CN113637126A - Star-polymer-doped perovskite solar cell and preparation method thereof - Google Patents

Star-polymer-doped perovskite solar cell and preparation method thereof Download PDF

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CN113637126A
CN113637126A CN202110895191.2A CN202110895191A CN113637126A CN 113637126 A CN113637126 A CN 113637126A CN 202110895191 A CN202110895191 A CN 202110895191A CN 113637126 A CN113637126 A CN 113637126A
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李炫华
曹琦
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Northwestern Polytechnical University
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Abstract

The invention provides a star-polymer-doped perovskite solar cell and a preparation method thereof, and solves the technical problem that the efficiency and stability of the perovskite solar cell cannot be improved simultaneously by the existing method for modifying a perovskite thin film by adding small molecules or polymers. According to the invention, star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) is synthesized based on molecular design, and star-shaped polymer POSP is added into the lead-based perovskite thin film by an anti-solvent method for the first time, so that on one hand, C ═ O in the POSP polymer and Pb in perovskite form a chelation effect, the perovskite crystal boundary and surface defects are passivated, and non-radiative recombination and charge transfer loss are inhibited. On the other hand, the interaction of POSP and perovskite materials slows down the growth of perovskite crystals, so that the randomly formed atomic nucleus is adjusted to the growth orientation in the total Gibbs free energy minimization and the thermodynamic optimal direction, and the perovskite thin film with larger grain size is obtained.

Description

Star-polymer-doped perovskite solar cell and preparation method thereof
Technical Field
The invention belongs to the technical field of Solar Cells, and particularly relates to a star-polymer-doped Perovskite Solar Cell (PSCs) and a preparation method thereof.
Background
The global economy is rapidly developed, the energy crisis and the environmental pollution are increasingly serious, and the development of clean, rich and renewable energy sources is urgent. As a clean energy, human beings directly convert light energy into electric energy by utilizing the solar cell through a photoelectric effect or a photochemical reaction, so that the solar cell is a way of solving energy crisis and has wide application prospect. The organic-inorganic hybrid perovskite material has wide attention due to the photoelectric characteristics of wide absorption spectrum, low exciton binding energy, high mobility, long carrier service life and the like, and has the advantage of low-cost preparation of low-temperature solution processing. In the past few years, the energy conversion efficiency (PCE) of perovskite solar cells has increased from 3.8% to over 25.5%, showing great commercial application prospects.
However, the perovskite absorption layer is poor in chemical stability and is easily decomposed under external environmental conditions such as electric field, oxygen, humidity, heat, and ultraviolet irradiation. To improve the PCE and long-term stability of the device, researchers have used various approaches including additive engineering, interface engineering, composite engineering, passivation techniques, and encapsulation. However, in such a rapidly developed photovoltaic technology, long-term stability of PSCs is to be solved, and there is a long way to go. Additive engineering has proven to be a simple and effective method to prepare high quality perovskite thin films and to address the problems of grain boundaries and surface defects to date. Additives such as small molecules and polymers are applied to modify the perovskite thin film based on the Lewis acid-base theory; small molecules with lone pair electrons on nitrogen, oxygen, or sulfur (e.g., pyridine, thiophene, and fullerene) have been used to enhance the optoelectronic properties of perovskites by passivating grain boundary defects; however, the high volatility and high diffusion coefficient of small molecules have difficulty addressing the stability of PSCs in operation under extreme conditions of humidity, electric field, high temperature, and intense light. For these reasons, several attempts have been made to use perovskite active layers incorporating polymer additives (e.g., polypropylene carbonate (PPC), fluorine-rich ferroelectric polymers) as crystal growth templates to affect crystallization and passivate grain boundary defects. However, these polymers have a linear structure and cannot solve the long-term stability.
In view of the problems of the conventional methods, it is necessary to explore a method capable of simultaneously improving the efficiency and stability of the perovskite solar cell.
Disclosure of Invention
The invention aims to solve the technical problem that the efficiency and stability of a perovskite solar cell cannot be improved simultaneously by the existing method for modifying a perovskite thin film by adding small molecules or polymers, and provides a star-polymer-doped perovskite solar cell and a preparation method thereof.
In order to achieve the purpose, the technical solution provided by the invention is as follows:
the application of star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) as an additive in the preparation of a lead-based perovskite film is as follows:
Figure BDA0003195047040000031
wherein n is 100-; the star-shaped cage-shaped polysilsesquioxane-poly (methyl methacrylate), namely the star-shaped polymer POSP, has an inorganic inner core formed by a silicon-oxygen framework in Si-O alternate connection, and can provide the three-dimensional structural stability of the POSP material; the inorganic core is surrounded by eight branches, and a poly (methyl methacrylate) molecular chain is arranged on each branch; meanwhile, the star polymer POSP contains a plurality of branches, and each branch has a plurality of chemical anchoring site carbon groups (C ═ O).
The star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) is synthesized by adopting molecular design, and the preparation method comprises the following steps:
octachloropropyl polyhedral oligomeric silsesquioxanes(POSS-(Cl)8) The synthesis of (2):
concentrated hydrochloric acid (8mL), 3-chloropropyltrimethoxysilane (10mL), and methanol (200mL) were added to a 500mL round bottom flask, followed by rapid stirring in a 40 ℃ oil bath for 5 days to complete the hydrolysis; washing the product with methanol for many times and vacuum drying to obtain white powder;
synthesizing a cage polysilsesquioxane-poly (methyl methacrylate) polymer:
the synthesis process adopts POSS- (Cl)8As a radical initiator, one-pot two-step atom transfer radical polymerization was carried out. During this process, dry N was continuously introduced into the flask2To remove O2. Then, POSS- (Cl)8(0.20g), toluene (20mL), methyl methacrylate (MMA, 20mL), pentamethyldiethylenetriamine (PMDETA, 0.12mL), and CuCl (0.02g) were mixed in a flask;
③ the flask was put in an oil bath equipped with a magnetic stirring bar and heated at 110 ℃ and, after 48 hours, the flask was cooled in ice water to terminate the polymerization reaction. And pouring the mixture into tetrahydrofuran for dilution, filtering the mixture through an alumina column to remove the catalyst, then pouring the mixture into a tenfold methanol-water mixed solvent, filtering the mixture, and drying the mixture for 24 hours at 40 ℃ under reduced pressure to obtain the final product, namely the star-shaped cage polysilsesquioxane-poly (methyl methacrylate) polymer.
The polymer is simple to synthesize and can be prepared on a large scale.
The lead-based perovskite thin film is characterized in that: cage polysilsesquioxane-poly (methyl methacrylate) doped with the star;
the C ═ O functional group of the star-shaped cage polysilsesquioxane-poly (methyl methacrylate) chelates Pb in the perovskite.
The preparation method of the lead-based perovskite thin film is characterized by comprising the following steps:
1) preparing a lead-based perovskite precursor solution; the preparation methods of different lead-based perovskite precursor solutions are slightly different;
2) spin-coating the lead-based perovskite precursor solution prepared in the step 1) on a substrate, and dropwise adding a chlorobenzene solution in which the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) is dissolved at a constant speed on the substrate in the spin-coating process; chlorobenzene can be replaced by other organic solvents, but consideration should be given to whether the organic solvent can dissolve the star-shaped cage polysilsesquioxane-poly (methyl methacrylate), and the effect of the organic solvent on the perovskite.
3) After the spin coating is finished, the substrate is placed at the temperature of 100-180 ℃ for annealing treatment for 10-30min, and the lead-based perovskite thin film is obtained.
Further, in the step 2), the concentration of the star-shaped cage type polysilsesquioxane-poly (methyl methacrylate) is 0.01-0.3 mg/mL;
the volume ratio of the lead-based perovskite precursor solution to the chlorobenzene solution for dissolving the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) is 1: 3-5.
Further, in the step 1), the perovskite precursor solution is MAPbI3Precursor solution and FAPBI3Precursor solution or Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3And (3) precursor solution.
Further, for MAPbI3Dripping chlorobenzene solution for dissolving star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) when the precursor solution is spin-coated for 40 +/-4 seconds;
for FAPBI3Dripping chlorobenzene solution dissolved with star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) when the precursor solution is spin-coated for 50 +/-5 seconds;
for Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The precursor solution was spin-coated for 25. + -.2 seconds, and then a chlorobenzene solution in which star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) was dissolved was added dropwise.
Further, for MAPbI3Precursor solution, spin coating parameters are as follows: 4000 +/-400 r/min for 60 +/-5 s;
for FAPBI3Precursor solution, spin coating parameters are as follows: 5000 ± -3500r/min 60±5s；
For Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Precursor solution, spin coating parameters are as follows: firstly, 10 + -2 s at 1000 + -100 r/min, and then 30 + -3 s at 6000 + -500 r/min.
A perovskite solar cell, characterized in that: the lead-based perovskite thin film modified with the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) is used as a light absorbing layer. The specific structure of the cell is formed by sequentially overlapping Indium Tin Oxide (ITO) conductive glass, a hole transport layer, a perovskite light absorption layer prepared by POSP modification, an electron transport layer, a barrier layer and a back electrode.
The preparation method of the perovskite solar cell is characterized by comprising the following steps:
s1, preprocessing a substrate;
s2, preparing a hole transport layer;
s3, preparing a perovskite light absorption layer;
when the lead-based perovskite precursor solution is spin-coated on the hole transport layer, dropwise adding a chlorobenzene solution containing the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) at a constant speed;
s4, preparing an electron transport layer;
s5, preparing a barrier layer;
s6 preparing an electrode to obtain the perovskite solar cell.
Taking specific materials as an example, the preparation method comprises the following specific steps:
s1, processing of ITO glass:
firstly, cleaning the surface of ITO glass by using a detergent, then sequentially carrying out ultrasonic treatment on the ITO glass in deionized water, acetone and absolute ethyl alcohol containing the detergent for 10-15min respectively, then blowing the ITO glass dry by using nitrogen, and finally carrying out UV treatment on the ITO glass for 15-20 min;
s2, spin coating of a hole transport layer:
NiOx is used as a hole transport material, namely, the prepared NiOx solution is dropwise coated on the ITO glass treated in the step S1, spin coating is carried out for 40 seconds at the speed of 2000r/min, then annealing is carried out for 10-15min at the temperature of 150 ℃ in the air, and cooling is carried out to the room temperature, thus obtaining a compact NiOx hole transport layer;
s3, preparing a perovskite light absorption layer by POSP modification:
s3.1 preparation of lead-based perovskite precursor solution
S3.2, spin-coating the prepared lead-based perovskite precursor solution on a substrate, and dropwise adding a chlorobenzene solution in which the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) is dissolved at a constant speed on the substrate in the spin-coating process;
and 3.3, after the spin coating is finished, annealing the substrate at the temperature of 100-180 ℃ for 10-30min to obtain the lead-based perovskite thin film.
S4, spin coating of the electron transmission layer:
dissolving 20-30mg of [6,6] -phenyl-C61-methyl butyrate (PCBM) and 5-10mg of fullerene (C60) in 1mL of chlorobenzene, spin-coating on the perovskite thin film at 3000-6000r/min for 60s, and then annealing on a heating table at 60-100 ℃ for 10-30 min;
s5, spin coating of a barrier layer:
cooling to room temperature, dissolving 0.5-1.0mg of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) in 1mL of isopropanol, spin-coating on the electron transport layer at 3000-;
s6, evaporating an electrode:
and (3) evaporating and plating a layer of 100-150nm thick Ag metal film on the barrier layer to be used as a back electrode, thus obtaining the perovskite solar cell.
A method for simultaneously improving efficiency and stability of a lead-based perovskite solar cell is characterized by comprising the following steps: and (3) dropwise adding a chlorobenzene solution containing the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) at a constant speed when the perovskite precursor solution is spin-coated.
The mechanism of the invention is as follows:
according to the invention, star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) (POSP) is synthesized based on molecular design, and the star-shaped polymer POSP is added into the perovskite thin film for the first time through an anti-solvent method, namely the perovskite thin film is modified through the star-shaped polymer POSP. On the other hand, the interaction of POSP and perovskite materials slows down the growth of perovskite crystals, so that the randomly formed atomic nucleus is adjusted to the growth orientation in the total Gibbs free energy minimization and the thermodynamic optimal direction, and the perovskite thin film with larger grain size is obtained.
The invention has the advantages that:
the invention solves the problems of efficiency and stability of the perovskite solar cell by directly crosslinking the three-dimensional perovskite structure in multiple directions through the star-shaped polymer. The core of the star polymer POSP material is an inorganic core consisting of silicon-oxygen frameworks which are alternately connected by Si-O, so that the structural stability of the POSP material can be provided; the core is surrounded by eight branches, on which are poly (methyl methacrylate) molecular chains. The POSP polymer contains a plurality of branched chains, and each branched chain is provided with a plurality of chemical anchoring site carbon groups (C ═ O), and the POSP polymer is used as a three-dimensional framework template to realize the passivation of perovskite crystal boundaries and surface defects, inhibit non-radiative recombination and charge transmission loss and improve the stability of the perovskite solar cell under illumination. Compared with the traditional method, the open circuit voltage (V) of the perovskite solar cell prepared by the methodoc) Short circuit current density (J)sc) And Fill Factor (FF) are both increased, such as MAPbI3PCE of perovskite solar cell rises from 17.88% to 20.63%, FAPBI3The PCE of perovskite solar cells rose from 18.56% to 22.29%, Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The PCE of perovskite solar cells rises from 18.27% to 21.55%; the efficiency of the device is up to 23% for the trans structure. After the maximum power of the POSP modified device is tracked for 1000 hours, the efficiency is reduced to 93 percent of the initial efficiency, and the POSP modified device has good operation stability. It was also confirmed that the star polymerization according to the invention is achieved by molecular designOn one hand, the material can passivate the defects of the crystal boundary and the surface of the perovskite light absorption layer (light absorption layer) and inhibit the recombination of carriers; on the other hand, the perovskite material can be reinforced through the interaction between the functional group and the perovskite material, the stability of the device is improved, and the efficient and stable perovskite solar cell is prepared.
Drawings
FIG. 1 shows the molecular formula of star polymer POSP designed by the invention.
FIG. 2 is a scanning electron microscope top view of the light-absorbing layer; (a) is a scanning electron microscope top view of the light absorption layer prepared by the traditional method; (b) cs prepared by POSP modification of star polymer0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Scanning electron microscope top view of the light absorbing layer.
FIG. 3 shows the star-shaped polymer POSP modified Cs with different concentrations under the irradiation of solar energy spectrum energy AM1.5G0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3J-V characteristic curve diagram of perovskite solar cell.
FIG. 4 conventional method of making and POSP modified Cs at 45 deg.C0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Maximum power point tracking characteristic curve of the encapsulated perovskite solar cell.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
comparative example one:
compared with the examples, the comparative example adopts the pure perovskite precursor solution to prepare the light absorption layer by spin coating, and the specific operation is as follows:
1) and (3) processing the ITO glass:
firstly, cleaning the surface of ITO glass with the size of 15mm multiplied by 15mm and the impedance of 10 omega/sq by using a detergent, then sequentially carrying out ultrasonic treatment on the surface of the ITO glass in deionized water, acetone and absolute ethyl alcohol containing the detergent for 15min, then carrying out blow-drying by using nitrogen, and finally carrying out UV treatment on the ITO glass for 15 min;
2) spin coating of hole transport layer: in the embodiment, NiOx is used as a hole transport material, namely, a prepared NiOx solution is dropwise coated on the ITO glass treated in the step 1), spin coating is carried out at the speed of 2000r/min for 40 seconds, then annealing is carried out in the air at the temperature of 100 ℃ for 10 minutes, and the annealing is slowly cooled to the room temperature, so as to obtain a compact NiOx hole transport layer;
3) preparation of perovskite light-absorbing layer (this part was subjected to preparation of three types of perovskite light-absorbing layers, respectively)
The first method comprises the following steps:
taking 1.5mol/L of bromomethylamine (MAI) and lead iodide (PbI) in equal molar ratio2) Adding the mixture into a mixed solvent of gamma-butyrolactone and dimethyl sulfoxide (DMSO) with a volume ratio of 7:3, and fully stirring to obtain MAPbI3A perovskite precursor solution. Then dripping the precursor solution on a NiOx hole transport layer, performing the process according to the program of 4000r/min and 60s, dripping chlorobenzene solution when the spin coating is performed for 40s, and heating for 10min at 100 ℃ to obtain a perovskite light absorption layer;
and the second method comprises the following steps:
1.70mol/L iodoformamidine (FAI), 0.67mol/L chloromethane (MACl) and 1.70mol/L lead iodide (PbI) are taken2) Dissolving in a solvent with the volume ratio of 8: 2 in a mixed solvent of N, N' -Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), heating and stirring for 2 hours at 60 ℃ to obtain FAPBI3And (3) precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the process according to the program of 60s at 5000r/min, dripping chlorobenzene solution when the spin-coating is performed for 40s, and then annealing the perovskite film at 150 ℃ for 10min to obtain a bright perovskite film;
and the third is that:
1.19mol/L iodoformamidine (FAI) and 0.21mol/L lead bromide (PbBr) are taken2) 0.07mol/L cesium iodide (CsI), 0.21mol/L bromomethylamine (MABr) and 1.30mol/L lead iodide (PbI)2) Dissolving in a solvent with the volume ratio of 8: 2, stirring for 2 hours to obtain Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Precursor solution；
Then, the perovskite solution is coated on the NiOx hole transport layer in a spinning mode, the procedure is carried out according to the procedure that firstly 1000r/min is carried out for 10s, then 6000r/min is carried out for 30s, chlorobenzene solution is dripped when the spinning is carried out for 25s, and then the perovskite film is annealed for 20min at the temperature of 100 ℃ to obtain a bright perovskite film;
4) spin coating of the electron transport layer: 20mg of [6,6] -phenyl-C61-butyric acid methyl ester (PCBM) and 5mg of fullerene (C60) were dissolved in 1mL of chlorobenzene and spin-coated on the perovskite thin film at 3000r/min for 60s, followed by annealing on a 60 ℃ heating stage for 10 min;
5) spin coating of the barrier layer: after cooling to room temperature, 0.5mg of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline (BCP) is dissolved in 1mL of isopropanol, spin-coated on the electron layer at 6000r/min for 30s, and then annealed on a heating table at 60 ℃ for 10 min;
6) evaporating an electrode: and (3) evaporating and plating a layer of Ag metal film with the thickness of 100nm on the barrier layer to be used as a back electrode, and obtaining the perovskite solar cell.
Based on MAPbI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.056 +/-0.008V and 21.26 +/-0.56 mA/cm20.795. + -. 0.023 and 17.88. + -. 0.58%.
Based on FAPBI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.080 +/-0.008V and 22.48 +/-0.54 mA/cm20.786 + -0.021 and 18.56 + -0.54%.
Based on Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.089 +/-0.008V and 21.69 +/-0.49 mA/cm20.769 plus or minus 0.019 and 18.27 plus or minus 0.64 percent.
The first embodiment is as follows:
1) and (3) processing the ITO glass: firstly, cleaning the surface of ITO glass with the size of 15mm multiplied by 15mm and the impedance of 10 omega/sq by using a detergent, then sequentially carrying out ultrasonic treatment on the surface of the ITO glass in deionized water, acetone and absolute ethyl alcohol containing the detergent for 15min, then carrying out blow-drying by using nitrogen, and finally carrying out UV treatment on the ITO glass for 15 min;
2) spin coating of hole transport layer: the method uses NiOx as a hole transport material, namely, the prepared NiOx solution is dropwise coated on the ITO glass treated in the step 1), spin-coated for 40 seconds at the speed of 2000r/min, then annealed for 10 minutes at the temperature of 100 ℃ in the air, and slowly cooled to room temperature to obtain a compact NiOx hole transport layer;
3) POSP modification to prepare perovskite light-absorbing layer (for comparison with comparative example, three types of perovskite light-absorbing layers were prepared separately in this section)
The first method comprises the following steps:
taking 1.5mol/L of bromomethylamine (MAI) and lead iodide (PbI) in equal molar ratio2) Adding the mixture into a mixed solvent of gamma-butyrolactone and dimethyl sulfoxide (DMSO) with a volume ratio of 7:3, and fully stirring to obtain MAPbI3A perovskite precursor solution. Then dropping the precursor solution on a NiOx hole transport layer, performing the process according to the program of 4000r/min and 60s, dropwise adding a chlorobenzene solution containing 0.04mg/mL POSP star-shaped polymer when the spin coating is performed for 40s, and heating for 10min at 100 ℃ to obtain a perovskite light absorption layer;
and the second method comprises the following steps:
1.70mol/L iodoformamidine (FAI), 0.67mol/L chloromethane (MACl) and 1.70mol/L lead iodide (PbI) are taken2) Dissolving in a solvent with the volume ratio of 8: 2 in a mixed solvent of N, N' -Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), heating and stirring for 2 hours at 60 ℃ to obtain FAPBI3And (3) precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the process according to the program of 60s at 5000r/min, dropwise adding a chlorobenzene solution containing 0.04mg/mL POSP star-shaped polymer when the spin-coating is performed for 40s, and then annealing the perovskite film at 150 ℃ for 10min to obtain a bright perovskite film;
and the third is that:
1.19mol/L iodoformamidine (FAI) and 0.21mol/L lead bromide (PbBr) are taken2) 0.07mol/L cesium iodide (CsI), 0.21mol/L bromomethylamine (MABr) and 1.30mol/L lead iodide (PbI)2) Dissolving in a solvent with the volume ratio of 8: 2N, N' -Dimethylformamide (DMF) and dimethyl sulfoxideStirring in a sulfone (DMSO) mixed solvent for 2h to obtain Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3And (3) precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the spin-coating according to the program of 1000r/min, 10s to 6000r/min 30s, dripping chlorobenzene solution containing 0.04mg/mL POSP star polymer when the spin-coating is performed for 25s, and then annealing the perovskite film at 100 ℃ for 20min to obtain a bright perovskite film;
4) spin coating of the electron transport layer: 20mg of [6,6] -phenyl-C61-butyric acid methyl ester (PCBM) and 5mg of fullerene (C60) were dissolved in 1mL of chlorobenzene and spin-coated on the perovskite thin film at 3000r/min for 60s, followed by annealing on a 60 ℃ heating stage for 10 min;
5) spin coating of the barrier layer: after cooling to room temperature, 0.5mg of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline (BCP) is dissolved in 1mL of isopropanol, spin-coated on the electron layer at 6000r/min for 30s, and then annealed on a heating table at 60 ℃ for 10 min;
6) evaporating an electrode: and (3) evaporating and plating a layer of Ag metal film with the thickness of 100nm on the barrier layer to be used as a back electrode, and obtaining the perovskite solar cell.
Based on MAPbI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.066 +/-0.008V and 22.26 +/-0.48 mA/cm20.806 + -0.024 and 18.56 + -0.49%.
Based on FAPBI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.086 +/-0.008V and 22.76 +/-0.45 mA/cm20.800 + -0.019 and 20.16 + -0.50%.
Based on Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.110 +/-0.008V and 22.79 +/-0.46 mA/cm20.789 ± 0.018 and 19.95 ± 0.61%.
Example two:
1) firstly, cleaning the surface of ITO glass with the size of 15mm multiplied by 15mm and the impedance of 10 omega/sq by using a detergent, then sequentially carrying out ultrasonic treatment on the surface of the ITO glass in deionized water, acetone and absolute ethyl alcohol containing the detergent for 15min, then carrying out blow-drying by using nitrogen, and finally carrying out UV treatment on the ITO glass for 15 min;
2) spin coating of hole transport layer: the method uses NiOx as a hole transport material, namely, the prepared NiOx solution is dropwise coated on the ITO glass treated in the step 1), spin-coated for 40 seconds at the speed of 2000r/min, then annealed for 10 minutes at the temperature of 100 ℃ in the air, and slowly cooled to room temperature to obtain a compact NiOx hole transport layer;
3) POSP modification to prepare perovskite light-absorbing layer (for comparison with comparative example and previous example, this section was also prepared for three types of perovskite light-absorbing layers, respectively)
The first method comprises the following steps:
taking 1.5mol/L of bromomethylamine (MAI) and lead iodide (PbI) in equal molar ratio2) Adding the mixture into a mixed solvent of gamma-butyrolactone and dimethyl sulfoxide (DMSO) with a volume ratio of 7:3, and fully stirring to obtain MAPbI3A perovskite precursor solution. Then dropping the precursor solution on a NiOx hole transport layer, performing the process according to the program of 4000r/min and 60s, dropwise adding a chlorobenzene solution containing 0.08mg/mL POSP star-shaped polymer when the spin coating is performed for 40s, and heating for 10min at 100 ℃ to obtain a perovskite light absorption layer;
and the second method comprises the following steps:
1.70mol/L iodoformamidine (FAI), 0.67mol/L chloromethane (MACl) and 1.70mol/L lead iodide (PbI) are taken2) Dissolving in a solvent with the volume ratio of 8: 2 in a mixed solvent of N, N' -Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), heating and stirring for 2 hours at 60 ℃ to obtain FAPBI3And (3) precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the process according to the program of 60s at 5000r/min, dripping chlorobenzene solution containing 0.08mg/mL POSP star polymer when spin-coating for 40s, and then annealing the perovskite film at 150 ℃ for 10min to obtain a bright perovskite film;
and the third is that:
1.19mol/L iodoformamidine (FAI) and 0.21mol/L lead bromide are taken(PbBr2) 0.07mol/L cesium iodide (CsI), 0.21mol/L bromomethylamine (MABr) and 1.30mol/L lead iodide (PbI)2) Dissolving in a solvent with the volume ratio of 8: 2, stirring for 2 hours to obtain Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3And (3) precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the spin-coating according to the program of 1000r/min, 10s to 6000r/min 30s, dripping chlorobenzene solution containing 0.08mg/mL POSP star polymer when the spin-coating is performed for 25s, and then annealing the perovskite film at 100 ℃ for 20min to obtain a bright perovskite film;
4) spin coating of the electron transport layer: 20mg of [6,6] -phenyl-C61-butyric acid methyl ester (PCBM) and 5mg of fullerene (C60) were dissolved in 1mL of chlorobenzene and spin-coated on the perovskite thin film at 3000r/min for 60s, followed by annealing on a 60 ℃ heating stage for 10 min;
5) spin coating of the barrier layer: after cooling to room temperature, 0.5mg of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline (BCP) is dissolved in 1mL of isopropanol, spin-coated on the electron layer at 6000r/min for 30s, and then annealed on a heating table at 60 ℃ for 10 min;
6) evaporating an electrode: and (3) evaporating and plating a layer of Ag metal film with the thickness of 100nm on the barrier layer to be used as a back electrode, and obtaining the perovskite solar cell.
Based on MAPbI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.086 +/-0.008V and 22.78 +/-0.34 mA/cm20.834 + -0.016 and 20.63 + -0.47%.
Based on FAPBI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.136 +/-0.008V and 23.76 +/-0.32 mA/cm20.826. + -. 0.019 and 22.29. + -. 0.43%.
Based on Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.128 +/-0.008V and 23.30 +/-0.30 mA/cm20.820. + -. 0.014 and 21.55. + -. 0.44%.
Example three:
1) and (3) processing the ITO glass: firstly, cleaning the surface of ITO glass with the size of 15mm multiplied by 15mm and the impedance of 10 omega/sq by using a detergent, then sequentially carrying out ultrasonic treatment on the surface of the ITO glass in deionized water, acetone and absolute ethyl alcohol containing the detergent for 15min, then carrying out blow-drying by using nitrogen, and finally carrying out UV treatment on the ITO glass for 15 min;
2) spin coating of hole transport layer: the method uses NiOx as a hole transport material, namely, the prepared NiOx solution is dropwise coated on the ITO glass treated in the step 1), spin-coated for 40 seconds at the speed of 2000r/min, then annealed for 10 minutes at the temperature of 100 ℃ in the air, and slowly cooled to room temperature to obtain a compact NiOx hole transport layer;
3) POSP modification to prepare perovskite light-absorbing layer (for comparison with comparative example and previous example, this section was also prepared for three types of perovskite light-absorbing layers, respectively)
The first method comprises the following steps:
taking 1.5mol/L of bromomethylamine (MAI) and lead iodide (PbI) in equal molar ratio2) Adding the mixture into a mixed solvent of gamma-butyrolactone and dimethyl sulfoxide (DMSO) with a volume ratio of 7:3, and fully stirring to obtain MAPbI3A perovskite precursor solution. Then dropping the precursor solution on a NiOx hole transport layer, performing the process according to the program of 4000r/min and 60s, dropwise adding a chlorobenzene solution containing 0.1mg/mL POSP star-shaped polymer when the spin coating is performed for 40s, and heating for 10min at 100 ℃ to obtain a perovskite light absorption layer;
and the second method comprises the following steps:
1.70mol/L iodoformamidine (FAI), 0.67mol/L chloromethane (MACl) and 1.70mol/L lead iodide (PbI) are taken2) Dissolving in a solvent with the volume ratio of 8: 2 in a mixed solvent of N, N' -Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), heating and stirring for 2 hours at 60 ℃ to obtain FAPBI3And (3) precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the procedure at 5000r/min for 60s, dripping a chlorobenzene solution containing 0.1mg/mL POSP star-shaped polymer when the coating is performed for 40s, and then thinning the perovskiteAnnealing the film at 150 ℃ for 10min to obtain a bright perovskite film;
and the third is that:
1.19mol/L iodoformamidine (FAI) and 0.21mol/L lead bromide (PbBr) are taken2) 0.07mol/L cesium iodide (CsI), 0.21mol/L bromomethylamine (MABr) and 1.30mol/L lead iodide (PbI)2) Dissolving in a solvent with the volume ratio of 8: 2, stirring for 2 hours to obtain Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3And (3) precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the spin-coating according to the program of 1000r/min, 10s to 6000r/min 30s, dripping chlorobenzene solution containing 0.1mg/mL POSP star polymer when the spin-coating is performed for 25s, and then annealing the perovskite film at 100 ℃ for 20min to obtain a bright perovskite film;
4) spin coating of the electron transport layer: 20mg of [6,6] -phenyl-C61-butyric acid methyl ester (PCBM) and 5mg of fullerene (C60) were dissolved in 1mL of chlorobenzene and spin-coated on the perovskite thin film at 3000r/min for 60s, followed by annealing on a 60 ℃ heating stage for 10 min;
5) spin coating of the barrier layer: after cooling to room temperature, 0.5mg of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline (BCP) is dissolved in 1mL of isopropanol, spin-coated on the electron layer at 6000r/min for 30s, and then annealed on a heating table at 60 ℃ for 10 min;
6) evaporating an electrode: and (3) evaporating and plating a layer of Ag metal film with the thickness of 100nm on the barrier layer to be used as a back electrode, and obtaining the perovskite solar cell.
Based on MAPbI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.075 +/-0.008V and 22.64 +/-0.38 mA/cm20.821. + -. 0.023 and 19.98. + -. 0.57%.
Based on FAPBI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are 1.118 +/-0.008V and 23.45 +/-0.36 mA/cm respectively20.817 ± 0.025 and 21.42 ± 0.53%.
Based onCs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.115 +/-0.008V and 23.10 +/-0.37 mA/cm20.810 + -0.022 and 20.86 + -0.63%.
Example four:
1) and (3) processing the ITO glass: firstly, cleaning the surface of ITO glass with the size of 15mm multiplied by 15mm and the impedance of 10 omega/sq by using a detergent, then sequentially carrying out ultrasonic treatment on the surface of the ITO glass in deionized water, acetone and absolute ethyl alcohol containing the detergent for 15min, then carrying out blow-drying by using nitrogen, and finally carrying out UV treatment on the ITO glass for 15 min;
2) spin coating of hole transport layer: the method uses NiOx as a hole transport material, namely, the prepared NiOx solution is dropwise coated on the ITO glass treated in the step 1), spin-coated for 40 seconds at the speed of 2000r/min, then annealed for 10 minutes at the temperature of 100 ℃ in the air, and slowly cooled to room temperature to obtain a compact NiOx hole transport layer;
3) POSP modification to prepare perovskite light-absorbing layer (for comparison with comparative example and previous example, this section was also prepared for three types of perovskite light-absorbing layers, respectively)
The first method comprises the following steps:
taking 1.5mol/L of bromomethylamine (MAI) and lead iodide (PbI) in equal molar ratio2) Adding the mixture into a mixed solvent of gamma-butyrolactone and dimethyl sulfoxide (DMSO) with a volume ratio of 7:3, and fully stirring to obtain MAPbI3A perovskite precursor solution. Then dropping the precursor solution on a NiOx hole transport layer, performing the process according to the program of 4000r/min and 60s, dropwise adding a chlorobenzene solution containing 0.3mg/mL POSP star-shaped polymer when the spin coating is performed for 40s, and heating for 10min at 100 ℃ to obtain a perovskite light absorption layer;
and the second method comprises the following steps:
1.70mol/L iodoformamidine (FAI), 0.67mol/L chloromethane (MACl) and 1.70mol/L lead iodide (PbI) are taken2) Dissolving in a solvent with the volume ratio of 8: 2 in a mixed solvent of N, N' -Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), heating and stirring for 2 hours at 60 ℃ to obtain FAPBI3Precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the process according to the program of 60s at 5000r/min, dripping chlorobenzene solution containing 0.3mg/mL POSP star polymer when spin-coating for 40s, and then annealing the perovskite film at 150 ℃ for 10min to obtain a bright perovskite film;
and the third is that:
1.19mol/L iodoformamidine (FAI) and 0.21mol/L lead bromide (PbBr) are taken2) 0.07mol/L cesium iodide (CsI), 0.21mol/L bromomethylamine (MABr) and 1.30mol/L lead iodide (PbI)2) Dissolving in a solvent with the volume ratio of 8: 2, stirring for 2 hours to obtain Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3And (3) precursor solution. Then spin-coating the perovskite solution on the NiOx hole transport layer, performing the spin-coating according to the program of 1000r/min, 10s to 6000r/min 30s, dripping chlorobenzene solution containing 0.3mg/mL POSP star polymer when the spin-coating is performed for 25s, and then annealing the perovskite film at 100 ℃ for 20min to obtain a bright perovskite film;
4) spin coating of the electron transport layer: 20mg of [6,6] -phenyl-C61-butyric acid methyl ester (PCBM) and 5mg of fullerene (C60) were dissolved in 1mL of chlorobenzene and spin-coated on the perovskite thin film at 3000r/min for 60s, followed by annealing on a 60 ℃ heating stage for 10 min;
5) spin coating of the barrier layer: after cooling to room temperature, 0.5mg of 2, 9-dimethyl-4, 7 diphenyl-1, 10-phenanthroline (BCP) is dissolved in 1mL of isopropanol, spin-coated on the electron layer at 6000r/min for 30s, and then annealed on a heating table at 60 ℃ for 10 min;
6) evaporating an electrode: and (3) evaporating and plating a layer of Ag metal film with the thickness of 100nm on the barrier layer to be used as a back electrode, and obtaining the perovskite solar cell.
Based on MAPbI3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.067 +/-0.008V and 21.53 +/-0.49 mA/cm20.795 + -0.026 and 18.26 + -0.66%.
Based on FAPBI3Photoelectric property measurement of thin film perovskite solar cellThe test results are as follows: voc、JscFF and PCE are respectively 1.114 +/-0.008V and 22.98 +/-0.46 mA/cm20.809 + -0.024 and 20.71 + -0.62 percent.
Based on Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The photoelectric performance test result of the thin film perovskite solar cell is as follows: voc、JscFF and PCE are respectively 1.113 +/-0.008V and 22.44 +/-0.53 mA/cm20.788 ± 0.024 and 19.68 ± 0.68.
As can be seen from FIG. 2, Cs prepared based on modification of POSP0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The perovskite layer has good crystallinity and the crystal size is large.
As can be seen in FIG. 3, Cs prepared based on modification of POSP0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Perovskite solar cell, in a standard light source (AM1.5G, 100 mW/cm)2) The measured J-V curve shows that the photoelectric conversion efficiency is higher.
As can be seen from FIG. 4, POSP modified Cs was present at a temperature of 45 deg.C0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3After 1000 hours of continuous operation of the device, the efficiency hardly changed.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present disclosure.

Claims (10)

1. The application of star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) as an additive in the preparation of a lead-based perovskite film is as follows:
Figure FDA0003195047030000011
wherein n is 100-.
2. A lead-based perovskite thin film characterized by: cage polysilsesquioxane-poly (methyl methacrylate) doped with the star of claim 1;
the C ═ O functional group of the star-shaped cage polysilsesquioxane-poly (methyl methacrylate) chelates Pb in the perovskite.
3. A method for producing a lead-based perovskite thin film as defined in claim 2, comprising the steps of:
1) preparing a lead-based perovskite precursor solution;
2) spin-coating the lead-based perovskite precursor solution prepared in the step 1) on a substrate, and dropwise adding a chlorobenzene solution in which the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) is dissolved at a constant speed on the substrate in the spin-coating process;
3) after the spin coating is finished, the substrate is placed at the temperature of 100-180 ℃ for annealing treatment for 10-30min, and the lead-based perovskite thin film is obtained.
4. The method for producing a lead-based perovskite thin film according to claim 3, characterized in that:
in the step 2), the concentration of the star-shaped cage type polysilsesquioxane-poly (methyl methacrylate) is 0.01-0.3 mg/mL;
the volume ratio of the lead-based perovskite precursor solution to the chlorobenzene solution in which the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) is dissolved is 1: 3-5.
5. The method for producing a lead-based perovskite thin film according to claim 4, characterized in that:
in the step 1), the perovskite precursor solution is MAPbI3Precursor solution and FAPBI3Precursor solution or Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3And (3) precursor solution.
6. The method for producing a lead-based perovskite thin film according to claim 5, characterized in that:
for MAPbI3Dripping chlorobenzene solution for dissolving star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) when the precursor solution is spin-coated for 40 +/-4 seconds;
for FAPBI3Dripping chlorobenzene solution dissolved with star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) when the precursor solution is spin-coated for 50 +/-5 seconds;
for Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3The precursor solution was spin-coated for 25. + -.2 seconds, and then a chlorobenzene solution in which star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) was dissolved was added dropwise.
7. The method for producing a lead-based perovskite thin film according to claim 6, characterized in that:
for MAPbI3Precursor solution, spin coating parameters are as follows: 4000 +/-400 r/min for 60 +/-5 s;
for FAPBI3Precursor solution, spin coating parameters are as follows: 5000 +/-500 r/min 60 +/-5 s;
for Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3Precursor solution, spin coating parameters are as follows: firstly 1000 + -100 r/min for 10 + -2 s, and then 6000 + -500 r/min for 30 + -3 s.
8. A perovskite solar cell, characterized in that: the light-absorbing layer was made of a lead-based perovskite thin film modified with the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) according to claim 1.
9. The method of fabricating the perovskite solar cell as defined in claim 8, comprising the steps of:
s1, preprocessing a substrate;
s2, preparing a hole transport layer;
s3, preparing a perovskite light absorption layer;
dropwise adding a chlorobenzene solution containing the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) according to claim 1 at a constant speed when the lead-based perovskite precursor solution is spin-coated on the hole transport layer;
s4, preparing an electron transport layer;
s5, preparing a barrier layer;
s6 preparing an electrode to obtain the perovskite solar cell.
10. A method for simultaneously improving efficiency and stability of a lead-based perovskite solar cell is characterized by comprising the following steps: and (3) dropwise adding a chlorobenzene solution containing the star-shaped cage-type polysilsesquioxane-poly (methyl methacrylate) in the claim 1 at a constant speed during the spin coating of the perovskite precursor solution.
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CN116744706A (en) * 2023-07-14 2023-09-12 河北师范大学 Application of cellulose triacetate in perovskite solar cell
CN117156875A (en) * 2023-10-31 2023-12-01 电子科技大学 High-performance solar cell based on non-contact passivation
CN117156875B (en) * 2023-10-31 2024-01-23 电子科技大学 High-performance solar cell based on non-contact passivation

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