CN113421971A - Method for preparing perovskite solar cell without charge transport layer through solvent pre-assistance - Google Patents
Method for preparing perovskite solar cell without charge transport layer through solvent pre-assistance Download PDFInfo
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- DGWCCAPYZIQYHH-UHFFFAOYSA-N [I-].C1(=CC=CS1)C[NH3+] Chemical compound [I-].C1(=CC=CS1)C[NH3+] DGWCCAPYZIQYHH-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
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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
- H10K30/80—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a method for preparing a perovskite solar cell without a charge transport layer by solvent pre-assistance. The perovskite material itself has ambipolar charge transport properties, meaning that electron transport layers and hole transport layers are not essential for perovskite solar cells. Their use causes problems of high price and instability of perovskite solar cells. Eliminating the charge transport layer may save material costs and reduce the coating process of the charge transport layer. The invention adopts a novel solution pre-assisted growth mode to prepare the 2D perovskite material in situ between the 3D perovskite thin film and the transparent electrode to form the 2D-3D heterojunction perovskite material. The band gap structure of the 2D perovskite material is accurately controlled by adjusting the type and concentration of the amine salt, so that the 2D perovskite material and the 3D perovskite material form a II-type energy level alignment structure, electrons or holes are transmitted through the II-type energy level alignment structure, and an electron-free transmission layer, a hole-free transmission layer or the simplest perovskite solar cell is prepared.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and relates to a method for preparing a perovskite solar cell without a charge transport layer by solvent pre-assistance.
Background
Perovskite Solar Cells (PSCs) become a research hotspot in the photovoltaic field as third-generation solar cells, and the authentication efficiency reaches 25.5 percent[https://www.nrel.gov/pv/ cell-efficiency.html]. Typical perovskite solar cells generally place the light absorbing layer perovskite material between an Electron Transport Layer (ETL) and a Hole Transport Layer (HTL). During operation, the perovskite material absorbs light to generate electrons and holes. Under the self-field-building drive between adjacent layers, electrons and holes are respectively transferred to an electron transport layer and a hole transport layer, and finally transferred to corresponding electrodes to form photocurrent. The electron transport layer is capable of collecting electrons and blocking holes, and is generally composed of a metal oxide, a metal sulfide, a fullerene derivative, or the like. The hole transport layer can collect holes and block electrons, and generally includes organic small molecules, organic high molecules, and inorganic compounds.
The perovskite material itself has the property of ambipolar charge transport, i.e. transporting both electrons and holes, which means that electron transport layers and hole transport layers are not essential for perovskite solar cells [ j.am. Their use causes problems of high price and instability of perovskite solar cells. Eliminating the electron transport layer can save material costs and reduce the coating process of the charge transport layer by at least one third or even half of the manufacturing cost and time [ adv. It has been investigated to fabricate perovskite solar cells without charge transport layers by passivating transparent conductive substrates [ angelw.chem., int.ed.,2020,59,20980], component engineering or doping [ chem.,2018,4,2405], heterojunction engineering [ nat. photonics,2016,10,196], and the like.
Disclosure of Invention
The invention provides a novel method for preparing a perovskite solar cell without a charge transport layer in a solvent pre-assisted manner, which is characterized in that a 2D-3D heterojunction perovskite thin film is constructed in situ to form a (cascade type) with a certain energy level gradient and transmit electrons in a II type energy level alignment manner, so that a device without the charge transport layer is prepared. The method simultaneously realizes the in-situ regulation of the energy level of the heterojunction perovskite material and improves the quality of the perovskite so as to solve the problem of electric leakage, and has the advantages of simple process, strong operability and low cost.
The technical scheme is as follows:
a method for preparing a perovskite solar cell without a charge transport layer in a solvent pre-assisted manner comprises the following steps:
the 2D perovskite material is prepared in situ between the 3D perovskite film and the transparent electrode by adopting a solution pre-assisted growth mode, and the solution of large-volume organic amine salt is coated on the surface of the transparent conductive substrate. According to the property of energy level regulation and control of the 2D perovskite material, the band gap structure of the 2D perovskite material is accurately controlled by regulating the type and concentration of amine salt, so that the 2D perovskite material and the 3D perovskite material form a II-type energy level alignment structure, and electrons or holes are transmitted. The preparation of devices without charge transport layers is classified into the following 4 classes:
the structure of the device without an electron transport layer is as follows: 2D perovskite amine salt materials with conduction band positions lower than those of the 3D perovskite materials are selected and prepared in situ between the 3D perovskite and the transparent conductive substrate, the formed 2D-3D heterojunction materials transmit electrons in a mode of II-type energy level alignment, and an electron-transport-layer-free device (ITO/2D-3DPVK/HTL/CE) is prepared.
The first preparation scheme is as follows:
step (1), cleaning and processing of transparent conductive substrate
Step (2), preparation of 2D-3D heterojunction perovskite thin film
1) Preparing a perovskite precursor solution: will be formed into ABX3Dissolving the medicine in solvent to obtain solution A with concentration of 0.7-1.5M, stirring at 25-35 deg.C for 2-5 hr, and filtering with 0.22 μ M filter membrane to obtain perovskite precursor solution;
2) preparation of large volume organic amine salt solution: dissolving a 2D perovskite amine salt material with a conduction band position lower than that of the 3D perovskite material in a solvent to prepare a solution B with the concentration of 200-700mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the aperture of 0.22 mu m to obtain a large-volume organic amine salt solution;
3) deposition of 2D-3D heterojunction perovskite thin film: coating the large-volume organic amine salt solution prepared in the step 1) and the perovskite precursor solution prepared in the step 2) on a transparent conductive substrate in sequence, and forming a 2D perovskite between the transparent conductive substrate and a 3D perovskite due to mutual reaction of the two solutions to prepare a 2D-3D heterojunction perovskite thin film;
step (3) preparation of hole transport layer
Depositing a hole transport layer on the surface of the 2D-3D heterojunction perovskite thin film;
step (4), preparing a metal counter electrode
And (3) placing the device prepared in the step into a mask plate, and evaporating metal electrodes in a vacuum evaporation chamber.
No hole transport layer device structure: 2D perovskite amine salt materials with valence band positions higher than those of the 3D perovskite materials are selected and prepared between the 3D perovskite and the transparent conductive substrate in situ, the 2D-3D heterojunction materials transmit holes in a mode of II-type energy level alignment, and a device without a hole transmission layer (ITO/2D-3DPVK/ETL/CE) is prepared.
The second preparation scheme is as follows:
step (1): cleaning and treating transparent conductive substrate
Step (2) preparation of 2D-3D heterojunction perovskite material
And (3) preparing a perovskite precursor liquid. Will be formed into ABX3Dissolving the medicine in solvent to obtain solution A with concentration of 0.7-1.5M, stirring at 25-35 deg.C for 2-5 hr, and filtering with 0.22 μ M filter membrane to obtain perovskite precursor solution.
Preparation of a large volume organic amine salt solution. Dissolving a 2D perovskite amine salt material with the valence band position higher than that of the 3D perovskite material in a solvent to prepare a solution B with the concentration of 200-700mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the aperture of 0.22 mu m to obtain a large-volume organic amine salt solution.
And (3) depositing a 2D-3D heterojunction perovskite thin film. And coating the large-volume organic amine salt solution on a transparent conductive substrate, and then depositing a perovskite layer to prepare the 2D-3D heterojunction perovskite film.
Step (3) preparation of the electron transport layer
And depositing an electron transport layer on the surface of the 2D-3D heterojunction perovskite.
Step (4) preparation of metal counter electrode
And (3) placing the device prepared in the step into a mask plate, and evaporating metal electrodes in a vacuum evaporation chamber.
Carbon-based simplest device structure: the simplest PSCs are prepared by selecting 2D-3D heterojunction perovskite for transmitting electrons in a mode of II-type energy level alignment, taking carbon materials as a hole transmission layer and a counter electrode, and the device structure is (ITO/2D-3D PVK/C).
The third preparation scheme is as follows:
the steps (1) to (2) are the same as the first preparation scheme.
Step (3) preparation of carbon electrode
And preparing a carbon electrode.
Fourthly, the simplest device structure: and selecting a 2D-3D perovskite material for transmitting holes in a mode of II-type energy level alignment, and forming another layer of 2D perovskite material on the surface of the 2D-3D perovskite by using an improved anti-solvent method to prepare the 2D-3D-2D heterojunction perovskite thin film. The kind and concentration of amine salt in the anti-solvent are adjusted to enable the amine salt to be close to one side of the counter electrode, the 3D-2D perovskite material transmits electrons in a mode of II-type energy level alignment, and the simplest device structure prepared is (ITO/2D-3D-2D PVK/CE).
The preparation scheme four is as follows:
step (1): cleaning and treating transparent conductive substrate
Step (2) preparation of 2D-3D-2D heterojunction perovskite material
And (3) preparing a perovskite precursor liquid. Will be formed into ABX3Dissolving the medicine in solvent to obtain solution A with concentration of 0.7-1.5M, stirring at 25-35 deg.C for 2-5 hr, and filtering with 0.22 μ M filter membrane to obtain perovskite precursor solution.
Preparation of a large volume organic amine salt solution. Dissolving a 2D perovskite amine salt material with the valence band position higher than that of the 3D perovskite material in a solvent to prepare a solution B with the concentration of 200-700mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the aperture of 0.22 mu m to obtain a large-volume organic amine salt solution.
Preparation of the modified anti-solvent solution. Dissolving 2D perovskite amine salt material with the conduction band position lower than that of the 3D perovskite material in an anti-solvent to prepare solution C with the concentration of 10-70mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the pore diameter of 0.22 mu m to obtain the improved anti-solvent solution.
And (3) depositing a 2D-3D-2D heterojunction perovskite thin film. Coating a large-volume organic amine salt solution on a transparent conductive substrate, then depositing a perovskite layer, and preparing the 2D-3D-2D heterojunction perovskite thin film by using an improved anti-solvent solution.
Step (3) preparation of metal counter electrode
And (3) placing the device prepared in the step into a mask plate, and evaporating metal electrodes in a vacuum evaporation chamber.
The transparent conductive substrate comprises a hard or flexible transparent conductive substrate, and can be SnO doped with fluorine2At least one of transparent conductive glass (FTO), indium tin oxide transparent conductive glass (ITO), aluminum-doped zinc oxide transparent conductive glass (AZO), transparent indium tin oxide conductive films (ITO-PET and ITO-PEN), and transparent cadmium telluride conductive film (CAT-PEN);
the perovskite has the chemical formula ABX3Wherein A is a monovalent cation, preferably CH3NH3 +、NH2-CH＝NH2 +、Cs+、Li+、C4H9NH3 +、CH6N3 +、Na+、K+B is a divalent cation, preferably Pb2 +、Cs+、Sn2+、Ge2+、Co2+、Fe2 +、Mn2+、Cu2+、Ni2+At least one of (1), X is Cl-、Br-、I-、SCN-、BF4 -At least one of; the solvent of perovskite and bulky organic amine salt can be selectedN, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methyl-2-pyrrolidone, and the like; wherein the antisolvent is at least one of toluene, xylene, chlorobenzene, acetonitrile, acetone, ethyl acetate, diethyl ether, n-butanol, ethanol and isopropanol;
the 2D perovskite is classified into RP type and DJ type according to the structural difference, and the structural general formula is (RNH)3)2An-1BnX3n+1And MAn-1BnX3n+1N is the number of octahedral layers, A is usually MA+(CH3NH3 +)、FA+(NH＝CHNH3 +)、Cs+B is usually Pb2+、Sn2+X is usually I-、Br-、Cl-. The 2D perovskite amine salt material is RNH3 +Bulky organic amine cationic groups represented by and M2+Diamine organic groups represented by wherein the 2D perovskite amine cation having a valence band position higher than that of the 3D perovskite material comprises a phenylethylamine cation (PEA)+) Polyethyleneimine cation (PEI)+) Etc.; the 2D perovskite amine cations with conduction band positions lower than that of the 3D perovskite material comprise n-butylamine cations (n-BA)+) 2-Thienylmethylamine cation (ThMA)+) Phenylenediamine cation (PDA)2+) Fluorinated phenethylamine cation (F-PEA)+) Etc.;
the 2D and 3D perovskite material deposition methods include spin coating, spray coating, blade coating, slot die coating, screen printing, and the like;
the Electron Transport Layer (ETL) is a dense layer of metal oxide, which may be TiO2、ZnO、SnO2、SnS2、[6,6]-phenyl-C61-butyric acid methyl ester(PCBM)、C60、WOxGraphene, Nb2O5CdSe, CdS and multicomponent compounds Zn2SnO4、BaSnO3、CuInS2、SrTiO3Or at least one of their dopants; the Hole Transport Layer (HTL) includes organic small molecules, organic high molecules, and inorganic compounds (e.g., NiO, CuSCN, etc.).
The invention has the beneficial effects that: compared with the prior art, the method disclosed by the invention is not only quick and convenient, simple to operate and low in cost, but also can solve the problems of energy level mismatch and electric leakage of the perovskite solar cell without the charge transmission layer, optimize the structure of the perovskite solar cell and prepare the perovskite solar cell without the electron transmission layer and with high photoelectric conversion efficiency.
Drawings
FIG. 1 is a schematic illustration of a 2D-3D perovskite material, a 2D-3D-2D perovskite material preparation;
FIG. 2 is a schematic diagram of a device structure without electron transport layer (ITO/2D-3D PVK/Spiro-OMeTAD/Au);
FIG. 3 is a graph of the performance and mechanism of the cell of FIG. 2;
FIG. 4 is a schematic diagram of a hole transport layer-free device structure (FTO/2D-3D PVK/PCBM (BCP)/Au);
FIG. 5 is a graph of the performance and mechanism of the cell of FIG. 4;
FIG. 6 is the simplest carbon-based device structure: (ITO/2D-3D PVK/C) schematic diagram;
FIG. 7 is a graph of the performance and mechanism of the cell of FIG. 6;
FIG. 8 is a schematic diagram of the simplest device structure (FTO/2D-3D-2D PVK/Au);
fig. 9 shows the performance and mechanism of the cell of fig. 8.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1:
a method for preparing an electron transport layer-free perovskite solar cell in a solvent pre-assisted mode comprises the following steps:
step (1): cleaning treatment of ITO substrate
The ITO substrate was washed in sequence with detergent, acetone, isopropanol and ethanol in an ultrasonic bath for 20 minutes, respectively, and then treated with UV-ozone for 15 minutes.
Step (2) preparation of 2D-3D heterojunction perovskite material
And (3) preparing a perovskite precursor liquid. Dissolving cesium iodide, bromomethylamine, lead bromide, iodoformamidine and lead iodide in a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide to obtain a solution A; wherein, the volume ratio of N, N-dimethylformamide to dimethyl sulfoxide in the solution is 4: 1, mixing; cesium iodide, bromomethylamine, lead bromide, iodoformamidine and lead iodide in a molar ratio of 0.07: 0.21: 0.21: 1.19: 1.31; the concentration is 0.7M; stirring the solution A for 2h at the temperature of 25 ℃, and then filtering the solution A by using a filter membrane with the aperture of 0.22 mu m to prepare the perovskite precursor solution.
Preparation of a large volume organic amine salt solution. Dissolving large volume organic amine salt n-butyl ammonium iodide in dimethyl sulfoxide to obtain solution B with concentration of 200mg/mL, stirring at 25 deg.C for 2h, and filtering with filter membrane with pore diameter of 0.22 μm to obtain large volume organic amine salt solution.
And (3) depositing a 2D-3D heterojunction perovskite thin film. Deposited by spin-coating. Mixing with 15 μ L/cm2Dropping large-volume organic amine salt solution on transparent conductive substrate ITO, spin-coating at low rotation speed of 1000rpm for 10s, and dropping 20 μ L/cm at 5s2A perovskite precursor liquid; spin coating at 4000rpm for 30s, and dripping 50 μ L/cm at 15s2Anti-solvent chlorobenzene; immediately after the spin coating was stopped, the film was annealed on a hot stage at 75 ℃ for 100min to prepare a 2D-3D heterojunction perovskite thin film, as shown in FIG. 1.
Step (3) preparation of hole transport layer Spiro-OMeTAD
1mol of Spiro-OMeTAD is added into 1mL of chlorobenzene solvent, and 17.5 mu L of Li-TFSI solution and 28.8 mu L of 4-tert-butylpyridine are added as additives to prepare solution C; stirring at 30 deg.C for 4h, dissolving completely, and filtering with filter membrane with pore diameter of 0.22 μm to obtain Spiro-OMeTAD hole transport layer solution; dropping 18 mu L/cm on the perovskite layer2The Spiro-OMeTAD solution was spin-coated at 3500rpm for 30 seconds to deposit as a hole transport layer on the perovskite film.
(4) Preparation of metal counter electrode and battery performance test
Placing the device prepared in the above steps into a mask plate, placing the mask plate into a vacuum evaporation chamber, and keeping the vacuum degree at 5 x 10-4Under Pa, first, the
At a rate of evaporating the Au electrode to a thickness of
And finishing evaporation.
The structure of the device is shown in FIG. 2, and the prepared device is subjected to standard simulated sunlight with AM 1.5G (100 mW/cm)2) The light intensity was corrected using a standard silicon cell (B5-520) and tested using a Keithley2460 instrument, and the J-V test results are shown in FIG. 3.
Example 2:
a method for preparing a hole transport layer-free perovskite solar cell in a solvent pre-assisted mode comprises the following steps:
step (1): cleaning treatment of FTO substrate
The FTO substrate was washed sequentially with detergent, acetone, isopropanol and ethanol in an ultrasonic bath for 20 minutes, respectively, and then treated with UV-ozone for 15 minutes.
Step (2) preparation of 2D-3D heterojunction perovskite material
And (3) preparing a perovskite precursor liquid. Dissolving lead iodide, iodomethylamine and iodoformamidine in N, N-dimethylformamide to obtain a solution A; wherein the molar ratio of lead iodide to iodomethylamine to iodoformamidine is 1: 0.7: 0.3; the concentration is 1.5M; stirring the solution A for 5h at the temperature of 35 ℃, and then filtering the solution A by using a filter membrane with the aperture of 0.22 mu m to prepare the perovskite precursor solution.
Preparation of a large volume organic amine salt solution. Dissolving large volume organic amine salt phenethyl ammonium iodide in dimethyl sulfoxide to obtain solution B with concentration of 700mg/mL, stirring at 35 deg.C for 5h, and filtering with filter membrane with pore diameter of 0.22 μm to obtain large volume organic amine salt solution.
And (3) depositing a 2D-3D heterojunction perovskite thin film. Deposited by knife coating. Mixing 7 mu L/cm2The large-volume organic amine salt solution is dripped on the transparent conductive substrate ITO and linearly brushed by a glass blade at the speed of 5.5 mm/s; mixing 10. mu.L/cm2The large-volume organic amine salt solution is dripped on the transparent conductive substrate ITO and is linearly brushed by a glass blade at the speed of 10 mm/s; immediately annealing at 75 deg.C on a hot bench for 100min, preparing the 2D-3D heterojunction perovskite thin film.
Step (3) preparation of electronic transmission layer PCBM (BCP)
Dissolving PCBM and BCP in chlorobenzene and isopropanol respectively to prepare a solution C with the concentration of 20mg/mL and a solution D with the concentration of 0.5 mg/mL; stirring the solution C and the solution D for 6h at the temperature of 30 ℃, and then filtering by using a filter membrane with the aperture of 0.22 mu m; firstly, 15 mu L/cm of the solution is dripped on a perovskite layer2The PCBM solution is spin-coated for 30s at the rotating speed of 2000rpm, and is annealed for 10min at the temperature of 75 ℃ so that the PCBM is deposited on the perovskite layer; after it is cooled to room temperature, 40 mu L/cm are added dropwise2Spin coating BCP solution at 5000rpm for 30s, and annealing at 75 deg.C for 5min to deposit BCP layer, thereby completing the preparation of electron transport layer PCBM (BCP)
(4) Preparation of metal counter electrode and battery performance test
Placing the device prepared in the above steps into a mask plate, placing the mask plate into a vacuum evaporation chamber, and keeping the vacuum degree at 5 x 10-4Under Pa, first, the
Evaporating Au electrode to a thickness of
And finishing evaporation.
The structure of the device is shown in FIG. 4, and the prepared device is subjected to standard simulated sunlight with AM 1.5G (100 mW/cm)2) The light intensity was corrected using a standard silicon cell (B5-520) and tested using a Keithley2460 instrument, and the J-V test results are shown in FIG. 5.
Example 3:
a method for preparing a simplest carbon-based perovskite solar cell through solvent pre-assistance comprises the following steps:
the steps (1) to (2) are the same as the first preparation scheme.
Step (3) preparation of carbon electrode
Coating conductive carbon slurry on the perovskite layer, and drying for 90min at 85 ℃ to obtain the simplest carbon-based perovskite solar cell; the amount of the conductive carbon paste is determined according to the requirements of users.
Device structure As shown in FIG. 6, the prepared device is subjected to standard simulated sunlight with AM 1.5G (100 mW/cm)2) The light intensity was corrected using a standard silicon cell (B5-520) and tested using a Keithley2460 instrument, and the J-V test results are shown in FIG. 7.
Example 4 of implementation:
a method for preparing the simplest perovskite solar cell by solvent pre-assistance comprises the following steps:
step (1): cleaning treatment of FTO substrate
The FTO substrate was washed sequentially with detergent, acetone, isopropanol and ethanol in an ultrasonic bath for 20 minutes, respectively, and then treated with UV-ozone for 15 min.
Step (2) preparation of 2D-3D-2D heterojunction perovskite material
And (3) preparing a perovskite precursor liquid. Dissolving lead iodide, iodomethylamine and chloromethane in a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide to obtain a solution A; wherein the molar ratio of lead iodide to lead chloride to iodomethylamine is 0.75: 0.25: 1; the concentration is 1.3M; wherein, the volume ratio of N, N-dimethylformamide to dimethyl sulfoxide in the solution is 7: 3, mixing; stirring the solution A for 3.5h at the temperature of 30 ℃, and then filtering the solution A by a filter membrane with the aperture of 0.22 mu m to prepare the perovskite precursor solution.
Preparation of a large volume organic amine salt solution. Dissolving large volume organic amine salt phenethyl ammonium iodide in dimethyl acetamide to obtain solution B with concentration of 450mg/mL, stirring at 30 deg.C for 3.5h, and filtering with filter membrane with pore diameter of 0.22 μm to obtain large volume organic amine salt solution.
Preparation of the modified anti-solvent solution. Dissolving 2-thienylmethylammonium iodide in ethyl acetate as an anti-solvent to obtain a solution C with a concentration of 35mg/mL, stirring at 30 ℃ for 3.5 hours, and filtering with a filter membrane with a pore size of 0.22 μm to obtain an improved anti-solvent solution.
And (3) depositing a 2D-3D-2D heterojunction perovskite thin film. Deposited by spin-coating. Mixing 10. mu.L/cm2Dropping the large-volume organic amine salt solution on the transparent conductive substrate FTO, spin-coating at low rotation speed of 2000rpm for 10s, and spin-coatingAdding dropwise 15 μ L/cm at the time of 5s2A perovskite precursor liquid; spin-coating at 5000rpm for 30s, and dripping 45 μ L/cm into the 15 th s2Modifying the anti-solvent solution; immediately after the spin coating was stopped, the film was annealed on a hot stage at 100 ℃ for 75min to prepare a 2D-3D-2D heterojunction perovskite thin film, as shown in FIG. 1.
Step (3) preparation of metal counter electrode and battery performance test
Placing the device prepared in the above steps into a mask plate, placing the mask plate into a vacuum evaporation chamber, and keeping the vacuum degree at 5 x 10-4Under Pa, first, the
Evaporating Au electrode to a thickness of
And finishing evaporation.
Device structure As shown in FIG. 8, the prepared device was subjected to standard simulated sunlight with AM 1.5G (100 mW/cm)2) The light intensity was corrected using a standard silicon cell (B5-520) and tested using a Keithley2460 instrument, and the J-V test results are shown in FIG. 9.
Claims (10)
1. A method for preparing a perovskite solar cell without a charge transport layer in a solvent pre-assisted manner is characterized by comprising the following steps:
preparing a 2D perovskite material in situ between the 3D perovskite film and the transparent electrode by adopting a solution pre-assisted growth mode, and coating a large-volume organic amine salt solution on the surface of the transparent conductive substrate; according to the property of energy level regulation and control of the 2D perovskite material, the band gap structure of the 2D perovskite material is accurately controlled by regulating the type and concentration of amine salt, so that the 2D perovskite material and the 3D perovskite material form a II-type energy level alignment structure to transmit electrons or holes; the preparation of devices without charge transport layers is classified into the following 4 classes: a non-electron transport layer device structure, a non-hole transport layer device structure, a carbon-based simplest device structure, and a simplest device structure.
2. The method of claim 1,
the device structure without the electron transport layer comprises: selecting a 2D perovskite amine salt material with a conduction band position lower than that of the 3D perovskite material, preparing the 2D perovskite amine salt material in situ between the 3D perovskite layer and the transparent conductive substrate, and transmitting electrons by the formed 2D-3D heterojunction material in a mode of II-type energy level alignment to prepare a device without an electron transmission layer;
the method comprises the following specific steps:
step (1), cleaning and processing of transparent conductive substrate
Step (2), preparation of 2D-3D heterojunction perovskite thin film
1) Preparing a perovskite precursor solution: will be formed into ABX3Dissolving the medicine in solvent to obtain solution A with concentration of 0.7-1.5M, stirring at 25-35 deg.C for 2-5 hr, and filtering with 0.22 μ M filter membrane to obtain perovskite precursor solution;
2) preparation of large volume organic amine salt solution: dissolving a 2D perovskite amine salt material with a conduction band position lower than that of the 3D perovskite material in a solvent to prepare a solution B with the concentration of 200-700mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the aperture of 0.22 mu m to obtain a large-volume organic amine salt solution;
3) deposition of 2D-3D heterojunction perovskite thin film: sequentially coating the large-volume organic amine salt solution prepared in the step 1) and the perovskite precursor solution prepared in the step 2) on a transparent conductive substrate, and reacting to form a 2D perovskite between the transparent conductive substrate and a 3D perovskite to prepare a 2D-3D heterojunction perovskite thin film;
step (3) preparation of hole transport layer
Depositing a hole transport layer on the surface of the 2D-3D heterojunction perovskite thin film;
step (4), preparing a metal counter electrode
And (3) placing the device prepared in the step into a mask plate, and evaporating metal electrodes in a vacuum evaporation chamber.
3. The method of claim 1,
device structure without hole transport layer: selecting a 2D perovskite amine salt material with the valence band position higher than that of the 3D perovskite material, preparing the 2D perovskite amine salt material in situ between the 3D perovskite and the transparent conductive substrate, and transmitting holes by the 2D-3D heterojunction material in a mode of II-type energy level alignment to prepare a device without a hole transmission layer;
the method comprises the following specific steps:
step (1): cleaning and treating transparent conductive substrate
Step (2) preparation of 2D-3D heterojunction perovskite material
1) Preparing a perovskite precursor solution: will be formed into ABX3Dissolving the medicine in solvent to obtain solution A with concentration of 0.7-1.5M, stirring at 25-35 deg.C for 2-5 hr, and filtering with 0.22 μ M filter membrane to obtain perovskite precursor solution;
2) preparation of large volume organic amine salt solution: dissolving a 2D perovskite amine salt material with a valence band position higher than that of the 3D perovskite material in a solvent to prepare a solution B with the concentration of 200-700mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the aperture of 0.22 mu m to obtain a large-volume organic amine salt solution;
3) deposition of 2D-3D heterojunction perovskite thin film: coating the large-volume organic amine salt solution on a transparent conductive substrate, and then depositing a perovskite layer to prepare a 2D-3D heterojunction perovskite film;
step (3) preparation of the electron transport layer
Depositing an electron transport layer on the surface of the 2D-3D heterojunction perovskite thin film;
step (4) preparation of metal counter electrode
And (3) placing the device prepared in the step into a mask plate, and evaporating metal electrodes in a vacuum evaporation chamber.
4. The method of claim 1,
carbon-based simplest device structure: selecting a 2D-3D heterojunction perovskite for transmitting electrons in a mode of II-type energy level alignment, and preparing simplest PSCs by using a carbon material as a hole transmission layer and a counter electrode, wherein the device structure is ITO/2D-3D PVK/C;
the method comprises the following specific steps:
step (1), cleaning and processing of transparent conductive substrate
Step (2), preparation of 2D-3D heterojunction perovskite thin film
1) Preparing a perovskite precursor solution: will be formed into ABX3Dissolving the medicine in solvent to obtain solution A with concentration of 0.7-1.5M, stirring at 25-35 deg.C for 2-5 hr, and filtering with 0.22 μ M filter membrane to obtain perovskite precursor solution;
2) preparation of large volume organic amine salt solution: dissolving a 2D perovskite amine salt material with a conduction band position lower than that of the 3D perovskite material in a solvent to prepare a solution B with the concentration of 200-700mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the aperture of 0.22 mu m to obtain a large-volume organic amine salt solution;
3) deposition of 2D-3D heterojunction perovskite thin film: sequentially coating the large-volume organic amine salt solution prepared in the step 1) and the perovskite precursor solution prepared in the step 2) on a transparent conductive substrate, and reacting to form a 2D perovskite between the transparent conductive substrate and a 3D perovskite to prepare a 2D-3D heterojunction perovskite thin film;
and (3) preparing a carbon electrode.
5. The method of claim 1,
the simplest device structure: selecting a 2D-3D perovskite material for transmitting holes in a II-type energy level alignment mode, and forming another layer of 2D perovskite material on the surface of the 2D-3D perovskite by using an improved anti-solvent method to prepare a 2D-3D-2D heterojunction perovskite thin film; adjusting the type and concentration of amine salt in the anti-solvent to enable the amine salt to be close to one side of the counter electrode, and enabling the 3D-2D perovskite material to transmit electrons in a mode of II-type energy level alignment, wherein the simplest device structure prepared is ITO/2D-3D-2D PVK/CE;
the method comprises the following specific steps:
step (1), cleaning and processing a transparent conductive substrate;
step (2), preparing a 2D-3D-2D heterojunction perovskite material;
1) preparing a perovskite precursor solution: will be formed into ABX3The drug is dissolved in a solvent and is formulated to have a concentration ofStirring 0.7-1.5M solution A at 25-35 deg.C for 2-5h, and filtering with 0.22 μ M filter membrane to obtain perovskite precursor solution;
2) preparation of large volume organic amine salt solution: dissolving a 2D perovskite amine salt material with a valence band position higher than that of the 3D perovskite material in a solvent to prepare a solution B with the concentration of 200-700mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the aperture of 0.22 mu m to obtain a large-volume organic amine salt solution;
3) preparation of modified anti-solvent solution: dissolving 2D perovskite amine salt material with the conduction band position lower than that of the 3D perovskite material in an anti-solvent to prepare solution C with the concentration of 10-70mg/mL, stirring for 2-5h at the temperature of 25-35 ℃, and then filtering by using a filter membrane with the pore diameter of 0.22 mu m to obtain an improved anti-solvent solution;
4) deposition of 2D-3D-2D heterojunction perovskite thin film: coating a large-volume organic amine salt solution on a transparent conductive substrate, then depositing a perovskite layer, and preparing a 2D-3D-2D heterojunction perovskite thin film by using an improved anti-solvent solution;
preparing a metal counter electrode;
and (3) placing the device prepared in the step into a mask plate, and evaporating metal electrodes in a vacuum evaporation chamber.
6. The method according to any one of claims 1 to 5, wherein the transparent conductive substrate comprises a rigid or flexible transparent conductive substrate of SnO doped with fluorine2Transparent conductive glass, indium tin oxide transparent conductive glass, aluminum-doped zinc oxide transparent conductive glass, transparent indium tin oxide conductive thin film, transparent cadmium telluride conductive thin film, etc.).
7. A process according to claim 6, wherein the perovskite has the formula ABX3Wherein A is a monovalent cation and is CH3NH3 +、NH2-CH＝NH2 +、Cs+、Li+、C4H9NH3 +、CH6N3 +、Na+、K+One of (1); b is a divalent cation, is Pb2 +、Cs+、Sn2+、Ge2+、Co2+、Fe2+、Mn2+、Cu2+、Ni2+One of (1); x is Cl-、Br-、I-、SCN-、BF4 -One of (1); the perovskite and the solvent of the large-volume organic amine salt are selected from N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide and N-methyl-2-pyrrolidone; the antisolvent is one of toluene, xylene, chlorobenzene, acetonitrile, acetone, ethyl acetate, diethyl ether, n-butanol, ethanol and isopropanol.
8. The method according to claim 7, wherein the 2D perovskite is classified into RP type and DJ type according to its structure, and has a general formula of (RNH)3)2An-1BnX3n+1And MAn-1BnX3n+1N is the number of octahedral layers, A is MA+(CH3NH3 +)、FA+(NH＝CHNH3 +)、Cs+B is Pb2+、Sn2+X is usually I-、Br-、Cl-(ii) a The 2D perovskite amine salt material is RNH3 +Bulky organic amine cationic groups represented by and M2+Diamine organic groups represented by wherein the 2D perovskite amine cations having a valence band position higher than that of the 3D perovskite material comprise phenylethylamine cations and polyethyleneimine cations; the 2D perovskite amine cations with conduction band positions below the 3D perovskite material include n-butylamine cations, 2-thiophenemethylamine cations, phenylenediamine cations, and fluoroethylamine cations.
9. The method of claim 8, wherein the electron transport layer is a dense layer of a metal oxide and is TiO2、ZnO、SnO2、SnS2、[6,6]-phenyl-C61-butyric acid methyl ester、C60、WOxGraphene, graphene,Nb2O5CdSe, CdS and multicomponent compounds Zn2SnO4、BaSnO3、CuInS2、SrTiO3Or at least one of their dopants; the hole transport layer includes small organic molecules, organic polymers, and inorganic compounds.
10. The method according to claim 9, wherein the 2D and 3D perovskite material deposition methods comprise spin coating, spray coating, blade coating, slot die coating, screen printing.
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| CN115377291A (en) * | 2022-10-21 | 2022-11-22 | 重庆大学 | Bottom-up 2D/3D perovskite heterojunction, preparation method thereof and application thereof in perovskite solar cell |
| CN115377291B (en) * | 2022-10-21 | 2024-02-02 | 重庆大学 | Bottom-up 2D/3D perovskite heterojunction, preparation method thereof and application thereof in perovskite solar cell |
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