Perovskite-type photovoltaic cell and method for manufacturing the same

Abstract

A perovskite-type photovoltaic cell (or solar cell) in which the photoactive layer of the perovskite contains at least one partially neutralized polyacrylic acid in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor. The above perovskite-type photovoltaic cell (or solar cell) can be advantageously used in various applications that require power generation by utilizing light energy, particularly solar radiation energy, such as building-integrated photovoltaic systems (building-integrated photovoltaics - BIPV), photovoltaic windows, greenhouses, photo-bioreactors, sound barriers, lighting engineering, design, advertising, and the automotive industry. The above perovskite-type photovoltaic cell (or solar cell) can be used in a stand-alone form or in a modular system.

Description

Technical Field

[0001] The present invention relates to perovskite solar cells (or photovoltaic cells).

[0002] More specifically, the present invention relates to a perovskite solar cell (or photovoltaic cell) in which the photoactive layer of perovskite contains at least one partially neutralized polyacrylic acid in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor.

[0003] The above perovskite solar cells (or photovoltaic cells) can be advantageously used in various applications that require power generation by utilizing light energy, particularly solar radiation energy, such as building-integrated photovoltaic systems (BIPV), photovoltaic windows, greenhouses, photobioreactors, sound barriers, lighting engineering, design, advertising, and the automotive industry. The above perovskite solar cells (or photovoltaic cells) can be used in either a stand-alone form or a modular system.

[0004] The present invention also relates to a method for manufacturing the above perovskite solar cells (or photovoltaic cells).

[0005] A further object of the present invention is also a composition comprising at least one perovskite and at least one partially neutralized polyacrylic acid in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor.

Background Art

[0006] A photovoltaic cell (or solar cell) is a device capable of converting the energy of light radiation into electrical energy. Currently, most of the photovoltaic cells (or solar cells) that can be used in practical applications utilize the chemical and physical properties of inorganic photoactive materials, especially high-purity crystalline silicon. However, while the above photovoltaic cells (or solar cells) exhibit interesting performance, especially in terms of efficiency and durability, they also show some drawbacks. For example, the rigidity and weight of the above silicon-based photovoltaic cells (or solar cells) often require the installation of on-site-only frames for their positioning, and the actual usage fields are significantly limited.

[0007] Some of the above drawbacks can be overcome by using organic polymer-type (organic solar cell - OPV) or perovskite-type (perovskite solar cell - PSC) photovoltaic cells (or solar cells).

[0008] In particular, perovskite-type photovoltaic cells (or solar cells) (perovskite solar cells - PSC) have recently become a rapidly promising option because they currently have a high power conversion efficiency (PCE) with a certified value reaching 25.5%. The typical characteristics of a series of organic polymer thin-film photovoltaic cells (or solar cells) (organic solar cells - OPV), such as lightness, flexibility, and the simplicity of the manufacturing method starting from suitable mixtures of various precursors, can enable the production of photovoltaic cells (or solar cells) by known established printing processes (which are also continuous) under mild conditions and sustainable costs.

[0009] However, perovskite-type photovoltaic cells (or solar cells) (perovskite solar cells - PSC) may also have some drawbacks, such as the high sensitivity of perovskite to atmospheric agents (especially humidity) and the non-optimal filling of the perovskite crystal phase, which adversely affects charge transport.

[0010] To address the above drawbacks, many research groups are developing various technologies for the construction of perovskite-type photovoltaic cells (or solar cells) (perovskite solar cells - PSC), including, for example, using polymer additives in the perovskite photoactive layer.

[0011] In the past few years, many polymers having both thermoplastic and elastomeric properties, as well as both hydrophobic and hydrophilic properties, have been adopted, and the results are summarized in the review by Kim K. et al., "Solar RRL" (2021), Vol. 5, pg. 2000783, doi.org / 10.1002 / solr.202000783. This review describes the role and contribution of polymer additives in perovskite solar cells. In particular, it is disclosed to use a polymer or polymer material as an additive to promote the nucleation and crystallization of the perovskite photoactive layer and increase the particle size of the perovskite crystals. Due to its high molecular weight, the above polymer can provide good passivation of the defects present at the ends of the perovskite crystals. Furthermore, the above polymer can increase its particle size and improve the filling between crystals by limiting the growth rate of the perovskite crystals. Additionally, some polymers can effectively separate charge carriers and reduce charge recombination by functioning as a charge carrier material in the interface layer. Moreover, some hydrophobic polymers can protect the perovskite photoactive layer from moisture, and elastomeric polymers can contribute to the mechanical elasticity of the perovskite photoactive layer through crosslinking and self-healing.

[0012] Ko Y. et al. reported in "Synthetic Metals" (2019), Vol. 249, pg. 47-51, the following layout: c-TiO2 / MAPbI 3-x Cl x-A method for manufacturing a perovskite solar cell having PMMA / PTAA / Au is reported. This method includes depositing a layer of a mixture of PbI2 and PbCl2, and subsequently immersing the resulting substrate in a solution containing MAI (20 mg / ml) and PMMA (the amount of PMMA is very small, about 1 / 4,000 by weight relative to MAI) to form a perovskite crystal phase in the presence of PMMA. In the above method, due to the improvement of the charge transport ability accompanied by the improvement of the morphology and crystallinity of the perovskite photoactive layer, a perovskite solar cell having a power conversion efficiency (PCE) equal to 15.3% can be obtained. However, the above manufacturing method performs the formation of the perovskite photoactive layer in two steps, and thus may be very complicated and difficult to use in the scaling-up step for the construction of large-area photovoltaic cells (or solar cells). Furthermore, in the above method, since the amount of PMMA effectively incorporated into the perovskite photoactive layer cannot be determined, the above method probably does not guarantee good reproducibility of the results.

[0013] Saraf R. et al. reported in "ACS Applied Energy Materials" (2019), Vol. 2, pg. 2214 - 2222, a method for manufacturing a perovskite solar cell with the following layout: ZnO / MAPbI3 - PS / spiro - OMeTAD / Au. This method involves depositing a perovskite photoactive layer from an equimolar solution of PbI2 and MAI containing various amounts of polystyrene (PS) (0.5 wt% - 14 wt%). By implementing under the most favorable conditions (i.e., PS = 1 wt%), this method can obtain a perovskite solar cell with a power conversion efficiency (PCE) equal to 12.27% due to an increase in the size of the particle granulometry of perovskite crystals determined by better crystallization kinetics. However, the above - mentioned manufacturing method involves an annealing process at 200 °C for the formation of the ZnO layer and a two - step process of adding a non - solvent for the formation of the perovskite photoactive layer, so it is considered not suitable for use in the up - scaling stage for the construction of large - area photovoltaic cells (or solar cells). This two - step process not only complicates the perovskite film deposition process but also may lead to a decrease in reproducibility. Furthermore, according to the authors' report, the polystyrene solution is not stable in the presence of PbI2 and seems to result in the formation of a partially cross - linked polymer material. Therefore, this phenomenon is considered likely to cause significant non - reproducibility in the performance of the photovoltaic cells (or solar cells) thus obtained.

[0014] Kim et al reported in "Journal of Materials Chemistry A" (2019), Vol. 7, pg. 20832 - 20839, a layout of: TiO2 / FA x MA 1-xA method for manufacturing a perovskite solar cell having PbI3-PDMS / spiro-OMeTAD / Au is reported. This method involves starting from a solution containing PbI2, MAI, FAI, and DMSO (molar ratio of 1:0.85:0.15:1) in DMF and depositing a perovskite photoactive layer by spin coating. During the spin coating process, 0.3 ml of a toluene solution containing various weights of polydimethylsiloxane (PDMS) is added to the substrate. By carrying out the process under the most favorable conditions (i.e., PDMS in toluene = 0.03 wt%), perovskite crystals with a more regular shape and a narrower size distribution can be obtained, resulting in a perovskite solar cell having a power conversion efficiency (PCE) equal to 15.44%. However, the above method involves an annealing process at 500 °C for the formation of the TiO2 layer and a two-step process of adding a non-solvent for the formation of the perovskite photoactive layer, and thus is considered not suitable for use in the upscaling stage for the construction of large-area photovoltaic cells (or solar cells). Furthermore, in the above method, the amount of PDMS effectively incorporated into the perovskite photoactive layer cannot be determined, and therefore, the above method probably does not guarantee good reproducibility of the results.

[0015] Liu G. et al. reported in "ACS Applied Materials & Interfaces" (2020), Vol. 12, pg. 14049, a method for manufacturing a perovskite solar cell having the following layout: PEDOT:PSS / FASnI3-EVA / PCBM-BTP / Ag. This method includes forming a perovskite photoactive layer by spin-coating a DMSO / DMF solution (1 / 4, v / v) containing equimolar amounts of SnI2 and FAI. During the spin-coating process, a solution of chlorobenzene containing various weight percentages of ethylene vinyl acetate (EVA) is added to the substrate. By carrying out under the most favorable conditions (i.e., EVA in chlorobenzene = 2 mg / ml), a perovskite photoactive layer of better quality is obtained, and the size of perovskite crystals increases, so that a perovskite solar cell with a power conversion efficiency (PCE) equal to 7.72% is obtained. However, since the above method includes a two-step process of adding a non-solvent for the formation of the perovskite photoactive layer, it is considered not suitable for use in the upscaling step for the construction of large-area photovoltaic cells (or solar cells). Furthermore, in the above method, since the amount of EVA actually incorporated into the perovskite photoactive layer cannot be determined, it is likely that good reproducibility of the results is not guaranteed in the above method.

[0016] Xue Q. et al. reported in "RSC Advances" (2015), Vol. 7, pg. 775 - 783, a method for manufacturing a perovskite solar cell with the following layout: PEDOT:PSS / MAPbI3 - PEOXA / PCBM / Al. There is no detailed report on either the manufacturing of perovskite solar cells or the manufacturing of the photoactive layer in the above - reported method. However, the authors stated that the obtained results strongly depend on the type of solvent used to dissolve the perovskite precursor and the amount of poly(2 - ethyl - 2 - oxazoline) (PEOXA) used. By implementing under the most favorable conditions (i.e., γ - butyrolactone (GBL) as the solvent and 1.5 wt% of PEOXA), since the crystallization process and the morphology of the perovskite photoactive layer are better controlled, a perovskite solar cell with a power conversion efficiency (PCE) equal to 6.16% is obtained.

[0017] Guo Y. et al. reported in "Advanced Energy Materials" (2016), Vol. 6, 1502317, a method for manufacturing a perovskite solar cell with the following layout: PEDOT:PSS / MAPbI x Cl 3-x -PVP / PCBM - PEIE / Ag. This method involves fabricating a perovskite photoactive layer by spin - coating a DMF solution containing perovskite precursors: MAI, PbI2 and PbCl2 (in a molar ratio of 4:1:1) and various amounts (0 wt% - 6 wt%) of polyvinylpyrrolidone (PVP). By implementing under the most favorable conditions (i.e., 3 wt% of PVP), a perovskite solar cell with a power conversion efficiency (PCE) equal to 7.91% is obtained for the improvement of the size and morphology of perovskite crystals, and a significant improvement is also obtained regarding the thermal stability of the perovskite photoactive layer.

[0018] From the above, it is clear that the importance of finding other polymers that can be used as additives to the perovskite photoactive layer, which can enable the production of perovskite solar cells (PSCs) with good power conversion efficiency (PCE), and even more so, a construction method suitable for use in the upscaling stage for the construction of large-area solar cells (or photovoltaic cells).

Summary of the Invention

[0019] Therefore, the applicant has faced the problem of finding a perovskite solar cell (or photovoltaic cell) that can have good power conversion efficiency (PCE), and even more so, a construction method suitable for use in the upscaling stage for the construction of large-area solar cells (or photovoltaic cells).

[0020] The applicant has now found that a perovskite photovoltaic cell (or solar cell) can have a good power conversion efficiency (PCE) (i.e., PCE > 10%) when the perovskite photoactive layer contains at least one partially neutralized polyacrylic acid in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor. In addition, a method for constructing a perovskite photovoltaic cell (or solar cell) has been found, in which the perovskite photoactive layer is deposited in a single step without using a non-solvent and with the deposition temperature of various layers being less than 120°C. Therefore, the above method is suitable for use in the upscaling stage for the construction of large-area photovoltaic cells (or solar cells). Furthermore, the above perovskite photovoltaic cell (or solar cell) can maintain good photovoltaic characteristics, i.e., good values of FF (fill factor), Voc (open-circuit voltage), and Jsc (short-circuit photocurrent). The above perovskite photovoltaic cell (or solar cell) can be advantageously used in various applications that require power generation by utilizing light energy, particularly solar radiation energy, such as building-integrated photovoltaic systems (building-integrated photovoltaics - BIPV), solar photovoltaic windows, greenhouses, photo-bioreactors, sound insulation walls, lighting engineering, design, advertising, and the automotive industry. Furthermore, the above perovskite photovoltaic cell (or solar cell) can be used in either a stand-alone form or a modular manner.

[0021] Accordingly, an object of the present invention is a perovskite photovoltaic cell (or solar cell), wherein the perovskite photoactive layer contains at least one partially neutralized polyacrylic acid in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor.

Brief Description of the Drawings

[0022]

Figure 1

Mode for Carrying Out the Invention

[0023] For the purposes of this specification and the appended claims, the definition of a numerical range always includes the extreme values, unless otherwise specified.

[0024] For the purposes of this specification and the appended claims, the term "comprising" also includes the terms "consisting essentially of" or "consisting of".

[0025] According to a preferred embodiment of the present invention, the above perovskite can be selected from, for example, organometallic trihalides represented by the following general formula. ABX3 (wherein, A represents a monovalent organic cation (for example, methylammonium (CH3NH3 + ), formamidinium [CH(NH2)2 + , n-butylammonium (C4H 12 NH3 + ), tetrabutylammonium (C 16 H 36 N + ) or a mixture thereof, etc.), or A represents a monovalent inorganic cation (for example, cesium (Cs + ), rubidium (Rb + ), potassium (K + ), lithium (Li + ), sodium (Na + ), copper (Cu + ), silver (Ag + ) or a mixture thereof, etc.), or represents a mixture thereof, B represents a divalent metal cation (for example, lead (Pb 2+ ), tin (Sn 2+ ) or a mixture thereof, etc.), X represents a halide anion (for example, iodine (I - ), chlorine (Cl - ), bromine (Br - ) or a mixture thereof, etc.).)

[0026] According to a more preferred embodiment of the present invention, the perovskite is, for example, methylammonium lead iodide (CH3NH3PbI3), methylammonium lead bromide (CH3NH3PbBr3), methylammonium lead chloride (CH3NH3PbCl3), methylammonium lead bromoiodide (CH3NH3PbI x Br 3-x ), methylammonium lead chloroiodide (CH3NH3PbI x Cl 3-x ), formamidinium lead iodide [CH(NH2)2PbI3], formamidinium lead bromide [CH(NH2)2PbBr3], formamidinium lead chloride [CH(NH2)2PbCl3], formamidinium lead bromoiodide [CH(NH2)2PbI x Br 3-x , formamidinium lead chloroiodide [CH(NH2)2PbI x Cl 3-x , methylammonium formamidinium lead iodide [(CH3NH3) x (CH(NH2)2) 1-x PbI3], methylammonium formamidinium lead bromide [(CH3NH3) x (CH(NH2)2) 1-x PbBr3], methylammonium formamidinium lead chloride [(CH3NH3) x (CH(NH2)2) 1-x PbCl3], methylammonium formamidinium lead chloroiodide [(CH3NH3) x (CH(NH2)2) 1-x PbI 3-y Cl y , methylammonium formamidinium lead bromoiodide [(CH3NH3) x (CH(NH2)2) 1-x PbI 3-y Br y , n-butylammonium lead iodide (C4H 12 NH3PbI3), tetrabutylammonium lead iodide (C 16 H 36 NPbI3), n-butylammonium lead bromide (C4H 12(NH3PbBr3), tetrabutylammonium lead bromide (C 16 H 36 NPbBr3), cesium lead iodide (CsPbI3), rubidium lead iodide (RbPbI3), potassium lead iodide (KPbI3), cesium methylammonium lead iodide [Cs x (CH3NH3) 1-x PbI3], potassium methylammonium lead iodide [K x (CH3NH3) 1-x PbI3], cesium methylammonium lead chloride iodide [Cs x (CH3NH3) 1-x PbI 3-y Cl y , cesium formamidinium lead iodide [Cs x (CH(NH2)2) 1-x PbI3], cesium formamidinium lead bromide [Cs x (CH(NH2)2) 1-x PbBr3], cesium formamidinium lead chloride iodide [Cs x (CH(NH2)2) 1-x PbI 3-y Cl y , methylammonium tin iodide (CH3NH3SnI3), methylammonium tin bromide (CH3NH3SnBr3), methylammonium tin bromide iodide (CH3NH3SnI x Br 3-x ), formamidinium tin iodide [CH(NH2)2SnI3], formamidinium tin bromide iodide [CH(NH2)2SnI x Br 3-x , n-butylammonium tin iodide (C4H 12 NH3SnI3), tetrabutylammonium tin iodide (C 16 H 36 NSnI3), n-butylammonium tin bromide (C4H 12 NH3SnBr3), tetrabutylammonium tin bromide (C 16 H 36 NSnBr3), methylammonium tin lead iodide (CH3NH3Sn x Pb 1-xI3), formamidinium tin lead iodide [CH(NH2)2Sn x Pb 1-x I3] or a mixture thereof. Preferably, methylammonium lead iodide (CH3NH3PbI3), formamidinium lead iodide [CH(NH2)2PbI3], methylammonium formamidinium lead chloride iodide [(CH3NH3) x (CH(NH2)2) 1-x PbI 3-y Cl y , cesium methylammonium lead chloride iodide [Cs x (CH3NH3) 1-x PbI 3-y Cl y , cesium formamidinium lead chloride iodide [Cs x (CH(NH2)2) 1-x PbI 3-y Cl y . More preferably, it is methylammonium lead iodide (CH3NH3PbI3).

[0027] According to a preferred embodiment of the present invention, the partially neutralized polyacrylic acid is represented by the following general formula (I).

Chemical formula

Chemical formula

Chemical formula

[0028] For the purposes of this specification and the appended claims, the term "C1-C 20 alkyl group" refers to a linear or branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms. C1-C 20 Specific examples of C1-C alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylheptyl, 2-ethylhexyl, 2-butenyl, 2-pentenyl, 2-ethyl-3-hexenyl, 3-octenyl, 1-methyl-4-hexenyl, 2-butyl-3-hexenyl.

[0029] For the purposes of this specification and the appended claims, the term "C1-C alkyl group optionally containing a heteroatom" refers to a linear or branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a heteroatom selected from halogen, e.g., fluorine, chlorine, bromine, preferably fluorine, nitrogen, sulfur, oxygen. C1-C alkyl group optionally containing a heteroatom 20 20 ​Specific examples of the alkyl group include fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, perfluoropentyl, perfluorooctyl, perfluorodecyl, ethyl-2-methoxy, propyl-3-ethoxy, butyl-2-thiomethoxy, hexyl-4-amino, hexyl-3-N,N'-dimethylamino, methyl-N,N'-dioctylamino, 2-methyl-hexyl-4-amino.

[0030] For the purposes of this specification and the appended claims, the term "aryl group" refers to an aromatic carbocyclic group containing 6 to 60 carbon atoms. The above aryl group may be arbitrarily substituted with one or more groups that are the same as or different from each other and are selected from a halogen atom, such as fluorine, chlorine, bromine, preferably fluorine, a hydroxyl group, C1-C 12 alkyl group, C1-C 12 alkoxy group, C1-C 12 thioalkoxy group, C3-C 24 trialkylsilyl group, polyethyleneoxyl group, cyano group, amino group, C1-C 12 monoalkylamino group or dialkylamino group, nitro group. Specific examples of the aryl group include phenyl, methylphenyl, trimethylphenyl, methoxyphenyl, hydroxyphenyl, phenyloxyphenyl, fluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl, nitrophenyl, dimethylaminophenyl, naphthyl, phenylnaphthyl, phenanthrene, anthracene.

[0031] For the purposes of this specification and the appended claims, the term "heteroaryl group" means an aromatic 5-membered or 6-membered heterocyclic group containing 4 to 60 carbon atoms and 1 to 4 heteroatoms selected from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus, and further means a benzocondensed compound or a heterobicyclic ring. The above heteroaryl group may be the same as or different from each other and may be arbitrarily substituted with a halogen atom, such as fluorine, chlorine, bromine, preferably fluorine, a hydroxyl group, C1-C12 An alkyl group, C1-C 12 An alkoxy group, C1-C 12 A thioalkoxy group, C3-C 24 A trialkylsilyl group, a polyethyleneoxyl group, a cyano group, an amino group, C1-C 12 It may be optionally substituted with one or more groups selected from a monoalkylamino group or a dialkylamino group, and a nitro group. Specific examples of the heteroaryl group include pyridine, methylpyridine, methoxypyridine, phenylpyridine, fluoropyridine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, quinoline, quinoxaline, quinazoline, furan, thiophene, hexylthiophene, bromothiophene, dibromothiophene, pyrrole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, pyrazole, imidazole, triazole, tetrazole, indole, benzofuran, benzothiophene, benzoxazole, benzothiazole, benzoxadiazole, benzothiadiazole, benzopyrazole, benzimidazole, benzotriazole, triazolopyridine, triazolopyrimidine, and coumarin.

[0032] For the purposes of this specification and the appended claims, the term "cycloalkyl group" refers to a cycloalkyl group having 3 to 60 carbon atoms. The cycloalkyl group may be a halogen atom, such as fluorine, chlorine, bromine, preferably fluorine, a hydroxyl group, C1-C 12 An alkyl group, C1-C 12 An alkoxy group, C1-C 12 A thioalkoxy group, C3-C 24 A trialkylsilyl group, a polyethyleneoxyl group, a cyano group, an amino group, C1-C 12It may be optionally substituted with one or more groups that are the same as or different from each other and are selected from a monoalkylamino group, a dialkylamino group, and a nitro group. Specific examples of the cycloalkyl group include cyclopropyl, 2,2-difluorocyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, methoxycyclohexyl, fluorocyclohexyl, phenylcyclohexyl, decalin, and abietyl.

[0033] For the purposes of this specification and the appended claims, the term "heterocyclic group" refers to a ring having 3 to 12 atoms, being saturated or unsaturated, containing at least one heteroatom selected from nitrogen, oxygen, sulfur, silicon, selenium, and phosphorus, and optionally condensed with another aromatic or non-aromatic ring. The above heterocyclic group may be a halogen atom, for example, fluorine, chlorine, bromine, preferably fluorine, a hydroxyl group, C1-C 12 alkyl group, C1-C 12 alkoxy group, C1-C 12 thioalkoxy group, C3-C 24 trialkylsilyl group, polyethyleneoxyl group, cyano group, amino group, C1-C 12 It may be optionally substituted with one or more groups that are the same as or different from each other and are selected from a monoalkylamino group, a dialkylamino group, and a nitro group. Specific examples of the heterocyclic group include pyrrolidine, methoxypyrrolidine, piperidine, fluoropiperidine, methylpiperidine, dihydropyridine, piperazine, morpholine, thiazine, indoline, phenylindoline, 2-ketoazetidine, diketopiperazine, tetrahydrofuran, and tetrahydrothiophene.

[0034] For the purposes of this specification and the appended claims, the term "cycle" refers to a system including a ring containing 1 to 12 carbon atoms and optionally containing a heteroatom selected from nitrogen, oxygen, sulfur, silicon, selenium, and phosphorus. Specific examples of the ring include toluene, benzonitrile, cycloheptatriene, cyclooctadiene, pyridine, piperidine, tetrahydrofuran, thiadiazole, pyrrole, thiophene, selenophene, and tert-butylpyridine.

[0035] For the purposes of this specification and the appended claims, the term "trialkylsilyl group or triarylsilyl group" refers to a group containing a silicon atom to which three C1-C 12 alkyl groups or three C6-C 24 aryl groups, or a combination thereof, are attached. Specific examples of trialkylsilyl groups or triarylsilyl groups are trimethylsilane, triethylsilane, trihexylsilane, tridodecylsilane, dimethyldodecylsilane, triphenylsilane, methyldiphenylsilane, dimethylnaphthylsilane.

[0036] For the purposes of this specification and the appended claims, the term "dialkylamino group or diarylamino group" refers to a group containing a nitrogen atom to which two C1-C 12 alkyl groups or two C6-C 24 aryl groups, or a combination thereof, are attached. Specific examples of dialkylamino groups or diarylamino groups are dimethylamine, diethylamine, dibutylamine, diisobutylamine, diphenylamine, methylphenylamine, dibenzylamine, ditolylamine, dinaphthylamine.

[0037] For the purposes of this specification and the appended claims, the term "dialkylphosphine group or diarylphosphine group" refers to a group containing a phosphorus atom to which two C1-C 12 alkyl groups or two C6-C 24 aryl groups, or a combination thereof, are attached. Specific examples of dialkylphosphine groups or diarylphosphine groups are dimethylphosphine, diethylphosphine, dibutylphosphine, diphenylphosphine, methylphenylphosphine, dinaphthylphosphine.

[0038] For the purposes of this specification and the appended claims, the term "C1-C 20 alkoxy group" refers to a group containing an oxygen atom to which a straight-chain or branched C1-C 20 alkyl group is attached. C1-C 20Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, and dodecyloxy.

[0039] For the purposes of this specification and the appended claims, the term "aryloxy group" refers to a group containing an oxygen atom to which an aryl group is attached. The aryloxy group may be optionally substituted with one or more groups selected from halogen atoms such as fluorine, chlorine, bromine, preferably fluorine, hydroxyl groups, C1-C 24 alkyl groups, C1-C 12 alkoxy groups, C1-C 12 thioalkoxy groups, C3-C 12 trialkylsilyl groups, cyano groups, amino groups, C1-C 24 monoalkylamino groups or dialkylamino groups, and nitro groups, which may be the same as or different from each other. Specific examples of the aryloxy group include phenoxy, paramethylphenoxy, parafluorophenoxy, orthobutylphenoxy, naphthyloxy, and anthracenoxy. 12 For the purposes of this specification and the appended claims, the term "thioalkoxy group or thioaryloxy group" refers to a group containing a sulfur atom to which a C1-C

[0040] alkoxy group or a C6-C 12 aryloxy group is attached. The thioalkoxy group or thioaryloxy group may be a halogen atom (e.g., fluorine, chlorine, bromine, preferably fluorine), a hydroxyl group, a C1-C 24 alkyl group, a C1-C 12 alkoxy group, a C1-C 12 thioalkoxy group, a C3-C 12 trialkylsilyl group, a cyano group, an amino group, a C1-C 24 monoalkylamino group or dialkylamino group, and a nitro group, which may be the same as or different from each other. 12It may be optionally substituted with one or more groups that are the same as or different from each other and are selected from a monoalkylamino group, a dialkylamino group, and a nitro group. Specific examples of the thioalkoxy group or thioaryloxy group include thiomethoxy, thioethoxy, thiopropoxy, thiobutoxy, thioisobutoxy, 2-ethylthiohexyl, thiophenoxy, paramethylthiophenoxy, parafluorothiophenoxy, orthobutylthiophenoxy, naphthylthiooxyl, and anthracenylthiooxyl.

[0041] According to a preferred embodiment of the present invention, in the above-mentioned partially neutralized polyacrylic acid, the free carboxyl groups are present in an amount of 1% to 99%, preferably 20% to 98%, more preferably 50% to 96% based on the total amount of carboxyl groups present in the polyacrylic acid.

[0042] The above-mentioned partially neutralized polyacrylic acid can be obtained according to a process known in the art. For example, the starting polyacrylic acid can be reacted with a carbonate or bicarbonate of an alkali metal selected from those listed above in the presence of water for a time necessary to obtain the desired amount of neutralized carboxyl groups. Further details regarding the preparation of the partially neutralized polyacrylic acid are shown in the following examples.

[0043] According to a preferred embodiment of the present invention, the starting polyacrylic acid (i.e., the non-partially neutralized one) may have a weight average molecular weight (M w ) within 700 Da to 4,000,000 Da, preferably within 1,000 Da to 1,000,000 Da, more preferably within 1,500 Da to 400,000 Da.

[0044] According to a preferred embodiment of the present invention, the above-mentioned perovskite-type photovoltaic cell (or solar cell) comprises the following. · A layer of transparent conductive oxide that constitutes the anode (transparent conductive oxide - TCO), generally a glass substrate coated with tin oxide doped with fluorine (SnO2:F) (fluorine-doped tin oxide - FTO) or indium tin oxide (indium tin oxide - ITO), · A layer based on a hole transport material (hole transport layer - HTL), preferably a layer of poly[bis(4-butylphenyl)-bisphenylbenzidine] (Poly-TPD), · Optionally, a layer based on a material useful for improving wettability, preferably a layer of poly[9,9-bis(3'-(N,N-dimethyl)-N-ethylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] diiodide (PFN-I) or a layer of poly[9,9-bis(3'-(N,N-dimethyl)-N-ethylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN), · A photoactive layer comprising at least one perovskite and at least one partially neutralized polyacrylic acid. The perovskite is preferably methylammonium lead iodide (CH3NH3PbI3) [methylammonium lead iodide (CH3NH3PbI3) is the most used structure because it has a high absorption coefficient over the UV and visible spectra, a bandgap equal to 1.57 eV, which is close to the optimal value for maximizing the conversion efficiency, and a significant diffusion distance (more than 100 nm) for both electrons and electron holes (or holes)]. At least one partially neutralized polyacrylic acid is preferably a polyacrylic acid partially neutralized with cesium or potassium, having an amount of free carboxyl groups in the range of 60% to 95%, · A layer based on an electron transport material (electron transport layer - ETL), preferably a layer of [6,6]-phenyl-C 61 -methyl ester of butyric acid (PC 61 BM), · Optionally, a layer based on a hole blocking material (hole blocking layer - HBL), preferably a layer of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine - BCP) or ethoxylated polyethyleneimine (PEIE), · A metal contact known as a back contact that forms the cathode, preferably a layer of gold, silver, or aluminum metal.

[0045] According to a preferred embodiment of the present invention, the electrical energy generated by the at least one perovskite-type photovoltaic cell (or solar cell) can be transported using a wiring system connected to the perovskite-type photovoltaic cell (or solar cell).

[0046] As described above, a further object of the present invention is a method for manufacturing the perovskite-type photovoltaic cell (or solar cell).

[0047] Next, a further object of the present invention is a method for manufacturing a perovskite-type photovoltaic cell (or solar cell), comprising: (a) Preparing a glass substrate coated with a transparent conductive oxide layer (transparent conductive oxide - TCO) (anode); (b) Depositing a hole transport material-based layer (hole transport layer - HTL) on the substrate obtained in step (a); (c) Optionally, depositing a layer based on a material useful for improving wettability on the hole transport material-based layer (hole transport layer - HTL) obtained in step (b); (d) Preparing a mixture comprising a perovskite precursor and at least one partially neutralized polyacrylic acid, wherein the partially neutralized polyacrylic acid is present in the mixture in an amount of 3 wt% or more, preferably within 4 wt% to 15 wt%, more preferably within 4.5 wt% to 12 wt% based on the total weight of the perovskite precursor; (e) Depositing the mixture obtained in step (d) on the hole transport material-based layer (hole transport layer - HTL) obtained in step (b) or on the layer based on a material useful for improving wettability obtained in step (c) to obtain a photoactive layer; (f) Depositing an electron transport material-based layer (electron transport layer - ETL) on the photoactive layer obtained in step (e). (g) Optionally, depositing a layer based on a hole blocking material (hole blocking layer - HBL) on top of the layer based on the electron transport material obtained in step (f) (electron transport layer - ETL); (h) Depositing a metal contact known as a back contact that constitutes the cathode on top of the layer based on the electron transport material obtained in step (f) (ETL), or on top of the layer based on the hole blocking material obtained in step (g) (hole blocking layer - HBL); The method includes steps (b), (c), (e), (f), and (g), which are carried out at a temperature below 120 °C, preferably in the range of 20 °C to 115 °C.

[0048] For the purposes of the above method, the above transparent conductive oxide (transparent conductive oxide - TCO), the layer based on the hole transport material (hole transport layer - HTL), the layer based on the electron transport material (electron transport layer - ETL), the layer based on the material useful for improving wettability, the layer based on the hole blocking material (hole blocking layer - HBL), and the above metal contact known as a back contact are selected from those listed above.

[0049] For the purposes of the above method, the above mixture containing a perovskite precursor and at least one polyacrylic acid includes the following. · As the perovskite precursor, at least one halide selected from the halides of the monovalent organic cations or monovalent inorganic cations listed above (preferably iodide, chloride, bromide, more preferably iodide [e.g., methylammonium iodide (MAI) (CH3NH3I)]), and at least one halide selected from the halides of the divalent metal cations listed above (preferably iodide, chloride, bromide, more preferably iodide [e.g., lead iodide (PbI2)]); · At least one partially neutralized polyacrylic acid (preferably partially neutralized with cesium or potassium), a polyacrylic acid having an amount of free carboxyl groups within 60% - 95%.

[0050] For the purpose of the above method, the above steps (b), (c), (e), (f) and (g) can be carried out according to deposition techniques known in the art, such as spin coating, spray coating, inkjet printing, slot die coating, gravure printing, screen printing.

[0051] For the purpose of the above method, the above step (h) can be carried out according to techniques known in the art, such as evaporation, sputtering, electron beam assisted deposition, sputtering, spin coating, gravure printing, flexographic printing, slot die coating.

[0052] As described above, the above perovskite-type photovoltaic cell (or solar cell) can be advantageously used in various applications that require power generation by utilizing light energy, particularly solar radiation energy, such as building-integrated photovoltaic systems (building-integrated photovoltaics - BIPV), solar power generation windows, greenhouses, photo-bioreactors, sound insulation walls, lighting engineering, design, advertising, and the automotive industry. In addition, the above perovskite-type photovoltaic cell (or solar cell) can be used in a stand-alone form or a modular system.

[0053] Next, a further object of the present invention is the use of the above perovskite-type photovoltaic cell (or solar cell) in building-integrated photovoltaic systems (building-integrated photovoltaics - BIPV), solar power generation windows, greenhouses, photo-bioreactors, sound insulation walls, lighting engineering, design, advertising, and the automotive industry.

[0054] As described above, a further object of the present invention is also a composition comprising at least one perovskite and at least one partially neutralized polyacrylic acid.

[0055] Next, a further object of the present invention is a composition comprising at least one perovskite and at least one partially neutralized polyacrylic acid in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor.

[0056] The above at least one perovskite and the above at least one partially neutralized polyacrylic acid can be selected from those reported above.

[0057] Here, the present invention will be described in more detail through embodiments with reference to FIG. 1 described below.

[0058] In particular, FIG. 1 represents a cross-sectional view of a perovskite solar cell (or photovoltaic cell) (1) comprising the following layers: a glass substrate (7) coated with a transparent conductive oxide layer (transparent conductive oxide - TCO) (anode) [e.g., indium tin oxide (ITO) or fluorine-doped tin oxide (SnO2:F) (fluorine-doped tin oxide - FTO)] (2), a hole transport material-based layer (hole transport layer - HTL) [e.g., poly[bis(4-butylphenyl)-bisphenylbenzidine] (Poly-TPD)] (3), optionally a layer based on a material useful for improving wettability [e.g., poly[9,9-bis(3'-(N,N-dimethyl)-N-ethylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] diiodide (PFN-I) or poly[9,9-bis(3'-(N,N-dimethyl)-N-ethylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN)] (not shown in FIG. 1), a photoactive layer (4) comprising at least one perovskite [e.g., methylammonium lead iodide (CH3NH3PbI3)] and at least one partially neutralized polyacrylic acid (e.g., polyacrylic acid partially neutralized with cesium or potassium having free carboxyl groups in an amount within 60% to 95%), a layer based on an electron transport material (electron transport layer - ETL) [e.g., [6,6]-phenyl-C 61 -methyl ester of butyric acid (PC 61BM)](5a), a layer based on a hole-blocking material (hole-blocking layer - HBL) [for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine - BCP) or ethoxylated polyethyleneimine (PEIE)] (5b), a metal contact known as a back contact constituting the cathode [for example, a layer of gold, silver, or metallic aluminum] (6).

[0059] To better understand and practice the present invention, some exemplary and non-limiting examples are shown below.

[0060] In the following examples, for simplicity, the term solar cell is used, which should be understood to have the same meaning as photovoltaic cell.

Examples

[0061] Preparation of polyacrylic acid partially neutralized with cesium (PACs5) 3.07 g of polyacrylic acid (monomer unit is 42.6 mmol) (weight average molecular weight (M w ) = 1,800 Da) (Aldrich) was charged into a 250 ml flask and dissolved in 75 ml of ultrapure water. The resulting solution was filtered using a Millipore filter (porosity 45 μm). 0.34 g of cesium carbonate (Cs2CO3) (2.08 mmol of cesium) (Aldrich) dissolved in 20 ml of ultrapure water was added to the filtered solution. The reaction mixture was left standing at room temperature (25 °C) for 5 minutes with stirring, then heated to a temperature of 80 °C to promote the removal of the generated carbon dioxide and maintained at this temperature for 2 hours with stirring. The solution was cooled to room temperature (25 °C) and filtered again using a Millipore filter (porosity 45 μm) to remove any impurities, followed by lyophilization to obtain 2.85 g of partially neutralized polyacrylic acid as a flaky white solid. As reported below, when the sample was analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry), a cesium content equal to 8.3% was shown, which corresponded to approximately 5% of the neutralized -COOH groups, that is, -COO - Cs + converted to, was equivalent to about 5%.

[0062] ICP-OES analysis (Inductively Coupled Plasma Optical Emission Spectrometry) The sample to be analyzed was prepared by acid digestion.

[0063] For this purpose, 50 mg of the partially neutralized polyacrylic acid obtained as described above was placed in a 200 ml flask, and 7.5 ml of nitric acid (65 wt% aqueous solution - Aldrich) and 2.5 ml of sulfuric acid (95 wt% aqueous solution - Aldrich) were added thereto. The resulting mixture was heated to 120 °C and maintained at this temperature for 20 hours, and then diluted with ultrapure water to a volume of 50 ml. The solution thus obtained was subsequently diluted in a ratio of 1:10 (v / v) in nitric acid (HNO3) (1% aqueous solution obtained by diluting a 65 wt% aqueous solution - Aldrich) and then analyzed by (Inductively Coupled Plasma Optical Emission Spectrometry) (Spectro Genesis, Ametek).

[0064] The calibration curves were obtained for each of the two metals analyzed [i.e., cesium (Cs) and potassium (K)] using five standard solutions with the following concentrations: 0.05 ppm, 0.10 ppm, 0.50 ppm, 1.00 ppm, and 5.00 ppm. All solutions were obtained by serial dilution starting from two stock solutions of 1,000 ppm for each metal. A solution of nitric acid (HNO3) (1% aqueous solution obtained by diluting a 65 wt% aqueous solution - Aldrich) was used as a blank.

[0065] The operating conditions used were as follows. Plasma gas flow rate: 0.5 L / min RF power: 1,400 W Measurement wavelength: 455 nm for cesium (Cs) analysis and 766 nm for potassium (K) analysis.

[0066] When the detection limit (LOD) was calculated using the background equivalent concentration (BEC) and the signal-to-background ratio (SBR), it was found that LOD(K) = 0.001 mg / L and LOD(Cs) = 0.003 mg / L.

Example

[0067] Preparation of Polyacrylic Acid Partially Neutralized with Cesium (PACs10) The polyacrylic acid partially neutralized with cesium (PACs10) was prepared as described in Example 1. The only difference was the use of different amounts of cesium carbonate (Cs2CO3).

[0068] For this purpose, 3.07 g of polyacrylic acid (monomer unit is 42.6 mmol) (weight average molecular weight (M w ) = 1,800 Da) (Aldrich) was reacted with 0.62 g of cesium carbonate (Cs2CO3) (4.16 mmol of cesium) (Aldrich) to obtain 2.98 g of partially neutralized polyacrylic acid in the form of flaky white solid. When the sample was analyzed by ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry) as described in Example 1, a cesium content equal to 15.4% was shown, which corresponded to approximately 10% of the neutralized -COOH groups, that is, those converted to -COO - Cs + converted to.

Example

[0069] Preparation of Polyacrylic Acid Partially Neutralized with Cesium (PACs20) The polyacrylic acid partially neutralized with cesium (PACs20) was prepared as described in Example 1. The only difference was due to the use of different amounts of cesium carbonate (Cs2CO3).

[0070] For this purpose, 3.07 g of polyacrylic acid (monomer unit is 42.6 mmol) (weight average molecular weight (M w) = 1,800 Da) (Aldrich) was reacted with 1.36 g of cesium carbonate (Cs2CO3) (8.32 mmol of cesium) (Aldrich) to obtain 3.22 g of partially neutralized polyacrylic acid in the form of a flaky white solid. When the sample was analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry) as described in Example 1, a cesium content equal to 26.7% was shown, which corresponded to approximately 20% of the neutralized -COOH groups, i.e., those converted to -COO - Cs + converted to.

Example

[0071] Preparation of polyacrylic acid partially neutralized with cesium (PACs40) Polyacrylic acid partially neutralized with cesium (PACs40) was prepared as described in Example 1. The only difference was due to using different amounts of cesium carbonate (Cs2CO3).

[0072] For this purpose, 3.07 g of polyacrylic acid (monomer units 42.6 mmol) (weight average molecular weight (M w ) = 1,800 Da) (Aldrich) was reacted with 2.72 g of cesium carbonate (Cs2CO3) (16.6 mmol of cesium) (Aldrich) to obtain 3.95 g of partially neutralized polyacrylic acid in the form of a flaky white solid. When the sample was analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry) as described in Example 1, a cesium content equal to 42.1% was shown, which corresponded to approximately 40% of the neutralized -COOH groups, i.e., those converted to -COO - Cs + converted to.

Example

[0073] Preparation of polyacrylic acid partially neutralized with potassium (PAK5) Partially neutralized polyacrylic acid (PAK5) with potassium was prepared as described in Example 1. The only difference was due to the use of different amounts of potassium bicarbonate (KHCO3).

[0074] For this purpose, 3.07 g of polyacrylic acid (monomer units: 42.6 mmol) (weight average molecular weight (M w ) = 1,800 Da) (Aldrich) was reacted with 0.21 g of potassium bicarbonate (KHCO3) (2.09 mmol of potassium) (Aldrich) to obtain 2.68 g of partially neutralized polyacrylic acid in the form of a flaky white solid. When the sample was analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry) as described in Example 1, a potassium content equal to 2.2% was shown, which corresponded to approximately 5% of the neutralized -COOH groups, i.e., those converted to -COO - K + -.

Example

[0075] Preparation of partially neutralized polyacrylic acid (PAK10) with potassium Partially neutralized polyacrylic acid (PAK10) with potassium was prepared as described in Example 1. The only difference was due to the use of different amounts of potassium bicarbonate (KHCO3).

[0076] For this purpose, 3.07 g of polyacrylic acid (monomer units: 42.6 mmol) (weight average molecular weight (M w ) = 1,800 Da) (Aldrich) was reacted with 0.42 g of potassium bicarbonate (KHCO3) (4.19 mmol of potassium) (Aldrich) to obtain 2.98 g of partially neutralized polyacrylic acid in the form of a flaky white solid. When the sample was analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry) as described in Example 1, a potassium content equal to 5% was shown, which corresponded to approximately 10% of the neutralized -COOH groups, i.e., those converted to -COO - K + -.

Example

[0077] Preparation of polyacrylic acid partially neutralized with potassium (PAK20) Polyacrylic acid partially neutralized with cesium (PAK20) was prepared as described in Example 1. The only difference was due to using different amounts of potassium carbonate (KHCO3).

[0078] For this purpose, 3.07 g of polyacrylic acid (monomer unit is 42.6 mmol) (weight average molecular weight (M w ) = 1,800 Da) (Aldrich) was reacted with 0.84 g of potassium carbonate (KHCO3) (8.39 mmol of potassium) (Aldrich), and 2.68 g of partially neutralized polyacrylic acid in the form of a flaky white solid was obtained. The sample was analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry) as described in Example 1, and a potassium content equal to 9.4% was shown, which corresponded to approximately 20% of the neutralized -COOH groups, i.e., -COO - K + converted to,

Example

[0079] Preparation of polyacrylic acid partially neutralized with potassium (PAK30) Polyacrylic acid partially neutralized with cesium (PAK30) was prepared as described in Example 1. The only difference was due to using different amounts of potassium carbonate (KHCO3).

[0080] For this purpose, 3.07 g of polyacrylic acid (monomer unit is 42.6 mmol) (weight average molecular weight (M w) = 1,800 Da) (Aldrich) was reacted with 1.26 g of potassium bicarbonate (KHCO3) (12.59 mmol of potassium) (Aldrich) to obtain 2.68 g of partially neutralized polyacrylic acid in the form of a flaky white solid. When the sample was analyzed by ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry) as described in Example 1, a potassium content equal to 12.3% was shown, which corresponded to approximately 30% of the neutralized -COOH groups, i.e., those converted to -COO - K + converted to.

Example

[0081] Fabrication of Perovskite Solar Cells For this purpose, a perovskite solar cell was fabricated on an ITO indium tin oxide (KT18086-1 from Kintec) coated and patterned glass substrate (dimensions 15 × 15 × 1 mm; surface resistance equal to 12 Ω / cm 2 resistance surface)), and was pre-treated with a cleaning procedure consisting of manual wiping with a lint-free cloth dipped in a cleaning agent diluted with deionized water. Subsequently, the substrate was rinsed with deionized water. Subsequently, the substrate was carefully cleaned by the following consecutive methods: in order (i) deionized water + cleaning agent (followed by manual drying with a lint-free cloth), (ii) distilled water [followed by manual drying with a lint-free cloth], (iii) acetone (Aldrich) and (iv) an ultrasonic bath in isopropanol (Aldrich). In particular, the substrate was placed in a beaker containing the solvent, placed in the ultrasonic bath, maintained at 40 °C and treated for 10 minutes. After treatments (iii) and (iv), the substrate was dried with a stream of compressed nitrogen.

[0082] Subsequently, the glass / ITO was further cleaned by treatment in an ozone device (UV Ozone Cleaning System EXPO3 - Astel) immediately before proceeding to the next step.

[0083] The substrate processed in this way was ready to deposit a layer based on a hole transport material (hole transport layer - HTL). For this purpose, a solution of poly[bis(4-butylphenyl)bisphenylbenzidine] (Poly-TPD) (Aldrich) in chlorobenzene (purity 99.5% - Aldrich) equal to a concentration of 1.5 mg / ml was deposited by spin coating carried out at a rotation speed of 4,000 rpm (acceleration equal to 500 rpm / second) for 60 seconds. Everything was subjected to a heat treatment (annealing) at 110 °C for 30 minutes. The thickness of the layer based on the hole transport material (hole transport layer - HTL) was found to be equal to 40 nm.

[0084] On the substrate thus obtained, a material useful for improving wettability was deposited. For this purpose, a solution of poly[(9,9-bis(3’-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) (Aldrich) in methanol (purity 99.5% - Aldrich) at a concentration of 0.1 mg / ml was deposited by spin coating carried out at a rotation speed of 5,000 rpm (acceleration equal to 1,000 rpm / second) for 40 seconds, and then the whole was subjected to a heat treatment (annealing) at 100 °C for 5 minutes.

[0085] Subsequently, the obtained substrate was placed in a dry box, and a layer of methylammonium lead iodide (CH3NH3PbI3) and polyacrylic acid partially neutralized with cesium (PACs5) obtained in Example 1 was deposited on a layer based on a material useful for improving wettability as follows. For this purpose, lead iodide (PbI2) (ultra-dry purity 99.999% - Alfa Aesar) (350.5 mg - 0.76 mmol), methylammonium iodide (MAI) (CH3NH3I) (GreatCell Solar) (120.8 mg - 0.76 mmol), and polyacrylic acid partially neutralized with cesium (PACs5) (23.6 mg) were dissolved in anhydrous dimethyl sulfoxide (purity 99.9% - Aldrich) (1 ml). The dissolution was carried out at a temperature of 80 °C for 3 hours with stirring, to obtain a solution containing 30 wt% of the perovskite precursor and 1.5 wt% of polyacrylic acid partially neutralized with cesium (PACs5), that is, a solution containing 5 wt% of polyacrylic acid partially neutralized with cesium (PACs5) with respect to the total weight of the other solid components (i.e., lead iodide (PbI2) + methylammonium iodide (MAI) (CH3NH3I)). The solution thus obtained was deposited on the layer based on the material useful for improving wettability described above by spin coating carried out at a rotational speed equal to 5,000 rpm (acceleration equal to 1,000 rpm / second) for 20 seconds, and the whole was subjected to a heat treatment (annealing) at 100 °C for 20 minutes. The thickness of the perovskite and polyacrylic acid (PAA) layer was found to be 325 nm.

[0086] The substrate thus obtained was ready for depositing a layer based on an electron transport material (electron transport layer - ETL). For this purpose, [6,6]-phenyl-C 61 -butyric acid methyl ester (PC 61The filtered solution of BM)(Nano-C Products)(25 mg) was deposited by spin coating performed at a rotational speed equal to 1,000 rpm (acceleration equal to 500 rpm / sec) for 60 seconds. The obtained substrate was left standing at room temperature (25 °C) for 10 minutes. The thickness of the layer based on the electron transport material (electron transport layer - HTL) was found to be equal to 50 nm.

[0087] The substrate thus obtained was ready for depositing a layer based on the hole blocking material (hole blocking layer - HBL). For this purpose, a solution of 2,9 - dimethyl - 4,7 - diphenyl - 1,10 - phenanthroline (bathocuproine - BCP) (purity 96% - Aldrich) (9 mg) in anhydrous isopropyl alcohol (purity 99.5% - Aldrich) (18 ml) obtained by stirring at 80 °C for 3 hours was deposited by spin coating performed at a rotational speed equal to 6,000 rpm (acceleration equal to 1,000 rpm / sec) for 20 seconds, and the obtained substrate was left standing at room temperature (25 °C) for 5 minutes. The thickness of the layer based on the hole blocking material (hole blocking layer - HBL) was found to be equal to 5 nm.

[0088] Subsequently, a back contact (cathode) in metallic aluminum (Al) was deposited on the above - mentioned layer based on the hole blocking material (hole blocking layer - HBL) by evaporation. For this purpose, an evaporator from Kurt J. Lesker was used, operated at a pressure equal to 2×10 -6 mmHg and a rate equal to 0.1 angstrom / sec, and the area of the solar cell was appropriately masked to obtain an active area equal to 4 mm 2 The thickness of the back contact (cathode) in metallic aluminum (Al) was found to be equal to 50 nm.

[0089] The thickness was measured by scanning electron microscopy using a JEOL 7600f scanning electron microscope (SEM) equipped with a field emission electron gun operated at an accelerating voltage in the range of 1 kV to 5 kV and utilizing the signal generated from secondary electrons.

[0090] The electrical characteristics of the perovskite solar cell thus obtained were evaluated at room temperature (25 °C). The current-voltage density (JV) curve was obtained using a Keithley (trademark) 2400 digital multimeter connected to a personal computer for data collection. The photocurrent was measured by exposing the solar cell to the light of a Newport 91160A solar simulator (Newport Corp) placed at a distance of 10 mm from the solar cell, equipped with a 300 W xenon light source and using illumination equal to 100 mm × 100 mm. The characteristic parameters are shown as average values in Table 1.

[0091] The light intensity was calibrated using a standard silicon solar cell (VLSI Standard Co., Ltd. - SRC-100-RTD-KG5).

[0092] In particular, Table 1 shows the reference example number, the composition of the photoactive layer of perovskite and partially neutralized polyacrylic acid, FF (fill factor - curve factor), Voc (open-circuit voltage), Jsc (short-circuit photocurrent density), and PCE (power conversion efficiency) in this order.

Example

[0093] Fabrication of Perovskite Solar Cell The perovskite solar cell was obtained using the same procedure as described in Example 9. The only differences were the use of a perovskite precursor and the use of partially neutralized polyacrylic acid containing different amounts of cesium.

[0094] For this purpose, lead iodide (PbI2) (ultra-dry purity 99.999% - Alfa Aesar) (350.5 mg - 0.76 mmol), methylammonium iodide (MAI) (CH3NH3I) (GreatCell Solar) (120.8 mg - 0.76 mmol), and polyacrylic acid partially neutralized with cesium (PACs10) (23.6 mg) obtained in Example 2 were dissolved in anhydrous dimethyl sulfoxide (purity 99.9% - Aldrich) (1 ml). The dissolution was carried out at a temperature of 80 °C for 3 hours under stirring to obtain a solution containing 30 wt% perovskite precursor and 1.5 wt% polyacrylic acid partially neutralized with cesium (PACs10), that is, a solution containing polyacrylic acid partially neutralized with cesium (PACs10) at 5 wt% with respect to the total weight of the other solid components (i.e., lead iodide (PbI2) + methylammonium iodide (MAI)(CH3NH3I)).

[0095] The electrical characteristics of the obtained perovskite solar cell were evaluated as described above. The characteristic parameters are listed in Table 1 as average values.

Example

[0096] Fabrication of Perovskite Solar Cell A perovskite solar cell was obtained using the same procedure as reported in Example 9. The only difference was the use of a perovskite precursor and a partially neutralized polyacrylic acid containing a different amount of cesium.

[0097] For this purpose, lead iodide (PbI2) (ultra-dry purity 99.999% - Alfa Aesar) (350.5 mg - 0.76 mmol), methylammonium iodide (MAI) (CH3NH3I) (GreatCell Solar) (120.8 mg - 0.76 mmol), and polyacrylic acid partially neutralized with cesium (PACs20) obtained in Example 3 (23.6 mg) were dissolved in anhydrous dimethyl sulfoxide (purity 99.9% - Aldrich) (1 ml). The dissolution was carried out at a temperature of 80 °C for 3 hours under stirring to obtain a solution containing 30 wt% perovskite precursor and 1.5 wt% polyacrylic acid partially neutralized with cesium (PACs20), that is, a solution containing polyacrylic acid partially neutralized with cesium (PACs20) at 5 wt% with respect to the total weight of the other solid components (i.e., lead iodide (PbI2) + methylammonium iodide (MAI) (CH3NH3I)).

[0098] The electrical characteristics of the obtained perovskite solar cell were evaluated as described above. The characteristic parameters are listed in Table 1 as average values.

Example

[0099] Fabrication of Perovskite Solar Cell The perovskite solar cell was obtained using the same procedure as reported in Example 9. The only difference is the use of a perovskite precursor and a partially neutralized polyacrylic acid containing a different amount of cesium.

[0100] For this purpose, lead iodide (PbI2) (ultra-dry purity 99.999% - Alfa Aesar) (350.5 mg - 0.76 mmol), methylammonium iodide (MAI) (CH3NH3I) (GreatCell Solar) (120.8 mg - 0.76 mmol), and polyacrylic acid partially neutralized with cesium (PACs40) obtained in Example 4 (23.6 mg) were dissolved in anhydrous dimethyl sulfoxide (purity 99.9% - Aldrich) (1 ml). The dissolution was carried out at a temperature of 80 °C for 3 hours under stirring to obtain a solution containing 30 wt% perovskite precursor and 1.5 wt% polyacrylic acid partially neutralized with cesium (PACs40), that is, a solution containing polyacrylic acid partially neutralized with cesium (PACs40) at 5 wt% with respect to the total weight of the other solid components (i.e., lead iodide (PbI2) + methylammonium iodide (MAI) (CH3NH3I)).

[0101] The electrical characteristics of the obtained perovskite solar cells were evaluated as described above. The characteristic parameters are listed in Table 1 as average values.

[0102]

Table 1

[0103] From the data listed in Table 1, it can be seen that the perovskite solar cell for the purpose of the present invention has good power conversion efficiency (PCE) (i.e., PCE > 10%) and good electrical characteristics, that is, good values of FF (fill factor), Voc (open-circuit voltage), and Jsc (short-circuit photocurrent density).

Example

[0104] Fabrication of Perovskite Solar Cells Perovskite solar cells were obtained using the same procedure as reported in Example 9. The only difference is the use of the perovskite precursor and the use of polyacrylic acid partially neutralized with potassium.

[0105] For this purpose, lead iodide (PbI2) (ultra-dry purity 99.999% - Alfa Aesar) (350.5 mg - 0.76 mmol), methylammonium iodide (MAI) (CH3NH3I) (GreatCell Solar) (120.8 mg - 0.76 mmol), and partially neutralized polyacrylic acid with potassium (PAK5) (23.6 mg) obtained in Example 5 were dissolved in anhydrous dimethyl sulfoxide (purity 99.9% - Aldrich) (1 ml). The dissolution was carried out at a temperature of 80 °C for 3 hours with stirring to obtain a solution containing 30 wt% perovskite precursor and 1.5 wt% polyacrylic acid partially neutralized with potassium (PAK5), that is, a solution containing polyacrylic acid partially neutralized with potassium (PAK5) at 5 wt% with respect to the total weight of the other solid components (i.e., lead iodide (PbI2) + methylammonium iodide (MAI) (CH3NH3I)).

[0106] The electrical characteristics of the obtained perovskite solar cell were evaluated as described above. The characteristic parameters are listed in Table 2 as average values.

[0107] In particular, Table 2 shows the reference example number, the composition of the photoactive layer of the perovskite and the partially neutralized polyacrylic acid, FF (fill factor), Voc (open-circuit voltage), Jsc (short-circuit photocurrent density), and PCE (power conversion efficiency) in this order.

Example

[0108] Fabrication of Perovskite Solar Cell The perovskite solar cell was obtained using the same procedure as reported in Example 9. The only difference is the use of a perovskite precursor and a partially neutralized polyacrylic acid containing a different amount of potassium from that in Example 13.

[0109] For this purpose, lead iodide (PbI2) (ultra-dry purity 99.999% - Alfa Aesar) (350.5 mg - 0.76 mmol), methylammonium iodide (MAI) (CH3NH3I) (GreatCell Solar) (120.8 mg - 0.76 mmol), and polyacrylic acid partially neutralized with potassium (PAK10) (23.6 mg) obtained in Example 6 were dissolved in anhydrous dimethyl sulfoxide (purity 99.9% - Aldrich) (1 ml). The dissolution was carried out at a temperature of 80 °C for 3 hours under stirring to obtain a solution containing 30 wt% perovskite precursor and 1.5 wt% polyacrylic acid partially neutralized with potassium (PAK10), that is, a solution containing polyacrylic acid partially neutralized with potassium (PAK10) at 5 wt% based on the total weight of the other solid components (i.e., lead iodide (PbI2) + methylammonium iodide (MAI)(CH3NH3I)).

[0110] The electrical characteristics of the obtained perovskite solar cell were evaluated as described above. The characteristic parameters are listed in Table 2 as average values.

Example

[0111] Fabrication of Perovskite Solar Cell The perovskite solar cell was obtained using the same procedure as reported in Example 9. The only differences were the use of the perovskite precursor, the use of polyacrylic acid partially neutralized with a different amount of potassium from Example 13, and the use of different concentrations based on the total weight of the other solid components (i.e., lead iodide (PbI2) + methylammonium iodide (MAI)(CH3NH3I)).

[0112] For this purpose, lead iodide (PbI2) (ultra-dry purity 99.999% - Alfa Aesar) (350.5 mg - 0.76 mmol), methylammonium iodide (MAI) (CH3NH3I) (GreatCell Solar) (120.8 mg - 0.76 mmol), and polyacrylic acid partially neutralized with potassium (PAK5) obtained in Example 5 (47.2 mg) were dissolved in anhydrous dimethyl sulfoxide (purity 99.9% - Aldrich) (1 ml). The dissolution was carried out at a temperature of 80 °C for 3 hours with stirring to obtain a solution containing 30 wt% of a perovskite precursor and 3.0 wt% of polyacrylic acid partially neutralized with potassium (PAK5), that is, a solution containing polyacrylic acid partially neutralized with potassium (PAK5) at 10 wt% based on the total weight of the other solid components (i.e., lead iodide (PbI2) + methylammonium iodide (MAI) (CH3NH3I)).

[0113] The electrical characteristics of the obtained perovskite solar cell were evaluated as described above. The characteristic parameters are listed in Table 2 as average values.

[0114]

Table 2

[0115] From the data listed in Table 2, it can be seen that the perovskite solar cell, which is the object of the present invention, has good power conversion efficiency (PCE) (i.e., PCE > 10%) and good electrical characteristics, that is, good values of FF (fill factor), Voc (open-circuit voltage), and Jsc (short-circuit photocurrent density).

Claims

1. A perovskite-type photovoltaic cell (or solar cell), wherein the photoactive layer of the perovskite contains at least one partially neutralized polyacrylic acid in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor. A perovskite-type photovoltaic cell (or solar cell).

2. The perovskite-type photovoltaic cell (or solar cell) according to claim 1, wherein the perovskite is selected from organometallic trihalides represented by the following general formula. ABX ３ (In the formula, A is methylammonium (CH ３ N.H. ３ ＋ ), formamide [CH(NH ２ ) ２ ＋ ], n-butylammonium (C ４ H １２ N ＋ ), tetrabutylammonium (C １６ H ３６ N ＋ ) or mixtures thereof, or A represents a monovalent organic cation such as cesium (Cs ＋ ), rubidium (Rb ＋ ), potassium (K ＋ ), Lithium (Li ＋ ), sodium (Na ＋ ), Copper (Cu ＋ ), silver (Ag ＋ ) or mixtures thereof, or mixtures thereof; B represents divalent metal cations such as lead (Pb ２＋ ), tin (Sn ２＋ ), or mixtures thereof, X represents a halide anion such as iodine (I － ), chlorine (Cl － ), bromine (Br － ), or a mixture thereof, etc.).

3. The perovskite is methylammonium lead iodide (CH ３ NH ３ PbI ３ ), methylammonium lead bromide (CH ３ NH ３ PbBr ３ ), methylammonium lead chloride (CH ３ NH ３ PbCl ３ ), methylammonium lead bromoiodide (CH ３ NH ３ PbI ｘ Br ３－ｘ ), methylammonium lead chloroiodide (CH ３ NH ３ PbI ｘ Cl ３－ｘ ), formamidinium lead iodide [CH(NH ２ )( ２ PbI ３ , formamidinium lead bromide [CH(NH ２ )( ２ PbBr ３ , formamidinium lead chloride [CH(NH ２ )( ２ PbCl ３ , formamidinium lead bromoiodide [CH(NH ２ )( ２ PbI ｘ Br ３－ｘ , formamidinium lead chloroiodide [CH(NH ２ )( ２ PbI ｘ Cl ３－ｘ , methylammonium formamidinium lead iodide [((CH ３ NH ３ )( ｘ CH(NH ２ )( ２ )) １－ｘ PbI ３ , methylammonium formamidinium lead bromide [(CH ３ NH ３ )( ｘ CH(NH ２ )( ２ )) １－ｘ PbBr ３ , methylammonium formamidinium lead chloride [(CH ３ NH ３ ) ｘ (CH(NH ２ ) ２ ) １－ｘ PbCl ３ [(CH ３ NH ３ ) ｘ (CH(NH ２ ) ２ ) １－ｘ PbI ３－ｙ Cl ｙ [(CH ３ NH ３ ) ｘ (CH(NH ２ ) ２ ) １－ｘ PbI ３－ｙ Br ｙ )[(C ４ H １２ NH ３ PbI ３ )[(C １６ H ３６ NPbI ３ )[(C ４ H １２ NH ３ PbBr ３ )[(C １６ H ３６ NPbBr ３ )[(CsPbI ３ )[(RbPbI ３ )[(KPbI ３ )[(Cs[(CH ｘ (CH ３ NH ３ ) １－ｘ PbI ３ )[(K[(CH ｘ (CH ３ NH ３ ) １－ｘ PbI ３ )[(Cs[(CH ｘ (CH ３ NH ３ ) １－ｘ PbI ３－ｙ Cl ｙ , cesium formamido lead iodide [Cs ｘ (CH(NH ２ )) ２ ) １－ｘ PbI ３ , cesium formamido lead bromide [Cs ｘ (CH(NH ２ )) ２ ) １－ｘ PbBr ３ , cesium formamido lead iodochloride [Cs ｘ (CH(NH ２ )) ２ ) １－ｘ PbI ３－ｙ Cl ｙ , methylammonium tin iodide (CH ３ NH ３ SnI ３ ), methylammonium tin bromide (CH ３ NH ３ SnBr ３ ), methylammonium tin bromoiodide (CH ３ NH ３ SnI ｘ Br ３－ｘ ), formamido tin iodide [CH(NH ２ )) ２ SnI ３ , formamido tin bromoiodide [CH(NH ２ )) ２ SnI ｘ Br ３－ｘ , n-butylammonium tin iodide (C ４ H １２ NH ３ SnI ３ ), tetrabutylammonium tin iodide (C １６ H ３６ NSnI ３ ), n-butylammonium tin bromide (C ４ H １２ NH ３ SnBr ３ ), tetrabutylammonium tin bromide (C １６ H ３６ NSnBr ３ ), methylammonium tin lead iodide (CH ３ NH ３ Sn ｘ Pb １－ｘ I ３ ), formamide tin lead iodide [CH(NH ２ ), ２ Sn ｘ Pb １－ｘ I ３ or a mixture thereof, Preferably, methylammonium lead iodide (CH ３ NH ３ PbI ３ ), formamidinium lead iodide [CH(NH ２ ２ PbI ３ , methylammonium formamidinium lead chloroiodide [(CH ３ NH ３ ｘ )(CH(NH ２ ２ １－ｘ PbI ３－ｙ Cl ｙ , cesium methylammonium lead chloroiodide [Cs ｘ (CH ３ NH ３ １－ｘ PbI ３－ｙ Cl ｙ , cesium formamidinium lead chloroiodide [Cs ｘ (CH(NH ２ ２ １－ｘ PbI ３－ｙ Cl ｙ , selected from​​​​​​​ More preferably, it is methylammonium lead iodide (CH ３ NH ３ PbI ３ ). The perovskite-type photovoltaic cell (or solar cell) according to claim 1 or 2.

4. The perovskite-type photovoltaic cell (or solar cell) according to any one of claims 1 to 3, wherein the polyacrylic acid is represented by the following general formula (I). 【Chemical 1】 (In the formula, n and m are integers, the sum of n + m is in the range of 10 to 60,000, preferably in the range of 15 to 15,000, more preferably in the range of 20 to 6,000, the ratio of n:m is in the range of 99:1 to 1:99, preferably in the range of 98:2 to 20:80, more preferably in the range of 95:5 to 50:50, M ＋ represents a monovalent metal cation selected from alkali metals such as lithium (Li ＋ ), sodium (Na ＋ ), potassium (K ＋ ), rubidium (Rb ＋ ), cesium (Cs ＋ ), preferably lithium (Li ＋ ), potassium (K ＋ ), rubidium (Rb ＋ ), cesium (Cs ＋ ), more preferably potassium (K ＋ ), cesium (Cs ＋ ), or other monovalent metals such as copper (Cu ＋ ), silver (Ag ＋ ), gold (Au ＋ ), mercury (Hg ＋ ), thallium (Tl ＋ ), preferably copper (Cu ＋ ), silver (Ag ＋ ), or represents a monovalent metal cation selected from M ＋ is a monovalent cation represented by the general formula (II), [Chemical 2] (In the formula, E represents a nitrogen atom, a phosphorus atom, preferably a nitrogen atom, R １ 、 R ２ 、 R ３ and R ４ are the same as or different from each other, represent a hydrogen atom, or are selected from a linear or branched, saturated or unsaturated alkyl group optionally containing a heteroatom, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group of C １ to C ２０ , preferably C １ to C １２ , or optionally substituted, or R １ and R ２ and / or R ２ and R ３ and / or R ３ and R ４ and / or R ４ and R １ may optionally, together with other atoms to which they are attached, be attached to each other to form a saturated, unsaturated or aromatic ring containing 2 to 12 carbon atoms, a straight-chain or branched, saturated or unsaturated alkyl group containing optionally a heteroatom, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, a trialkylsilyl group or a triarylsilyl group, a dialkylamino group or a diarylamino group, a dialkylphosphine group or a diarylphosphine group, a straight-chain or branched, saturated or unsaturated alkyl group containing C １ to C ２０ , preferably C １ to C １２ , a straight-chain or branched, saturated or unsaturated, optionally substituted alkylene group, an optionally substituted aryloxy group, an optionally substituted thioalkoxyl group or thioaryloxy group, optionally substituted with a cyano group, said ring optionally containing heteroatoms such as oxygen, sulfur, nitrogen, silicon, phosphorus, selenium, preferably oxygen, nitrogen), or １ to C ２０ , preferably C ２ to C １０ a straight-chain or branched, saturated or unsaturated alkyl group, an optionally substituted aryloxy group, an optionally substituted thioalkoxyl group or thioaryloxy group, optionally substituted with a cyano group, said ring optionally containing heteroatoms such as oxygen, sulfur, nitrogen, silicon, phosphorus, selenium, preferably oxygen, nitrogen), or M ＋ is a monovalent cation represented by the general formula (III). [Chemical Formula 3] (In the formula, R ５ represents a hydrogen atom, or represents a halogen atom such as fluorine, chlorine, bromine, iodine, preferably fluorine, chlorine, etc., or C １ to C ２０ , preferably C １ to C １２ selected from a linear or branched, saturated or unsaturated alkyl group optionally containing a heteroatom, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, and R ５ is preferably hydrogen or methyl, R ６ 、 R ７ 、 R ８ and R ９ are the same as or different from each other, represent a hydrogen atom, or are selected from a linear or branched, saturated or unsaturated alkyl group optionally containing a heteroatom, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group of C １ to C ２０ , preferably C １ to C １２ , or an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, and are optionally selected from a linear or branched, saturated or unsaturated alkyl group containing a heteroatom, or R ７ and R ８ and / or R ９ and R １０ may optionally be bonded to each other together with other atoms to which they are bonded to form a saturated, unsaturated or aromatic ring containing 2 to 12 carbon atoms, a linear or branched C １ to C ２０ saturated or unsaturated alkyl group optionally containing heteroatoms, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted cycloalkyl group, optionally substituted heterocyclic group, trialkylsilyl group or triarylsilyl group, dialkylamino group or diarylamino group, dialkylphosphine group or diarylphosphine group, C １ to C ２０ preferably C ２ to C １０ linear or branched, saturated or unsaturated alkoxy group, optionally substituted aryloxyl group, optionally substituted thioalkoxyl group or thioaryloxyl group, optionally substituted with a cyano group, said ring optionally containing heteroatoms such as oxygen, sulfur, nitrogen, silicon, phosphorus, selenium, preferably oxygen, nitrogen, etc., preferably R ６ R ７ R ８ and R ９ represent a hydrogen atom.)

5. In the partially neutralized polyacrylic acid, the free carboxylic acid groups are present in an amount of 1% to 99%, preferably 20% to 98%, more preferably 50% to 96%, based on the total amount of the carboxylic acid groups present in the polyacrylic acid. The perovskite-type photovoltaic cell (or solar cell) according to any one of claims 1 to 4.

6. The weight average molecular weight (M ｗ ) of the starting polyacrylic acid (i.e., the non-neutralized one) is in the range of 700 Da to 4,000,000 Da, preferably in the range of 1,000 Da to 1,000,000 Da, more preferably in the range of 1,500 Da to 400,000 Da, the perovskite type photovoltaic cell (or solar cell) according to any one of claims 1 to 5.

7. The perovskite-type photovoltaic cell (or solar cell) according to any one of claims 1 to 6, comprising the following layers. The transparent conductive oxide layer (transparent conductive oxide - TCO) that constitutes the anode, generally tin oxide doped with fluorine (SnO ２ :F) (FTO) or a glass substrate coated with indium tin oxide (ITO), and A layer based on a hole transport material (hole transport layer - HTL), preferably a layer of poly[bis(4-butylphenyl)-bisphenylbenzidine] (Poly-TPD), and Optionally, a layer based on a material useful for improving wettability, preferably a layer of poly[9,9-bis(3'-(N,N-dimethyl)-N-ethylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] diiodide (PFN-I) or a layer of poly[9,9-bis(3'-(N,N-dimethyl)-N-ethylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN), and At least one perovskite, preferably methylammonium lead iodide (CH ３ NH ３ PbI ３ ), [methylammonium lead iodide (CH ３ NH ３ PbI ３ ) is the most used structure because it has a high absorption coefficient over the UV and visible spectra, a "band gap" equal to 1.57 eV, which is close to the optimal value for maximizing the conversion efficiency, and a significant diffusion distance (greater than 100 nm) of electrons and electron holes (or holes)] and at least one partially neutralized polyacrylic acid, preferably cesium- or potassium-partially neutralized polyacrylic acid having an amount of free carboxylic acid groups in the range of 60% to 95%, and a photoactive layer comprising A layer based on an electron transport material (electron transport layer - ETL), preferably a layer of [6,6]-phenyl-C ６１ -methyl ester of butyric acid (PC ６１ BM) and Optionally, a layer based on a hole-blocking material (HBL), preferably a layer of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine - BCP) or ethoxylated polyethyleneimine (PEIE), and A metal contact known as a back contact constituting the cathode, preferably a layer of metal gold, silver or aluminum.

8. The perovskite-type photovoltaic cell (or solar cell) according to any one of claims 1 to 7, wherein the electrical energy generated by at least one of the perovskite-type photovoltaic cells (or solar cells) is transported using a wiring system connected to the perovskite-type photovoltaic cell (or solar cell).

9. A method for manufacturing a perovskite-type photovoltaic cell (or solar cell), comprising (a) preparing a glass substrate coated with a transparent conductive oxide layer (transparent conductive oxide - TCO) (anode); (b) depositing a layer based on a hole transport material (hole transport layer - HTL) on the substrate obtained in step (a); (c) optionally, depositing a layer based on a material useful for improving wettability on the base layer of the hole transport material (hole transport layer - HTL) obtained in step (b); (d) preparing a mixture comprising a perovskite precursor and at least one partially neutralized polyacrylic acid, wherein the partially neutralized polyacrylic acid is present in the mixture in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor; (e) depositing the mixture obtained in step (d) on the layer based on the hole transport material (hole transport layer - HTL) obtained in step (b) or on the layer based on the material for improving wettability obtained in step (c) to obtain a photoactive layer. (f) depositing a layer based on an electron transport material (electron transport layer - ETL) on the photoactive layer obtained in the step (e); (g) optionally, depositing a layer based on a hole-blocking material (hole-blocking layer - HBL) on the layer based on the electron transport material (electron transport layer - ETL) obtained in the step (f); (h) depositing a metal contact known as a back contact constituting a cathode on the layer based on the electron transport material (electron transport layer - ETL) obtained in the step (f) or on the layer based on the hole-blocking material (hole-blocking layer - HBL) obtained in the step (g); A method, including the steps above, wherein the steps (b), (c), (e), (f) and (g) are carried out at a temperature below 120 °C, preferably in the range of 20 °C to 115 °C.

10. Use of the perovskite photovoltaic cell (or solar cell) according to any one of claims 1 to 8 in a building-integrated solar power generation system (building-integrated photovoltaics - BIPV), a solar power generation window, a greenhouse, a photo-bioreactor, a sound insulation wall, lighting engineering, design, advertising, and the automotive industry.

11. A composition comprising at least one perovskite and at least one partially neutralized polyacrylic acid, wherein the at least one partially neutralized polyacrylic acid is included in an amount of 3% by weight or more, preferably within 4% to 15% by weight, more preferably within 4.5% to 12% by weight, based on the total weight of the perovskite precursor.

12. The composition according to claim 11, wherein the perovskite is selected from the perovskites according to claim 2 or 3, and the partially neutralized polyacrylic acid is selected from the polyacrylic acids according to any one of claims 4 to 6.

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