Perovskite light-absorbing material and preparation method thereof, perovskite solar cell and preparation method thereof

Abstract

The invention discloses a perovskite light-absorbing material and a preparation method thereof, and a perovskite solar cell and a preparation method thereof, the perovskite light-absorbing material has a structural general formula of ABX3, A comprises any one or more of CH3NH3 +, CH (NH2) 2 +, (CH3) 2NH2 + and Cs +; b comprises any one or two of Pb < 2 + > and Sn < 2 + >; x is any one or more of halide ions I <->, Br <-> and Cl <->; and the particle size of the perovskite light-absorbing material is 50-2000 nm. The perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light-absorbing capability of the film is enhanced, the stability is improved, and the hysteresis effect is inhibited. The two-dimensional perovskite precursor reacts with incompletely reacted lead iodide in the three-dimensional perovskite thin film, and the two-dimensional perovskite can passivate defects in the three-dimensional perovskite, fill the perovskite crystal boundary position, inhibit halogen ion migration, improve the overall crystallinity and enhance the device stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of solar cells, and in particular relates to a perovskite light-absorbing material and a preparation method thereof, a perovskite solar cell and a preparation method thereof. Background Art

[0002] At present, with the acceleration of the pace of social modernization, the "energy crisis" and environmental pollution caused by the burning of fossil energy have also arisen. It is imperative to expand renewable and environmentally friendly new energy. The "inexhaustible" solar energy is the cleanest energy and is easy to obtain, which is crucial for the sustainable development of society. In this context, perovskite solar cells, with their advantages of high efficiency, low cost and easy preparation, have provided strong support for promoting the global clean energy transformation. At present, the photoelectric conversion efficiency of a single perovskite cell has reached 26.7%, which is very close to the theoretical efficiency limit of 33.7%. However, in reality, perovskite solar cells have a variety of unavoidable thermal and optical losses, so it will be increasingly difficult to further improve the efficiency of a single perovskite solar cell. The use of a new type of perovskite / crystalline silicon tandem cell technology can theoretically achieve a higher theoretical efficiency limit, with a theoretical conversion efficiency of more than 42%. However, the key to preparing efficient tandem cells lies in preparing efficient top perovskite solar cells.

[0003] For top perovskite solar cells used in tandem cells, how to improve their conversion efficiency and stability is one of the unresolved issues. Due to the complex composition of perovskite itself, the quality of its thin film crystallization is low and there is a serious V OC Due to the loss and photoinduced phase separation phenomenon, there is serious interfacial non-radiative recombination at the interface of perovskite film / charge transfer layer, which seriously damages the stability of perovskite solar cells. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a perovskite light-absorbing material and a preparation method thereof, a perovskite solar cell and a preparation method thereof in view of the above-mentioned deficiencies in the prior art. The perovskite grain size of the perovskite light-absorbing material is increased, the grain boundaries are reduced, the light-absorbing ability of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed.

[0005] The technical solution adopted to solve the technical problem of the present invention is to provide a method for preparing a perovskite light absorbing layer, comprising the following steps:

[0006] Depositing a two-dimensional perovskite precursor deposition liquid and performing a first annealing treatment to obtain a deposited two-dimensional perovskite cation precursor layer;

[0007] A three-dimensional perovskite precursor deposition liquid is coated on the two-dimensional perovskite cation precursor layer to perform deposition to form a three-dimensional perovskite precursor wet film, and a second heating annealing treatment is performed. The two-dimensional perovskite cation precursor layer reacts in situ with lead iodide in the three-dimensional perovskite precursor wet film to obtain a first interface layer and a three-dimensional perovskite light-absorbing layer disposed on the first interface layer. The material of the three-dimensional perovskite light-absorbing layer is a perovskite light-absorbing material.

[0008] Preferably, the first heating annealing treatment is performed at a temperature of 60 to 100° C. and for a time of 3 to 6 minutes.

[0009] Preferably, the second heating annealing step is specifically:

[0010] First anneal at 55-65°C for 1-4 minutes;

[0011] Then anneal at 100-130°C for 5-17 minutes.

[0012] Preferably, the first interface layer is a two-dimensional-three-dimensional mixed dimensional perovskite layer obtained by an in-situ reaction between a two-dimensional perovskite cation precursor layer and lead iodide in a three-dimensional perovskite precursor wet film, and the material of the two-dimensional perovskite layer is any one or more of 1,4-butanediamine cation two-dimensional perovskite (BDA) PbI4, n-butylamine cation two-dimensional perovskite (BA) 2PbI4, phenylethylamine cation two-dimensional perovskite (PEA) 2PbI4, and ethylamine cation two-dimensional perovskite (EA) 2PbI4.

[0013] Preferably, the two-dimensional perovskite precursor is an organic amine halide;

[0014] The three-dimensional perovskite precursors are metal halide perovskites.

[0015] Preferably, the concentration of the two-dimensional perovskite precursor in the two-dimensional perovskite precursor deposition solution is 0.5-5 mg / ml.

[0016] The present invention also provides a perovskite light-absorbing material, which is a material of a three-dimensional perovskite light-absorbing layer obtained by the above preparation method. The general structural formula of the perovskite light-absorbing material is ABX3, wherein A includes CH3NH3 + 、CH(NH2)2 + 、(CH3)2NH2 + , Cs + Any one or more of; B includes Pb 2+ Sn 2+ Any one or two of; X is a halogen ion I - Br - , Cl - Any one or more of the following. Among them, CH3NH3 + (methylamine ion, MA+ )、(CH3)2NH2 + (dimethylammonium ion, DMA + )、CH(NH2)2 + (Formamidinium ion, FA + ) is an organic amine.

[0017] Preferably, the particle size of the perovskite light absorbing material is 50 to 2000 nm.

[0018] The present invention also provides a perovskite solar cell, comprising a conductive substrate, a first carrier transport layer, a first interface layer, a perovskite light absorption layer, a second interface layer, a second carrier transport layer, a buffer layer, and an electrode layer arranged in sequence, wherein the perovskite light absorption layer is a three-dimensional perovskite light absorption layer obtained by the above preparation method.

[0019] Preferably, the first carrier transport layer is a first hole transport layer, and the second carrier transport layer is a first electron transport layer;

[0020] The first carrier transport layer is a second electron transport layer, and the second carrier transport layer is a second hole transport layer.

[0021] Preferably, the conductive substrate includes any one of ITO, FTO and AZO.

[0022] Preferably, the material of the first hole transport layer or the second hole transport layer is [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid (4PADCB), [2-(9H-carbazole-9-yl)ethyl]phosphoric acid (2PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid (Me-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphoric acid (MeO-2PACz), 2,2',7,7'-tetra[N,N- Spiro-TTB), 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene-2,5-diyl) (P3HT), poly[bis(4-phenyl)(4-butylphenyl)amine] (poly-TPD), nickel oxide (NiO x ), cuprous thiocyanate (CuSCN).

[0023] Preferably, the thickness of the first carrier transport layer is 10-100 nm.

[0024] Preferably, the first interface layer is a two-dimensional perovskite layer, and the material of the two-dimensional perovskite layer is any one or more of 1,4-butanediamine two-dimensional perovskite (BDA) PbI4, n-butylamine two-dimensional perovskite (BA) 2PbI4, phenylethylamine two-dimensional perovskite (PEA) 2PbI4, and ethylamine two-dimensional perovskite (EA) 2PbI4.

[0025] The first interface layer has a passivation effect.

[0026] Preferably, the thickness of the first interface layer is 1 to 30 nm.

[0027] Preferably, the thickness of the perovskite light absorbing layer is 300-800 nm.

[0028] Preferably, the material of the second interface layer includes a basic amino acid-porphyrin conjugate, in which a basic amino acid is introduced as a substituent into the porphyrin ring to be conjugated with the porphyrin.

[0029] Preferably, the basic amino acid is any one or more of lysine, histidine and arginine.

[0030] Preferably, the basic amino acids are a combination of lysine, histidine and arginine, which have a synergistic effect.

[0031] Preferably, the thickness of the second interface layer is 1-10 nm.

[0032] The function of the second interface layer is passivation.

[0033] Preferably, the material of the first electron transport layer or the second electron transport layer includes C 60 ,[6,6]-phenyl-C 61 -Any one of butyric acid methyl ester (PCBM), SnO2, ZnO, and TiO2.

[0034] Preferably, the thickness of the second carrier transport layer is 10-100 nm.

[0035] Preferably, the material of the buffer layer is SnO2 or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP).

[0036] Preferably, the thickness of the buffer layer is 2-5 nm.

[0037] Preferably, the electrode layer is a metal electrode layer, and the material of the electrode layer includes any one of gold, silver and copper.

[0038] Preferably, the thickness of the electrode layer is 70 to 150 nm.

[0039] The present invention also provides a method for preparing the above-mentioned perovskite solar cell, comprising the following steps:

[0040] depositing a first carrier transport layer on a conductive substrate;

[0041] Depositing a two-dimensional perovskite precursor deposition liquid on the first carrier transport layer and performing a first annealing treatment to obtain a deposited two-dimensional perovskite cation precursor layer;

[0042] Coating a three-dimensional perovskite precursor deposition liquid on the two-dimensional perovskite cation precursor layer to deposit and form a three-dimensional perovskite precursor wet film, and performing a second heating annealing treatment, wherein the two-dimensional perovskite cation precursor layer reacts in situ with lead iodide in the three-dimensional perovskite precursor wet film to obtain a first interface layer and a three-dimensional perovskite light-absorbing layer disposed on the first interface layer;

[0043] depositing a basic amino acid-porphyrin conjugate deposition liquid on the perovskite light absorbing layer, and performing a third heating annealing treatment to obtain a second interface layer;

[0044] A second carrier transport layer, a buffer layer and an electrode layer are sequentially deposited on the second interface layer to obtain a perovskite solar cell.

[0045] Preferably, the temperature of the first heating annealing treatment is 60-100° C. and the time is 3-10 minutes;

[0046] The second heating annealing treatment step is specifically: first annealing at 55-65° C. for 1-4 minutes, and then annealing at 100-130° C. for 5-17 minutes.

[0047] Preferably, the third heating annealing is performed at a temperature of 60 to 100° C. and for a time of 3 to 6 minutes.

[0048] Preferably, the method for preparing the perovskite solar cell further comprises the following steps: preparing a basic amino acid-porphyrin conjugate deposition liquid, specifically mixing the basic amino acid-porphyrin conjugate and a solvent, wherein the solvent is any one of ethanol and isopropanol; the content of the basic amino acid-porphyrin conjugate in the basic amino acid-porphyrin conjugate deposition liquid is 1 to 3 mg / ml.

[0049] Preferably, the deposition method of the first carrier transport layer, the second carrier transport layer, and the perovskite light absorbing layer includes any one of spin coating, spray coating, blade coating, slit coating, thermal evaporation, magnetron sputtering, and atomic layer deposition.

[0050] Preferably, the electrode layer is deposited by thermal evaporation at a deposition rate of

[0051] The perovskite light-absorbing material and preparation method thereof, the perovskite solar cell and preparation method thereof in the present invention increase the perovskite grain size of the perovskite light-absorbing material, reduce the grain boundaries, enhance the light-absorbing ability of the film, and improve the stability, and the hysteresis effect is suppressed. The lower surface modification adopts a two-dimensional perovskite control strategy, and the two-dimensional perovskite precursor reacts with the unreacted lead iodide in the three-dimensional perovskite film to generate a two-dimensional perovskite structure and the three-dimensional perovskite to form a mixed-dimensional perovskite layer. The two-dimensional perovskite can passivate the defects in the three-dimensional perovskite, and can fill the perovskite grain boundary position, inhibit the migration of halogen ions, and reduce the unreacted lead iodide content in the three-dimensional perovskite film, thereby improving the overall crystallinity of the film and enhancing the stability of the device.

[0052] The present invention uses a dual-interface modification method to passivate the surface defects of the perovskite film while blocking the halogen migration path in the perovskite material, inhibiting the phase separation phenomenon induced by halogen migration, regulating the growth and crystallization process of the perovskite film, enhancing the crystallinity of the perovskite film, and ultimately improving the efficiency and stability of the perovskite solar cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 Schematic diagram of the structure of a perovskite solar cell;

[0054] Figure 2 It is the structural formula of basic amino acid-porphyrin conjugate;

[0055] Figure 3 is the structural formula of the two-dimensional perovskite precursor material;

[0056] Figure 4 This is a comparison chart of battery stability;

[0057] Figure 5 An electron microscope photograph of a perovskite film of a perovskite light absorbing layer in a comparative example;

[0058] Figure 6 Electron microscopy of the perovskite film of the perovskite light absorbing layer in Example 2

[0059] photo

[0060] Figure 7 The X-ray diffraction spectrum of the perovskite film of the perovskite light absorbing layer in the comparative example;

[0061] Figure 8 This is the X-ray diffraction spectrum of the perovskite film of the perovskite light absorbing layer in Example 2. DETAILED DESCRIPTION

[0062] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings and specific implementation methods.

[0063] Example 1

[0064] This embodiment provides a perovskite light-absorbing material, whose general structural formula is ABX3, wherein A includes CH3NH3 + 、CH(NH2)2 + 、(CH3)2NH2 + , Cs + Any one or more of; B includes Pb 2+ Sn 2+ Any one or two of; X is a halogen ion I - Br - , Cl - Any one or more of the .

[0065] This embodiment also provides a method for preparing a perovskite light absorbing layer, comprising the following steps:

[0066] Depositing a two-dimensional perovskite precursor deposition liquid and performing a first annealing treatment to obtain a deposited two-dimensional perovskite cation precursor layer;

[0067] A three-dimensional perovskite precursor deposition liquid is coated on the two-dimensional perovskite cation precursor layer to perform deposition to form a three-dimensional perovskite precursor wet film, and a second heating annealing treatment is performed. The two-dimensional perovskite cation precursor layer reacts in situ with the lead iodide in the three-dimensional perovskite precursor wet film to obtain a first interface layer and a three-dimensional perovskite light-absorbing layer disposed on the first interface layer. The material of the three-dimensional perovskite light-absorbing layer is the above-mentioned perovskite light-absorbing material.

[0068] This embodiment also provides a perovskite solar cell, comprising a conductive substrate, a first carrier transport layer, a first interface layer, a perovskite light absorption layer, a second interface layer, a second carrier transport layer, a buffer layer, and an electrode layer arranged in sequence, wherein the perovskite light absorption layer is a three-dimensional perovskite light absorption layer obtained by the above preparation method.

[0069] This embodiment also provides a method for preparing the above-mentioned perovskite solar cell, comprising the following steps:

[0070] depositing a first carrier transport layer on a conductive substrate;

[0071] Depositing a two-dimensional perovskite precursor deposition liquid on the first carrier transport layer and performing a first annealing treatment to obtain a deposited two-dimensional perovskite cation precursor layer;

[0072] Coating a three-dimensional perovskite precursor deposition liquid on the two-dimensional perovskite cation precursor layer to deposit and form a three-dimensional perovskite precursor wet film, and performing a second heating annealing treatment, wherein the two-dimensional perovskite cation precursor layer reacts in situ with lead iodide in the three-dimensional perovskite precursor wet film to obtain a first interface layer and a three-dimensional perovskite light-absorbing layer disposed on the first interface layer;

[0073] depositing a basic amino acid-porphyrin conjugate deposition liquid on the perovskite light absorbing layer, and performing a third heating annealing treatment to obtain a second interface layer;

[0074] A second carrier transport layer, a buffer layer and an electrode layer are sequentially deposited on the second interface layer to obtain a perovskite solar cell.

[0075] The perovskite light-absorbing material and preparation method thereof, the perovskite solar cell and preparation method thereof in this embodiment, the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced and the stability is improved, and the hysteresis effect is suppressed. The lower surface modification adopts a two-dimensional perovskite control strategy, and the two-dimensional perovskite precursor reacts with the unreacted lead iodide in the three-dimensional perovskite film to generate a two-dimensional perovskite structure and a three-dimensional perovskite to form a mixed-dimensional perovskite layer. The two-dimensional perovskite can passivate the defects in the three-dimensional perovskite, and can fill the perovskite grain boundary position, inhibit the migration of halogen ions, and reduce the unreacted lead iodide content in the three-dimensional perovskite film, improve the overall crystallinity of the film, and enhance the stability of the device.

[0076] This embodiment uses a dual interface modification method to passivate the surface defects of the perovskite film while blocking the halogen migration path in the perovskite material, inhibiting the phase separation phenomenon induced by halogen migration, regulating the growth and crystallization process of the perovskite film, enhancing the crystallinity of the perovskite film, and ultimately improving the efficiency and stability of the perovskite solar cell.

[0077] Example 2

[0078] This embodiment provides a perovskite light-absorbing material, whose general structural formula is ABX3, wherein A includes CH3NH3 + 、CH(NH2)2 + 、(CH3)2NH2 + , Cs + Any one or more of; B includes Pb 2+ Sn 2+ Any one or two of; X is a halogen ion I - Br - , Cl - Any one or more of the following; the particle size of the perovskite light absorbing material is 50 to 2000 nm. Among them, CH3NH3 + (methylamine ion, MA +)、C2H8N + (dimethylammonium ion, DMA + )、CH(NH2)2 + (Formamidinium ion, FA + ) is an organic amine.

[0079] This embodiment also provides a method for preparing the above-mentioned perovskite light absorbing layer, comprising the following steps:

[0080] Depositing a two-dimensional perovskite precursor deposition liquid and performing a first annealing treatment to obtain a deposited two-dimensional perovskite cation precursor layer;

[0081] A three-dimensional perovskite precursor deposition liquid is coated on the two-dimensional perovskite cation precursor layer to perform deposition to form a three-dimensional perovskite precursor wet film, and a second heating annealing treatment is performed. The two-dimensional perovskite cation precursor layer reacts in situ with the lead iodide in the three-dimensional perovskite precursor wet film to obtain a first interface layer and a three-dimensional perovskite light-absorbing layer disposed on the first interface layer. The material of the three-dimensional perovskite light-absorbing layer is the above-mentioned perovskite light-absorbing material.

[0082] Preferably, the first heating annealing treatment is performed at a temperature of 60 to 100° C. and for a time of 3 to 6 minutes.

[0083] Preferably, the second heating annealing step is specifically:

[0084] First anneal at 55-65°C for 1-4 minutes;

[0085] Then anneal at 100-130°C for 5-17 minutes.

[0086] Preferably, the first interface layer is a two-dimensional-three-dimensional mixed dimensional perovskite layer obtained by an in-situ reaction between a two-dimensional perovskite cation precursor layer and lead iodide in a three-dimensional perovskite precursor wet film, and the material of the two-dimensional perovskite layer is any one or more of 1,4-butanediamine cation two-dimensional perovskite (BDA) PbI4, n-butylamine cation two-dimensional perovskite (BA) 2PbI4, phenylethylamine cation two-dimensional perovskite (PEA) 2PbI4, and ethylamine cation two-dimensional perovskite (EA) 2PbI4.

[0087] The first interface layer is a mixed dimensional perovskite layer, which is obtained by introducing a two-dimensional perovskite cation precursor at the bottom of the perovskite and reacting it with unreacted lead iodide in the three-dimensional perovskite film in situ to obtain a two-dimensional-three-dimensional mixed dimensional perovskite layer. The first interface layer is constructed by mixing a two-dimensional perovskite layer with a three-dimensional perovskite layer.

[0088] Preferably, the two-dimensional perovskite precursor is an organic amine halide;

[0089] The three-dimensional perovskite precursors are metal halide perovskites.

[0090] Preferably, the concentration of the precursor in the two-dimensional perovskite precursor deposition solution is 0.5-5 mg / ml.

[0091] like Figure 1 As shown, this embodiment also provides a perovskite solar cell, comprising a conductive substrate, a first carrier transport layer, a first interface layer, a perovskite light absorption layer, a second interface layer, a second carrier transport layer, a buffer layer, and an electrode layer arranged in sequence from bottom to top, wherein the perovskite light absorption layer is a three-dimensional perovskite light absorption layer obtained by the above preparation method.

[0092] Preferably, the first carrier transport layer is a first hole transport layer, and the second carrier transport layer is a first electron transport layer;

[0093] The first carrier transport layer is a second electron transport layer, and the second carrier transport layer is a second hole transport layer.

[0094] Preferably, the conductive substrate includes any one of ITO, FTO and AZO.

[0095] Preferably, the material of the first hole transport layer or the second hole transport layer is [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid (4PADCB), [2-(9H-carbazole-9-yl)ethyl]phosphoric acid (2PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid (Me-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphoric acid (MeO-2PACz), 2,2',7,7'-tetra[N,N- Spiro-TTB), 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3-hexylthiophene-2,5-diyl) (P3HT), poly[bis(4-phenyl)(4-butylphenyl)amine] (poly-TPD), nickel oxide (NiO x ), cuprous thiocyanate (CuSCN).

[0096] Preferably, the thickness of the first carrier transport layer is 10-100 nm.

[0097] Preferably, the first interface layer is a two-dimensional perovskite layer, and the material of the two-dimensional perovskite layer is any one or more of 1,4-butanediamine two-dimensional perovskite (BDA) PbI4, n-butylamine two-dimensional perovskite (BA) 2PbI4, phenylethylamine two-dimensional perovskite (PEA) 2PbI4, and ethylamine two-dimensional perovskite (EA) 2PbI4.

[0098] The first interface layer has a passivation effect.

[0099] Preferably, the thickness of the first interface layer is 1 to 30 nm.

[0100] Preferably, the thickness of the perovskite light absorbing layer is 300-800 nm.

[0101] like Figure 2 As shown, preferably, the material of the second interface layer includes a basic amino acid-porphyrin conjugate, in which the basic amino acid is introduced as a substituent into the porphyrin ring to conjugate with the porphyrin.

[0102] Preferably, the basic amino acid is any one or more of lysine, histidine and arginine.

[0103] Preferably, the basic amino acids are a combination of lysine, histidine and arginine, which have a synergistic effect.

[0104] Preferably, the thickness of the second interface layer is 1-10 nm.

[0105] The function of the second interface layer is passivation.

[0106] Preferably, the material of the first electron transport layer or the second electron transport layer includes C 60 ,[6,6]-phenyl-C 61 -Any one of butyric acid methyl ester (PCBM), SnO2, ZnO, and TiO2.

[0107] Preferably, the thickness of the second carrier transport layer is 10-100 nm.

[0108] Preferably, the material of the buffer layer is SnO2 or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP).

[0109] Preferably, the thickness of the buffer layer is 2-5 nm.

[0110] Preferably, the electrode layer is a metal electrode layer, and the material of the electrode layer includes any one of gold, silver and copper.

[0111] Preferably, the thickness of the electrode layer is 70 to 150 nm.

[0112] This embodiment also provides a method for preparing the above-mentioned perovskite solar cell, comprising the following steps:

[0113] Cleaning conductive substrates;

[0114] depositing a first carrier transport layer on a conductive substrate;

[0115] Mixing a two-dimensional perovskite precursor material with a solvent to obtain a two-dimensional perovskite precursor solution with a concentration of 0.5-5 mg / mL, depositing a two-dimensional perovskite cation precursor layer on the first carrier transport layer, and performing a first annealing treatment to obtain a deposited two-dimensional perovskite cation precursor layer;

[0116] A three-dimensional perovskite precursor deposition liquid is coated on the two-dimensional perovskite cation precursor layer to perform deposition to form a three-dimensional perovskite precursor wet film, and a second heating annealing treatment is performed, wherein the two-dimensional perovskite cation precursor layer at the bottom reacts in situ with the lead iodide in the three-dimensional perovskite precursor wet film to obtain a first interface layer and a three-dimensional perovskite light-absorbing layer disposed on the first interface layer, wherein the three-dimensional perovskite light-absorbing layer is the above-mentioned perovskite light-absorbing material, and a two-dimensional-three-dimensional mixed perovskite layer is formed at the bottom of the three-dimensional perovskite light-absorbing layer, wherein the two-dimensional-three-dimensional mixed perovskite layer is the first interface layer;

[0117] depositing a basic amino acid-porphyrin conjugate deposition liquid on the perovskite light absorbing layer, and performing a third heating annealing treatment to obtain a second interface layer;

[0118] A second carrier transport layer, a buffer layer and an electrode layer are sequentially deposited on the second interface layer to obtain a perovskite solar cell.

[0119] Preferably, the temperature of the first heating annealing treatment is 60-100° C. and the time is 3-10 minutes;

[0120] The second heating annealing treatment step is specifically: first annealing at 55-65° C. for 1-4 minutes, and then annealing at 100-130° C. for 5-17 minutes.

[0121] Preferably, the third heating annealing is performed at a temperature of 60 to 100° C. and for a time of 3 to 6 minutes.

[0122] Preferably, the method for preparing the perovskite solar cell further comprises the following steps: preparing a basic amino acid-porphyrin conjugate deposition liquid, specifically mixing the basic amino acid-porphyrin conjugate and a solvent, wherein the solvent is any one of ethanol and isopropanol; the content of the basic amino acid-porphyrin conjugate in the basic amino acid-porphyrin conjugate deposition liquid is 1 to 3 mg / ml.

[0123] Preferably, the deposition method of the first carrier transport layer, the second carrier transport layer, and the perovskite light absorbing layer includes any one of spin coating, spray coating, blade coating, slit coating, thermal evaporation, magnetron sputtering, and atomic layer deposition.

[0124] Preferably, the electrode layer is deposited by thermal evaporation at a deposition rate of

[0125] Specifically, in this embodiment, interface passivation layers are disposed on the upper and lower surfaces of the perovskite light absorbing layer, and the first interface layer and the second interface layer are both interface passivation layers.

[0126] The second interface layer of the upper surface passivation layer is an alkaline amino acid-porphyrin conjugate containing amino groups, which coordinate with Pb through the electron donation effect of the amino group to form metal porphyrin and stabilize the perovskite structure. At the same time, the alkaline amino acid can effectively reduce the defect density of the perovskite light-absorbing layer, reduce the non-radiative recombination of carriers, and extend the life of carriers. The perovskite grain size is increased, the grain boundaries are reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed. The alkaline amino acid-porphyrin conjugate can enhance the interface contact between the second carrier transport layer and the perovskite light-absorbing layer through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite light-absorbing layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0127] The lower surface modification adopts the first interface layer two-dimensional perovskite regulation strategy. The two-dimensional perovskite precursor reacts with the unreacted lead iodide in the three-dimensional perovskite film to generate a two-dimensional perovskite structure and a three-dimensional perovskite to form a mixed-dimensional perovskite layer. The two-dimensional perovskite can passivate the defects in the three-dimensional perovskite and fill the three-dimensional perovskite grain boundary position, inhibit the migration of halogen ions, and at the same time reduce the unreacted lead iodide content in the three-dimensional perovskite film, thereby improving the overall crystallinity of the film and enhancing the stability of the device.

[0128] Specifically, this embodiment provides a method for preparing the above-mentioned perovskite solar cell, comprising the following steps:

[0129] (1) Treating the conductive substrate: ITO conductive glass was used as the conductive substrate, and glass cleaning agent, deionized water, ethanol, acetone, isopropanol and ethanol were ultrasonicated for 10 min in sequence, and then the conductive substrate was blown dry with dry air, followed by UV-ozone treatment for 15 min;

[0130] (2) preparing a first carrier transport layer: spin coating a 0.7 mg / mL ethanol solution of [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid on the pre-cleaned ITO conductive glass at a spin coating speed of 4000 rpm for 10 s, and then annealing at 100° C. for 10 min to obtain a first carrier transport layer having a thickness of 20 nm;

[0131] (3) Preparation of two-dimensional perovskite precursor layer: two-dimensional perovskite precursor material BDAI (such as Figure 3) was mixed with N,N-dimethylformamide to obtain a two-dimensional perovskite precursor solution with a concentration of 1 mg / mL, and then spin-coated at a rate of 4000 rpm for 30 s, followed by a first annealing at a temperature of 100°C for 5 min to obtain a two-dimensional perovskite precursor layer composed of BDAI material.

[0132] (4) Preparation of perovskite light-absorbing layer (wet film): The three-dimensional perovskite precursor deposition liquid is spin-coated on the two-dimensional perovskite precursor layer in steps. The first step is spin-coated at a rate of 1000 rpm for 10 s, and the second step is spin-coated at a rate of 3000 rpm for 20 s. At the same time, after rotating at 1000 rpm for 10 s, ether solution is added as an anti-solvent. After the spin coating is completed, a wet film of the perovskite light-absorbing layer is obtained.

[0133] (5) In-situ reaction to form the first interface layer and the perovskite light absorbing layer: The device obtained in step (4) is subjected to a second annealing step by step, wherein the first annealing temperature is 60°C for 2 min, and the second annealing temperature is 120°C for 15 min. During the annealing process, the two-dimensional perovskite precursor present at the bottom of the perovskite light absorbing layer wet film reacts in situ with the unreacted lead iodide in the perovskite light absorbing layer wet film. After the annealing is completed, a first interface layer composed of (BAD)PbI4-Cs 0.2 FA 0.8 Pb(I 0.75 Br 0.25 )3 The first interface layer composed of two-dimensional-three-dimensional mixed perovskite, Cs 0.2 FA 0.8 Pb(I 0.75 Br 0.25 )3-dimensional perovskite light absorbing layer, the thickness of the first interface layer is 15nm, and the thickness of the perovskite light absorbing layer is 500nm. .

[0134] (6) Preparing a second interface layer: mixing a basic amino acid-porphyrin conjugate and isopropanol, wherein the basic amino acid is lysine, to obtain an interface passivation solution with a concentration of 2 mg / mL, and then spin coating at a rate of 2000 rpm / 10 s, a third annealing temperature of 100° C., and a time of 4 min to obtain a second interface layer, which is an interface passivation layer, and a thickness of the second interface layer is 5 nm;

[0135] (7) Preparation of the second carrier transport layer: Using the evaporation method, C 60 Evaporation is performed on the second interface layer at a rate of The thickness of C is 30nm. 60 layer;

[0136] (8) Preparation of buffer layer and electrode layer: A 4 nm thick 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) layer and a 100 nm thick silver layer were sequentially deposited on the first carrier transport layer by evaporation method. The deposition rate of the silver layer was The perovskite solar cell is obtained.

[0137] The perovskite light-absorbing material and preparation method thereof, the perovskite solar cell and preparation method thereof in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0138] The lower surface modification adopts a two-dimensional perovskite regulation strategy. The two-dimensional perovskite precursor reacts with the unreacted lead iodide in the three-dimensional perovskite film to generate a two-dimensional perovskite structure and a three-dimensional perovskite to form a mixed-dimensional perovskite layer. The two-dimensional perovskite can passivate the defects in the three-dimensional perovskite, fill the perovskite grain boundary positions, inhibit the migration of halogen ions, and reduce the unreacted lead iodide content in the three-dimensional perovskite film, thereby improving the overall crystallinity of the film and enhancing the stability of the device.

[0139] Wide-bandgap perovskite solar cells face the problems of low crystal quality of perovskite films, high defect state density, and serious ion migration. The interface modifier modification effect of improving device performance and stability in wide-bandgap perovskite solar cells disclosed in the prior art is limited. Most of the existing interface modifiers focus on reducing the opening voltage loss of wide-bandgap perovskites, and there is no technology that focuses on inhibiting ion migration to improve phase stability. At the same time, the existing interface modification technology focuses on the upper surface of the perovskite film, and the optimization of the lower surface of the perovskite film is often ignored by researchers. In addition, the halogen ion migration problem generated by wide-bandgap perovskites after illumination has a significant impact on battery stability. Therefore, inhibiting ion migration is also an important factor in obtaining efficient and stable wide-bandgap perovskite solar cells.

[0140] This embodiment uses a dual interface modification method to passivate the surface defects of the wide-bandgap perovskite film while blocking the halogen migration path in the perovskite material, inhibiting the phase separation phenomenon induced by halogen migration, regulating the growth and crystallization process of the perovskite film, enhancing the crystallinity of the perovskite film, and ultimately improving the efficiency and stability of the wide-bandgap perovskite solar cell.

[0141] Example 3

[0142] The difference between Example 3 and Example 2 is that the first interface layer is not provided, and the preparation method and parameters of the remaining perovskite solar cells are consistent with those of Example 2.

[0143] Example 4

[0144] The difference between Example 4 and Example 2 is that the second interface layer is not provided, and the preparation method and parameters of the rest of the perovskite solar cell are consistent with those of Example 2.

[0145] Example 5

[0146] The difference between Example 5 and Example 2 is that the two-dimensional perovskite precursor material is ethylammonium iodide EAI, and the preparation method and parameters of the rest of the perovskite solar cell are consistent with Example 2.

[0147] Example 6

[0148] The difference between Example 6 and Example 2 is that the two-dimensional perovskite precursor material is butylamine iodide BAI, and the preparation method and parameters of the rest of the perovskite solar cell are consistent with Example 2.

[0149] Example 7

[0150] The difference between Example 7 and Example 2 is that the two-dimensional perovskite precursor material is phenethylammonium iodide PEAI, and the preparation method and parameters of the rest of the perovskite solar cell are consistent with Example 2.

[0151] Comparative Example

[0152] The difference between the comparative example and the embodiment 2 is that the first interface layer and the second interface layer are not provided. The preparation method and parameters of the rest of the perovskite solar cell are consistent with those of the embodiment 2.

[0153] Performance Testing

[0154] The batteries prepared in the examples and comparative examples were subjected to current-voltage characteristic (JV) tests, using AM1.5G light source, 100 mW cm -2 Sunlight simulates the light source. The open circuit voltage of the battery (V OC ), short-circuit current density (J SC ), fill factor (FF) and power conversion efficiency (PCE), among which the open circuit voltage (VOC ), short-circuit current density (J SC ), fill factor (FF) is obtained from the tested JV characteristic curve, power conversion efficiency (PCE) = (V OC ×J SC ×FF) / 100mW cm -2 The test results are recorded in Table 1.

[0155] The batteries prepared in the comparative example, embodiment 2, embodiment 3 and embodiment 4 were placed in the air, and their JV characteristic curves were periodically measured to obtain the power conversion efficiency (PCE) of the battery and normalize the PCE data to obtain Figure 4 ,The purpose of normalization is to facilitate the comparison of PCE data at the same ,starting point.

[0156] Combined with Table 1 and Figure 4 As shown, Example 2 has the highest conversion efficiency and the best stability, indicating that in the perovskite light-absorbing material and its preparation method, the perovskite solar cell and its preparation method described in this embodiment, the basic amino acid-porphyrin conjugate contains an amino group, and the basic amino acid-porphyrin conjugate coordinates with Pb through the electron-donating effect of the amino group to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0157] Embodiment 3 and embodiment 4 respectively use the first interface layer and the second interface layer to optimize the performance of the solar cell. Since only a single interface layer is used, the cell efficiency and cell stability performance lag behind that of embodiment 2, but are better than those of the comparative example.

[0158] In Examples 5, 6 and 7, different organic amine halides are used to in-situ form two-dimensional perovskite materials, and the battery conversion efficiency is higher than that of the comparative example, indicating that the method for preparing the perovskite light-absorbing layer described in the present technical solution can use a variety of two-dimensional perovskite precursor materials and has universal applicability.

[0159] Different types of perovskite materials are selected in Examples 8, 9 and 10, and the battery conversion efficiency is higher than that of the comparative example, indicating that the technical solution can be applied to different types of perovskite materials and has universal applicability.

[0160] Example 11 uses a regular perovskite solar cell structure, and the cell conversion efficiency is higher than that of the comparative example, indicating that the technical solution can be applied to regular structure and reverse structure perovskite solar cells and has universal applicability.

[0161] Different transmission materials are selected in Example 12, Example 13, Example 14 and Example 15, and the battery conversion efficiency is higher than that of the comparative example, indicating that the technical solution can match different types of transmission layer materials and has universal applicability.

[0162] Figure 5 , Figure 6 The scanning electron microscope photos of the perovskite thin film of the perovskite light absorbing layer prepared by the method described in the comparative example and Example 2 were compared, and the model of the scanning electron microscope was JEOL-6701F, and the magnification was 30000 times. The perovskite film in Example 2 has a larger grain size, which proves that the two-dimensional perovskite grown in situ in Example 2 can promote the grain growth of the three-dimensional perovskite film, so that the perovskite film has a larger grain size.

[0163] Figure 7 , Figure 8 The XRD data of the perovskite thin film of the perovskite light absorbing layer prepared by the method described in the comparative example and Example 2 were compared, and the model of the X-ray diffractometer used was Rigaku, D / max 2500VB25 / PC. The peak intensity of the XRD diffraction spectrum of the perovskite thin film in Example 2 was greater than that in the comparative example, indicating that the perovskite thin film had a higher crystallinity, which proved that the in-situ grown two-dimensional perovskite in Example 2 promoted the growth of the three-dimensional perovskite thin film.

[0164] Table 1 Battery performance table

[0165]

[0166]

[0167] Example 8

[0168] This embodiment provides a perovskite light-absorbing material, whose general structural formula is ABX3, wherein A includes CH3NH3 + ; B includes Pb 2+ Sn 2+ (the molar ratio of the two is 1:1); X is a halogen ion I - ; The particle size of the perovskite light-absorbing material is 50 to 2000 nm.

[0169] This embodiment also provides a method for preparing the above-mentioned perovskite light absorbing layer, comprising the following steps:

[0170] Preparation of two-dimensional perovskite precursor layer: two-dimensional perovskite precursor material BDAI (such as Figure 3 ) was mixed with N,N-dimethylformamide to obtain a two-dimensional perovskite precursor solution with a concentration of 0.5 mg / mL, and then spin-coated at a rate of 4000 rpm for 30 s, followed by a first annealing at a temperature of 60°C for 3 min to obtain a two-dimensional perovskite precursor layer composed of 1,4-butanediamine hydroiodide BDAI material.

[0171] Preparation of perovskite light-absorbing layer (wet film): The three-dimensional perovskite precursor deposition liquid is spin-coated on the two-dimensional perovskite precursor layer in steps. The first step spin coating rate is 1000 rpm, the time is 10 s, and the second step spin coating rate is 3000 rpm, the time is 20 s. At the same time, after rotating at 1000 rpm for 10 s, ether solution is added as an anti-solvent. After the spin coating is completed, a wet film of the perovskite light-absorbing layer is obtained.

[0172] In-situ reaction to form the first interface layer and the perovskite light absorbing layer: the device obtained in step (4) is subjected to a second annealing step by step, the first step annealing temperature is 55°C, the time is 3 minutes, and the second step annealing temperature is 130°C, the time is 14 minutes. During the annealing process, the two-dimensional perovskite precursor present at the bottom of the perovskite light absorbing layer wet film reacts in-situ with the unreacted lead iodide in the perovskite light absorbing layer wet film. After the annealing is completed, a first interface layer composed of (BAD)PbSnI4-MAPbSnI3 two-dimensional-three-dimensional mixed perovskite is formed, and a MAPbSnI3 three-dimensional perovskite light absorbing layer is formed on the first interface layer. The thickness of the first interface layer is 30nm, and the thickness of the perovskite light absorbing layer is 300nm. The three-dimensional perovskite light absorbing layer is formed by the perovskite light absorbing material.

[0173] This embodiment also provides a perovskite solar cell, comprising a conductive substrate, a first carrier transport layer, a first interface layer, a perovskite light absorption layer, a second interface layer, a second carrier transport layer, a buffer layer, and an electrode layer, which are arranged in sequence from bottom to top, wherein the material of the perovskite light absorption layer is the above-mentioned perovskite light absorption material.

[0174] This embodiment provides a method for preparing the above-mentioned perovskite solar cell, comprising the following steps:

[0175] (1) Treating the conductive substrate: FTO conductive glass was used as the conductive substrate, and glass cleaning agent, deionized water, ethanol, acetone, isopropanol and ethanol were ultrasonicated for 10 min in sequence, and then the conductive substrate was blown dry with dry air, followed by UV-ozone treatment for 15 min;

[0176] (2) Preparation of the first carrier transport layer: Spin coating a 0.7 mg / mL ethanol solution of [2-(9H-carbazole-9-yl)ethyl]phosphoric acid (2PACz) on the pre-cleaned FTO conductive glass at a spin coating speed of 4000 rpm for 10 s, and then annealing at 100° C. for 10 min to obtain a first carrier transport layer having a thickness of 1 nm;

[0177] (3) Preparation of two-dimensional perovskite precursor layer: two-dimensional perovskite precursor material BDAI (such as Figure 3 ) was mixed with N,N-dimethylformamide to obtain a two-dimensional perovskite precursor solution with a concentration of 0.5 mg / mL, and then spin-coated at a rate of 4000 rpm for 30 s, followed by a first annealing at a temperature of 60°C for 3 min to obtain a two-dimensional perovskite precursor layer composed of BDAI material.

[0178] (4) Preparation of perovskite light-absorbing layer (wet film): The three-dimensional perovskite precursor deposition liquid is spin-coated on the two-dimensional perovskite precursor layer in steps. The first step is spin-coated at a rate of 1000 rpm for 10 s, and the second step is spin-coated at a rate of 3000 rpm for 20 s. At the same time, after rotating at 1000 rpm for 10 s, ether solution is added as an anti-solvent. After the spin coating is completed, a wet film of the perovskite light-absorbing layer is obtained.

[0179] (5) In-situ reaction to form the first interface layer and the perovskite light-absorbing layer: The device obtained in step (4) is subjected to a second annealing step by step. The first annealing temperature is 55°C for 3 minutes, and the second annealing temperature is 130°C for 14 minutes. During the annealing process, the two-dimensional perovskite precursor present at the bottom of the perovskite light-absorbing layer wet film reacts in situ with the unreacted lead iodide in the perovskite light-absorbing layer wet film. After the annealing is completed, a first interface layer composed of (BAD)PbSnI4-MAPbSnI3 two-dimensional-three-dimensional mixed perovskite is formed, and a MAPbSnI3 three-dimensional perovskite light-absorbing layer is formed on the first interface layer. The thickness of the first interface layer is 30nm, and the thickness of the perovskite light-absorbing layer is 300nm.

[0180] (6) Preparing a second interface layer: mixing a basic amino acid-porphyrin conjugate with ethanol, wherein the basic amino acids are histidine and arginine (the molar ratio of the two is 1:4), to obtain an interface passivation solution with a concentration of 1 mg / mL, and then spin coating at a rate of 2000 rpm / 10 s, a third annealing temperature of 100° C., and a time of 4 min to obtain a second interface layer, which is an interface passivation layer, and a thickness of the second interface layer is 1 nm;

[0181] (7) Preparation of the second carrier transport layer: Spray coating of [6,6]-phenyl-C 61-Butyric acid methyl ester (PCBM) was sprayed on the second interface layer to obtain a [6,6]-phenyl-C 61 - butyrate methyl ester (PCBM) layer;

[0182] (8) Preparation of buffer layer and electrode layer: A 2 nm thick SnO2 layer and a 120 nm thick silver layer were sequentially deposited on the first carrier transport layer by atomic layer deposition. The deposition rate of the silver layer was The perovskite solar cell is obtained.

[0183] The perovskite light-absorbing material and preparation method thereof, the perovskite solar cell and preparation method thereof in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0184] Example 9

[0185] This embodiment provides a perovskite light-absorbing material, whose general structural formula is ABX3, wherein A includes CH3NH3 + 、CH(NH2)2 + 、(CH3)2NH2 + , Cs + ; B includes Pb 2+ ; X is a halogen ion I - Br - ; The particle size of the perovskite light-absorbing material is 50 to 2000 nm.

[0186] This embodiment also provides a method for preparing the above-mentioned perovskite light absorbing layer, comprising the following steps:

[0187] Preparation of two-dimensional perovskite precursor layer: two-dimensional perovskite precursor material BAI (such as Figure 3 ) was mixed with N,N-dimethylformamide to obtain a two-dimensional perovskite precursor solution with a concentration of 3 mg / mL, and then spin-coated at a rate of 4000 rpm for 30 s, followed by a first annealing at a temperature of 80°C for 5 min to obtain a two-dimensional perovskite precursor layer composed of BAI material.

[0188] Preparation of perovskite light-absorbing layer (wet film): The three-dimensional perovskite precursor deposition liquid is spin-coated on the two-dimensional perovskite precursor layer in steps. The first step spin coating rate is 1000 rpm, the time is 10 s, and the second step spin coating rate is 3000 rpm, the time is 20 s. At the same time, after rotating at 1000 rpm for 10 s, ether solution is added as an anti-solvent. After the spin coating is completed, a wet film of the perovskite light-absorbing layer is obtained.

[0189] In-situ reaction to form the first interface layer and the perovskite light absorbing layer: the device obtained in step (4) is subjected to a second annealing step by step, the first step annealing temperature is 65°C, the time is 4 minutes, and the second step annealing temperature is 110°C, the time is 13 minutes. During the annealing process, the two-dimensional perovskite precursor present at the bottom of the perovskite light absorbing layer wet film reacts in-situ with the unreacted lead iodide in the perovskite light absorbing layer wet film. After the annealing is completed, the first interface layer and the perovskite light absorbing layer are formed. 0.1 Cs 0.25 FA 0.6 MA 0.05 PbI 2.7 Br 0.3 The first interface layer composed of 2D-3D hybrid perovskite, DMA formed on the first interface layer 0.1 Cs 0.25 FA 0.6 MA 0.05 PbI 2. 7Br 0.3 The three-dimensional perovskite light absorbing layer has a first interface layer with a thickness of 20 nm and a perovskite light absorbing layer with a thickness of 400 nm. The three-dimensional perovskite light absorbing layer is formed of a perovskite light absorbing material.

[0190] This embodiment also provides a perovskite solar cell, comprising a conductive substrate, a first carrier transport layer, a first interface layer, a perovskite light absorption layer, a second interface layer, a second carrier transport layer, a buffer layer, and an electrode layer, which are arranged in sequence from bottom to top, wherein the material of the perovskite light absorption layer is the above-mentioned perovskite light absorption material.

[0191] This embodiment provides a method for preparing the above-mentioned perovskite solar cell, comprising the following steps:

[0192] (1) Treating the conductive substrate: AZO conductive glass was used as the conductive substrate, and glass cleaning agent, deionized water, ethanol, acetone, isopropanol and ethanol were ultrasonicated for 10 min in sequence, and then the conductive substrate was blown dry with dry air, followed by UV-ozone treatment for 15 min;

[0193] (2) Preparation of the first carrier transport layer: Spin coating a 0.7 mg / mL ethanol solution of [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid (Me-4PACz) on the pre-cleaned AZO conductive glass at a spin coating speed of 4000 rpm for 10 s, and then annealing at 100° C. for 10 min to obtain a first carrier transport layer having a thickness of 40 nm;

[0194] (3) Preparation of two-dimensional perovskite precursor layer: two-dimensional perovskite precursor material BAI (such as Figure 3 ) was mixed with N,N-dimethylformamide to obtain a two-dimensional perovskite precursor solution with a concentration of 3 mg / mL, and then spin-coated at a rate of 4000 rpm for 30 s, followed by a first annealing at a temperature of 80°C for 5 min to obtain a two-dimensional perovskite precursor layer composed of BDAI material.

[0195] (4) Preparation of perovskite light-absorbing layer (wet film): The three-dimensional perovskite precursor deposition liquid is spin-coated on the two-dimensional perovskite precursor layer in steps. The first step is spin-coated at a rate of 1000 rpm for 10 s, and the second step is spin-coated at a rate of 3000 rpm for 20 s. At the same time, after rotating at 1000 rpm for 10 s, ether solution is added as an anti-solvent. After the spin coating is completed, a wet film of the perovskite light-absorbing layer is obtained.

[0196] (5) In-situ reaction to form the first interface layer and the perovskite light absorbing layer: The device obtained in step (4) is subjected to a second annealing step by step, wherein the first annealing temperature is 65°C for 4 min, and the second annealing temperature is 110°C for 13 min. During the annealing process, the two-dimensional perovskite precursor present at the bottom of the perovskite light absorbing layer wet film reacts in situ with the unreacted lead iodide in the perovskite light absorbing layer wet film. After the annealing is completed, a BA2PbI4-DMA is formed. 0.1 Cs 0.25 FA 0.6 MA 0.05 PbI 2.7 Br 0.3 The first interface layer composed of 2D-3D hybrid perovskite, DMA formed on the first interface layer 0.1 Cs 0.25 FA 0.6 MA 0.05 PbI 2.7 Br 0.3 Three-dimensional perovskite light-absorbing layer, the thickness of the first interface layer is 20nm, and the thickness of the perovskite light-absorbing layer is 400nm.

[0197] (6) Preparing a second interface layer: mixing a basic amino acid-porphyrin conjugate and isopropanol, wherein the basic amino acid is histidine, to obtain an interface passivation solution with a concentration of 3 mg / mL, and then spin coating at a rate of 2000 rpm / 10 s, a third annealing temperature of 60° C., and a time of 4 min to obtain a second interface layer, which is an interface passivation layer, and a thickness of the second interface layer is 10 nm;

[0198] (7) Preparation of the second carrier transport layer: Using the evaporation method, C 60 Evaporation is performed on the second interface layer at a rate of The thickness of C is 30nm. 60 layer;

[0199] (8) Preparation of buffer layer and electrode layer: A SnO2 layer with a thickness of 5 nm and a copper layer with a thickness of 150 nm were sequentially deposited on the first carrier transport layer by evaporation at a deposition rate of The perovskite solar cell is obtained.

[0200] The perovskite light-absorbing material and preparation method thereof, the perovskite solar cell and preparation method thereof in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0201] Example 10

[0202] This embodiment provides a perovskite light-absorbing material, whose general structural formula is ABX3, wherein A includes CH(NH2)2 + , Cs + ; B includes Pb 2+ ; X is a halogen ion I - Br - , Cl - ; The particle size of the perovskite light-absorbing material is 50 to 2000 nm.

[0203] This embodiment also provides a method for preparing the above-mentioned perovskite light absorbing layer, comprising the following steps:

[0204] Preparation of two-dimensional perovskite precursor layer: two-dimensional perovskite precursor material PEAI (such as Figure 3 ) was mixed with N,N-dimethylformamide to obtain a two-dimensional perovskite precursor solution with a concentration of 5 mg / mL, and then spin-coated at a rate of 4000 rpm for 30 s, followed by a first annealing at a temperature of 90°C for 6 min to obtain a two-dimensional perovskite precursor layer composed of PEAI material.

[0205] Preparation of perovskite light-absorbing layer (wet film): The three-dimensional perovskite precursor deposition liquid is spin-coated on the two-dimensional perovskite precursor layer in steps. The first step spin coating rate is 1000 rpm, the time is 10 s, and the second step spin coating rate is 3000 rpm, the time is 20 s. At the same time, after rotating at 1000 rpm for 10 s, ether solution is added as an anti-solvent. After the spin coating is completed, a wet film of the perovskite light-absorbing layer is obtained.

[0206] In-situ reaction to form the first interface layer and the perovskite light absorbing layer: the device obtained in step (4) is subjected to a second annealing step by step, the first step annealing temperature is 63 ° C, the time is 2 min, and the second step annealing temperature is 125 ° C, the time is 17 min. During the annealing process, the two-dimensional perovskite precursor present at the bottom of the perovskite light absorbing layer wet film reacts in situ with the unreacted lead iodide in the perovskite light absorbing layer wet film. After the annealing is completed, the first interface layer and the perovskite light absorbing layer are formed. 0.22 FA 0.78 Pb(I 0.85 Br 0.15 )3-CsPbCl3 two-dimensional-three-dimensional mixed perovskite composed of the first interface layer, forming Cs 0.22 FA 0.78 Pb(I 0.85 Br 0.15 )3-CsPbCl3 three-dimensional perovskite light absorbing layer, the thickness of the first interface layer is 1nm, and the thickness of the perovskite light absorbing layer is 800nm. The three-dimensional perovskite light absorbing layer is formed by a perovskite light absorbing material.

[0207] This embodiment also provides a perovskite solar cell, comprising a conductive substrate, a first carrier transport layer, a first interface layer, a perovskite light absorption layer, a second interface layer, a second carrier transport layer, a buffer layer, and an electrode layer, which are arranged in sequence from bottom to top, wherein the material of the perovskite light absorption layer is the above-mentioned perovskite light absorption material.

[0208] This embodiment provides a method for preparing the above-mentioned perovskite solar cell, comprising the following steps:

[0209] (1) Treating the conductive substrate: ITO conductive glass was used as the conductive substrate, and glass cleaning agent, deionized water, ethanol, acetone, isopropanol and ethanol were ultrasonicated for 10 min in sequence, and then the conductive substrate was blown dry with dry air, followed by UV-ozone treatment for 15 min;

[0210] (2) preparing the first carrier transport layer: spin coating a 0.7 mg / mL ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphoric acid (MeO-2PACz) on the pre-cleaned ITO conductive glass at a spin coating speed of 4000 rpm for 10 s, and then annealing at 100° C. for 10 min to obtain the first carrier transport layer;

[0211] (3) Preparation of two-dimensional perovskite precursor layer: two-dimensional perovskite precursor material PEAI (such as Figure 3 ) was mixed with N,N-dimethylformamide to obtain a two-dimensional perovskite precursor solution with a concentration of 5 mg / mL, and then spin-coated at a rate of 4000 rpm for 30 s, followed by a first annealing at a temperature of 90°C for 6 min to obtain a two-dimensional perovskite precursor layer composed of PEAI material.

[0212] (4) Preparation of perovskite light-absorbing layer (wet film): The three-dimensional perovskite precursor deposition liquid is spin-coated on the two-dimensional perovskite precursor layer in steps. The first step is spin-coated at a rate of 1000 rpm for 10 s, and the second step is spin-coated at a rate of 3000 rpm for 20 s. At the same time, after rotating at 1000 rpm for 10 s, ether solution is added as an anti-solvent. After the spin coating is completed, a wet film of the perovskite light-absorbing layer is obtained.

[0213] (5) In-situ reaction to form the first interface layer and the perovskite light absorbing layer: The device obtained in step (4) is subjected to a second annealing step by step, wherein the first annealing temperature is 63°C for 2 min, and the second annealing temperature is 125°C for 17 min. During the annealing process, the two-dimensional perovskite precursor present at the bottom of the perovskite light absorbing layer wet film reacts in situ with the unreacted lead iodide in the perovskite light absorbing layer wet film. After the annealing is completed, a first interface layer composed of (PEA)2PbI4-Cs 0.22 FA 0.78 Pb(I 0.85 Br 0.15 )3-CsPbCl3 two-dimensional-three-dimensional mixed perovskite composed of the first interface layer, forming Cs 0.22 FA 0.78 Pb(I 0.85 Br 0.15 )3-CsPbCl3 three-dimensional perovskite light absorbing layer, the thickness of the first interface layer is 1nm, and the thickness of the perovskite light absorbing layer is 800nm. .

[0214] (6) preparing the second interface layer: a basic amino acid-porphyrin conjugate and isopropanol, the basic amino acid is a combination of lysine, histidine and arginine (molar ratio of 1:1:1), to obtain an interface passivation solution with a concentration of 2 mg / mL, and then spin coating at a rate of 2000 rpm / 10 s, a third annealing temperature of 80° C., and a time of 4 min to obtain a second interface layer, which is an interface passivation layer, and the thickness of the second interface layer is 8 nm;

[0215] (7) Preparing the second carrier transport layer: magnetron sputtering ZnO on the second interface layer at a magnetron sputtering rate of A ZnO layer with a thickness of 40 nm is obtained;

[0216] (8) Preparation of buffer layer and electrode layer: A 3 nm thick 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) layer and a 70 nm thick gold layer were sequentially deposited on the first carrier transport layer by evaporation method. The deposition rate of the silver layer was The perovskite solar cell is obtained.

[0217] The perovskite light-absorbing material and preparation method thereof, the perovskite solar cell and preparation method thereof in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0218] Embodiment 11

[0219] This embodiment provides a perovskite solar cell, which is different from that in Embodiment 2 in that:

[0220] The material of the first carrier transport layer is 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD).

[0221] The material of the second carrier transport layer includes SnO2.

[0222] This embodiment provides a method for preparing the above-mentioned perovskite solar cell, which differs from that in Embodiment 2 in that:

[0223] (2) Prepare the first carrier transport layer by spin coating SnO2 on the conductive substrate at a spinning speed of 3000 rpm for 30 seconds, and finally anneal at a temperature of 150°C for 30 minutes.

[0224] (7) Preparation of the second carrier transport layer: Spiro-OMeTAD was spin-coated on the second interface layer by a spin coating method at a rotation speed of 4000 rpm for 30 s to obtain a Spiro-OMeTAD layer with a thickness of 70 nm.

[0225] The perovskite solar cell and its preparation method in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0226] Example 12

[0227] This embodiment provides a perovskite solar cell, which is different from that in Embodiment 2 in that:

[0228] The material of the first carrier transport layer is poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA).

[0229] This embodiment provides a method for preparing the above-mentioned perovskite solar cell, which differs from that in Embodiment 2 in that:

[0230] Step (7) Preparation of the second carrier transport layer: Slit coating ZnO on the second interface layer by slit coating to obtain a ZnO layer with a thickness of 40 nm.

[0231] The perovskite solar cell and its preparation method in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0232] Embodiment 13

[0233] This embodiment provides a perovskite solar cell, which is different from that in Embodiment 2 in that:

[0234] The material of the first carrier transport layer is poly(3-hexylthiophene-2,5-diyl) (P3HT).

[0235] This embodiment provides a method for preparing the above-mentioned perovskite solar cell, which differs from that in Embodiment 2 in that:

[0236] Step (2) prepares the first carrier transport layer by spin coating.

[0237] The perovskite solar cell and its preparation method in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0238] Embodiment 14

[0239] This embodiment provides a perovskite solar cell, which is different from that in Embodiment 2 in that:

[0240] The material of the first carrier transport layer is poly[bis(4-phenyl)(4-butylphenyl)amine] (poly-TPD).

[0241] This embodiment provides a method for preparing the above-mentioned perovskite solar cell, which differs from that in Embodiment 2 in that:

[0242] Step (5) prepares the perovskite light absorbing layer by a scraping method.

[0243] The perovskite solar cell and its preparation method in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0244] Embodiment 15

[0245] This embodiment provides a perovskite solar cell, which is different from that in Embodiment 2 in that:

[0246] The material of the first carrier transport layer is NiO x .

[0247] This embodiment provides a method for preparing the above-mentioned perovskite solar cell, which differs from that in Embodiment 2 in that:

[0248] Step (5) prepares the perovskite light absorbing layer by thermal evaporation.

[0249] The perovskite solar cell and its preparation method in this embodiment, wherein the material of the upper surface passivation layer is a basic amino acid-porphyrin conjugate, the basic amino acid-porphyrin conjugate contains an amino group, and the electron-donating effect of the amino group coordinates with Pb to form a metal porphyrin, stabilizes the perovskite structure, and the basic amino acid can effectively reduce the defect density of the perovskite layer, reduce the non-radiative recombination of carriers, and prolong the life of carriers. And the perovskite grain size of the perovskite light-absorbing material is increased, the grain boundary is reduced, the light absorption capacity of the film is enhanced, and the stability is improved, and the hysteresis effect is suppressed; the basic amino acid-porphyrin conjugate can enhance the interface contact between the transport layer and the perovskite through chemical bonds, efficiently passivate the interface defects between the second carrier transport layer and the perovskite layer, improve the charge transfer performance, and block the ion migration path, so that the efficiency and stability of the battery are significantly improved.

[0250] It is to be understood that the above embodiments are merely exemplary embodiments used to illustrate the principles of the present invention, but the present invention is not limited thereto. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered to be within the scope of protection of the present invention.

Claims

1. A method for preparing a perovskite light-absorbing layer, characterized in that: The following steps are involved: Depositing a two-dimensional perovskite precursor deposition liquid and performing a first annealing treatment to obtain a deposited two-dimensional perovskite cation precursor layer; A three-dimensional perovskite precursor deposition liquid is coated on the two-dimensional perovskite cation precursor layer to perform deposition to form a three-dimensional perovskite precursor wet film, and a second heating annealing treatment is performed. The two-dimensional perovskite cation precursor layer reacts in situ with lead iodide in the three-dimensional perovskite precursor wet film to obtain a first interface layer and a three-dimensional perovskite light-absorbing layer disposed on the first interface layer. The material of the three-dimensional perovskite light-absorbing layer is a perovskite light-absorbing material.

2. The method for preparing the perovskite light absorbing layer according to claim 1, characterized in that: The temperature of the first heating annealing treatment is 60-100° C., and the time is 3-6 minutes.

3. The method for preparing the perovskite light absorbing layer according to claim 1, characterized in that: The second heating annealing step is specifically as follows: First anneal at 55-65°C for 1-4 minutes; Then anneal at 100-130°C for 5-17 minutes.

4. The method for preparing the perovskite light absorbing layer according to claim 1, characterized in that: The first interface layer is a two-dimensional-three-dimensional mixed dimensional perovskite layer obtained by an in-situ reaction between a two-dimensional perovskite cation precursor layer and lead iodide in a three-dimensional perovskite precursor wet film. The material of the two-dimensional perovskite layer is any one or more of 1,4-butanediamine cation two-dimensional perovskite (BDA) PbI4, n-butylamine cation two-dimensional perovskite (BA) 2PbI4, phenylethylamine cation two-dimensional perovskite (PEA) 2PbI4, and ethylamine cation two-dimensional perovskite (EA) 2PbI4.

5. The method for preparing the perovskite light absorbing layer according to claim 1, characterized in that: The 2D perovskite precursors are organic amine halides; The three-dimensional perovskite precursors are metal halide perovskites.

6. The method for preparing the perovskite light absorbing layer according to claim 1, characterized in that: The concentration of the two-dimensional perovskite precursor in the two-dimensional perovskite precursor deposition solution is 0.5 to 5 mg / ml.

7. A perovskite light-absorbing material, characterized in that: It is a material for the three-dimensional perovskite light-absorbing layer obtained by the preparation method according to any one of claims 1 to 6, and the general structural formula of the perovskite light-absorbing material is ABX3, wherein A includes CH3NH3 + 、CH(NH2)2 + 、(CH3)2NH2 + , Cs + Any one or more of; B includes Pb 2+ Sn 2+ Any one or two of; X is a halogen ion I - Br - , Cl - Any one or more of the .

8. The perovskite light absorbing material according to claim 7, characterized in that: The particle size of the perovskite light absorbing material is 50 to 2000 nm.

9. A perovskite solar cell, characterized in that: It comprises a conductive substrate, a first carrier transport layer, a first interface layer, a perovskite light absorption layer, a second interface layer, a second carrier transport layer, a buffer layer, and an electrode layer arranged in sequence, wherein the perovskite light absorption layer is a three-dimensional perovskite light absorption layer obtained by the preparation method according to any one of claims 1 to 6.

10. The perovskite solar cell according to claim 9, characterized in that The conductive substrate includes any one of ITO, FTO and AZO.

11. The perovskite solar cell according to claim 9, characterized in that The first carrier transport layer is a first hole transport layer, and the second carrier transport layer is a first electron transport layer; The first carrier transport layer is a second electron transport layer, and the second carrier transport layer is a second hole transport layer.

12. The perovskite solar cell according to claim 11, characterized in that The material of the first hole transport layer or the second hole transport layer is any one of [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid, [2-(9H-carbazole-9-yl)ethyl]phosphoric acid, [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphoric acid, 2,2',7,7'-tetrakis[N,N-di(4-methylphenyl)amino]-9,9'-spirobifluorene, 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly(3-hexylthiophene-2,5-diyl), poly[bis(4-phenyl)(4-butylphenyl)amine], nickel oxide, and cuprous thiocyanate.

13. The perovskite solar cell according to claim 11, characterized in that The material of the first electron transport layer or the second electron transport layer includes C 60 ,[6,6]-phenyl-C 61 -Any one of methyl butyrate, SnO2, ZnO, and TiO2.

14. The perovskite solar cell according to claim 9, characterized in that The thickness of the first carrier transport layer is 10-100 nm, and the thickness of the second carrier transport layer is 10-100 nm.

15. The perovskite solar cell according to claim 9, characterized in that The first interface layer is a two-dimensional perovskite layer, and the material of the two-dimensional perovskite layer is any one or more of 1,4-butanediamine cation two-dimensional perovskite, n-butylamine cation two-dimensional perovskite, phenylethylamine cation two-dimensional perovskite, and ethylamine cation two-dimensional perovskite; The thickness of the first interface layer is 1 to 30 nm.

16. The perovskite solar cell according to claim 9, characterized in that The thickness of the perovskite light-absorbing layer is 300 to 800 nm.

17. The perovskite solar cell according to claim 9, characterized in that The material of the second interface layer includes a basic amino acid-porphyrin conjugate, in which a basic amino acid is introduced as a substituent into the porphyrin ring to conjugate with the porphyrin; The thickness of the second interface layer is 1-10 nm.

18. The perovskite solar cell according to claim 17, characterized in that The basic amino acid is any one or more of lysine, histidine and arginine.

19. The perovskite solar cell according to claim 9, characterized in that The material of the buffer layer is SnO2 or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline; The thickness of the buffer layer is 2 to 5 nm.

20. The perovskite solar cell according to claim 9, characterized in that The electrode layer is a metal electrode layer, and the material of the electrode layer includes any one of gold, silver and copper; The thickness of the electrode layer is 70 to 150 nm.

21. A method for preparing a perovskite solar cell according to any one of claims 9 to 20, characterized in that: The following steps are involved: depositing a first carrier transport layer on a conductive substrate; Depositing a two-dimensional perovskite precursor deposition liquid on the first carrier transport layer and performing a first annealing treatment to obtain a deposited two-dimensional perovskite cation precursor layer; Coating a three-dimensional perovskite precursor deposition liquid on the two-dimensional perovskite cation precursor layer to deposit and form a three-dimensional perovskite precursor wet film, and performing a second heating annealing treatment, wherein the two-dimensional perovskite cation precursor layer reacts in situ with lead iodide in the three-dimensional perovskite precursor wet film to obtain a first interface layer and a three-dimensional perovskite light-absorbing layer disposed on the first interface layer; depositing a basic amino acid-porphyrin conjugate deposition liquid on the perovskite light absorbing layer, and performing a third heating annealing treatment to obtain a second interface layer; A second carrier transport layer, a buffer layer and an electrode layer are sequentially deposited on the second interface layer to obtain a perovskite solar cell.

22. The method for preparing a perovskite solar cell according to claim 21, characterized in that: The first heating annealing treatment is performed at a temperature of 60 to 100° C. for 3 to 10 minutes. The second heating annealing treatment step is specifically: first annealing at 55-65° C. for 1-4 minutes, and then annealing at 100-130° C. for 5-17 minutes.

23. The method for preparing a perovskite solar cell according to claim 21, characterized in that: The temperature of the third heating annealing is 60-100° C., and the time is 3-6 minutes.

24. The method for preparing a perovskite solar cell according to claim 21, characterized in that: The method also includes the following steps of preparing a basic amino acid-porphyrin conjugate deposition liquid, specifically, mixing the basic amino acid-porphyrin conjugate and a solvent, wherein the solvent is any one of ethanol and isopropanol; the content of the basic amino acid-porphyrin conjugate in the basic amino acid-porphyrin conjugate deposition liquid is 1 to 3 mg / ml.

25. The method for preparing a perovskite solar cell according to claim 21, characterized in that: The deposition method of the first carrier transport layer, the second carrier transport layer, and the perovskite light absorption layer includes any one of spin coating, spray coating, scraper coating, slit coating, thermal evaporation, magnetron sputtering, and atomic layer deposition.

26. The method for preparing a perovskite solar cell according to claim 21, characterized in that: The electrode layer is deposited by thermal evaporation, and the deposition rate is

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