CN108389977B - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a perovskite solar cell and a preparation method thereof, wherein the solar cell sequentially comprises the following components from bottom to top: the electronic transmission layer comprises a compact layer at the lower layer and a mesoporous layer at the upper layer, the compact layer and the mesoporous layer are both made of the same metal oxide material, the mesoporous layer is a mixed crystal phase metal oxide mesoporous film modified by quantum dots, and the quantum dots are positioned between the mesoporous layer and the perovskite light absorption layer. The invention adopts quantum dot materials with excellent photoelectric characteristics to modify the mixed crystal phase metal oxide film with higher carrier mobility, improves the transmission performance of electrons, and obtains the perovskite solar cell with high current density and high efficiency.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a method for preparing a high-efficiency perovskite solar cell by regulating and controlling an interface between an electron transport layer and a perovskite layer.
Background
With the increasing consumption of non-renewable energy, the shortage of energy and deterioration of environment become more serious problems for people in the new century, and the development and utilization of clean renewable energy are more and more regarded by people. Solar energy is an inexhaustible green and environment-friendly energy. The development of photovoltaic devices to convert solar energy into electric energy provides an important outlet for solving energy problems.
In recent years, perovskite solar cells have attracted much attention because of their high photoelectric conversion efficiency. Currently, the highest conversion efficiency of perovskite solar cell experiments is reported to exceed 22%. The electron transport layer is an important component of the perovskite solar cell and plays a role in electron extraction and transport in the perovskite solar cell. TiO 22、ZnO、SnO2、WO3、BaSnO4、SrTiO3、Zn2SnO4The equal-width forbidden metal oxide semiconductor material has good light transmission, stable chemical property and good charge separation and electron transmission performance. With TiO2For example, TiO2The energy gap is 3.2eV, the chemical stability is good, and the material is the most commonly used electron transport material in the perovskite solar cell. However, TiO2The electron transport materials still have defects, which affect the battery conversion efficiency: (1) TiO 22The nano material has a large amount of oxygen defects and vacancies, and charge recombination is easy to occur; (2) TiO 22And CH3NH3PbI3The perovskite materials have larger energy level difference to influence the rapid injection of electrons and the open-circuit voltage; (3) electrons in TiO2The mobility ratio in the electron transport layer is low, and recombination of electrons and holes easily occurs. Furthermore, anatase and rutile phase TiO2Rutile phase TiO with similar chemical properties and structure2The UV-absorbing material is stable, has a relatively small forbidden band width of about 3.0eV, has a high dielectric constant and refractive index, and can well scatter and absorb UV rays. Anatase phase TiO2Is a metastable phase, has a forbidden band width larger than that of a rutile phase (3.2eV), and has higher activity. TiO of dye sensitization solar battery2The related research of the photo-anode shows that when rutile and anatase phase TiO are in the photo-anode2When mixed in a certain proportion, the electron transmission efficiency is higher, and the efficiency of the battery is optimal.
The quantum dots have novel electronic and optical properties and can be used in many important fields such as electronics, photoelectronics, photovoltaics, biomedicine and the like. When the particle size enters the nanometer level, the size confinement causes size effect, quantum confinement effect, macroscopic quantum tunneling effect and surface effect, thereby having physical properties different from those of macroscopic systems and microscopic systems and exhibiting a plurality of unique physicochemical properties. Therefore, surface modification of the electron transport layer with quantum dots is an effective method for improving the performance of the battery.
Disclosure of Invention
The invention aims to solve the technical problems that the mobility ratio of electrons in an electron transport layer is low and the recombination of electrons and holes is easy to occur in the existing metal oxide electron transport layer, and improve the conversion efficiency of a battery.
To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, the present invention provides a method for preparing a high efficiency perovskite solar cell by controlling the conductivity of a metal oxide electron transport layer through a combination of a synthetic mixed crystal phase and a surface treatment.
The perovskite solar cell structure sequentially comprises the following components from bottom to top: the electron transport layer is formed on the anode layer. The electron transmission layer comprises a compact layer on the lower layer and a mesoporous layer on the upper layer, the compact layer and the mesoporous layer are both made of the same metal oxide material, the mesoporous layer is a mixed crystal phase metal oxide mesoporous film modified by quantum dots, and the quantum dots are positioned between the mesoporous layer and the perovskite light absorption layer.
Preferably, the metal oxide is TiO2、ZnO、SnO2、WO3、BaSnO4、SrTiO3、Zn2SnO4One of them. The mixed crystal phase metal oxide comprises at least two isomeric crystals.
Preferably, the dense layer is prepared by one of spin coating, spray coating, roll coating, spray pyrolysis, LB film or ink jet method, and the thickness of the dense layer is 10-100 nm.
Preferably, the mesoporous layer is synthesized by a hydrothermal method, and the thickness of the mesoporous layer is 100-2000 nm.
Preferably, the quantum dots are one or more of graphene quantum dots, carbon quantum dots, black phosphorus quantum dots, silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, lead sulfide quantum dots, zinc sulfide quantum dots, indium copper sulfide quantum dots, indium zinc sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, cadmium selenide quantum dots, zinc selenide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, indium arsenide quantum dots, indium gallium arsenide quantum dots, gallium nitride quantum dots, indium gallium nitride quantum dots or zinc oxide quantum dots, and the diameters of the quantum dots are 1-10 nm.
The perovskite light absorption layer is CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH(NH2)2PbI3、CH(NH2)2PbBr3、CH(NH2)2PbCl3、CsPbI3、CH3NH3SnI3、CH(NH2)2SnI3、CsSnI3、CsSnBr3、CsSnCl3、CH3NH3PbIxBr3-x、CH3NH3PbIxCl3-x、CH(NH2)2PbIxBr3-x、CH(NH2)2PbIxCl3-x、(CH3NH3)x(CH(NH2)2)1-xPbI3、Csx(CH3NH3)y(CH(NH2)2)1-x-yPbImBr3-m、Csx(CH3NH3)1-xPbI3、Csx(CH3NH3)1- xPbIxCl3-x、Csx(CH3NH3)1-xPbIxBr3-x、Csx(CH3NH3)y(CH(NH2)2)1-x-yPbImBrnCl3-m-n、Csx(CH3NH3)y(CH(NH2)2)1-x-yPbI3、Csx(CH(NH2)2)1-xPbIxBr3-x、Csx(CH(NH2)2)1-xPbIxCl3-x、Csx(CH3NH3)y(CH(NH2)2)1-x-yPbImCl3-m、Csx(CH(NH2)2)1-xPbI3One or more of (a).
The anode layer is one of gold, silver, nickel and copper.
The preparation method of the perovskite solar cell comprises the following steps:
s1, coating the prepared metal oxide precursor solution on a conductive substrate by a spin coating method or a spray coating method or a roller coating method or a spray pyrolysis method or an LB film method or an ink-jet method to prepare a metal oxide compact layer, and heating and annealing;
s2, preparing a metal salt hydrothermal reaction solution with a certain concentration, and growing a mixed crystal phase metal oxide mesoporous film on the compact layer by a hydrothermal method, namely a mesoporous layer;
s3, soaking the mesoporous film prepared in the step S2 in a quantum dot solution for modification, wherein quantum dots are attached to the surface of the mesoporous layer and partially enter pores of the mesoporous layer, and then blowing the mesoporous film with nitrogen for drying, wherein the concentration of the quantum dot solution is 0.0001-0.1 mol/L;
s4, preparing a perovskite light absorption layer on the quantum dot modified mesoporous film, so that the quantum dot is positioned between the mesoporous layer and the perovskite light absorption layer;
s5, preparing a hole transport layer on the perovskite light absorption layer;
and S6, preparing a hole transport layer, and preparing a metal anode layer in a thermal evaporation chamber with high vacuum degree to obtain the solar cell.
Preferably, before performing operation S1, the conductive substrate is pretreated by: and cleaning the conductive substrate with the surface roughness less than 1nm, drying by using dry nitrogen after cleaning, and performing ultraviolet light and ozone treatment.
Preferably, the titanium ore light absorption layer and the hole transport layer are both prepared by a spin coating method, a roll coating method or a spray coating method.
Preferably, the method for manufacturing a perovskite solar cell further comprises the step of placing the solar cell manufactured in the step S6 in a glove box filled with inert gas for encapsulation.
The invention has the advantages that:
(1) the quantum dots have novel photoelectronics and other properties, and the interface between the mixed crystal phase metal oxide electron transmission layer and the perovskite layer is modified by the quantum dots, so that the synergistic effect of the quantum dots and the mixed crystal phase is exerted, the photoproduction electrons generated by the quantum dots can be more quickly transmitted to the conduction band of the metal oxide electron transmission layer, the electron traps can be more effectively filled, the conductivity of the metal oxide electron transmission layer is improved, and the photoelectric conversion efficiency of the battery is remarkably improved.
(2) The mixed crystal phase metal oxide semiconductor is provided as an electron transmission layer, so that the transmission and collection efficiency of carriers can be obviously improved; the mixed crystal phase structure can be prepared by regulating and controlling by a hydrothermal method, has low equipment requirement, simple operation, low cost and easy synthesis, and is beneficial to realizing the commercial application of the perovskite battery.
Drawings
Fig. 1 is a schematic structural view of a perovskite solar cell in example 1.
FIG. 2 TiO in example 12XRD pattern of the mesoporous film.
FIG. 3, SEM topography and EDS elemental analysis of the electron transport layer in example 1: (a) mesoporous TiO 22SEM topography of electron transport layer, (b) TiO modified by graphene quantum dots2Electron transport layer SEM topography, (c) mesoporous TiO2EDS (electron emission spectroscopy) map of electron transport layer, and (d) TiO modified by graphene quantum dots2Electron transport layer EDS spectra.
FIG. 4 deposition on TiO in example 12TiO modified by electron transport layer and graphene quantum dot2CH of electron transport layer3NH3PbI3Time-resolved fluorescence spectroscopy testing of thin films (a) and electrochemical impedance spectroscopy of perovskite solar cells (b).
FIG. 5 Standard solar illumination in example 1 (AM1.5, 100 mW/cm)2) J-V curves for perovskite solar cells.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
As shown in fig. 1, a perovskite solar cell sequentially comprises, from bottom to top: conductive substrate 1, TiO2An electron transport layer 2, a perovskite light absorption layer 3, a hole transport layer 4, and an anode layer 5.
Example 1
A method of fabricating a perovskite solar cell, comprising the steps of:
step S1, selecting FTO (F-doped tin oxide) conductive glass with the surface roughness less than 1nm as a conductive substrate, firstly cleaning the FTO conductive substrate, drying the FTO conductive substrate with dry nitrogen after cleaning, and performing ultraviolet light and ozone treatment to obtain a clean FTO conductive substrate; preparation of TiO on clean FTO conductive substrate2The dense layer film has a film thickness of 60nm, and the specific operation method comprises the following steps: preparing ethanol solution of titanium isopropoxide with a certain concentration (0.25mol/L), and preparing TiO on the FTO conductive substrate by adopting a spin coating method, a spraying method, a roller coating method, a spray pyrolysis method, an LB membrane method or an ink-jet method2And (3) heating and annealing the dense layer film at 500 ℃ for 30 min.
S2, preparing a titanium salt hydrothermal reaction precursor solution by using 15ml of concentrated hydrochloric acid, 15ml of deionized water and 0.7ml of butyl titanate, and preparing the TiO 12The compact layer is used as a seed layer, and the mixed crystal TiO is grown on the compact layer by a hydrothermal method for one time2Mesoporous film (mesoporous layer), film thickness is 400 nm.
Step S3, the TiO prepared in the step S22The mesoporous film is soaked in graphene quantum dot solution with the concentration of 0.001mg/ml for modification, so that the graphene quantum dots enter pores of the mesoporous film and are attached to the surface of the mesoporous film, and then the mesoporous film is dried by nitrogen.
Step S4, spinning and coating a perovskite precursor solution on the mesoporous film prepared in the step S3, wherein the perovskite precursor solution is formed by dissolving 1.2mmol of CH in 1ml of N, N-dimethyl imide3NH3I and 1.2mmol of PbI2After the spin coating is finished, the prepared sample is placed on a heating table and heated at 100 ℃ for 20min to obtain CH3NH3PbI3A perovskite light absorbing layer.
And S5, spin-coating a hole transport solution on the perovskite light absorption layer prepared in the step S4 to prepare a hole transport layer, wherein the hole transport solution comprises 0.06mmol of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 0.03mmol of lithium bistrifluoromethanesulfonylimide and 0.2mmol of 4-tert-butylpyridine in 1ml of chlorobenzene, and after the spin-coating is finished, placing the prepared sample in an oven at 40 ℃ for 3-5 hours.
And S6, evaporating and plating a silver electrode on the hole transport layer prepared in the S5 by adopting a vacuum thermal evaporation method, and obtaining the perovskite solar cell.
Example 2
A method of fabricating a perovskite solar cell, comprising the steps of:
step S1, selecting FTO (F-doped tin oxide) conductive glass with the surface roughness less than 1nm as a conductive substrate, firstly cleaning the FTO conductive substrate, drying the FTO conductive substrate with dry nitrogen after cleaning, and performing ultraviolet light and ozone treatment to obtain a clean FTO conductive substrate; preparation of TiO on clean FTO conductive substrate (F-doped tin oxide)2The dense layer film has a film thickness of 30nm, and the specific operation method comprises the following steps: preparing ethanol solution of titanium isopropoxide with a certain concentration (0.25mol/L), and preparing TiO on the FTO conductive substrate by adopting a spin coating method, a spraying method, a roller coating method, a spray pyrolysis method, an LB membrane method or an ink-jet method2And (3) heating and annealing the dense layer film at 500 ℃ for 30 min.
S2, preparing a titanium salt hydrothermal reaction precursor solution by using 15ml of concentrated hydrochloric acid, 15ml of deionized water and 0.7ml of butyl titanate, and preparing the TiO 12The compact layer is used as a seed layer, and the mixed crystal TiO is grown on the compact layer by a hydrothermal method for one time2Mesoporous film (mesoporous layer), film thickness is 400 nm.
Step S3, the TiO prepared in the step S22The mesoporous film is soaked in graphene quantum dot solution with the concentration of 0.0015mg/ml for modification, so that the graphene quantum dots enter pores of the mesoporous film and are attached to the surface of the mesoporous film, and then the mesoporous film is dried by nitrogen.
Step S4 and step S3The prepared mesoporous film is spin-coated with perovskite precursor solution, and the perovskite precursor solution consists of 1.2mmol of CH dissolved in 1ml of N, N-dimethyl imide3NH3I and 1.2mmol of PbI2After the spin coating is finished, the prepared sample is placed on a heating table and heated at 100 ℃ for 20min to obtain CH3NH3PbI3A perovskite light absorbing layer.
And S5, spin-coating a hole transport solution on the perovskite light absorption layer prepared in the step S4 to prepare a hole transport layer, wherein the hole transport solution comprises 0.06mmol of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 0.03mmol of lithium bistrifluoromethanesulfonylimide and 0.2mmol of 4-tert-butylpyridine in 1ml of chlorobenzene, and after the spin-coating is finished, placing the prepared sample in an oven at 40 ℃ for 3-5 hours.
And S6, evaporating and plating a silver electrode on the hole transport layer prepared in the S5 by adopting a vacuum thermal evaporation method, and obtaining the perovskite solar cell.
Example 3
A method of fabricating a perovskite solar cell, comprising the steps of:
step S1, selecting FTO (F-doped tin oxide) conductive glass with the surface roughness less than 1nm as a conductive substrate, firstly cleaning the FTO conductive substrate, drying the FTO conductive substrate with dry nitrogen after cleaning, and performing ultraviolet light and ozone treatment to obtain a clean FTO conductive substrate; preparation of TiO on clean FTO conductive substrate (F-doped tin oxide)2The dense layer film has a film thickness of 30nm, and the specific operation method comprises the following steps: preparing ethanol solution of titanium isopropoxide with a certain concentration (0.25mol/L), and preparing TiO on the FTO conductive substrate by adopting a spin coating method, a spraying method, a roller coating method, a spray pyrolysis method, an LB membrane method or an ink-jet method2And (3) heating and annealing the dense layer film at 500 ℃ for 30 min.
S2, preparing a titanium salt hydrothermal reaction precursor solution by using 15ml of concentrated hydrochloric acid, 15ml of deionized water and 0.7ml of butyl titanate, and preparing the TiO 12The compact layer is used as a seed layer, and the mixed crystal TiO is grown on the compact layer by a hydrothermal method for one time2Mesoporous film (mesoporous layer), film thickness is 400 nm.
Step S3, the TiO prepared in the step S22The mesoporous film is soaked in a mixed quantum dot solution containing graphene electronic dots and carbon quantum dots for modification, the concentration of the graphene quantum dots in the mixed quantum dot solution is 0.01mg/ml, the concentration of the carbon quantum dots in the mixed quantum dot solution is 0.01mg/ml, so that the graphene electronic dots and the carbon quantum dots enter pores of the mesoporous film and are attached to the surface of the mesoporous film, and then the mesoporous film is dried by nitrogen.
S4, S3, wherein the mesoporous film is coated with perovskite precursor solution by spinning, and the perovskite precursor solution is formed by dissolving 1.2mmol of CH in 1ml of N, N-dimethyl imide3NH3I and 1.2mmol of PbI2After the spin coating is finished, the prepared sample is placed on a heating table and heated at 100 ℃ for 20min to obtain CH3NH3PbI3A perovskite light absorbing layer.
And S5, spin-coating a hole transport solution on the perovskite light absorption layer prepared in the step S4 to prepare a hole transport layer, wherein the hole transport solution comprises 0.06mmol of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 0.03mmol of lithium bistrifluoromethanesulfonylimide and 0.2mmol of 4-tert-butylpyridine in 1ml of chlorobenzene, and after the spin-coating is finished, placing the prepared sample in an oven at 40 ℃ for 3-5 hours.
And S6, evaporating and plating a silver electrode on the hole transport layer prepared in the S5 by adopting a vacuum thermal evaporation method, and obtaining the perovskite solar cell.
Example 4
A method of fabricating a perovskite solar cell, comprising the steps of:
step S1, selecting FTO (F-doped tin oxide) conductive glass with the surface roughness less than 1nm as a conductive substrate, firstly cleaning the FTO conductive substrate, drying the FTO conductive substrate with dry nitrogen after cleaning, and performing ultraviolet light and ozone treatment to obtain a clean FTO conductive substrate; preparation of TiO on clean FTO conductive substrate (F-doped tin oxide)2The dense layer film has a film thickness of 30nm, and the specific operation method comprises the following steps: preparing ethanol solution of titanium isopropoxide with a certain concentration (0.25mol/L), and performing spin coating, spray coating, roller coating, spray pyrolysis, LB film method or ink-jet methodPreparing TiO on FTO conductive substrate2And (3) heating and annealing the dense layer film at 500 ℃ for 30 min.
S2, preparing a titanium salt hydrothermal reaction precursor solution by using 15ml of concentrated hydrochloric acid, 15ml of deionized water and 0.7ml of butyl titanate, and preparing the TiO 12The compact layer is used as a seed layer, and the mixed crystal TiO is grown on the compact layer by a hydrothermal method for one time2Mesoporous film (mesoporous layer), film thickness is 400 nm.
Step S3, the TiO prepared in the step S22The mesoporous film is soaked in a mixed quantum dot solution containing graphene electronic dots, carbon quantum dots and black phosphorus quantum dots for modification, the concentration of the graphene quantum dots in the mixed quantum dot solution is 0.01mg/ml, the concentration of the carbon quantum dots in the mixed quantum dot solution is 0.015mg/ml, and the concentration of the black phosphorus quantum dots in the mixed quantum dot solution is 0.1mg/ml, so that the three quantum dots can enter pores of the mesoporous film and be attached to the surface of the mesoporous film, and then the mesoporous film is dried by nitrogen.
S4, S3, wherein the mesoporous film is coated with perovskite precursor solution by spinning, and the perovskite precursor solution is formed by dissolving 1.0mmol of CH in 1ml of N, N-dimethyl imide3NH3I、0.2mmol CH(NH2)2I and 1.2mmol of PbI2After the spin coating is finished, the prepared sample is placed on a heating table and heated at 100 ℃ for 20min to obtain (CH)3NH3)x(CH(NH2)2)1-xPbI3I.e. the perovskite light absorbing layer.
And S5, spin-coating a hole transport solution on the perovskite light absorption layer prepared in the step S4 to prepare a hole transport layer, wherein the hole transport solution comprises 0.06mmol of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 0.03mmol of lithium bistrifluoromethanesulfonylimide and 0.2mmol of 4-tert-butylpyridine in 1ml of chlorobenzene, and after the spin-coating is finished, placing the prepared sample in an oven at 40 ℃ for 3-5 hours.
And S6, evaporating and plating a layer of gold electrode on the hole transport layer prepared in the S5 by adopting a vacuum thermal evaporation method, and obtaining the perovskite solar cell.
Example 5
A method of fabricating a perovskite solar cell, comprising the steps of:
step S1, selecting FTO (F-doped tin oxide) conductive glass with the surface roughness less than 1nm as a conductive substrate, firstly cleaning the FTO conductive substrate, drying the FTO conductive substrate with dry nitrogen after cleaning, and performing ultraviolet light and ozone treatment to obtain a clean FTO conductive substrate; preparation of TiO on clean FTO conductive substrate (F-doped tin oxide)2The dense layer film has a film thickness of 30nm, and the specific operation method comprises the following steps: preparing ethanol solution of titanium isopropoxide with a certain concentration (0.25mol/L), and preparing TiO on the FTO conductive substrate by adopting a spin coating method, a spraying method, a roller coating method, a spray pyrolysis method, an LB membrane method or an ink-jet method2And (3) heating and annealing the dense layer film at 500 ℃ for 30 min.
S2, preparing a titanium salt hydrothermal reaction precursor solution by using 15ml of concentrated hydrochloric acid, 15ml of deionized water and 0.7ml of butyl titanate, and preparing the TiO 12The compact layer is used as a seed layer, and the mixed crystal TiO is grown on the compact layer by a hydrothermal method for one time2Mesoporous film (mesoporous layer), film thickness is 400 nm.
Step S3, the TiO prepared in the step S22The mesoporous film is soaked in cadmium telluride quantum dot solution with the concentration of 0.001mg/ml for modification, so that the graphene quantum dots enter pores of the mesoporous film and are attached to the surface of the film, and then the film is dried by nitrogen.
Step S4, spinning and coating a perovskite precursor solution on the mesoporous film prepared in the step S3, wherein the perovskite precursor solution is formed by dissolving 1.0mmol of CH in 1ml of N, N-dimethyl imide3NH3I、0.15mmol CH(NH2)2I. 0.05mmol CsI and 1.2mmol PbI2Placing the prepared sample on a heating table after the spin coating is finished, and heating at 100 ℃ for 20min to obtain Csx(CH3NH3)y(CH(NH2)2)1-x-yPbI, perovskite light absorbing layers.
And S5, spin-coating a hole transport solution on the perovskite light absorption layer prepared in the step S4 to prepare a hole transport layer, wherein the hole transport solution comprises 0.06mmol of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 0.03mmol of lithium bistrifluoromethanesulfonylimide and 0.2mmol of 4-tert-butylpyridine in 1ml of chlorobenzene, and after the spin-coating is finished, placing the prepared sample in an oven at 40 ℃ for 3-5 hours.
And S6, evaporating and plating a layer of gold electrode on the hole transport layer prepared in the S5 by adopting a vacuum thermal evaporation method, and obtaining the perovskite solar cell.
Example 6
Step S1, selecting FTO (F-doped tin oxide) conductive glass as a conductive substrate, and preparing a ZnO dense layer film as a seed layer on the pretreated clean conductive substrate, wherein the thickness of the film is 30 nm; the specific preparation operation method comprises the following steps: preparing 0.45mol/L zinc acetate solution (the solution composition is that 1g of zinc acetate dihydrate and 0.28 mul of ethanolamine are dissolved in 10ml of di-methoxy ethanol), preparing the ZnO dense layer film on the FTO conductive substrate by adopting a spin coating method or a spray coating method or a roller coating method or a spray pyrolysis method or an LB film method or an ink-jet method, and heating and annealing at 500 ℃ for 30 min.
And S2, preparing a zinc salt hydrothermal reaction precursor solution by using 30ml of deionized water, 0.2677g of zinc nitrate hexahydrate and 0.1262g of hexamethylenetetramine, and growing a ZnO mesoporous film on the ZnO seed layer prepared in the step S1 by a hydrothermal method, wherein the thickness of the film is 300 nm.
And S3, soaking the ZnO mesoporous film prepared in the step S2 in a carbon quantum dot solution with the concentration of 0.001mg/ml for modification, and then drying the modified ZnO mesoporous film by using nitrogen.
And S5, spin-coating a hole transport solution on the perovskite layer prepared in the step S4 to prepare a hole transport layer, wherein the hole transport solution comprises 0.06mmol of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 0.03mmol of lithium bistrifluoromethanesulfonylimide and 0.2mmol of 4-tert-butylpyridine in 1ml of chlorobenzene, and after the spin-coating is finished, placing the prepared sample in an oven at 40 ℃ for 3-5 hours.
And S6, evaporating a layer of gold electrode on the sample prepared in the step S5 by adopting a vacuum thermal evaporation method, and obtaining the perovskite solar cell.
Example 7
Step S1, selecting FTO (F-doped tin oxide) conductive glass as a conductive substrate, and preparing dense SnO on the cleaned FTO conductive glass after pretreatment2The compact layer is used as a seed layer, and the thickness of the film is 30 nm; the specific preparation operation method comprises the following steps: preparing 0.5mol/L tin dichloride solution (the solution composition is 1.1283g of tin dichloride dihydrate dissolved in 10ml of ethanol), preparing a ZnO dense layer film on an FTO conductive substrate by adopting a spin coating method, a spray coating method, a roller coating method, a spray pyrolysis method, an LB film method or an ink-jet method, and heating and annealing at 500 ℃ for 30 min.
Step S2 SnO prepared in step S12SnO growth on seed layer by hydrothermal method2The thickness of the mesoporous film is 300 nm;
step S3, SnO prepared in step S22Soaking the mesoporous layer in a cadmium sulfide quantum dot solution with the concentration of 0.001mg/ml for modification, and then blowing the mesoporous layer with nitrogen;
s4, S3, the prepared sample is spin-coated with perovskite precursor solution, the perovskite precursor solution is composed of 1ml of N, N-dimethyl imide dissolved with 1.0mmol of CH3NH3I、0.15mmol CH(NH2)2I. 0.05mmol CsI and 1.2mmol PbI2Placing the prepared sample on a heating table after the spin coating is finished, and heating at 100 ℃ for 20min to obtain Csx(CH3NH3)y(CH(NH2)2)1-x-yPbI, perovskite light absorbing layers.
And S5, spin-coating a hole transport solution on the perovskite layer prepared in the step S4 to prepare a hole transport layer, wherein the hole transport solution comprises 0.06mmol of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 0.03mmol of lithium bistrifluoromethanesulfonylimide and 0.2mmol of 4-tert-butylpyridine in 1ml of chlorobenzene, and after the spin-coating is finished, placing the prepared sample in an oven at 40 ℃ for 3-5 hours.
And S6, evaporating a layer of gold electrode on the sample prepared in the step S5 by adopting a vacuum thermal evaporation method, and obtaining the perovskite solar cell.
The performance test of the solar cell prepared in example 1 is characterized as follows:
FIG. 2 shows TiO in example 12XRD test pattern of mesoporous film shows that TiO grown by hydrothermal method2The film is a rutile and anatase mixed crystal phase structure.
FIG. 3 shows TiO in example 12TiO modified by electron transport layer and 0.001mg/ml graphene quantum dot2SEM topography and EDS elemental analysis of the electron transport layer. Wherein (a) is mesoporous TiO2SEM topography of electron transport layer, and (b) TiO modified by graphene quantum dots2An SEM topography of an electron transport layer, and (c) is mesoporous TiO2EDS atlas of electron transport layer, (d) TiO modified by graphene quantum dots2Electron transport layer EDS spectra. From the test results, the content of the element C in the electron transport layer is increased after the graphene quantum dots are modified, which indicates that the graphene quantum dots are adsorbed on TiO2On the mesoporous film, on TiO2The film acts to increase the content of C element.
FIG. 4 is CH in example 13NH3PbI3Deposition of perovskite thin films on TiO2TiO modified by electron transport layer and graphene quantum dot2Time-resolved fluorescence spectroscopy testing of electron transport layers (a) and electrochemical impedance spectroscopy of perovskite solar cells (b). It can be seen that the perovskite thin film is deposited with TiO modified by graphene quantum dots2On the electron transport layer, the recombination lifetime of the carriers is shorter, which shows that electrons are faster transported from the perovskite layer to the TiO modified by the graphene quantum dots2And the electron transport layer reduces electron recombination.
Under the room temperature environment, the light intensity is 100mW/cm2The current-voltage curve of the battery obtained in example 1 was measured under the conditions, and the results are shown in the figure5, the effective area of the cell is 0.12cm2. The test result shows that the concentration of the graphene quantum dot modified TiO is 0.001mg/ml2The photoelectric conversion efficiency of the cell is 19.21 percent, and the TiO film is2The photoelectric conversion efficiency of the mesoporous film battery which is not modified by graphene quantum dots is 17.86%.
In conclusion, the mixed crystal phase metal oxide semiconductor film with high carrier mobility is modified by adopting the quantum dot material with excellent photoelectric characteristics, the synergistic effect of the quantum dot and the mixed crystal phase is exerted, the electron trap can be filled more effectively, the conductivity of the electron trap is improved, the transmission performance of electrons is improved, and the perovskite solar cell with high current density and high efficiency is obtained.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A perovskite solar cell comprises the following components from bottom to top in sequence: the electronic transmission layer comprises a compact layer at the lower layer and a mesoporous layer at the upper layer, wherein the compact layer and the mesoporous layer are both made of titanium dioxide, the mesoporous layer is a titanium dioxide mesoporous film with a rutile and anatase mixed crystal phase structure modified by graphene quantum dots, and the graphene quantum dots are positioned between the mesoporous layer and the perovskite light absorption layer;
the preparation method of the mesoporous layer comprises the following steps:
step 1, preparing titanium salt hydrothermal reaction precursor solution by using concentrated hydrochloric acid, deionized water and butyl titanateBy TiO 22The compact layer is used as a seed layer, and the mixed crystal TiO is grown on the compact layer by a hydrothermal method for one time2The mesoporous film has the film thickness of 400 nm;
step 2, adding TiO2The mesoporous film is soaked in graphene quantum dot solution with the concentration of 0.001mg/ml for modification, so that the graphene quantum dots enter pores of the mesoporous film and are attached to the surface of the mesoporous film, and then the mesoporous film is dried by nitrogen.
2. The perovskite solar cell of claim 1, wherein the dense layer is prepared by one of spin coating, spray coating, roll coating, spray pyrolysis, LB film or ink-jet method, and the thickness of the dense layer is 10-100 nm.
3. A method of manufacturing a perovskite solar cell as claimed in claim 1 or 2, comprising the steps of:
s1, coating the prepared ethanol solution precursor solution of titanium isopropoxide on a conductive substrate by a spin-coating method or a spraying method or a roller coating method or a spray pyrolysis method or an LB (Langmuir-Blodgett) film method or an ink-jet method to prepare a titanium dioxide compact layer, and heating and annealing;
s2, preparing titanium salt hydrothermal reaction precursor solution by using concentrated hydrochloric acid, deionized water and butyl titanate, and preparing the precursor solution by using TiO2The compact layer is used as a seed layer, and the mixed crystal TiO is grown on the compact layer by a hydrothermal method for one time2The mesoporous film has the film thickness of 400 nm;
s3, mixing TiO2Soaking the mesoporous film in a graphene quantum dot solution with the concentration of 0.001mg/ml for modification, so that the graphene quantum dots enter pores of the mesoporous film and are attached to the surface of the mesoporous film, and then blowing the mesoporous film by using nitrogen;
s4, preparing a perovskite light absorption layer on the quantum dot modified mesoporous film;
s5, preparing a hole transport layer on the perovskite light absorption layer;
and S6, preparing a hole transport layer, and preparing a metal anode layer in a thermal evaporation chamber with high vacuum degree to obtain the solar cell.
4. The method of fabricating a perovskite solar cell as claimed in claim 3, wherein the conductive substrate is pretreated before performing operation S1 by: and cleaning the conductive substrate with the surface roughness less than 1nm, drying by using dry nitrogen after cleaning, and performing ultraviolet light and ozone treatment.
5. The method of making the perovskite solar cell of claim 4, wherein the titanium ore light absorbing layer and the hole transport layer are both made by spin coating or roll coating or spray coating.
6. The method for producing a perovskite solar cell as claimed in claim 3, wherein the solar cell produced in the step 6 is placed in a glove box filled with an inert gas for encapsulation.
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| CN113675343A (en) * | 2021-08-17 | 2021-11-19 | 华南农业大学 | Perovskite thin film adopting multifunctional group ligand quantum dots and preparation and application thereof |
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| CN114975785A (en) * | 2022-04-25 | 2022-08-30 | 厦门大学 | Solar cell electron transport layer and preparation method thereof |
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