is the same as that of example 1. The curve of the photoelectric conversion efficiency of the perovskite solar cell along with the introduction of the P123 copolymer concentration is shown in FIG. 5, as can be seen from FIG. 5, the photoelectric conversion efficiency shows a trend of first-increasing and then-decreasing changes, the improvement of the concentration of the copolymer P123 can better passivate perovskite crystal grain boundary defects, but when the concentration of the copolymer P123 is too high, a passivation layer formed at the perovskite crystal grain boundary is thicker, and due to the insulating property of the copolymer P123, the separation and transmission of photo-generated charges are hindered, and the performance of a device is seriously influenced; the copolymer has the best photoelectric property when the concentration of the copolymer in the perovskite precursor solution is 5.0 mg/mL, the copolymer with the concentration can passivate perovskite defects, the quality and the electrical property of a perovskite thin film can be kept, and the photovoltaic response characteristic of a device is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. Mo-SnO2The preparation method of the perovskite solar cell as the electron transport layer is characterized by comprising the following steps:
(1) deposition of Mo-SnO on clean ITO electrodes2The electron transport layer comprises the following specific processes: Mo-SnO2Diluting the water dispersion solution with deionized water, adjusting pH to 9-10 with ammonia water, and spin-coating the pH-adjusted Mo-SnO2Depositing the aqueous dispersion solution on a clean ITO electrode, and annealing to obtain Mo-SnO2An electron transport layer;
(2) in Mo-SnO2Deposition of NH on the electron transport layer4Cl/KCl is used as an interface modification layer;
(3) at NH4Deposition of P123-containing (FA) on Cl/KCl interface modification layer0.85MA0.15)1-xCsxPb(I1-yBry)3The value range of x is 0.01-0.1, and the value range of y is 0.1-0.5;
(4) depositing a Spiro-OMeTAD hole transport layer on the photosensitive layer;
(5) and (4) evaporating an Au counter electrode on the Spiro-OMeTAD hole transport layer to obtain the composite material.
2. The Mo-SnO as claimed in claim 12A method for producing a perovskite solar cell as an electron transport layer, characterized in that the Mo-SnO2The aqueous dispersion solution was obtained by the following method:
(a) mixing Sn powder and MoO3Mixing the powders, and adding deionized water; stirring in an ice water bath, wherein the molar weight of Mo accounts for 1-8% of that of Sn;
(b) dropwise adding acetic acid into the obtained substance in the step (a), and stirring the mixture at the temperature of below 50 ℃ until Sn powder and MoO3Completely dissolving;
(c) adding H dropwise to the solution of step (b)2O2
(d) Dropwise adding ammonia water into the solution obtained in the step (c), and stirring to obtain a precipitate; aging the precipitate for 12-24 h under the stirring state, repeatedly carrying out suction filtration and washing until the conductivity of the filtrate is less than or equal to 250 mu S cm-1To obtain Mo-SnO2Precursor solution;
(e) the obtained Mo-SnO2Diluting the precursor solution with deionized water, adjusting the pH value to 9-10 with ammonia water, and carrying out hydrothermal reaction at 120-230 ℃ for 12-24 h to obtain Mo-SnO2An aqueous dispersion solution.
3. The Mo-SnO as claimed in claim 22The preparation method of the perovskite solar cell as the electron transport layer is characterized in that when 10 g of Sn powder is used, 55-65 mL of acetic acid with the concentration of 15-20 wt% is added in the step (b), and 3-5 mL of H with the concentration of 10-20 wt% is added in the step (c)2O2And (d) adding 55-65 mL of 10-15 wt% ammonia water.
4. The Mo-SnO as claimed in claim 12Method for producing a perovskite solar cell as an electron transport layer, characterized in that the NH is4The preparation process of the Cl/KCl interface modification layer is as follows: reacting NH4Adding deionized water into Cl and KCl according to the molar ratio of 1:1Stirring to dissolve the two components sufficiently to obtain NH4The total concentration of Cl and KCl is 0.5 mg mL-1Mixing the solution, and depositing 60 mu L NH at one time4Cl/KCl solution to Mo-SnO2And annealing the electron transport layer to obtain the final product.
5. The Mo-SnO as claimed in claim 12A method for producing a perovskite solar cell as an electron transport layer, characterized in that the P123-containing (FA) is0.85MA0.15)1-xCsxPb(I1-yBry)3The photosensitive layer was prepared by weighing 0.85 × (1-x) mmol of FAI, 0.15 × (1-x) mmol of MAI, and (3(1-y) -1)/2 mmol of PbI in that order2、3y/2mmol PbBr2X mmol CsI and 9.12 mg Pb (SCN)2Mixing, adding a mixed solvent of DMSO and DMF in a volume ratio of 1:4, standing at 60 ℃ until the solid is completely dissolved to obtain a perovskite precursor solution, adding a triblock copolymer P123, wherein the concentration of the triblock copolymer P123 in the perovskite precursor solution is 2.5 mg/mL-10.0 mg/mL, and stirring at room temperature for 1-2 h in a sealing manner to obtain (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3Precursor solution; will obtain (FA)0.85MA0.15)1-xCsxPb(I1- yBry)3Deposition of precursor solution to NH4Annealing the Cl/KCl interface modification layer to obtain (FA)0.85MA0.15)1-xCsxPb(I1- yBry)3A photosensitive layer.
6. The Mo-SnO as claimed in claim 52A method for producing a perovskite solar cell as an electron transport layer, characterized in that (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3The photosensitive layer is specifically (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3The preparation method comprises the following specific steps: 0.8075 mmol of FAI, 0.1425 mmol of MAI and 0.85 mmol of MAI are weighed in sequence mmol PbI2、0.15mmol PbBr20.05 mmoleCsI and 9.12 mg Pb (SCN)2Mixing, adding 600 muL DMF and 150 muL DMSO, and placing the solution on a 60 ℃ hot table in a glove box for 12h until the solid is completely dissolved; adding a triblock copolymer P123, wherein the concentration of the triblock copolymer P123 in the perovskite precursor solution is 2.5 mg/mL-10.0 mg/mL, and hermetically stirring at room temperature for 1-2 h to obtain (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3Precursor solution; 72 muL (FA)0.85MA0.15)0.95Cs0.05PbI2.7Br0.3Deposition of precursor solution to NH4And (3) on the Cl/KCl interface modification layer, keeping the first step at 1000 rpm for 10 s during spin coating, keeping the second step at 5000 rpm for 30 s, depositing 200 mu L chlorobenzene during spin coating 10 s before the second step is finished, and annealing to obtain (FA/KCl) interface modification layer0.85MA0.15)0.95Cs0.05PbI2.7Br0.3A photosensitive layer.
7. The Mo-SnO as claimed in claim 12The preparation method of the perovskite solar cell as the electron transport layer is characterized in that the annealing in the step (1) is annealing at 120 ℃ for 30 min.
8. The Mo-SnO as claimed in claim 62The preparation method of the perovskite solar cell used as the electron transport layer is characterized in that annealing in the preparation process of the photosensitive layer is annealing at 100 ℃ for 30 min.
9. Mo-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 Mo-SnO is sequentially arranged on the substrate from bottom to top2Electron transport layer, NH4Cl/KCl interface modification layer and (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3A photosensitive layer, a cyclone-OMeTAD hole transport layer, and an Au counter electrode layer, wherein Mo-SnO2Thickness of electron transport layer is 25nm, NH4The thickness of the Cl/KCl interface modification layer is 2-4 nm, (FA)0.85MA0.15)1-xCsxPb(I1-yBry)3The thickness of the photosensitive layer is 580 nm, the thickness of the Spiro-OMeTAD hole transport layer is 120nm, and the thickness of the Au counter electrode layer is 80 nm.
CN202010510530.6A 2020-06-08 2020-06-08 Perovskite solar cell with Mo-tin dioxide as electron transport layer and preparation method thereof Pending CN111668377A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010510530.6A CN111668377A (en) 2020-06-08 2020-06-08 Perovskite solar cell with Mo-tin dioxide as electron transport layer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010510530.6A CN111668377A (en) 2020-06-08 2020-06-08 Perovskite solar cell with Mo-tin dioxide as electron transport layer and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111668377A true CN111668377A (en) 2020-09-15

Family

ID=72386950

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010510530.6A Pending CN111668377A (en) 2020-06-08 2020-06-08 Perovskite solar cell with Mo-tin dioxide as electron transport layer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111668377A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103872348A (en) * 2012-12-11 2014-06-18 财团法人工业技术研究院 Accelerant, electrode, and manufacturing method thereof
WO2015164731A1 (en) * 2014-04-24 2015-10-29 Northwestern University Solar cells with perovskite-based light sensitization layers
CN109103023A (en) * 2018-08-14 2018-12-28 河南大学 A kind of Sb- stannic oxide-AgNWs/CBS-GNs flexible thin-film solar cell and preparation method thereof
CN109265664A (en) * 2018-09-17 2019-01-25 福州大学 A method of perovskite material stability in water is improved using embedding polymer altogether
CN110265557A (en) * 2019-06-05 2019-09-20 南京邮电大学 A kind of flexible white light device and preparation method thereof
CN110311039A (en) * 2019-06-28 2019-10-08 河南大学 A kind of Nb- stannic oxide nanometer presoma utilizes it as the method that electron transfer layer prepares perovskite solar battery
CN110311043A (en) * 2019-06-28 2019-10-08 河南大学 A kind of Sb- stannic oxide nanometer presoma utilizes it as the method that electron transfer layer prepares perovskite solar battery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103872348A (en) * 2012-12-11 2014-06-18 财团法人工业技术研究院 Accelerant, electrode, and manufacturing method thereof
WO2015164731A1 (en) * 2014-04-24 2015-10-29 Northwestern University Solar cells with perovskite-based light sensitization layers
CN109103023A (en) * 2018-08-14 2018-12-28 河南大学 A kind of Sb- stannic oxide-AgNWs/CBS-GNs flexible thin-film solar cell and preparation method thereof
CN109265664A (en) * 2018-09-17 2019-01-25 福州大学 A method of perovskite material stability in water is improved using embedding polymer altogether
CN110265557A (en) * 2019-06-05 2019-09-20 南京邮电大学 A kind of flexible white light device and preparation method thereof
CN110311039A (en) * 2019-06-28 2019-10-08 河南大学 A kind of Nb- stannic oxide nanometer presoma utilizes it as the method that electron transfer layer prepares perovskite solar battery
CN110311043A (en) * 2019-06-28 2019-10-08 河南大学 A kind of Sb- stannic oxide nanometer presoma utilizes it as the method that electron transfer layer prepares perovskite solar battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JITENDRA BAHADUR等: "Solution processed Mo doped SnO2 as an effective ETL in the fabrication of low temperature planer perovskite solar cell under ambient conditions", 《ORGANIC ELECTRONICS》 *
YINGXIA ZONG等: "Continuous Grain-Boundary Functionalization for High-Efficiency Perovskite Solar Cells with Exceptional Stability", 《CHEM》 *

Similar Documents

Publication Publication Date Title
Jiang et al. A two-terminal perovskite/perovskite tandem solar cell
Yang et al. Ammonium-iodide-salt additives induced photovoltaic performance enhancement in one-step solution process for perovskite solar cells
CN103700768A (en) Perovskite structural solar battery and preparation method thereof
CN104362253A (en) All solid state perovskite microcrystalline silicon composite solar battery and preparation method thereof
Tai et al. Ultrathin Zn2SnO4 (ZTO) passivated ZnO nanocone arrays for efficient and stable perovskite solar cells
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
CN108389967B (en) Light absorption layer material of solar cell, wide-band-gap perovskite solar cell and preparation method thereof
CN105609643A (en) Perovskite-type solar cell and preparation method
CN109065724B (en) Mo-titanium dioxide-AgNWs flexible perovskite solar cell and preparation method thereof
CN109103023B (en) Sb-tin dioxide-AgNWs/CBS-GNs flexible thin-film solar cell and preparation method thereof
CN108767117B (en) Perovskite solar cell based on carbon quantum dot doped anti-solvent passivated grain boundary defects 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
Zheng et al. Mesostructured perovskite solar cells based on Zn2SnO4 single crystal mesoporous layer with efficiency of 18.32%
CN109904318B (en) Perovskite thin film preparation method based on anti-solution bath and solar cell
CN111668378B (en) Perovskite solar cell with V-tin dioxide as electron transport layer and preparation method thereof
CN111668377A (en) Perovskite solar cell with Mo-tin dioxide as electron transport layer and preparation method thereof
CN108598268B (en) Method for preparing planar heterojunction perovskite solar cell by printing under environmental condition
CN108117568B (en) Silicon-based triphenylamine derivative, preparation method thereof and application thereof in perovskite solar cell
CN108389969B (en) Green solvent system and mixed solution for preparing perovskite layer of perovskite solar cell
CN107887513B (en) Solar cell based on ternary inorganic flat heterojunction thin film and preparation method thereof
CN109817810A (en) A kind of perovskite solar battery and preparation method adulterating triazolium ion liquid
CN113421970A (en) Perovskite solar cell with HCl modified tin dioxide as electron transport layer and preparation method thereof
CN110335945B (en) Double-electron-transport-layer inorganic perovskite solar cell and manufacturing method and application thereof
CN113421969A (en) Perovskite solar cell with HF modified tin dioxide as electron transport layer and preparation method thereof
CN109851571B (en) Conjugated organic small molecule interface modification material, preparation method and organic solar cell formed by conjugated organic small molecule interface modification material

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