Perovskite precursor solution, perovskite thin film, preparation method of perovskite thin film, photoelectric device and electric device

Abstract

The invention relates to the technical field of photoelectric devices, in particular to a perovskite precursor solution, a perovskite thin film, a preparation method of the perovskite thin film, a photoelectric device and an electric device. The perovskite precursor solution comprises a perovskite precursor material, a metal salt and a solvent, the metal salt comprises one or more of rubidium salt and zinc salt, and the metal salt has one or more of the following characteristics: (1) negative ions of the rubidium salt are halide ions; the mass volume concentration of rubidium salt in the perovskite precursor solution is 5 mg / mL-12 mg / mL; (2) anions of the zinc salt comprise one or more of halide ions and organic acid radical ions; the mass volume concentration of the zinc salt in the perovskite precursor solution is 0.05 mg / mL to 10 mg / mL. The rubidium salt and the zinc salt added into the perovskite precursor solution provided by the invention can effectively participate in the crystallization process of the perovskite precursor material, so that the crystallization quality of a perovskite film is improved, defects are reduced, and the photoelectric property of a photoelectric device is improved.

Description

Technical Field

[0001] The present application relates to the technical field of optoelectronic devices, and in particular to a perovskite precursor solution, a perovskite film and a preparation method thereof, an optoelectronic device, and an electrical device. Background Art

[0002] Benefiting from the wide bandgap adjustability and solution low-temperature processing characteristics, wide-bandgap perovskite solar cells are considered to be ideal top cells for tandem solar cells and have received widespread attention.

[0003] In order to prepare high-performance perovskite solar cells, lead bromide (PbBr2) is generally doped into perovskite films. Although the addition of lead bromide can adjust the band gap of perovskite solar cells, when preparing perovskite films, there are differences in crystallization between lead bromide and perovskite materials, which will destroy the crystallization balance of perovskite films and have a negative impact on device performance. Summary of the invention

[0004] Based on this, the present application provides a perovskite precursor solution, a perovskite film and a preparation method thereof, an optoelectronic device, and an electrical device. The rubidium salt and the zinc salt added to the perovskite precursor solution provided in the present application can effectively participate in the crystallization process of the perovskite precursor material to improve the crystallization quality of the perovskite film and reduce defects, thereby improving the optoelectronic performance of the optoelectronic device.

[0005] In a first aspect of the present application, a perovskite precursor solution is provided, the perovskite precursor solution comprising a perovskite precursor material, a metal salt and a solvent; the metal salt comprises one or more of a rubidium salt and a zinc salt, wherein the metal salt has one or more of the following characteristics:

[0006] (1) The anion of the rubidium salt is a halogen ion; the mass volume concentration of the rubidium salt in the perovskite precursor solution is 5 mg / mL to 12 mg / mL;

[0007] (2) The anion of the zinc salt includes one or more of a halogen ion and an organic acid ion; and the mass volume concentration of the zinc salt in the perovskite precursor solution is 0.05 mg / mL to 10 mg / mL.

[0008] In one embodiment, the organic acid ion is selected from one or more ions having structural features shown in formula (I-1) to formula (I-2):

[0009] and ;

[0010] Wherein, R1 is selected from C1~C6 alkyl or ; R2 is selected from a single bond or a C1~C6 alkylene group; R3 is selected from H or a C1~C6 alkyl group, and n is selected from any integer from 1 to 5.

[0011] In one embodiment, the zinc salt includes a zinc salt whose anion is an organic acid ion.

[0012] In one embodiment, the perovskite precursor solution has one or more of the following characteristics:

[0013] (1) The rubidium salt includes one or more of RbCl, RbBr and RbI;

[0014] (2) The zinc salt includes one or more of ZnCl2, ZnBr2, ZnI2, zinc gluconate and zinc 4-methylbenzoate.

[0015] In one embodiment, the perovskite film has one or more of the following characteristics:

[0016] (1) The perovskite precursor material includes AX material and BX2 material; wherein A includes FA + 、MA + , Cs + and K + One or more of, B includes Pb 2+ , Cu 2+ , Ga 2+ , Ca 2+ Sn 2+ and Ge 2+ One or more of, each occurrence of X is independently selected from Cl - Br - ,I - and SCN - One or more of;

[0017] (2) The perovskite precursor solution includes the rubidium salt and the zinc salt.

[0018] A second aspect of the present application provides a method for preparing a perovskite film, comprising the following steps:

[0019] forming a perovskite precursor film on a substrate using a perovskite precursor solution;

[0020] After annealing the perovskite precursor film, the perovskite film is prepared;

[0021] Wherein, the perovskite precursor solution is the perovskite precursor solution described in any embodiment of the first aspect of the present application.

[0022] The third aspect of the present application provides a perovskite film prepared by the preparation method described in the second aspect of the present application.

[0023] In one embodiment, the perovskite film has one or more of the following characteristics:

[0024] (1) The thickness of the perovskite film is 10 nm to 100 μm;

[0025] (2) The band gap of the perovskite film is 0.9 eV ~3 eV.

[0026] According to a fourth aspect of the present application, a photoelectric device is provided, wherein the photoelectric device comprises a perovskite film, wherein the perovskite film is the perovskite film described in the third aspect of the present application or a perovskite film prepared by the preparation method described in the second aspect of the present application.

[0027] In one embodiment, the optoelectronic device comprises a stacked perovskite top cell, an intermediate layer and a crystalline silicon bottom cell, wherein the perovskite top cell comprises the perovskite film;

[0028] Optionally, the perovskite top cell includes a self-assembled small molecule layer, the perovskite film, a passivation layer and an electron transport layer which are sequentially stacked in a direction from the crystalline silicon bottom cell to the middle layer.

[0029] In one embodiment, the perovskite top cell has one or more of the following features:

[0030] (1) The material of the self-assembled small molecule layer includes one or more of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] and 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline;

[0031] (2) The material of the passivation layer includes one or more of 2-phenylethylamine hydrochloride, 4-trifluoromethyl-aniline hydrochloride, 2-thiopheneethylamine hydrochloride, ethylamine hydrochloride, n-butylamine hydrochloride, phenylethylamine iodine, octylamine iodine and 1,4-phenylenediamine hydroiodide;

[0032] (3) The material of the electron transport layer includes one or more of titanium dioxide, tin dioxide, indium oxide, zinc oxide, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, fullerene derivatives, graphene and graphene derivatives.

[0033] The fifth aspect of the present application provides an electrical device, comprising the optoelectronic device described in the fourth aspect of the present application.

[0034] The perovskite precursor solution provided in this application has at least the following beneficial effects:

[0035] At least one of the rubidium salt and the zinc salt added to the perovskite precursor solution of the present application can effectively improve the crystallization quality of the perovskite. Among them, the rubidium salt can improve the crystallization quality of the perovskite precursor material, promote the crystal growth of the perovskite material and reduce the grain boundary and vacancy defects, and reduce the scattering and recombination of carriers at the defects. At the same time, a specific type of zinc salt can suppress the defect state density in the formed perovskite film, reduce the non-radiative recombination of carriers, and enhance the stability of the film. Therefore, the perovskite precursor solution of the present application can effectively improve the crystallization quality of the perovskite film and reduce defects, and improve the photoelectric properties such as the open circuit voltage and photoelectric conversion efficiency of the photoelectric device. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0037] Figure 1 A schematic diagram of the structure of a perovskite / crystalline silicon tandem solar cell provided as an example of the present application;

[0038] Figure 2 A schematic diagram of the structure of a perovskite top cell provided as an example of this application;

[0039] Figure 3 A schematic diagram of the structure of a crystalline silicon bottom cell provided as an example of the present application;

[0040] Figure 4 A schematic structural diagram of a perovskite / crystalline silicon tandem solar cell provided as another example of the present application;

[0041] Figure 5 A schematic diagram of the structure of a perovskite solar cell provided as an example of the present application.

[0042] In the figure, perovskite top cell -10, middle layer -20, crystalline silicon bottom cell -30, self-assembled small molecule layer -101, perovskite film -102, passivation layer -103, electron transport layer -104, transparent conductive layer -105, front electrode -106, anti-reflection layer -107, p-type crystalline silicon -301, back electrode -302, first transport layer -A, second transport layer -B. DETAILED DESCRIPTION

[0043] The following is a further complete and clear description of the perovskite precursor solution, the perovskite film and its preparation method, the optoelectronic device, and the electrical device in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0044] In the present application, "alkyl" may represent a straight chain, branched chain and / or cyclic alkyl. Phrases containing this term, for example, "C1-C6 alkyl" refers to an alkyl group containing 1 to 6 carbon atoms, each occurrence of which may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 4-methyl-2-pentyl, n-hexyl or cyclohexyl.

[0045] It can be understood that in the present application, "alkylene" is a subunit derived from "alkyl" by removing a hydrogen atom. The quality of the perovskite film is inseparable from the performance of the light-emitting device. The perovskite film contains a perovskite material, in which the nucleation sites of the perovskite material itself are relatively randomly distributed, and it is difficult to form a uniform and high-density nucleation center. Therefore, some areas of the perovskite film will nucleate too quickly to produce a large number of tiny grains, while other areas will nucleate too slowly or even have nucleation missing, so that the final perovskite film has grain sizes of different sizes and uneven distribution. This uneven grain structure will produce a large number of grain boundaries and cause a variety of defects, which will seriously affect the quality of the film, and then lead to an increase in the scattering and recombination probability of carriers at the grain boundaries, hindering the optimization and improvement of the performance of the light-emitting device.

[0046] In order to regulate the nucleation and crystallization of perovskite films and improve the crystallization quality of perovskite films, the current main approach is to introduce additives into the perovskite precursor solution to control the crystal phase structure and reduce defects during the formation of perovskite materials. Traditional additives mainly include lead bromide and metal thiocyanate. There is a crystallization difference between lead bromide and perovskite materials, which will destroy the crystallization balance of perovskite films and have a negative impact on device performance. Thiocyanate can increase the open circuit voltage of single-junction perovskite cells to 1.3V, and can increase the open circuit voltage of calcium-silicon two-terminal stacked cells to 1.97V, but the light stability of thiocyanate is relatively poor, which will eventually affect the overall performance of optoelectronic devices.

[0047] Based on this, the present application provides a perovskite precursor solution, which includes a perovskite precursor material, a metal salt and a solvent; the metal salt includes one or more of a rubidium salt and a zinc salt.

[0048] Wherein, the anion of the rubidium salt is a halogen ion.

[0049] Wherein, the anion of the zinc salt includes one or more of halogen ions and organic acid radical ions.

[0050] In the present application, "organic acid radical ion" refers to the negatively charged ion portion remaining after the organic acid molecule ionizes the hydrogen ion in the aqueous solution. For example, the organic acid molecule includes a carboxylic acid group. The organic acid radical ion includes COO — .

[0051] In this application, "halogen ion" includes but is not limited to F — , Cl — Br — or I — .

[0052] The rubidium salt and zinc salt added to the perovskite precursor solution of the present application can effectively improve the crystallization quality of perovskite. Among them, the rubidium salt can improve the crystallization quality of the perovskite precursor material, promote the crystal growth of the perovskite material and reduce the grain boundary and vacancy defects, and reduce the scattering and recombination of carriers at the defects. At the same time, the zinc salt can suppress the defect state density in the formed perovskite film, reduce the non-radiative recombination of carriers, and enhance the stability of the film. Therefore, the perovskite precursor solution of the present application can effectively improve the crystallization quality of the perovskite film and reduce defects, and improve the photoelectric properties such as the open circuit voltage and photoelectric conversion efficiency of the photoelectric device.

[0053] In one example, the rubidium salt includes one or more of RbCl, RbBr and RbI.

[0054] In one example, the organic acid radical ion is selected from one or more ions having structural features shown in Formula (I-1) to Formula (I-2):

[0055] and .

[0056] Wherein, R1 is selected from C1~C6 alkyl or . R2 is selected from a single bond or a C1~C6 alkylene group; R3 is selected from H or a C1~C6 alkyl group. n is selected from any integer from 1 to 5. It is understood that the C1~C6 alkyl group may be substituted by a substituent. For example, the substituent of the substituted C1~C6 alkyl group includes halogen, hydroxyl or C1~C3 alkyl. It is understood that when R2 is selected from a single bond, the carboxyl group is directly connected to the benzene ring.

[0057] Further, R1 is selected from -CH3, -CH2CH3, -CH2CH2CH3 or For example, when the anion of the zinc salt is an ion with the structural characteristics shown in formula (I-1), the zinc salt includes zinc acetate (CH3COO)2Zn, zinc propionate (CH3CH2COO)2Zn, zinc butyrate (CH3CH2CH2COO)2Zn and zinc gluconate (CH6H 11 O7)2Zn or more.

[0058] Further, R2 is selected from a single bond, -CH3, -CH2CH3 or -CH2CH2CH3. R3 is selected from H, -CH3, -CH2CH3 or -CH2CH2CH3. For example, when the anion of the zinc salt is an ion with the structural characteristics shown in formula (I-2), the anion is selected from 2-methylbenzoate ion , 3-methylbenzoate ion , 4-methylbenzoate ion , 2-methylphenylacetate ion , 3-methylphenylacetate ion or 4-methylphenylacetate ion When the anion of the zinc salt is an ion having the structural characteristics shown in formula (I-1), the zinc salt includes one or more of 2-methyl benzoic acid zinc, 3-methyl benzoic acid zinc, 4-methyl benzoic acid zinc, 2-methyl phenyl acetate zinc, 3-methyl phenyl acetate zinc and 4-methyl phenyl acetate zinc.

[0059] In one example, the zinc salt includes one or more of ZnCl2, ZnBr2, ZnI2, zinc acetate, zinc propionate, zinc butyrate, zinc gluconate, zinc 2-methylbenzoate, zinc 3-methylbenzoate, zinc 4-methylbenzoate, zinc 2-methylphenylacetate, zinc 3-methylphenylacetate and zinc 4-methylphenylacetate.

[0060] Illustratively, the zinc salt includes one or more of ZnCl2, ZnBr2, ZnI2, zinc gluconate, and zinc 4-methylbenzoate.

[0061] Furthermore, the zinc salt includes a zinc salt whose anion is an organic acid ion.

[0062] The present application finds that when the anion of zinc salt is selected from organic acid radical ions, it has a larger molecular size and steric hindrance, which can effectively suppress the agglomeration in the crystal growth process of perovskite material, make the crystal quality of perovskite film higher, the crystal size is more uniform, reduce the defect state density, thereby improving the photoelectric performance and stability of the film. On the other hand, the interaction between organic acid radical ions and perovskite material lattices is relatively weak, is not easy to cause lattice distortion, is conducive to maintaining the integrity of perovskite structure, and has better chemical stability. And at this time, the synergistic effect of zinc salt and rubidium salt is more excellent, which can effectively improve the photoelectric performance such as open circuit voltage and photoelectric conversion efficiency of photoelectric devices.

[0063] In one example, the perovskite precursor material includes AX material and BX2 material. Wherein A includes FA + 、MA + , Cs + and K + One or more of. B includes Pb 2+ , Cu 2+ , Ga 2+ , Ca 2+ Sn 2+ and Ge 2+ One or more of. X, when it appears each time, is independently selected from Cl - Br - ,I - and SCN - One or more of.

[0064] In one example, in the perovskite precursor solution, the mass volume concentration of the AX material is 200 mg / mL to 300 mg / mL. For example, the mass volume concentration of the AX material includes but is not limited to 200 mg / mL, 220 mg / mL, 240 mg / mL, 260 mg / mL, 280 mg / mL, 285 mg / mL, 290 mg / mL or 300 mg / mL, or any two of the above points as endpoint values.

[0065] In one example, in the perovskite precursor solution, the mass volume concentration of the BX2 material is 700 mg / mL to 800 mg / mL. For example, the mass volume concentration of the BX2 material is 700 mg / mL, 720 mg / mL, 750 mg / mL, 780 mg / mL or 800 mg / mL, or within a range formed by any two of the above point values ​​as endpoint values.

[0066] In one example, the solvent includes one or more of methanol, ethanol, isopropanol, N,N-dimethylformamide and dimethyl sulfoxide.

[0067] In one example, the mass volume concentration of the rubidium salt in the perovskite precursor solution is 5 mg / mL~12 mg / mL. This concentration range is conducive to the uniform dispersion of the rubidium salt in the perovskite precursor solution, ensuring that it is fully mixed and interacted with the perovskite precursor material and other components during the film formation process, thereby effectively regulating the crystal structure and growth orientation of the perovskite material, making the crystal growth more regular and orderly, and reducing the defect state density. At the same time, the appropriate concentration can also enhance the stability of the perovskite film, inhibit ion migration and defect formation. For example, the mass volume concentration of the rubidium salt in the perovskite precursor solution includes but is not limited to 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, 9.5 mg / mL, 9.8 mg / mL, 10 mg / mL, 10.1 mg / mL, 10.5 mg / mL, 11 mg / mL or 12 mg / mL, or any two of the above point values ​​as the range of endpoint values.

[0068] In one example, the mass volume concentration of the zinc salt in the perovskite precursor solution is 0.05 mg / mL to 10 mg / mL. For example, the mass volume concentration of the zinc salt in the perovskite precursor solution includes but is not limited to 0.05 mg / mL, 0.1 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.2 mg / mL, 1.5 mg / mL, 1.8 mg / mL, 2 mg / mL, 4 mg / mL, 6 mg / mL, 8 mg / mL or 10 mg / mL, or any two of the above point values ​​as endpoint values.

[0069] The perovskite precursor solution includes the rubidium salt and the zinc salt.

[0070] In the perovskite precursor solution, limiting the mass volume concentration of the perovskite precursor material, rubidium salt and zinc salt plays a vital role in ensuring the quality of the perovskite film. The appropriate mass volume concentration of the perovskite precursor material, rubidium salt and zinc salt can optimize the crystal structure of the perovskite material, make the perovskite crystal growth more regular and orderly, reduce the defect state density, and thus enhance the absorption of light and the transmission efficiency of carriers; the three can work together to further optimize the photoelectric properties of the perovskite film, and ultimately achieve a significant improvement in the photoelectric conversion efficiency and enhanced stability of the perovskite film.

[0071] A second aspect of the present application provides a method for preparing a perovskite film, comprising the following steps:

[0072] forming a perovskite precursor film on a substrate using a perovskite precursor solution;

[0073] After annealing the perovskite precursor film, the perovskite film is prepared;

[0074] Wherein, the perovskite precursor solution is the perovskite precursor solution described in the first aspect of the present application.

[0075] In one example, the step of forming a perovskite precursor thin film precursor on a substrate using a perovskite precursor solution includes coating and removing a solvent. The coating method includes but is not limited to spin coating, spray coating, slit coating or scraping. The solvent removal method includes but is not limited to heating, anti-solvent, vacuum or flash evaporation.

[0076] In one example, the annealing temperature is 80° C. to 120° C. Specifically, the annealing temperature includes but is not limited to 80° C., 85° C., 90° C., 95° C., 98° C., 100° C., 102° C., 105° C., 110° C. or 120° C.

[0077] In the present application, the method of forming a perovskite precursor film on a substrate using a perovskite precursor solution is preferably a spin coating method.

[0078] A third aspect of the present application provides a perovskite film, which is prepared by the preparation method described in the second aspect of the present application.

[0079] In one example, the thickness of the perovskite film is 10nm~100μm. It is understandable that the thickness of the perovskite film can be selected from any value between 10nm~100μm. For example, the thickness of the perovskite film includes but is not limited to 10nm, 30 nm, 50 nm, 80 nm, 1μm, 10μm, 20μm, 30μm, 50μm, 80μm, 90μm or 100μm, or within the range of any two of the above point values. The thickness of the perovskite film is limited to the above range, which can achieve rapid carrier transport, reduce the probability of carrier recombination, and improve the photoelectric conversion efficiency; at the same time, it can increase the light absorption path, improve the light absorption efficiency, and thus enhance the ability to utilize sunlight.

[0080] In one example, the band gap of the perovskite film is 0.9 eV ~3eV. The band gap range of the perovskite film plays an important role in its absorption of visible light and near-infrared light, improving light absorption efficiency; and reducing the recombination probability of electrons and holes, and improving the photoelectric conversion efficiency and photovoltaic performance of the perovskite film. For example, the band gap of the perovskite film includes but is not limited to 0.9eV, 1 eV, 1.2 eV, 1.4 eV, 1.6 eV, 1.8 eV, 2 eV, 2.2 eV, 2.5 eV, 2.8 eV or 3 eV, or any two of the above point values ​​as endpoint values.

[0081] According to a fourth aspect of the present application, a photoelectric device is provided, which includes a perovskite film, wherein the perovskite film is the perovskite film described in any example of the third aspect of the present application or a perovskite film prepared by the preparation method according to the second aspect of the present application.

[0082] The optoelectronic devices mentioned in this application include but are not limited to perovskite solar single junction cells and perovskite tandem cells. For example, the perovskite tandem cell is a perovskite / perovskite tandem solar cell, a perovskite / crystalline silicon tandem solar cell or a perovskite / CIGS tandem solar cell.

[0083] See also Figure 1 In one example, the optoelectronic device is a perovskite / crystalline silicon stacked solar cell. The optoelectronic device includes a stacked perovskite top cell 10, an intermediate layer 20, and a crystalline silicon bottom cell 30. The perovskite top cell includes a perovskite film. The perovskite film is the perovskite film described in the third aspect of the present application.

[0084] See also Figure 2 In one example, the perovskite top cell 10 includes a self-assembled small molecule layer 101, a perovskite film 102, a passivation layer 103 and an electron transport layer 104 which are stacked in sequence from the crystalline silicon bottom cell 30 to the intermediate layer 20.

[0085] In one example, the material of the self-assembled small molecule layer 101 includes one or more of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] and 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline;

[0086] In one example, the material of the passivation layer 103 includes one or more of 2-phenylethylamine hydrochloride, 4-trifluoromethyl-aniline hydrochloride, 2-thiopheneethylamine hydrochloride, ethylamine hydrochloride, n-butylamine hydrochloride, phenylethylamine iodine, octylamine iodine and 1,4-phenylenediamine hydroiodide;

[0087] In one example, the material of the electron transport layer 104 includes one or more of titanium dioxide, tin dioxide, indium oxide, zinc oxide, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, fullerene derivatives, graphene, and graphene derivatives.

[0088] In one example, the perovskite top cell 10 further includes a stacked transparent conductive layer 105, a front electrode 106 and an anti-reflection layer 107. The transparent conductive layer 105 is disposed on a surface of the electron transport layer 104 that is away from the passivation layer 103.

[0089] In one example, the material of the transparent conductive layer 105 includes one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), indium-doped zinc oxide (IZO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped tungsten oxide (IWO), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyimide (PI) and polydimethylsiloxane (PDMS).

[0090] In one example, the material of the front electrode 106 includes one or more of gold (Au), silver (Ag), copper (Cu), aluminum (Al), titanium (Ti), nickel (Ni), and molybdenum (Mo).

[0091] In one example, the material of the anti-reflection layer 107 includes metal fluoride. For example, the metal fluoride includes one or more of MgF2 and CaF2.

[0092] In one example, the perovskite top cell 10 includes a self-assembled small molecule layer 101, a perovskite film 102, a passivation layer 103, an electron transport layer 104, a transparent conductive layer 105, a front electrode 106 and an anti-reflection layer 107 stacked in a direction away from the intermediate layer 20.

[0093] In one example, the material of the intermediate layer includes one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), indium-doped zinc oxide (IZO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO) and indium-doped tungsten oxide (IWO).

[0094] See also Figure 3 In one example, the crystalline silicon bottom cell 30 includes a p-type crystalline silicon 301 and a back electrode 302 stacked along the direction of the intermediate layer 20 .

[0095] In one example, the material of the back electrode 302 includes one or more of gold (Au), silver (Ag), copper (Cu), aluminum (Al), titanium (Ti), nickel (Ni), and molybdenum (Mo).

[0096] See also Figure 4In one example, the optoelectronic device includes an anti-reflection layer 107, a front electrode 106, a transparent conductive layer 105, an electron transport layer 104, a passivation layer 103, a perovskite film 102, a self-assembled small molecule layer 101, an intermediate layer 20, p-type crystalline silicon 301 and a back electrode 302 stacked in a direction from a light-receiving surface to a backlight surface.

[0097] The optoelectronic device provided in the present application can improve the photoelectric conversion efficiency, carrier collection efficiency, and overall stability and reliability of the device under the synergistic effect of various layers, so that the optoelectronic device has excellent photoelectric performance and a longer service life.

[0098] For example, see Figure 5 The perovskite solar cell comprises a transparent conductive layer 105, a perovskite film 102 and a back electrode 302. The perovskite film 102 is disposed between the transparent conductive layer 105 and the back electrode 302.

[0099] The perovskite solar cell includes a transparent conductive layer 105, a first transmission layer A, a perovskite film 102, a second transmission layer B and a back electrode 302 which are stacked in sequence.

[0100] In one example, the first transport layer A is an electron transport layer, and the second transport layer B is a hole transport layer.

[0101] In another example, the first transport layer A is a hole transport layer, and the second transport layer B is an electron transport layer.

[0102] It can be understood that the material of the transparent conductive layer can be the same as the material in the aforementioned stacked battery, so it will not be described in detail here.

[0103] In one example, the material of the electron transport layer 104 may be the same as the material in the aforementioned stacked battery, so it will not be described in detail here.

[0104] In one example, the hole transport layer includes cuprous thiocyanate (CuSCN), cuprous iodide (CuI), nickel oxide (NiO x ), molybdenum oxide (MoO x ), tungsten oxide (WO x), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz) and its derivatives, 4-(2,7-dibromo-9,9-dimethylacridine-10(9H)-yl)butyl)phosphonic acid and its derivatives and self-assembled monolayer SAM materials. For example, the self-assembled monolayer SAM material includes one or more of carbazole and porphyrin materials.

[0105] In one example, the material of the back electrode 302 may be the same as that of the aforementioned stacked battery, so it will not be described in detail here.

[0106] In one example, the preparation method of the electron transport layer and the hole transport layer includes one or more of the thin film preparation methods such as spin coating, slit coating, blade coating, screen printing, inkjet printing, evaporation, magnetron sputtering, physical vapor deposition (PVD), etc. Optionally, the preparation methods of the electron transport layer and the hole transport layer may be the same or different. In the fifth aspect of the present application, an electrical device is provided, including the optoelectronic device described in the fourth aspect of the present application.

[0107] The following further specific examples are provided to explain the present application in detail. It should also be understood that the following examples are only used to further explain the present application and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present application belong to the scope of protection of the present application. The specific process parameters of the following embodiments are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not necessarily limited to the specific values ​​of the embodiments below.

[0108] Example 1

[0109] Embodiment 1 of the present application provides a photoelectric device and a method for preparing the same.

[0110] Structure of optoelectronic devices: see Figure 4 The optoelectronic device includes an anti-reflection layer 107, a front electrode 106, a transparent conductive layer 105, an electron transport layer 104, a passivation layer 103, a perovskite film 102, a self-assembled small molecule layer 101, an intermediate layer 20, a p-type crystalline silicon 301 and a back electrode 302 stacked from the light receiving surface to the back light surface.

[0111] The method for preparing a photoelectric device comprises the following steps:

[0112] (1) An ITO intermediate layer 20 (thickness of about 15 nm) is sputtered on a p-type crystalline silicon 301 substrate (thickness of about 1 μm) having a velvet pyramid structure.

[0113] (2) A self-assembled small molecule layer 101 is prepared on the ITO intermediate layer 20 by a one-step spin coating method; wherein the material of the self-assembled small molecule layer 101 is (4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid, and the thickness is about 1 nm.

[0114] (3) Preparation of perovskite precursor solution: 22.1 mg CsI, 28.6 mg MABr, 233.9 mg FAI, 190.9 mg PbBr2 and 559.6 mg PbI2 were added to 1 mL of a DMF and DMSO mixed solvent (the volume ratio of DMF to DMSO was 4:1), and then 10 mg of rubidium salt RbI and 1 mg of zinc salt zinc gluconate (C6H 11 O7)2Zn was stirred on a magnetic stirrer at a rotation speed of 600 rpm for 8 h and filtered to obtain a perovskite precursor solution.

[0115] (4) Take 100 μL of the perovskite precursor solution and spin coat it at a speed of 600 rpm / min and an acceleration of 1000 rpm / s for 6 seconds for the first spin coating treatment; then spin coat it at a speed of 2000 rpm / min and an acceleration of 1000 rpm / s for 50 seconds for the second spin coating treatment; finally, spin coat it at a speed of 6000 rpm / min and an acceleration of 1000 rpm / s for 15 seconds for the third spin coating treatment, and coat the perovskite precursor solution on the surface of the self-assembled small molecule layer 101. At the beginning of the third spin coating treatment, 300 μL of anti-solvent (ether) is added dropwise. After completion, it is transferred to an annealing hot plate and heated at 100°C for 30 minutes to complete annealing; to form a perovskite film 102 (thickness is about 600 nm).

[0116] (5) Spin-coating a passivation layer 103 on the perovskite film 102; wherein the material of the passivation layer 103 is 1,4-phenylenediamine hydroiodide (PDADI) with a thickness of about 1 nm.

[0117] (6) A 15 nm thick C60 layer is prepared by thermal evaporation; and a 15 nm thick SnO2 layer is prepared by thermal evaporation to prepare the electron transport layer 104.

[0118] (7) Magnetron sputtering is used to prepare IZO with a thickness of 30 nm to prepare the transparent conductive layer 105.

[0119] (8) Double-sided Ag electrodes with a thickness of 400 nm were prepared on the transparent conductive layer 105 and the p-type crystalline silicon 301 substrate respectively by thermal evaporation to obtain the front electrode 106 and the back electrode 302 .

[0120] (9) A MgF2 anti-reflection layer 107 with a thickness of 130 nm is prepared on the surface of the front electrode 106 by thermal evaporation.

[0121] Example 2

[0122] The structure of the optoelectronic device is the same as that of Example 1.

[0123] Preparation method of photoelectric device: Same as Example 1. The main difference is that the type of zinc salt included in the perovskite precursor solution in step (4) of Example 2 is zinc chloride (ZnCl2).

[0124] Example 3

[0125] The structure of the optoelectronic device is the same as that of Example 1.

[0126] Preparation method of photoelectric device: Same as Example 1. The main difference is that the type of zinc salt included in the perovskite precursor solution in step (4) of Example 3 is zinc 4-methylbenzoate.

[0127] Example 4

[0128] The structure of the optoelectronic device is the same as that of Example 1.

[0129] Preparation method of photoelectric device: the same as Example 1. The main difference is that the zinc salt zinc gluconate (C6H 11 The mass volume concentration of O7)2Zn is 0.5 mg / mL.

[0130] Example 5

[0131] The structure of the optoelectronic device is the same as that of Example 1.

[0132] Preparation method of photoelectric device: the same as Example 1. The main difference is that the zinc salt zinc gluconate (C6H 11 The mass volume concentration of O7)2Zn is 2 mg / mL.

[0133] Example 6

[0134] The structure of the optoelectronic device is the same as that of Example 1.

[0135] Preparation method of optoelectronic device: Same as Example 1. The main difference is that the mass volume concentration of rubidium salt RbI included in the perovskite precursor solution in step (4) of Example 6 is 5 mg / mL.

[0136] Example 7

[0137] The structure of the optoelectronic device is the same as that of Example 1.

[0138] Preparation method of optoelectronic device: Same as Example 1. The main difference is that the mass volume concentration of rubidium salt RbI included in the perovskite precursor solution in step (4) of Example 7 is 7 mg / mL.

[0139] Example 8

[0140] The structure of the optoelectronic device is the same as that of Example 1.

[0141] Preparation method of photoelectric device: Same as Example 1. The main difference is that the perovskite precursor solution in step (4) of Example 8 does not include zinc salt zinc gluconate (C6H 11 O7)2Zn.

[0142] Example 9

[0143] The structure of the optoelectronic device is the same as that of Example 1.

[0144] Preparation method of optoelectronic device: Same as Example 1. The main difference is that the perovskite precursor solution in step (4) of Example 9 does not include rubidium salt RbI.

[0145] Comparative Example 1

[0146] The structure of the optoelectronic device is the same as that of Example 1.

[0147] Preparation method of photoelectric device: the same as Example 1. The main difference is that the perovskite precursor solution in step (4) of Comparative Example 1 does not include rubidium salt RbI and zinc salt zinc gluconate (C6H 11 O7)2Zn.

[0148] Comparative Example 2

[0149] The structure of the optoelectronic device is the same as that of Example 1.

[0150] Preparation method of photoelectric device: the same as Example 1. The main difference is that the rubidium salt in the perovskite precursor solution in step (4) of Comparative Example 2 is RbSCN.

[0151] The above-mentioned optoelectronic device is subjected to performance testing, and the testing method includes:

[0152] (1) At a light intensity of 100 mW cm -2 Under the conditions of simulated sunlight AM1.5G irradiation, the open circuit voltage (VOC), short circuit current (JSC), fill factor (FF), and photoelectric conversion efficiency (PCE) of the optoelectronic devices of the above embodiments and comparative examples were tested, and the corresponding test results are shown in Table 1.

[0153] Table 1

[0154]

[0155] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0156] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A perovskite precursor solution, characterized in that: The perovskite precursor solution comprises a perovskite precursor material, a metal salt and a solvent; the metal salt comprises one or more of a rubidium salt and a zinc salt, wherein the metal salt has one or more of the following characteristics: (1) The anion of the rubidium salt is a halogen ion; the mass volume concentration of the rubidium salt in the perovskite precursor solution is 5 mg / mL to 12 mg / mL; (2) The anion of the zinc salt includes one or more of a halogen ion and an organic acid ion; and the mass volume concentration of the zinc salt in the perovskite precursor solution is 0.05 mg / mL to 10 mg / mL.

2. The perovskite precursor solution according to claim 1, characterized in that The organic acid radical ion is selected from one or more ions having structural characteristics shown in formula (I-1) to formula (I-2): and ; Wherein, R1 is selected from C1~C6 alkyl or ; R2 is selected from a single bond or a C1~C6 alkylene group; R3 is selected from H or a C1~C6 alkyl group, and n is selected from any integer from 1 to 5.

3. The perovskite precursor solution according to claim 2, characterized in that The zinc salt includes a zinc salt whose anion is an organic acid ion.

4. The perovskite precursor solution according to claim 1 or 2, characterized in that: The perovskite precursor solution has one or more of the following characteristics: (1) The rubidium salt includes one or more of RbCl, RbBr and RbI; (2) The zinc salt includes one or more of ZnCl2, ZnBr2, ZnI2, zinc gluconate and zinc 4-methylbenzoate.

5. The perovskite precursor solution according to claim 1 or 2, characterized in that: The perovskite precursor solution has one or more of the following characteristics: (1) The perovskite precursor material includes AX material and BX2 material; wherein A includes FA + 、MA + , Cs + and K + One or more of, B includes Pb 2+ , Cu 2+ , Ga 2+ , Ca 2+ Sn 2+ and Ge 2+ One or more of, each occurrence of X is independently selected from Cl - Br - ,I - and SCN - One or more of; (2) The perovskite precursor solution includes the rubidium salt and the zinc salt.

6. A method for preparing a perovskite film, characterized in that: The following steps are involved: forming a perovskite precursor film on a substrate using a perovskite precursor solution; After annealing the perovskite precursor film, the perovskite film is prepared; Wherein, the perovskite precursor solution is the perovskite precursor solution according to any one of claims 1 to 5.

7. A perovskite film, characterized in that: It is prepared by the preparation method described in claim 6.

8. The perovskite film according to claim 7, characterized in that: The perovskite film has one or more of the following characteristics: (1) The thickness of the perovskite film is 10 nm to 100 μm; (2) The band gap of the perovskite film is 0.9 eV ~3 eV.

9. A photoelectric device, characterized in that: The optoelectronic device comprises a perovskite film, and the perovskite film is the perovskite film according to claim 7 or 8 or a perovskite film prepared by the preparation method according to claim 6.

10. The optoelectronic device according to claim 9, characterized in that: The optoelectronic device comprises a stacked perovskite top cell, an intermediate layer and a crystalline silicon bottom cell, wherein the perovskite top cell comprises the perovskite film; Optionally, the perovskite top cell includes a self-assembled small molecule layer, the perovskite film, a passivation layer and an electron transport layer which are sequentially stacked in a direction from the crystalline silicon bottom cell to the middle layer.

11. The optoelectronic device according to claim 10, characterized in that: The perovskite top cell has one or more of the following characteristics: (1) The material of the self-assembled small molecule layer includes one or more of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] and 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline; (2) The material of the passivation layer includes one or more of 2-phenylethylamine hydrochloride, 4-trifluoromethyl-aniline hydrochloride, 2-thiopheneethylamine hydrochloride, ethylamine hydrochloride, n-butylamine hydrochloride, phenylethylamine iodine, octylamine iodine and 1,4-phenylenediamine hydroiodide; (3) The material of the electron transport layer includes one or more of titanium dioxide, tin dioxide, indium oxide, zinc oxide, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, fullerene derivatives, graphene and graphene derivatives.

12. An electrical device, characterized in that: The optoelectronic device comprises the optoelectronic device according to any one of claims 9 to 11.

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