Perovskite solar cell and preparation method thereof

Abstract

The invention provides a perovskite solar cell and a preparation method thereof, the perovskite solar cell comprises a substrate, a conductive anode, a hole transport layer, a perovskite light absorption layer, an electron tunneling protection layer, a hole barrier layer and a conductive cathode which are stacked in sequence, and the material of the electron tunneling protection layer comprises aluminum oxide and / or molybdenum oxide; the hole blocking layer is made of tin oxide and / or IZO. According to the invention, the electron tunneling protection layer is arranged between the perovskite light absorption layer and the hole blocking layer, so that the damage to perovskite in the process of depositing the buffer layer of the hole blocking layer is blocked, and the stability of the cell is greatly improved; and tin oxide and / or IZO can be directly deposited without using C60, so that the manufacturing cost is greatly reduced, and a device with higher stability is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of solar cells and relates to a perovskite solar cell and a preparation method thereof. Background Art

[0002] Although the power conversion efficiency (PCE) of perovskite solar cells (PSCs) has reached 26.7%, exceeding many traditional thin-film solar technologies, it is difficult for perovskite solar cells to achieve long-term stability due to their fragile interfaces. Perovskites will degrade under the combined effects of various environmental factors (such as humidity, oxygen, temperature changes and light), thereby reducing the performance and life of the cell.

[0003] In inverse PSCs, deep traps are formed at the perovskite-hole blocking layer interface, leading to efficiency loss. 60 The high cost and poor mechanical properties of fullerene ETLs have prompted the search for alternatives.

[0004] However, potential alternatives, such as metal oxides, are difficult to be compatible with existing processes. The thermal stability of perovskites is also an issue that needs to be addressed, with high-temperature annealing usually used for optimal metal oxide processing.

[0005] CN117337057A discloses a perovskite solar cell and a preparation method thereof, wherein the perovskite solar cell comprises: a first carrier transport layer; a perovskite light absorption layer, arranged on one side of the first carrier transport layer; a second carrier transport layer, arranged on the side of the perovskite light absorption layer away from the first carrier transport layer; and a top electrode, arranged on the side of the second carrier transport layer away from the perovskite light absorption layer, wherein the top electrode is a carbon electrode composited with a heat dissipation material.

[0006] CN118785732A discloses a perovskite solar cell and a preparation method thereof. The perovskite solar cell comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an interface passivation layer, an electron transport layer and an electrode which are arranged in sequence.

[0007] The above scheme directly prepares an electron transport layer or a hole blocking layer on the perovskite light-absorbing layer. Sputtering oxide will damage the perovskite surface, and even if an interface passivation layer is set, it is difficult to avoid this problem. Directly depositing a hole blocking layer on the perovskite will produce chemical reactions and interface barriers. The passivation layer cannot eliminate the interface barrier, and it will still cause the PCE of the device to be lower than the normal value. Summary of the invention

[0008] The purpose of the present invention is to provide a perovskite solar cell and a preparation method thereof. The present invention adopts a method of setting an electron tunneling protection layer between the perovskite light absorbing layer and the hole blocking layer to block the damage to the perovskite during the process of depositing the buffer layer of the hole blocking layer, which greatly improves the stability of the battery. The electron tunneling protection layer does not affect the electron transmission, and there is no need to use C 60 Tin oxide and / or IZO, i.e. zinc-doped indium oxide, can be directly deposited, which greatly reduces the manufacturing cost and obtains a device with higher stability.

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a perovskite solar cell, the perovskite solar cell comprising a substrate, a conductive anode, a hole transport layer, a perovskite light absorption layer, an electron tunneling protection layer, a hole blocking layer and a conductive cathode stacked in sequence;

[0011] The material of the electron tunneling protection layer includes aluminum oxide and / or molybdenum oxide;

[0012] The hole blocking layer may be made of tin oxide and / or IZO.

[0013] The present invention sets an electron tunneling protection layer composed of aluminum oxide and / or molybdenum oxide between the perovskite light absorption layer and the hole blocking layer. The electron tunneling protection layer can be used as a buffer layer for the subsequent preparation of the hole blocking layer to avoid chemical reactions and interface barriers in the process of preparing the hole transport layer, which leads to the problem that the PCE of the device is far lower than the normal value. The electron tunneling protection layer also has the ability to separate carriers, which can also improve the performance of the device. The present invention uses tin oxide and / or IZO as a durable inorganic hole blocking layer instead of C 60 Fullerenes significantly reduce costs and improve the mechanical properties of batteries. At the same time, by setting up an electron tunneling protection layer, harmful chemical reactions and interface barriers between perovskite and the hole blocking layer are eliminated without hindering the normal transmission of electrons, which greatly improves the stability of perovskite components and has broad application prospects.

[0014] The solar cell described in the present invention is not limited to a single cell, but can also be made into a perovskite solar module composed of multiple cells.

[0015] Preferably, the substrate includes any one of a glass substrate, a silicon substrate, a polyethylene terephthalate (PET) substrate or a polyimide (PI) substrate, or a combination of at least two of them. Typical but non-limiting combinations include a combination of a glass substrate and a silicon substrate, a combination of a PET substrate and a PI substrate, or a combination of a silicon substrate and a PET substrate, etc.

[0016] Preferably, the material of the conductive anode includes any one of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO) or silver nanowires, or a combination of at least two of them. Typical but non-limiting combinations include a combination of ITO and FTO, a combination of ITO and silver nanowires, or a combination of FTO and silver nanowires, etc.

[0017] Preferably, the material of the hole transport layer includes NiO x , Cu2O, poly 3-hexylthiophene (P3HT), poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine (PTAA) or 2,2',7,7'-tetrakis [N,N-di (4-methoxyphenyl) amino] -9,9'-spirobifluorene (Spiro-OMeTAD) or any one or a combination of at least two thereof, a typical but non-limiting combination includes NiO x The combination of P3HT and Cu2O, the combination of P3HT and PTAA, or the combination of PTAA and Spiro-OMeTAD, etc.

[0018] Preferably, the thickness of the hole transport layer is 15 nm to 20 nm, for example, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm or 20 nm.

[0019] Preferably, the perovskite solar cell further comprises a first etching groove, a second etching groove and a third etching groove.

[0020] Preferably, the first etching groove, the second etching groove and the third etching groove are parallel to each other.

[0021] Preferably, the first etching groove runs through the conductive anode, and the first etching groove is filled with the same material as that of the hole transport layer.

[0022] Preferably, the second etching groove runs through the hole transport layer, the perovskite light absorption layer, the electron tunneling protection layer and the hole blocking layer, and the second etching groove is filled with the same material as the conductive cathode.

[0023] Preferably, the third etching groove at least penetrates the conductive cathode.

[0024] Preferably, the material of the perovskite light-absorbing layer includes ABX3 type perovskite, wherein A is any one of cesium ion, rubidium ion, methylamine ion or formamidinium ion, or a combination of at least two thereof, and typical but non-limiting combinations include a combination of cesium ion and formamidinium ion, a combination of cesium ion and rubidium ion, or a combination of methylamine ion and formamidinium ion, etc., B is lead ion and / or tin ion, and X is any one of bromide ion, iodide ion or chloride ion, or a combination of at least two thereof, and typical but non-limiting combinations include a combination of bromide ion and iodide ion, a combination of bromide ion and chloride ion, or a combination of chloride ion and iodide ion, etc.

[0025] Preferably, the thickness of the perovskite light absorbing layer is 400 nm to 500 nm, for example, 400 nm, 420 nm, 450 nm, 480 nm or 500 nm, etc., and is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0026] Preferably, a passivation layer is further provided between the perovskite light absorption layer and the electron tunneling protection layer.

[0027] Preferably, the material of the passivation layer includes any one of butylammonium bromide, hexylammonium bromide or phenylethylamine iodide, or a combination of at least two of them. Typical but non-limiting combinations include a combination of butylammonium bromide and phenylethylamine iodide, a combination of hexylammonium bromide and phenylethylamine iodide, or a combination of butylammonium bromide and hexylammonium bromide, etc.

[0028] Preferably, the thickness of the passivation layer is 3 nm to 5 nm, for example, 3 nm, 3.5 nm, 4 nm, 4.5 nm or 5 nm.

[0029] Preferably, the thickness of the electron tunneling protection layer is 3 nm to 7 nm, for example, 3 nm, 4 nm, 5 nm, 6 nm or 7 nm, etc., and is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] Preferably, the thickness of the hole blocking layer is 50 nm to 150 nm, for example, 50 nm, 80 nm, 100 nm, 120 nm or 150 nm, etc., and is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0031] Preferably, the material of the conductive cathode includes any one of Au, Ag, Cu, Pt or C, or a combination of at least two of them.

[0032] Preferably, the thickness of the conductive cathode is 120 nm to 180 nm, for example, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm or 180 nm, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] In a second aspect, the present invention provides a method for preparing a perovskite solar cell as described in the first aspect, the preparation method comprising the following steps:

[0034] Compounding a conductive anode on a substrate to obtain an anode conductive substrate, and preparing a hole transport layer on the anode conductive substrate;

[0035] A perovskite light absorbing layer is prepared on the hole transport layer, an electron tunneling protection layer is prepared on the perovskite light absorbing layer, and a hole blocking layer is prepared on the electron tunneling protection layer;

[0036] A conductive cathode is prepared on the hole blocking layer to obtain the perovskite solar cell.

[0037] Preferably, before preparing the hole transport layer, P1 etching is performed on the anode conductive substrate to form a first etching groove penetrating the conductive anode.

[0038] Preferably, the method for preparing the hole transport layer comprises any one of spin coating, slit coating, inkjet printing, vacuum thermal deposition, electron beam evaporation, magnetron sputtering or atomic layer deposition, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of spin coating and atomic layer deposition, a combination of spin coating and slit coating, or a combination of vacuum thermal deposition and electron beam evaporation, etc.

[0039] Preferably, the method for preparing the perovskite light-absorbing layer comprises any one of solution spin coating, slit coating or inkjet printing, or a combination of at least two of them. Typical but non-limiting combinations include a combination of solution spin coating and inkjet printing, a combination of solution spin coating and slit coating, or a combination of slit coating and inkjet printing, etc.

[0040] Preferably, after preparing the perovskite light absorbing layer, a passivation layer is prepared on the perovskite light absorbing layer.

[0041] Preferably, the method for preparing the passivation layer comprises dissolving the passivation material in an organic solvent to obtain an organic passivation solution, coating the organic passivation solution on the perovskite light absorbing layer by solution spin coating, slit coating or inkjet printing, and obtaining the passivation layer by annealing.

[0042] Preferably, the mass concentration of the passivation material in the organic passivation solution is 1 g / L to 5 g / L, for example: 1 g / L, 2 g / L, 3 g / L, 4 g / L or 5 g / L, etc., not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0043] Preferably, the annealing temperature is 80°C to 120°C, for example, 80°C, 90°C, 100°C, 110°C or 120°C, etc., and is not limited to the listed values, and other values ​​not listed within the range are also applicable.

[0044] Preferably, the annealing treatment time is 3 min to 8 min, for example, 3 min, 4 min, 5 min, 6 min, 7 min or 8 min, etc., not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] Preferably, the method for preparing the electron tunneling protection layer includes any one of spin coating, slit coating, inkjet printing, vacuum thermal deposition, electron beam evaporation, magnetron sputtering or atomic layer deposition, or a combination of at least two of them. Typical but non-limiting combinations include a combination of spin coating and atomic layer deposition, a combination of spin coating and slit coating, or a combination of vacuum thermal deposition and electron beam evaporation, etc.

[0046] Preferably, the method for preparing the hole blocking layer comprises any one of spin coating, slit coating, inkjet printing, vacuum thermal deposition, electron beam evaporation, magnetron sputtering or atomic layer deposition, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of spin coating and atomic layer deposition, a combination of spin coating and slit coating, or a combination of vacuum thermal deposition and electron beam evaporation, etc.

[0047] Preferably, after the hole blocking layer is prepared, the hole transport layer, the perovskite light absorbing layer, the electron tunneling protection layer and the hole blocking layer are subjected to P2 etching to form a second etching groove.

[0048] Preferably, the method for preparing the conductive cathode comprises any one of spin coating, slit coating, inkjet printing, vacuum thermal deposition, electron beam evaporation, magnetron sputtering or atomic layer deposition, or a combination of at least two thereof.

[0049] Preferably, after preparing the conductive cathode, the conductive cathode is subjected to P3 etching to form a third etching groove.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] (1) The present invention adopts a method of setting an electron tunneling protection layer between the perovskite light absorbing layer and the hole blocking layer to prevent the damage to the perovskite during the process of depositing the buffer layer of the hole blocking layer, which greatly improves the stability of the battery. The electron tunneling protection layer does not affect the electron transmission, and there is no need to use C 60 Tin oxide and / or IZO can be directly deposited, which greatly reduces the manufacturing cost and obtains a device with higher stability.

[0052] (2) The short-circuit current of the perovskite solar cell of the present invention can reach above 0.531A, the open-circuit voltage can reach above 43.397V, the fill factor can reach above 64%, and the photoelectric conversion efficiency can reach above 16.434%. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 It is a schematic cross-sectional view of each layer in the perovskite solar cell provided by an embodiment of the present invention.

[0054] Figure 2It is a photoelectric conversion efficiency attenuation curve diagram of the perovskite solar cells prepared in Example 1 of the present invention and Comparative Example 1. DETAILED DESCRIPTION

[0055] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0056] Example 1

[0057] This embodiment provides a perovskite solar cell, wherein the perovskite solar cell has a cross-sectional schematic diagram as shown in FIG. Figure 1 As shown:

[0058] The perovskite solar cell comprises a substrate 1, a conductive anode 2, a hole transport layer 3, a perovskite light absorption layer 4, a passivation layer 5, an electron tunneling protection layer 6, a hole blocking layer 7 and a conductive cathode 8 which are stacked in sequence;

[0059] The perovskite solar cell further includes a first etching groove 9, a second etching groove 10 and a third etching groove 11;

[0060] The first etching groove 9, the second etching groove 10 and the third etching groove 11;

[0061] The first etching groove 9 runs through the conductive anode 2, and the first etching groove is filled with the same material as the hole transport layer 3;

[0062] The second etching groove 10 penetrates the hole transport layer 3, the perovskite light absorption layer 4, the passivation layer 5, the electron tunneling protection layer 6 and the hole blocking layer 7, and the second etching groove 10 is filled with the same material as the conductive cathode 8;

[0063] The third etching groove 11 at least penetrates the conductive cathode 8 .

[0064] The preparation method of the perovskite solar cell is as follows:

[0065] P1 etching was performed on the FTO anode conductive substrate to form a first etching groove penetrating the ITO conductive anode. The etched FTO anode conductive substrate was scrubbed with deionized water, and then ultrasonicated with deionized water, acetone, and isopropanol for 30 minutes each. NiO with a thickness of 18 nm was prepared on the anode conductive substrate by vacuum thermal deposition. x hole transport layer;

[0066] In a nitrogen glove box, CsI, FAI, MAI, PbI2, and PbBr2 were weighed according to the molar ratio. The perovskite component is Cs 0.05 MA 0.05 FA0.9 Pb(I 0.95 Br 0.05 ), dissolved in DMF:DMSO=4:1 solvent, the precursor concentration is about 1.0 mol / L, and the slit coating method is used on NiO x A 450nm thick perovskite light-absorbing layer is prepared on the hole transport layer, butylammonium bromide is dissolved in isopropanol to prepare a butylammonium bromide passivator with a concentration of 1g / L, the passivator is coated on the perovskite light-absorbing layer by a slit coating method, and then annealed at 100°C for 5min to obtain a 4nm thick butylammonium bromide passivation layer, a 5nm thick Al2O3 electron tunneling protection layer is prepared on the passivation layer by a thermal evaporation method, a 120nm thick tin dioxide hole blocking layer is deposited on the electron tunneling protection layer by an atomic layer deposition method, and the hole transport layer, the perovskite light-absorbing layer, the electron tunneling protection layer and the hole blocking layer are P2 etched by laser scribing to form a second etched groove;

[0067] A Cu conductive cathode layer with a thickness of about 150 nm is deposited on the hole blocking layer by thermal evaporation, and laser scribing is performed again to form a third etching groove penetrating the conductive cathode, thereby obtaining the perovskite solar cell.

[0068] Example 2

[0069] This embodiment provides a perovskite solar cell, wherein the perovskite solar cell has a cross-sectional schematic diagram as shown in FIG. Figure 1 As shown:

[0070] The perovskite solar cell comprises a substrate 1, a conductive anode 2, a hole transport layer 3, a perovskite light absorption layer 4, a passivation layer 5, an electron tunneling protection layer 6, a hole blocking layer 7 and a conductive cathode 8 which are stacked in sequence;

[0071] The perovskite solar cell further includes a first etching groove 9, a second etching groove 10 and a third etching groove 11;

[0072] The first etching groove 9, the second etching groove 10 and the third etching groove 11;

[0073] The first etching groove 9 runs through the conductive anode 2, and the first etching groove is filled with the same material as the hole transport layer 3;

[0074] The second etching groove 10 penetrates the hole transport layer 3, the perovskite light absorption layer 4, the passivation layer 5, the electron tunneling protection layer 6 and the hole blocking layer 7, and the second etching groove 10 is filled with the same material as the conductive cathode 8;

[0075] The third etching groove 11 at least penetrates the conductive cathode 8 .

[0076] The preparation method of the perovskite solar cell is as follows:

[0077] P1 etching is performed on the FTO anode conductive substrate to form a first etching groove penetrating the FTO conductive anode, the etched FTO anode conductive substrate is scrubbed with deionized water, and then deionized water, acetone, and isopropanol are ultrasonicated for 30 minutes each, and a Ni2O hole transport layer with a thickness of 120 nm is prepared on the anode conductive substrate by a vacuum thermal deposition method;

[0078] In a nitrogen glove box, CsI, FAI, MAI, PbI2, and PbBr2 were weighed according to the molar ratio. The perovskite component is Cs 0.05 MA 0.05 FA 0.9 Pb(I 0.95 Br 0.05 ), dissolved in DMF:DMSO=4:1 solvent, the precursor concentration is about 1.0 mol / L, a 400 nm thick perovskite light absorbing layer is prepared on the Ni2O hole transport layer by a slit coating method, butyl ammonium bromide is dissolved in isopropanol to prepare a hexyl ammonium bromide passivator with a concentration of 5 g / L, the passivator is coated on the perovskite light absorbing layer by a slit coating method, and then annealed at 120°C for 3 min to obtain a 5 nm thick hexyl ammonium bromide passivation layer, a 3 nm thick Al2O3 electron tunneling protection layer is prepared on the passivation layer by a thermal evaporation method, an IZO hole blocking layer of about 120 nm is deposited on the electron tunneling protection layer by an atomic layer deposition method, and the hole transport layer, the perovskite light absorbing layer, the electron tunneling protection layer and the hole blocking layer are P2 etched by laser scribing to form a second etched groove;

[0079] A layer of Ag conductive cathode with a thickness of about 150 nm is deposited on the hole blocking layer by thermal evaporation, and laser scribing is performed again to form a third etching groove penetrating the conductive cathode, thereby obtaining the perovskite solar cell.

[0080] Example 3

[0081] This embodiment provides a perovskite solar cell, wherein the perovskite solar cell has a cross-sectional schematic diagram as shown in FIG. Figure 1 As shown:

[0082] The perovskite solar cell comprises a substrate 1, a conductive anode 2, a hole transport layer 3, a perovskite light absorption layer 4, a passivation layer 5, an electron tunneling protection layer 6, a hole blocking layer 7 and a conductive cathode 8 which are stacked in sequence;

[0083] The perovskite solar cell further includes a first etching groove 9, a second etching groove 10 and a third etching groove 11;

[0084] The first etching groove 9, the second etching groove 10 and the third etching groove 11;

[0085] The first etching groove 9 runs through the conductive anode 2, and the first etching groove is filled with the same material as the hole transport layer 3;

[0086] The second etching groove 10 penetrates the hole transport layer 3, the perovskite light absorption layer 4, the passivation layer 5, the electron tunneling protection layer 6 and the hole blocking layer 7, and the second etching groove 10 is filled with the same material as the conductive cathode 8;

[0087] The third etching groove 11 at least penetrates the conductive cathode 8 .

[0088] The preparation method of the perovskite solar cell is as follows:

[0089] P1 etching is performed on the FTO anode conductive substrate to form a first etching groove penetrating the FTO conductive anode, the etched FTO anode conductive substrate is scrubbed with deionized water, and then deionized water, acetone, and isopropanol are ultrasonicated for 30 minutes each, and a Ni2O hole transport layer with a thickness of 120 nm is prepared on the anode conductive substrate by a vacuum thermal deposition method;

[0090] In a nitrogen glove box, CsI, FAI, MAI, PbI2, and PbBr2 were weighed according to the molar ratio. The perovskite component is Cs 0.05 MA 0.05 FA 0.9 Pb(I 0.95 Br 0.05 ), dissolved in DMF:DMSO=4:1 solvent, the precursor concentration is about 1.0 mol / L, a 500 nm thick perovskite light absorbing layer is prepared on the Ni2O hole transport layer by a slit coating method, butyl ammonium bromide is dissolved in isopropanol to prepare a hexyl ammonium bromide passivator with a concentration of 1 g / L, the passivator is coated on the perovskite light absorbing layer by a slit coating method, and then annealed at 80°C for 8 min to obtain a 5 nm thick hexyl ammonium bromide passivation layer, a molybdenum oxide electron tunneling protection layer with a thickness of about 7 nm is prepared on the passivation layer by a thermal evaporation method, a tin dioxide hole blocking layer with a thickness of about 150 nm is deposited on the electron tunneling protection layer by an atomic layer deposition method, and the hole transport layer, the perovskite light absorbing layer, the electron tunneling protection layer and the hole blocking layer are P2 etched by laser scribing to form a second etched groove;

[0091] A Cu conductive cathode layer with a thickness of about 180 nm is deposited on the hole blocking layer by thermal evaporation, and laser scribing is performed again to form a third etching groove penetrating the conductive cathode, thereby obtaining the perovskite solar cell.

[0092] Example 4

[0093] The only difference between this embodiment and the first embodiment is that the thickness of the electron tunneling protection layer is 1 nm, and the other conditions and parameters are exactly the same as those in the first embodiment.

[0094] Example 5

[0095] The only difference between this embodiment and the first embodiment is that the thickness of the electron tunneling protection layer is 10 nm, and the other conditions and parameters are exactly the same as those in the first embodiment.

[0096] Example 6

[0097] The only difference between this embodiment and embodiment 1 is that no passivation layer is provided, and other conditions and parameters are exactly the same as those in embodiment 1.

[0098] Comparative Example 1

[0099] The only difference between this comparative example and Example 1 is that no electron tunneling protection layer is provided, and other conditions and parameters are exactly the same as those in Example 1.

[0100] Performance Testing:

[0101] The perovskite solar cells prepared in the embodiment and the comparative example are respectively connected in series to form a perovskite solar module. The number of perovskite solar cells in a single perovskite solar module is 41. A solar simulator and a digital source meter are used to characterize the current Isc, open circuit voltage Voc, fill factor FF, and photoelectric conversion efficiency Eff of the perovskite solar module. The characterization results are shown in Table 1:

[0102] Table 1

[0103]

[0104]

[0105] As can be seen from Table 1, from Examples 1-6, the short-circuit current of the perovskite solar cell of the present invention can reach more than 0.522A, the open-circuit voltage can reach more than 42.344V, the fill factor can reach more than 57.5%, and the photoelectric conversion efficiency can reach more than 14.702%. By adjusting the thickness of the electron tunneling protection layer and adding a passivation layer, the short-circuit current of the perovskite solar cell can reach more than 0.531A, the open-circuit voltage can reach more than 43.397V, the fill factor can reach more than 64%, and the photoelectric conversion efficiency can reach more than 16.434%.

[0106] By comparing Example 1 with Examples 4-5, it can be seen that in the perovskite solar cell described in the present invention, the thickness of the electron tunneling protection layer responds to its performance. When the thickness of the electron tunneling protection layer is controlled at 3 to 7 nm, the performance of the perovskite solar cell obtained is better. If the thickness of the electron tunneling protection layer is too large, it will block the transmission of electrons and cause excessive steric hindrance, reducing the FF from 64.3% in Example 1 to 57.5% in Example 5. If the thickness of the electron tunneling protection layer is too small, it cannot effectively isolate the chemical reaction of atomic layer deposition SnO2, causing the FF in Example 4 to be significantly reduced to 59.3%.

[0107] By comparing Example 1 with Example 6, it can be seen that in the perovskite solar cell of the present invention, the passivation layer can effectively reduce the defect state density on the surface of the perovskite and improve the V OC With FF.

[0108] The photoelectric conversion efficiency attenuation curves of the perovskite solar cells obtained in Example 1 of the present invention and Comparative Example 1 are as follows: Figure 2 As shown by Figure 2 It can be seen that the T80 life of comparative example 1 is 200h, while the T80 life of the device of embodiment 1 using Al2O3 electron tunneling protection layer to directly atomically deposit SnO2 can reach 1300h. It can be seen that after using Al2O3 electron tunneling protection layer to directly atomically deposit SnO2, the stability of the device has been greatly improved. The present invention sets an electron tunneling protection layer composed of aluminum oxide and / or molybdenum oxide materials between the perovskite light absorbing layer and the hole blocking layer. The electron tunneling protection layer can be used as a buffer layer for the subsequent preparation of the hole blocking layer to avoid chemical reactions and interface barriers in the process of preparing the hole transport layer, resulting in the problem that the PCE of the device is far lower than the normal value. The electron tunneling protection layer also has the ability to separate carriers, which can also improve the performance of the device. The present invention uses tin oxide and / or IZO as a durable inorganic hole blocking layer instead of C 60 Fullerenes significantly reduce costs and improve the mechanical properties of batteries. At the same time, by setting up an electron tunneling protection layer, harmful chemical reactions and interface barriers between perovskite and the hole blocking layer are eliminated without hindering the normal transmission of electrons, which greatly improves the stability of perovskite components and has broad application prospects.

[0109] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A perovskite solar cell, characterized in that: The perovskite solar cell comprises a substrate, a conductive anode, a hole transport layer, a perovskite light absorption layer, an electron tunneling protection layer, a hole blocking layer and a conductive cathode which are stacked in sequence; The material of the electron tunneling protection layer includes aluminum oxide and / or molybdenum oxide; The hole blocking layer may be made of tin oxide and / or IZO.

2. The perovskite solar cell according to claim 1, characterized in that The substrate includes any one of a glass substrate, a silicon substrate, a PET substrate or a PI substrate, or a combination of at least two thereof; Preferably, the material of the conductive anode includes any one of ITO, FTO or silver nanowires or a combination of at least two thereof; Preferably, the material of the hole transport layer comprises NiO x , Cu2O, P3HT, PTAA or Spiro-OMeTAD, or a combination of at least two thereof; Preferably, the hole transport layer has a thickness of 15 to 20 nm.

3. The perovskite solar cell according to claim 1 or 2, characterized in that: The perovskite solar cell further comprises a first etching groove, a second etching groove and a third etching groove; Preferably, the first etching groove, the second etching groove and the third etching groove are parallel to each other; Preferably, the first etching groove runs through the conductive anode, and the first etching groove is filled with the same material as the hole transport layer; Preferably, the second etching groove penetrates the hole transport layer, the perovskite light absorption layer, the electron tunneling protection layer and the hole blocking layer, and the second etching groove is filled with the same material as the conductive cathode; Preferably, the third etching groove at least penetrates the conductive cathode.

4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that: The material of the perovskite light-absorbing layer includes ABX3 type perovskite, wherein A is any one of cesium ion, rubidium ion, methylamine ion or methylammonium ion or a combination of at least two thereof, B is lead ion and / or tin ion, and X is any one of bromide ion, iodide ion or chloride ion or a combination of at least two thereof; Preferably, the thickness of the perovskite light absorbing layer is 400nm to 500nm.

5. The perovskite solar cell according to any one of claims 1 to 4, characterized in that: A passivation layer is also provided between the perovskite light absorption layer and the electron tunneling protection layer; Preferably, the material of the passivation layer includes any one of butylammonium bromide, hexylammonium bromide or phenylethylamine iodide or a combination of at least two thereof; Preferably, the thickness of the passivation layer is 3-5 nm.

6. The perovskite solar cell according to any one of claims 1 to 5, characterized in that: The thickness of the electron tunneling protection layer is 3nm-7nm.

7. The perovskite solar cell according to any one of claims 1 to 6, characterized in that: The thickness of the hole blocking layer is 50nm-150nm.

8. The perovskite solar cell according to any one of claims 1 to 7, characterized in that: The material of the conductive cathode includes any one of Au, Ag, Cu, Pt or C or a combination of at least two thereof; Preferably, the thickness of the conductive cathode is 120 nm to 180 nm.

9. A method for preparing a perovskite solar cell according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: Compounding a conductive anode on a substrate to obtain an anode conductive substrate, and preparing a hole transport layer on the anode conductive substrate; A perovskite light absorbing layer is prepared on the hole transport layer, an electron tunneling protection layer is prepared on the perovskite light absorbing layer, and a hole blocking layer is prepared on the electron tunneling protection layer; A conductive cathode is prepared on the hole blocking layer to obtain the perovskite solar cell.

10. The preparation method according to claim 9, characterized in that: Before preparing the hole transport layer, P1 etching is performed on the anode conductive substrate to form a first etching groove penetrating the conductive anode; The method for preparing the hole transport layer includes any one or a combination of at least two of spin coating, slit coating, inkjet printing, vacuum thermal deposition, electron beam evaporation, magnetron sputtering or atomic layer deposition; Preferably, the method for preparing the perovskite light absorbing layer comprises any one or a combination of at least two of a solution spin coating method, a slit coating method or an inkjet printing method; Preferably, after preparing the perovskite light absorbing layer, a passivation layer is prepared on the perovskite light absorbing layer. Preferably, the method for preparing the passivation layer comprises dissolving the passivation material in an organic solvent to obtain an organic passivation solution, coating the organic passivation solution on the perovskite light absorbing layer by solution spin coating, slit coating or inkjet printing, and obtaining the passivation layer by annealing; Preferably, the mass concentration of the passivation material in the organic passivation solution is 1 g / L to 5 g / L; Preferably, the annealing temperature is 80°C to 120°C; Preferably, the annealing treatment time is 3 min to 8 min; Preferably, the method for preparing the electron tunneling protection layer comprises any one or a combination of at least two of spin coating, slit coating, inkjet printing, vacuum thermal deposition, electron beam evaporation, magnetron sputtering or atomic layer deposition; Preferably, the method for preparing the hole blocking layer comprises any one or a combination of at least two of spin coating, slit coating, inkjet printing, vacuum thermal deposition, electron beam evaporation, magnetron sputtering or atomic layer deposition; Preferably, after the hole blocking layer is prepared, the hole transport layer, the perovskite light absorption layer, the electron tunneling protection layer and the hole blocking layer are subjected to P2 etching to form a second etching groove; Preferably, the method for preparing the conductive cathode comprises any one or a combination of at least two of spin coating, slit coating, inkjet printing, vacuum thermal deposition, electron beam evaporation, magnetron sputtering or atomic layer deposition; Preferably, after preparing the conductive cathode, the conductive cathode is subjected to P3 etching to form a third etching groove.

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