CN114203910A - Flexible perovskite solar cell and preparation method thereof - Google Patents

Flexible perovskite solar cell and preparation method thereof Download PDF

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Publication number
CN114203910A
CN114203910A CN202111419364.XA CN202111419364A CN114203910A CN 114203910 A CN114203910 A CN 114203910A CN 202111419364 A CN202111419364 A CN 202111419364A CN 114203910 A CN114203910 A CN 114203910A
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perovskite
layer
electrode
light absorption
azobenzene
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王亚丽
侯丽新
王佳
韩美英
樊迪
宋鑫
刘贤豪
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China Lucky Group Corp
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China Lucky Group Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • 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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    • 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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Abstract

The application discloses a flexible perovskite solar cell and a preparation method thereof. The battery structure comprises a flexible substrate, and a transparent electrode, an electrode modification layer, a block polymer interface layer, a perovskite light absorption layer, an electrode buffer layer and a metal electrode which are sequentially stacked on the flexible substrate, wherein the perovskite light absorption layer comprises perovskite and azobenzene micromolecule additives. Therefore, the flexible perovskite solar cell has good bending resistance and higher photoelectric conversion efficiency and stability.

Description

Flexible perovskite solar cell and preparation method thereof
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a flexible perovskite solar cell and a preparation method thereof.
Background
In recent years, Perovskite Solar Cells (PSCs) have been one of the most disruptive competitors of the solar cell industry by virtue of their extraordinary photoelectric conversion efficiency (PCE, exceeding 25%), and have attracted considerable attention in academic and industrial fields. Because perovskite solar cell still has advantages such as but low temperature solution processing, light in weight, with low costs, can satisfy novel energy system in the future to light, low energy consumption and tensile demand, promote portable energy and close on spacecraft energy system optimization innovation.
The perovskite thin film is prepared on a flexible substrate, and the unavoidable brittleness and poor crystallinity can cause the thin film to generate more crystal boundaries, cause carrier recombination and ion migration, and cause the reduction of the efficiency and the environmental stability of the battery. Non-radiative recombination caused by interfacial and grain boundary defects is a major obstacle to achieving efficient long-term stability of PSCs, compared to negligible charge recombination inside perovskite grains. When bending the perovskite thin film, cracks appear on grain boundaries firstly, and the cracks are difficult to repair by self, so that the bending stability of the battery is poor. How to prepare a high-quality and bending-resistant perovskite thin film on a flexible substrate is a key problem to be solved urgently.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a flexible perovskite solar cell and a preparation method thereof, wherein the flexible perovskite solar cell has good bending resistance and high photoelectric conversion efficiency and stability.
In one aspect of the invention, a flexible perovskite solar cell is presented. According to the embodiment of the invention, the battery structure comprises a flexible substrate, and a transparent electrode, an electrode modification layer, a block polymer interface layer, a perovskite light absorption layer, an electrode buffer layer and a metal electrode which are sequentially stacked on the flexible substrate, wherein the perovskite light absorption layer comprises perovskite and azobenzene micromolecule additives.
According to the flexible perovskite solar cell provided by the embodiment of the invention, the azobenzene micromolecule additive is introduced into the perovskite light absorption layer, the azobenzene micromolecule additive has amino groups, carboxyl groups, hydroxyl groups or sulfonic acid groups, ions in the perovskite jointly act on the functional groups, the ion migration is inhibited, and the perovskite crystallization nucleation and grain growth processes are regulated and controlled. Meanwhile, the benzene ring has a firm structure and high cohesive energy, and azobenzene micromolecules are easy to form hydrophobic passivation, so that the photoelectric conversion efficiency and stability of the cell can be improved. In addition, the block polymer interface layer is introduced in front of the perovskite light absorption layer, the block polymer has the deformation resistance and fatigue resistance of the interface layer, the perovskite can be locally infiltrated into the perovskite light absorption layer during film forming, and the elastic insulating polymer enriched at the crystal boundary effectively plays a role in stress buffering, so that the bending resistance of the flexible perovskite battery can be improved. In summary, the flexible perovskite solar cell of the application has good bending resistance and higher photoelectric conversion efficiency and stability.
In addition, the flexible perovskite solar cell according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the invention, the feedstock for the block polymer interface layer comprises t-butyl acrylate monomer, aliphatic urethane diacrylate monomer, and initiator. Thus, hydrogen bonding interactions between the block polymer groups result in an interfacial layer with good resistance to deformation and fatigue.
In some embodiments of the present invention, the mass of the aliphatic urethane diacrylate monomer is 5 to 20% of the total mass of the t-butyl acrylate monomer and the aliphatic urethane diacrylate monomer. Therefore, the flexible perovskite solar cell has good bending resistance.
In some embodiments of the present invention, the initiator is a polyolefin thermoplastic elastomer, and the mass of the initiator is 0.2 to 0.3% of the total mass of the tert-butyl acrylate monomer and the aliphatic polyurethane diacrylate monomer. Therefore, the flexible perovskite solar cell has good bending resistance.
In some embodiments of the present invention, the thickness of the block polymer interface layer is 1 to 10 nm. Therefore, the flexible perovskite solar cell has good bending resistance.
In some embodiments of the invention, in the perovskite light absorption layer, the mass ratio of the perovskite to the azobenzene small molecule additive is (35-60): (0.1-0.5). Therefore, the flexible perovskite solar cell has high photoelectric conversion efficiency and stability.
In some embodiments of the invention, the azobenzene small molecule additive comprises at least one of 4,4 '-dicarboxyiazobenzene, 4' -diaminoazobenzene, 4-aminoazobenzene-3-disulfonic acid, 2-amino-5 (3-sulfonicazophenyl) azobenzene, 4-dimethylaminophenylazobenzenesulfonyl chloride, 2, 4-diamino-3 '-trifluoromethylazobenzene, 4' -azobenzene dicarboxylate ethyl ester, 4-aminophenylazobenzene-2-sulfonic acid, 4-hydroxy-4 '-carboxyazobenzene, p-aminoazobenzene-4-sulfonic acid, and 2,4,3' -triamineazobenzene. Therefore, the flexible perovskite solar cell has high photoelectric conversion efficiency and stability.
In some embodiments of the invention, the perovskite has the general chemical formula ABXmY3-mWherein A comprises Cs, H, NH4、CH3NH3、CH3CH2NH3、CH3(CH2)2NH3、CH3(CH2)3NH3And NH2＝CHNH2At least one of; b comprises at least one of Pb, Sn and Ge; x and Y independently include Cl, Br, I and BF4SCN and PF6At least one of; m is 0 to 3.
In some embodiments of the present invention, the thickness of the perovskite light absorption layer is 100-1000 nm. Therefore, the flexible perovskite solar cell has high photoelectric conversion efficiency and stability.
In some embodiments of the present invention, the electrode modification layer is an electron transport layer, the electrode buffer layer is a hole transport layer, and the electron transport layer comprises TiO2、SnO2、ZnO、PC61BM、PC71BM, TIPD, ICBA and C60-bis, the hole transport layer being formed using an organic material and/or an inorganic material, wherein the organic material comprises at least one of Spiro-OMeTAD, P3HT, PCPDTBT, PEDOT: PSS, NPB and TPD, and the inorganic material comprises CuI, CuSCN, NiOX、V2O5And MoO3At least one of (a).
In some embodiments of the invention, the electrode modification layer is a hole transport layer, the electrode buffer layer is an electron transport layer, and the hole transport layer comprises PTAA, PEDOT: PSS, CuI, CuSCN, NiOX、V2O5And MoO3The electron transport layer comprises TiO2、SnO2、ZnO、PC61BM、PC71BM, TIPD, ICBA and C60-at least one of bis.
In some embodiments of the present invention, the thickness of the electrode modification layer is 5 to 150 nm.
In some embodiments of the present invention, the thickness of the electrode buffer layer is 5 to 300 nm.
In a second aspect of the invention, the invention proposes a method of manufacturing a flexible perovskite solar cell as described above. According to an embodiment of the invention, the method comprises:
(1) sequentially forming a transparent electrode and an electrode modification layer on a flexible substrate;
(2) mixing tert-butyl acrylate, aliphatic polyurethane diacrylate and an initiator, coating the mixture on the surface of the electrode modification layer, and then carrying out photocuring so as to form a block polymer interface layer on the surface of the electrode modification layer;
(3) mixing a perovskite precursor material, an azobenzene micromolecule additive and an organic solvent so as to obtain a mixed solution containing perovskite and the azobenzene micromolecule additive;
(4) coating the mixed solution on the surface of the block polymer interface layer and carrying out annealing treatment so as to form a perovskite light absorption layer on the surface of the block polymer interface layer;
(5) and sequentially forming an electrode buffer layer and a metal electrode on the surface of the perovskite light absorption layer so as to obtain the flexible perovskite solar cell.
According to the method for preparing the flexible perovskite solar cell, the transparent electrode and the electrode modification layer are sequentially formed on the flexible substrate; mixing tert-butyl acrylate, aliphatic polyurethane diacrylate and an initiator, coating the mixture on the surface of the electrode modification layer, and carrying out photocuring to form a block polymer interface layer on the surface of the electrode modification layer; then mixing a perovskite precursor material, an azobenzene micromolecule additive and an organic solvent, and reacting the perovskite precursor material to generate perovskite, thereby obtaining a mixed solution containing perovskite and the azobenzene micromolecule additive; coating the mixed solution on the surface of a block polymer interface layer and carrying out annealing treatment, so that a perovskite light absorption layer can be formed on the surface of the block polymer interface layer, annealing treatment is adopted to form a film, film-forming auxiliary means such as vacuum pumping, air knife and anti-solvent are not additionally adopted, the large-area high-quality perovskite film can be obtained, and the process is simple and easy to implement; and finally, sequentially forming an electrode buffer layer and a metal electrode on the surface of the perovskite light absorption layer to obtain the flexible perovskite solar cell. According to the method, the azobenzene micromolecule additive is introduced into the perovskite light absorption layer, the azobenzene micromolecule additive is provided with amino groups, carboxyl groups, hydroxyl groups or sulfonic acid groups, ions in the perovskite jointly act on the functional groups, ion migration is inhibited, and the perovskite crystal nucleation and grain growth processes are regulated and controlled. Meanwhile, the benzene ring has a firm structure and high cohesive energy, and azobenzene micromolecules are easy to form hydrophobic passivation, so that the photoelectric conversion efficiency and stability of the cell can be improved. In addition, the block polymer interface layer is introduced in front of the perovskite light absorption layer, the block polymer has the deformation resistance and fatigue resistance of the interface layer, the perovskite can be locally infiltrated into the perovskite light absorption layer during film forming, and the elastic insulating polymer enriched at the crystal boundary effectively plays a role in stress buffering, so that the bending resistance of the flexible perovskite battery can be improved. In conclusion, the flexible perovskite solar cell with good bending resistance, high photoelectric conversion efficiency and high stability can be prepared by the method, and the preparation process is simple.
In addition, the method for manufacturing the flexible perovskite solar cell according to the embodiment of the invention may further have the following additional technical features:
in some embodiments of the present invention, in the step (2), the ultraviolet light used for the photocuring has a wavelength of 300 to 400nm and an irradiation time of 5 to 20 minutes.
In some embodiments of the invention, in the step (3), the concentration of the perovskite in the mixed solution is 35 to 60 wt%, and the concentration of the azobenzene small-molecule additive is 0.1 to 0.5 wt%. Therefore, the flexible perovskite solar cell has high photoelectric conversion efficiency and stability.
In some embodiments of the present invention, in step (2), the organic solvent comprises at least one of dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, γ -butyrolactone, dimethylacetamide, 2-butoxyethanol, dimercaptoethanol, and acetonitrile.
In some embodiments of the present invention, in the step (4), the temperature of the annealing treatment is 100 to 150 ℃ for 10 to 90 min. Therefore, large-area high-quality perovskite thin films can be obtained without additionally adopting auxiliary film forming means such as vacuum pumping, air knife, anti-solvent and the like, and the process is simple and easy to realize.
In some embodiments of the present invention, the flexible substrate is preheated to 40-60 ℃ in advance before performing step (4). Thus, initial crystal nuclei can be formed on the surface of the substrate at the moment when the mixed solution containing perovskite and the azobenzene small-molecule additive contacts the substrate.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic structural diagram of a flexible perovskite solar cell according to one embodiment of the invention;
fig. 2 is a schematic flow diagram of a method of fabricating a flexible perovskite solar cell according to one embodiment of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In a first aspect of the invention, the invention proposes a flexible perovskite solar cell. According to an embodiment of the present invention, referring to fig. 1, the cell structure includes a flexible substrate 1, and a transparent electrode 2, an electrode modification layer 3, a block polymer interface layer 4, a perovskite light absorption layer 5, an electrode buffer layer 6 and a metal electrode 7 sequentially stacked on the flexible substrate 1, wherein the perovskite light absorption layer 5 includes perovskite and azobenzene small molecule additives.
The inventor finds that through introducing the azobenzene small-molecule additive into the perovskite light absorption layer, the azobenzene small-molecule additive has amino groups, carboxyl groups, hydroxyl groups or sulfonic acid groups, ions in the perovskite jointly act on the functional groups, the ion migration is inhibited, and the perovskite crystal nucleation and grain growth processes are regulated and controlled. Meanwhile, the benzene ring has a firm structure and high cohesive energy, and azobenzene micromolecules are easy to form hydrophobic passivation, so that the photoelectric conversion efficiency and stability of the cell can be improved. In addition, the block polymer interface layer is introduced in front of the perovskite light absorption layer, the block polymer has the deformation resistance and fatigue resistance of the interface layer, the perovskite can be locally infiltrated into the perovskite light absorption layer during film forming, and the elastic insulating polymer enriched at the crystal boundary effectively plays a role in stress buffering, so that the bending resistance of the flexible perovskite battery can be improved.
In some embodiments of the present invention, the raw material of the block polymer interface layer 4 includes a tert-butyl acrylate monomer, an aliphatic urethane diacrylate monomer and an initiator, and the block polymer interface layer 4 is formed by mixing the tert-butyl acrylate monomer, the aliphatic urethane diacrylate monomer and the initiator and then performing photo-curing polymerization. Thus, hydrogen bonding interactions between the block polymer groups result in an interfacial layer with good resistance to deformation and fatigue. Specifically, the ultraviolet wavelength used for photocuring is 300-400 nm, and the irradiation time is 5-20 minutes.
Furthermore, the mass of the aliphatic polyurethane diacrylate monomer accounts for 5-20% of the total mass of the tert-butyl acrylate monomer and the aliphatic polyurethane diacrylate monomer. The inventor finds that if the aliphatic polyurethane diacrylate monomer is added too little, the function of increasing the elasticity of the polymer cannot be achieved; if the aliphatic polyurethane diacrylate monomer is added too much, the viscosity of the polymer precursor solution is too high, so that the block polymer interface layer is too thick and cannot transmit carriers.
It should be noted that the specific type of the above initiator can be selected by those skilled in the art according to actual needs, and for example, the initiator can be a polyolefin thermoplastic elastomer. Furthermore, the mass of the initiator accounts for 0.2-0.3% of the total mass of the tert-butyl acrylate monomer and the aliphatic polyurethane diacrylate monomer. The inventors found that if the initiator is added too little, polymerization is not sufficiently carried out; if the initiator is added too much, local polymerization is accelerated, and the film forming quality is affected. Therefore, the addition amount of the initiator can enable the tert-butyl acrylate monomer and the aliphatic polyurethane diacrylate monomer to achieve the best polymerization effect, and the film forming quality of the polymer interface layer is high.
Further, the thickness of the block polymer interface layer is 1 to 10 nm. The inventors found that if the thickness of the block polymer interface layer is too small, it cannot function to induce crystallization of the perovskite thin film; if the thickness of the block polymer interface layer is too large, the transmission of carriers is affected, and the photoelectric performance of the battery device is affected. Therefore, the thickness of the polymer interface layer is beneficial to inducing crystallization of the perovskite thin film and transmission of current carriers.
In some embodiments of the invention, in the perovskite light absorption layer, the mass ratio of perovskite to azobenzene small molecule additive is (35-60): (0.1-0.5). The inventors have found that if the mass ratio is too small, the mass of the perovskite light absorbing layer is affected; if the mass ratio is too large, the perovskite crystal cannot be induced to nucleate or the auxiliary grain size growth. Therefore, by adopting the mass ratio of the flexible perovskite solar cell, the obtained perovskite light absorption layer has good quality, and the photoelectric conversion efficiency and the stability of the flexible perovskite solar cell are high.
It should be noted that the specific type of the azobenzene small molecule additive is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the azobenzene small molecule additive is selected from the group consisting of 4,4' -dicarboxylazobenzene, 4' -diaminoazobenzene, 4-aminoazobenzene-3-disulfonic acid, 2-amino-5 (3-sulfonicazophenyl) azobenzene, 4-dimethylaminophenylazobenzene sulfonyl chloride, 2, 4-diamino-3 ' -trifluoromethylazobenzene, 4' -azobenzene dicarboxylate, 4-aminophenylazobenzene-2-sulfonic acid, 4-hydroxy-4 ' -carboxyazobenzene, p-aminoazobenzene-4-sulfonic acid and 2, at least one of 4,3' -triamine azobenzene.
Further, the chemical formula of the perovskite is ABXmY3-m. Wherein A comprises Cs, H, NH4、CH3NH3、CH3CH2NH3、CH3(CH2)2NH3、CH3(CH2)3NH3And NH2＝CHNH2At least one of; b comprises at least one of Pb, Sn and Ge; x and Y independently include Cl, Br, I and BF4SCN and PF6At least one of; m is 0 to 3.
Furthermore, the thickness of the perovskite light absorption layer is 100-1000 nm. The inventor finds that if the thickness of the perovskite light absorption layer is too small, sunlight cannot be sufficiently absorbed, and the current of the device is low; if the thickness of the perovskite light absorption layer is too large, film forming defects of a light absorption layer film are increased, and current carriers are seriously compounded on the light absorption layer, so that the performance of the device is reduced. Therefore, the perovskite light absorption layer thickness is adopted, and the performance of the device is good.
In some embodiments of the present invention, the electrode modification layer is an electron transport layer, and the electrode buffer layer is a hole transport layer, and it should be noted that a person skilled in the art can select specific types of the electron transport layer and the hole transport layer according to actual needs, for example, the electron transport layer includes TiO2、SnO2、ZnO、PC61BM、PC71BM, TIPD, ICBA and C60-at least one of bis; the hole transport layer is formed by adopting an organic material and/or an inorganic material, and particularly, the hole transport layer is formed by adopting an organic material; or the hole transport layer is formed by adopting an inorganic material; or the hole transport layer is formed by organic material and inorganic material, namely the hole transport layer comprises a first hole transport layer and a second hole transport layer, one layer is formed by organic material, the other layer is formed by inorganic material, the organic material comprises at least one of Spiro-OMeTAD, P3HT, PCPDTBT, PEDOT: PSS, NPB and TPD, and the inorganic material comprises CuI, CuSCN and NiOX、V2O5And MoO3At least one of (a).
In some embodiments of the invention, the electrode modification layer is a hole transport layer, and the electrode buffer layer is an electron transport layer. It should be noted that the specific types of the electron transport layer and the hole transport layer can be selected by those skilled in the art according to actual needs, for example, the hole transport layer includes PTAA, PEDOT: PSS, CuI, CuSCN, NiOX、V2O5And MoO3At least one of, the electron transport layer comprises TiO2、SnO2、ZnO、PC61BM、PC71BM, TIPD, ICBA and C60-at least one of bis.
Further, the thickness of the electrode modification layer is 5-150 nm, preferably 10-50 nm; the thickness of the electrode buffer layer is 5 to 300nm, preferably 10 to 150 nm. It should be noted that the specific types of the flexible substrate 1, the transparent electrode 2 and the metal electrode 7 are not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the flexible substrate 1 includes at least one of PET and PEN; the transparent electrode 2 may be ITO; the metal electrode 7 includes at least one of gold, silver, copper, and aluminum.
In a second aspect of the invention, the invention proposes a method of manufacturing a flexible perovskite solar cell as described above. According to an embodiment of the invention, referring to fig. 2, the method comprises:
s100: sequentially forming a transparent electrode and an electrode modification layer on a flexible substrate
In the step, a flexible substrate containing a transparent conducting layer is subjected to laser etching to form an electrode pattern P1, and then the flexible substrate is cleaned, dried and treated by ultraviolet/ozone for 18-22 min, preferably 20min, so that a transparent electrode can be formed on the flexible substrate, specifically, the cleaning mode can be that a detergent, deionized water, absolute ethyl alcohol, acetone and isopropanol are sequentially subjected to ultrasonic cleaning for 4-6 min, preferably 5 min; the drying mode can be drying or blow-drying by nitrogen. And then coating the precursor solution of the electrode modification layer on the surface of the transparent electrode, and then putting the transparent electrode into a hot bench for drying at 140-160 ℃, preferably 150 ℃ for 25-35 min, preferably 30min, so as to form the electrode modification layer on the surface of the transparent electrode. It should be noted that the specific types and thicknesses of the transparent electrode and the electrode modification layer are the same as those described above, and are not described herein again.
S200: mixing tert-butyl acrylate, aliphatic polyurethane diacrylate and initiator, coating the mixture on the surface of an electrode modification layer, and carrying out photocuring
In the step, tert-butyl acrylate, aliphatic polyurethane diacrylate and an initiator are mixed and then coated on the surface of the electrode modification layer, and then UV light curing is carried out, so that a block polymer interface layer can be formed on the surface of the electrode modification layer. The inventors have found that hydrogen bonding interactions between the block polymer groups give the interfacial layer good resistance to deformation and fatigue. It should be noted that, the above-mentioned coating method can be selected by those skilled in the art according to actual needs, and for example, the coating method can be spin coating, spray coating or knife coating. Specifically, the ultraviolet wavelength used for photocuring is 300-400 nm, and the irradiation time is 5-20 minutes. The inventors found that if the irradiation time is too short, the monomer cannot be sufficiently cured; and if the irradiation time is too long, the sample wafer is overheated and deforms. Therefore, by adopting the irradiation time of the application, on one hand, the full curing of the monomer can be ensured; on the other hand, the sample wafer can be prevented from being deformed due to overheating. It should be noted that the mixing ratio of t-butyl acrylate, aliphatic urethane diacrylate and initiator, the specific type of initiator and the thickness of the block polymer interface layer are the same as those described above, and will not be described again here.
S300: mixing perovskite precursor material, azobenzene micromolecule additive and organic solvent
In the step, a perovskite precursor material, an azobenzene micromolecule additive and an organic solvent are mixed, wherein the perovskite precursor material reacts to generate perovskite, and therefore a mixed solution containing perovskite and the azobenzene micromolecule additive is obtained. Preferably, the mixing process is heating and stirring at 55-70 ℃, preferably 60 ℃ for 6-12 h, so that the perovskite precursor material can be fully dissolved, and a transparent mixed solution can be obtained after the final reaction. It should be noted that the skilled person can select the specific type of the perovskite precursor material according to actual needs, as long as the perovskite precursor material can react to form ABXmY3-mThe perovskite of (b) may be, and the specific type of A, B, X, Y in the general formula and the value range of m are the same as those described above, and are not described herein again.
Furthermore, the concentration of the perovskite in the mixed perovskite solution is 35-60 wt%, and the concentration of the azobenzene micromolecule additive is 0.1-0.5 wt%. The inventor finds that if the concentration of the perovskite is too low, the thickness of the light absorption layer is too low, and the short-circuit current of the battery is influenced; if the concentration of the perovskite is too high, film forming defects of a light absorption layer are obviously increased, carrier recombination is serious, and the performance of a device is reduced. Therefore, by adopting the perovskite concentration, the perovskite light absorption layer has proper thickness, and the performance of the device is better. Meanwhile, if the concentration of the azobenzene micromolecule additive is too low, the azobenzene micromolecule additive cannot play a role in inducing perovskite crystal nucleation or assisting grain size growth; and if the concentration of the azobenzene micromolecule additive is too high, the quality of the perovskite light absorption layer is influenced.
It should be noted that the specific type of the organic solvent can be selected by those skilled in the art according to actual needs, and for example, the organic solvent includes at least one of dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, γ -butyrolactone, dimethylacetamide, 2-butoxyethanol, dimercaptoethanol, and acetonitrile. In addition, the specific type of the azobenzene small molecule additive is the same as that described above, and is not described herein again.
S400: coating the mixed solution on the surface of a block polymer interface layer and annealing
In the step, the perovskite light absorption layer can be formed on the surface of the block polymer interface layer by coating the mixed solution on the surface of the block polymer interface layer and carrying out annealing treatment. The inventor finds that through introducing the azobenzene small-molecule additive into the perovskite light absorption layer, the azobenzene small-molecule additive has amino groups, carboxyl groups, hydroxyl groups or sulfonic acid groups, ions in the perovskite jointly act on the functional groups, the ion migration is inhibited, and the perovskite crystal nucleation and grain growth processes are regulated and controlled. Meanwhile, the benzene ring has a firm structure and high cohesive energy, and azobenzene micromolecules are easy to form hydrophobic passivation, so that the photoelectric conversion efficiency and stability of the cell can be improved. Meanwhile, when the perovskite is formed into a film, the block polymer interface layer with good deformation resistance and fatigue resistance can locally permeate into the perovskite light absorption layer, and the elastic insulating polymer enriched at the crystal boundary effectively plays a role in stress buffering, so that the bending resistance of the flexible perovskite battery can be improved. In addition, the annealing treatment is adopted for film formation, film formation auxiliary means such as vacuumizing, air knife and anti-solvent are not additionally adopted, the large-area high-quality perovskite film can be obtained, and the process is simple and easy to realize.
Preferably, the flexible substrate is preheated to 40 to 60 ℃ in advance before the mixed solution is applied. Thus, initial crystal nuclei can be formed on the surface of the substrate at the moment when the mixed solution containing perovskite and the azobenzene small-molecule additive contacts the substrate. The inventors found that if the preheating temperature is too low, initial crystal nuclei cannot be formed; if the preheating temperature is too high, crystal nucleus precipitation is too fast, and the grain size growth of the light absorption layer film is limited. Therefore, the preheating temperature is favorable for inducing the perovskite film to crystallize, and perovskite film grains with larger sizes are obtained. Preferably, the process of forming the perovskite light absorbing layer is performed under an inert gas shield (e.g., nitrogen). The coating method can be selected by those skilled in the art according to actual needs, and may be, for example, knife coating, spin coating, spray coating, slit coating, or inkjet printing.
Further, the temperature of the annealing treatment is 100-150 ℃, and the time is 10-90 min. The inventor finds that if the annealing temperature is too low, a perovskite crystal structure cannot be formed; if the annealing temperature is too high, decomposition of the perovskite thin film is induced. Meanwhile, if the annealing treatment time is too short, the solvent is not sufficiently volatilized, and the perovskite crystal form is not sufficiently formed; and if the annealing treatment time is too long, the surface roughness of the perovskite thin film is too large. Therefore, the solvent in the perovskite thin film can be fully volatilized by high-temperature annealing, and the perovskite thin film can rapidly grow from the initial crystal nucleus, so that the size and the shape of the crystal grains of the perovskite thin film are controlled.
It should be noted that the thickness of the perovskite light absorption layer is the same as that described above, and is not described herein again.
S500: sequentially forming an electrode buffer layer and a metal electrode on the surface of the perovskite light absorption layer
In the step, firstly, coating an electrode buffer layer precursor solution on the surface of a perovskite light absorption layer, and performing laser etching to form P2; and then preparing a metal electrode on the surface of the electrode buffer layer, and performing laser etching to form P3, thus obtaining the flexible perovskite solar cell. The coating method and the preparation method of the metal electrode are not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the coating method can be spin coating, spray coating or blade coating; the metal electrode can be prepared by adopting a vacuum evaporation mode. In addition, the specific types and thicknesses of the electrode buffer layer and the metal electrode are the same as those described above, and are not described herein again.
The inventor finds that the transparent electrode and the electrode modification layer are formed on the flexible substrate in sequence; mixing tert-butyl acrylate, aliphatic polyurethane diacrylate and an initiator, coating the mixture on the surface of the electrode modification layer, and carrying out photocuring to form a block polymer interface layer on the surface of the electrode modification layer; then mixing a perovskite precursor material, an azobenzene micromolecule additive and an organic solvent, and reacting the perovskite precursor material to generate perovskite, thereby obtaining a mixed solution containing perovskite and the azobenzene micromolecule additive; coating the mixed solution on the surface of a block polymer interface layer and carrying out annealing treatment, so that a perovskite light absorption layer can be formed on the surface of the block polymer interface layer, annealing treatment is adopted to form a film, film-forming auxiliary means such as vacuum pumping, air knife and anti-solvent are not additionally adopted, the large-area high-quality perovskite film can be obtained, and the process is simple and easy to implement; and finally, sequentially forming an electrode buffer layer and a metal electrode on the surface of the perovskite light absorption layer to obtain the flexible perovskite solar cell. According to the method, the azobenzene micromolecule additive is introduced into the perovskite light absorption layer, the azobenzene micromolecule additive is provided with amino groups, carboxyl groups, hydroxyl groups or sulfonic acid groups, ions in the perovskite jointly act on the functional groups, ion migration is inhibited, and the perovskite crystal nucleation and grain growth processes are regulated and controlled. Meanwhile, the benzene ring has a firm structure and high cohesive energy, and azobenzene micromolecules are easy to form hydrophobic passivation, so that the photoelectric conversion efficiency and stability of the cell can be improved. In addition, the block polymer interface layer is introduced in front of the perovskite light absorption layer, the block polymer has the deformation resistance and fatigue resistance of the interface layer, the perovskite can be locally infiltrated into the perovskite light absorption layer during film forming, and the elastic insulating polymer enriched at the crystal boundary effectively plays a role in stress buffering, so that the bending resistance of the flexible perovskite battery can be improved. In conclusion, the flexible perovskite solar cell with good bending resistance, high photoelectric conversion efficiency and high stability can be prepared by the method, and the preparation process is simple.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Step one, preparing a transparent electrode:
and (3) carrying out laser etching on PET/ITO to form an electrode pattern P1, sequentially carrying out ultrasonic cleaning in glass cleaning solution, deionized water, absolute ethyl alcohol, acetone and isopropanol for 5min, then carrying out nitrogen blow-drying, and carrying out ultraviolet/ozone treatment for 20 min.
Step two, preparing an electrode modification layer:
coating low-temperature nano TiO on the surface of the transparent electrode2And drying the precursor solution of the particle colloid in a hot stage at 150 ℃ for 30min to form an electrode modification layer with the thickness of 45 nm.
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 5% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. Curing with 365nm ultraviolet light for 5min to obtain a cured product with a thickness of 1 nm.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: using mixed solvent (DMF/DMSO volume ratio: 4/1) according to Cs0.05(FA0.92MA0.08)0.95Pb(I0.92Br0.08)3The formulation of (A) dissolves PbI2、PbBr2CsI, amitraz and iodomethylamine perovskite precursor, and the perovskite precursor reacts to generate perovskite Cs0.05(FA0.92 MA0.08)0.95Pb(I0.92Br0.08)3Adding azoThe benzene micromolecule additive 4,4' -dicarboxy azobenzene is heated and stirred for 6 hours at the temperature of 60 ℃, and the concentration of the perovskite in the obtained mixed solution is 45 wt%, and the concentration of the additive is 0.1 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating the flexible substrate to 40 ℃, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of the polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 150 ℃ for 15min to form the perovskite light absorption layer with the thickness of 300 nm.
Fifthly, preparing an electrode buffer layer:
under the protection of nitrogen, preparing a hole transport layer on the perovskite light absorption layer by adopting a spin coating method, adding 90mg of Spiro-OMeTAD, 27.5ml of t-BP and 17.5ml of Li-TFSI into 1ml of chlorobenzene, dissolving to prepare a solution, and spin-coating the solution on the surface of the perovskite light absorption layer at the rotating speed of 3000rpm for 30s to obtain an electrode buffer layer with the thickness of 120 nm.
P2 was formed by scribing with a laser at 532nm wavelength.
Sixthly, preparing a metal electrode:
preparing gold electrode on the surface of the electrode buffer layer by thermal evaporation at 5 × 10-4Under Pa vacuum degree, a gold film with a thickness of 80nm was vacuum-deposited to form a metal electrode. P3 was formed by scribing with a laser at 532nm wavelength.
The device structure of the large-area flexible perovskite thin-film solar cell prepared by the method is shown in figure 1: PET/ITO/TiO2Block polymer interface layer/perovskite light absorption layer/Spiro-OMeTAD/Au with effective area of 25cm2The photoelectric conversion efficiency data are shown in table 1, and the test conditions are as follows: spectral distribution AM1.5G, illumination intensity 1000W/m2AAA solar simulator (model XES-502S + ELS155, SAN-EI, Japan), I-V curves were measured using a Keithly model 2400 digital Source Meter, all tests were performed in an atmospheric environment (25 deg.C, 45 RH%). The bending resistance of the battery was tested by using a bending resistance tester (Flextest-TM-L, Nakan, Hunan) with a bending radius of 2.5 mm.
Example 2
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 15% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. 365m ultraviolet light curing for 7min, the thickness is 5 nm.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: using mixed solvent (DMF/DMSO volume ratio: 4/1) according to Cs0.05(FA0.92MA0.08)0.95Pb(I0.92Br0.08)3The formulation of (A) dissolves PbI2、PbBr2CsI, amitraz and iodomethylamine perovskite precursor, and the perovskite precursor reacts to generate perovskite Cs0.05(FA0.92 MA0.08)0.95Pb(I0.92Br0.08)3Adding 4-aminoazobenzene-3-disulfonic acid serving as an azobenzene micromolecule additive, heating and stirring at 60 ℃ for 8 hours to obtain a mixed solution with the perovskite concentration of 45 wt% and the additive concentration of 0.3 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating the flexible substrate to 40 ℃, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of the polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 130 ℃ for 30min to form the perovskite light absorption layer with the thickness of 400 nm.
The other steps of the preparation method are the same as example 1.
The device structure of the organic-inorganic hybrid perovskite thin-film solar cell prepared by the method is shown in figure 1: PET/ITO/TiO2Block polymer interface layer/perovskite light absorption layer/Spiro-OMeTAD/Au with effective area of 25cm2The photoelectric conversion efficiency data are shown in table 1, and the test conditions are the same as in example 1.
Example 3
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 20% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. Curing with 365nm ultraviolet light for 7min to obtain a cured product with a thickness of 5 nm.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: using mixed solvent (DMF/DMSO volume ratio: 4/1) according to Cs0.05(FA0.92MA0.08)0.95Pb(I0.92Br0.08)3The formulation of (A) dissolves PbI2、PbBr2CsI, amitraz and iodomethylamine perovskite precursor, and the perovskite precursor reacts to generate perovskite Cs0.05(FA0.92 MA0.08)0.95Pb(I0.92Br0.08)3Adding 4-aminoazobenzene-3-disulfonic acid serving as an azobenzene micromolecule additive, heating and stirring at 60 ℃ for 8 hours to obtain a mixed solution with the perovskite concentration of 35 wt% and the additive concentration of 0.3 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating the flexible substrate to 40 ℃, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of the polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 130 ℃ for 30min to form the perovskite light absorption layer with the thickness of 400 nm.
The other steps of the preparation method are the same as example 1.
The device structure of the organic-inorganic hybrid perovskite thin-film solar cell prepared by the method is shown in figure 1: PET/ITO/TiO2Block polymer interface layer/perovskite light absorption layer/Spiro-OMeTAD/Au with effective area of 25cm2The photoelectric conversion efficiency data are shown in table 1, and the test conditions are the same as in example 1.
Example 4
Step one, preparing a transparent electrode:
and performing laser etching on PEN/ITO to form an electrode pattern P1, sequentially performing ultrasonic cleaning in glass cleaning solution, deionized water, absolute ethyl alcohol, acetone and isopropanol for 5min, blow-drying by nitrogen, and performing ultraviolet/ozone treatment for 30 min.
Step two, preparing an electrode modification layer:
weighing NiO with the particle size of 5nmxDissolving the powder in deionized water, performing ultrasonic dispersion with the concentration of 30mg/ml, spin-coating on the surface of the transparent electrode at the rotation speed of 1000rpm of a spin coater for 30s, and drying at 100 ℃ for 5min to form a film, thereby forming an electrode modification layer with the thickness of 30 nm.
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 10% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. Curing with 365nm ultraviolet light for 20min to obtain a cured product with a thickness of 5 nm.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: will PbI2、PbCl2、CH3NH3I. 4-dimethylamino phenyl azobenzene sulfonyl chloride according to a certain mass ratio (PbI)2、PbCl2、CH3NH3I molar ratio 1:1:4) were dissolved together in a 2-ME/CAN (volume ratio 2/1) mixed solvent, and then heated and stirred at 60 ℃ for 6 hours, to obtain a mixed solution in which the perovskite concentration was 45 wt% and the additive concentration was 0.5 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating a flexible substrate to 60 ℃, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of a polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 100 ℃ for 45min to form CH with the thickness of 550nm3NH3PbIxCl3-x(x is 0 to 3) a perovskite light-absorbing layer.
Fifthly, preparing an electrode buffer layer:
spin coating PCBM chlorobenzene solution with concentration of 20mg/ml on the surface of perovskite light absorption layer, drying at 70 deg.C for 10min at rotation speed of 1000rpm for 40s to form electrode buffer layer with thickness of 40nm,
p2 was formed by scribing with a laser at 532nm wavelength.
Sixthly, preparing a metal electrode:
at 5X 10-4And (3) carrying out vacuum evaporation on an aluminum film with the thickness of 120nm on the surface of the electrode buffer layer under the Pa vacuum degree to form a metal electrode. P3 was formed by scribing with a laser at 532nm wavelength.
The device structure of the large-area flexible perovskite thin-film solar cell prepared by the method is shown in figure 1: PEN/ITO/NiOxBlock polymer interface layer/CH3NH3PbIxCl3-xPCBM/Al with an effective area of 25cm2The photoelectric conversion efficiency data are shown in table 2, and the test conditions are as follows: spectral distribution AM1.5G, illumination intensity 1000W/m2AAA solar simulator (model XES-502S + ELS155, SAN-EI, Japan), I-V curves were measured using a Keithly model 2400 digital Source Meter, all tests were performed in an atmospheric environment (25 deg.C, 45 RH%).
Example 5
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 20% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. Curing with 365nm ultraviolet light for 15min to obtain a film with a thickness of 6 nm.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: will PbI2、PbCl2、CH3NH3I. 4,4' -azobenzene dicarboxylic ester ethyl ester according to a certain mass ratio (PbI)2、PbCl2、CH3NH3I molar ratio 1:1:4) were dissolved together in a 2-ME/CAN (volume ratio 2/1) mixed solvent, and then heated and stirred at 70 ℃ for 12 hours, to obtain a mixed solution in which the perovskite concentration was 60 wt% and the additive concentration was 0.2 wt%.
Calcium titaniumPreparing a light absorption layer of the ore: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating a flexible substrate to 60 ℃, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of a polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 100 ℃ for 45min to form CH with the thickness of 550nm3NH3PbIxCl3-x(x is 0 to 3) a perovskite light-absorbing layer.
The other steps of the preparation method are the same as example 4.
The device structure of the large-area flexible perovskite solar cell prepared by the method is shown in the PEN/ITO/NiO shown in figure 1xBlock polymer interface layer/CH3NH3PbIxCl3-xPCBM/Al with an effective area of 25cm2The photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as those in example 4.
Example 6
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 10% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. Curing with 365nm ultraviolet light for 20min to obtain 8nm thick film.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: will PbI2、PbCl2、CH3NH3I. 4-dimethylamino phenyl azobenzene sulfonyl chloride according to a certain mass ratio (PbI)2、PbCl2、CH3NH3I molar ratio 1:1:4) were dissolved together in a 2-ME/CAN (volume ratio 2/1) mixed solvent, and then heated and stirred at 70 ℃ for 8 hours, to obtain a mixed solution in which the perovskite concentration was 35 wt% and the additive concentration was 0.1 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating a flexible substrate to 60 ℃, taking a certain volume of perovskite solution, and spin-coating the perovskite solution on a polymer interfaceSurface of the layer, rotating speed of 5000rpm for 30s, and then annealing at 100 deg.C for 45min to form 350nm thick CH3NH3PbIxCl3-x(x is 0 to 3) a perovskite light-absorbing layer.
The other steps of the preparation method are the same as example 4.
The device structure of the large-area flexible perovskite solar cell prepared by the method is shown in the PEN/ITO/NiO shown in figure 1xBlock polymer interface layer/CH3NH3PbIxCl3-xPCBM/Al with an effective area of 25cm2The photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as those in example 4.
Comparative example 1
The preparation of the block polymer interface layer is not carried out,
fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: using mixed solvent (DMF/DMSO volume ratio: 4/1) according to Cs0.05(FA0.92MA0.08)0.95Pb(I0.92Br0.08)3The formulation of (A) dissolves PbI2、PbBr2CsI, amitraz and iodomethylamine perovskite precursor, and reacting to generate perovskite Cs0.05(FA0.92 MA0.08)0.95Pb(I0.92Br0.08)3 Azobenzene micromolecule additive 4,4' -dicarboxy azobenzene is added, and then the mixture is heated and stirred for 6 hours at the temperature of 60 ℃, so that the concentration of perovskite in the obtained mixed solution is 35 wt%, and the concentration of the additive is 0.1 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating a flexible substrate to 40 ℃, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of a polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 150 ℃ for 15min to form the 350nm thick perovskite light absorption layer.
The other steps of the preparation method are the same as example 1.
The device structure of the large-area flexible perovskite thin-film solar cell prepared by the method is shown in figure 1: PET/ITO/TiO2Block polymer interface layer/perovskiteLight absorbing layer/cyclone-OMeTAD/Au with effective area of 25cm2The photoelectric conversion efficiency data are shown in table 1, and the test conditions are the same as in example 1.
Comparative example 2 No Azobenzene Small molecule additive
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: using mixed solvent (DMF/DMSO volume ratio: 4/1) according to Cs0.05(FA0.92MA0.08)0.95Pb(I0.92Br0.08)3The formulation of (A) dissolves PbI2、PbBr2CsI, amitraz and iodomethylamine perovskite precursor, and reacting to generate perovskite Cs0.05(FA0.92 MA0.08)0.95Pb(I0.92Br0.08)3Then, after heating and stirring at 60 ℃ for 6 hours, the concentration of perovskite in the resulting perovskite solution was 45 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating the flexible substrate to 40 ℃, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of the polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 150 ℃ for 15min to form the perovskite light absorption layer with the thickness of 300 nm.
The other steps of the preparation method are the same as example 1.
The device structure of the organic-inorganic hybrid perovskite thin-film solar cell prepared by the method is shown in figure 1: PET/ITO/TiO2A block polymer interface layer/perovskite light absorption layer/spiro-OMeTAD/Au with an effective area of 25cm2The photoelectric conversion efficiency data are shown in table 1, and the test conditions are the same as in example 1.
Comparative example 3 No preheating of the Flexible substrate
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 5% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. Curing with 365nm ultraviolet light for 5min to obtain a cured product with a thickness of 1 nm.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: using mixed solvent (DMF/DMSO volume ratio: 4/1) according to Cs0.05(FA0.92MA0.08)0.95Pb(I0.92Br0.08)3The formulation of (A) dissolves PbI2、PbBr2CsI, amitraz and iodomethylamine perovskite precursor, and reacting to generate perovskite Cs0.05(FA0.92 MA0.08)0.95 Azobenzene micromolecule additive 4,4' -dicarboxy azobenzene is added, and then the mixture is heated and stirred for 6 hours at the temperature of 60 ℃, so that the concentration of perovskite in the obtained mixed solution is 45 wt%, and the concentration of the additive is 0.1 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of the polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 150 ℃ for 15min to form the perovskite light absorption layer with the thickness of 400 nm.
The other steps of the preparation method are the same as example 1.
The device structure of the organic-inorganic hybrid perovskite thin-film solar cell prepared by the method is shown in figure 1: PET/ITO/TiO2A block polymer interface layer/perovskite light absorption layer/spiro-OMeTAD/Au with an effective area of 25cm2The photoelectric conversion efficiency data are shown in table 1, and the test conditions are the same as in example 1.
Comparative example 4
The preparation of the block polymer interface layer is not carried out,
fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: will PbI2、PbCl2、CH3NH3I. 4-dimethylamino phenyl azobenzene sulfonyl chloride according to a certain mass ratio (PbI)2、PbCl2、CH3NH3I molar ratio of 1:1:4) were dissolved in a 2-ME/CAN (volume ratio of 2/1) mixed solvent together, and after heating and stirring at 70 ℃ for 6 hours, the resulting mixed solution was concentrated in perovskiteThe degree was 55 wt% and the concentration of the additive was 0.5 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, heating a flexible substrate to 60 ℃, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of a polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 100 ℃ for 45min to form CH with the thickness of 550nm3NH3PbIxCl3-x(x is 0 to 3) a perovskite light-absorbing layer.
The other steps of the preparation method are the same as example 4.
The device structure of a large-area flexible solar cell prepared by the method is shown in figure 1: PEN/ITO/NiOxBlock polymer interface layer/CH3NH3PbIxCl3-xPCBM/Al with an effective area of 25cm2The photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as those in example 4.
Comparative example 5 No Azobenzene Small molecule additive
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 10% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. Curing with 365nm ultraviolet light for 20min to obtain a cured product with a thickness of 5 nm.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: will PbI2、PbCl2、CH3NH3I, according to a certain mass ratio (PbI)2、PbCl2、CH3NH3I molar ratio 1:1:4) were dissolved together in a 2-ME/CAN (volume ratio 2/1) mixed solvent, and then heated and stirred at 70 ℃ for 6 hours, to obtain a mixed solution in which the perovskite concentration was 45 wt% and the additive concentration was 0.3 wt%.
Preparing a perovskite light absorption layer: preparing perovskite light absorption layer and flexible lining by one-step solution method under nitrogen protectionHeating to 60 deg.C, spin-coating perovskite solution on the surface of polymer interface layer at 5000rpm for 30s, and annealing at 100 deg.C for 45min to form CH with thickness of 550nm3NH3PbIxCl3-x(x is 0 to 3) a perovskite light-absorbing layer.
The other steps of the preparation method are the same as example 4.
The device structure of a large-area flexible solar cell prepared by the method is shown in figure 1: PEN/ITO/NiOxBlock polymer interface layer/CH3NH3PbIxCl3-xPCBM/Al with an effective area of 25cm2The photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as those in example 4.
Comparative example 6 No preheating of the Flexible substrate
Step three, preparing a polymer interface layer:
and spin-coating a segmented copolymer precursor solution on the surface of the electrode modification layer, wherein the precursor solution is formed by adding an initiator into tert-butyl acrylate (tBA) and aliphatic polyurethane diacrylate (AUD) monomers. The mass of AUD accounts for 10% of the total mass of AUD and tBA; the light curing initiator is polyolefin thermoplastic elastomer (TPO), and the mass of the TPO is 0.2 percent of the total mass of AUD and tBA. Curing with 365nm ultraviolet light for 20min to obtain a cured product with a thickness of 5 nm.
Fourthly, preparing a perovskite light absorption layer:
preparing a perovskite coating liquid: will PbI2、PbCl2、CH3NH3I. 4-dimethylamino phenyl azobenzene sulfonyl chloride according to a certain mass ratio (PbI)2、PbCl2、CH3NH3I molar ratio 1:1:4) were dissolved together in a 2-ME/CAN (volume ratio 2/1) mixed solvent, and then heated and stirred at 60 ℃ for 8 hours, to obtain a mixed solution in which the perovskite concentration was 45 wt% and the additive concentration was 0.5 wt%.
Preparing a perovskite light absorption layer: preparing a perovskite light absorption layer by a one-step solution method under the protection of nitrogen, taking a certain volume of perovskite solution, spin-coating the perovskite solution on the surface of a polymer interface layer, rotating at 5000rpm for 30s, and then heating and annealing at 100 ℃ for 45min to form CH with the thickness of 550nm3NH3PbIxCl3-x(x is 0 to 3) a perovskite light-absorbing layer.
The other steps of the preparation method are the same as example 4.
The device structure of the organic-inorganic hybrid perovskite-based solar cell prepared by the method is shown in figure 1: PEN/ITO/NiOxBlock polymer interface layer/CH3NH3PbIxCl3-xPCBM/Al with an effective area of 25cm2The photoelectric conversion efficiency data are shown in Table 2, and the test conditions are the same as those in example 4.
Table 1: performance characterization of the batteries prepared in examples 1-3 and comparative examples 1-3
Figure BDA0003376685340000171
Table 2: performance characterization of the batteries prepared in examples 4 to 6 and comparative examples 4 to 6
Figure BDA0003376685340000172
Figure BDA0003376685340000181
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. The flexible perovskite solar cell is characterized in that the cell structure comprises a flexible substrate, and a transparent electrode, an electrode modification layer, a block polymer interface layer, a perovskite light absorption layer, an electrode buffer layer and a metal electrode which are sequentially stacked on the flexible substrate, wherein the perovskite light absorption layer comprises perovskite and azobenzene micromolecule additives.
2. The flexible perovskite solar cell of claim 1, wherein the feedstock for the block polymer interface layer comprises a t-butyl acrylate monomer, an aliphatic urethane diacrylate monomer, and an initiator;
optionally, the mass of the aliphatic polyurethane diacrylate monomer accounts for 5-20% of the total mass of the tert-butyl acrylate monomer and the aliphatic polyurethane diacrylate monomer;
optionally, the initiator is a polyolefin thermoplastic elastomer, the mass of the initiator accounts for 0.2-0.3% of the total mass of the tert-butyl acrylate monomer and the aliphatic polyurethane diacrylate monomer,
optionally, the thickness of the block polymer interface layer is 1-10 nm.
3. The flexible perovskite solar cell according to claim 1, wherein the mass ratio of the perovskite to the azobenzene small molecule additive in the perovskite light absorption layer is (35-60): (0.1 to 0.5);
optionally, the azobenzene small molecule additive comprises at least one of 4,4 '-dicarboxylazobenzene, 4' -diaminoazobenzene, 4-aminoazobenzene-3-disulfonic acid, 2-amino-5 (3-sulfonicazophenyl) azobenzene, 4-dimethylaminophenylazobenzenesulfonyl chloride, 2, 4-diamino-3 '-trifluoromethylazobenzene, 4' -azobenzene dicarboxylate ethyl ester, 4-aminophenylazobenzene-2-sulfonic acid, 4-hydroxy-4 '-carboxyazobenzene, p-aminoazobenzene-4-sulfonic acid, and 2,4,3' -triamineazobenzene.
4. The flexible perovskite solar cell of claim 1, wherein the perovskite has the general chemical formula ABXmY3-mWherein A comprises Cs, H, NH4、CH3NH3、CH3CH2NH3、CH3(CH2)2NH3、CH3(CH2)3NH3And NH2＝CHNH2At least one of; b comprises at least one of Pb, Sn and Ge; x and Y independently include Cl, Br, I and BF4SCN and PF6At least one of; m is 0-3;
optionally, the thickness of the perovskite light absorption layer is 100-1000 nm.
5. The flexible perovskite solar cell of claim 1, wherein the electrode modification layer is an electron transport layer, the electrode buffer layer is a hole transport layer, and the electron transport layer comprises TiO2、SnO2、ZnO、PC61BM、PC71BM, TIPD, ICBA and C60-bis, the hole transport layer being formed using an organic material and/or an inorganic material, wherein the organic material comprises at least one of Spiro-OMeTAD, P3HT, PCPDTBT, PEDOT: PSS, NPB and TPD, and the inorganic material comprises CuI, CuSCN, NiOX、V2O5And MoO3At least one of;
optionally, the electrode modification layer is a hole transport layer, the electrode buffer layer is an electron transport layer, and the hole transport layer comprises PTAA, PEDOT PSS, CuI, CuSCN and NiOX、V2O5And MoO3The electron transport layer comprises TiO2、SnO2、ZnO、PC61BM、PC71BM, TIPD, ICBA and C60-at least one of bis;
optionally, the thickness of the electrode modification layer is 5-150 nm;
optionally, the thickness of the electrode buffer layer is 5-300 nm.
6. A method of manufacturing a flexible perovskite solar cell as defined in any one of claims 1 to 5, comprising:
(1) sequentially forming a transparent electrode and an electrode modification layer on a flexible substrate;
(2) mixing tert-butyl acrylate, aliphatic polyurethane diacrylate and an initiator, coating the mixture on the surface of the electrode modification layer, and then carrying out photocuring so as to form a block polymer interface layer on the surface of the electrode modification layer;
(3) mixing a perovskite precursor material, an azobenzene micromolecule additive and an organic solvent so as to obtain a mixed solution containing perovskite and the azobenzene micromolecule additive;
(4) coating the mixed solution on the surface of the block polymer interface layer and carrying out annealing treatment so as to form a perovskite light absorption layer on the surface of the block polymer interface layer;
(5) and sequentially forming an electrode buffer layer and a metal electrode on the surface of the perovskite light absorption layer so as to obtain the flexible perovskite solar cell.
7. The method of claim 6, wherein in the step (2), the ultraviolet light used for the photocuring has a wavelength of 300-400 nm and an irradiation time of 5-20 minutes.
8. The method according to claim 6, wherein in the step (3), the concentration of the perovskite in the mixed solution is 35-60 wt%, and the concentration of the azobenzene small-molecule additive is 0.1-0.5 wt%;
optionally, in step (2), the organic solvent includes at least one of dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, γ -butyrolactone, dimethylacetamide, 2-butoxyethanol, dimercaptoethanol, and acetonitrile.
9. The method according to claim 6, wherein in the step (4), the annealing treatment is performed at a temperature of 100 to 150 ℃ for 10 to 90 min.
10. The method according to claim 6, wherein the flexible substrate is preheated to 40-60 ℃ in advance before the step (4) is performed.
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Cited By (3)

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CN115189229A (en) * 2022-07-18 2022-10-14 广西科技大学 Local plasma enhanced perovskite laser based on DBR structure
CN115260027A (en) * 2022-06-27 2022-11-01 清华大学 Stress sustained-release agent and preparation method and application thereof
CN115717009A (en) * 2022-11-29 2023-02-28 江苏集萃有机光电技术研究所有限公司 Perovskite ink and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260027A (en) * 2022-06-27 2022-11-01 清华大学 Stress sustained-release agent and preparation method and application thereof
CN115260027B (en) * 2022-06-27 2023-08-25 清华大学 Stress sustained release agent and preparation method and application thereof
CN115189229A (en) * 2022-07-18 2022-10-14 广西科技大学 Local plasma enhanced perovskite laser based on DBR structure
CN115717009A (en) * 2022-11-29 2023-02-28 江苏集萃有机光电技术研究所有限公司 Perovskite ink and preparation method and application thereof

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