Perovskite solar cell and preparation method thereof

Abstract

The invention relates to the technical field of cells, in particular to a perovskite solar cell and a preparation method thereof. The invention provides a perovskite solar cell. The perovskite solar cell comprises a substrate, a transparent conductive film, a functional layer, an electrode layer and an up-conversion material layer, the substrate, the transparent conductive film, the functional layer and the electrode layer are sequentially stacked; the up-conversion material layer is arranged between the substrate and the transparent conductive film; or the up-conversion material layer is arranged on one side, deviating from the transparent conductive film, of the substrate; or the up-conversion material layer is arranged on the side, away from the functional layer, of the electrode layer. According to the perovskite solar cell provided by the invention, the available wave band of sunlight is widened, and the utilization efficiency of the sunlight is increased, so that the current density of the perovskite solar cell is improved.

Description

Technical Field

[0001] The present invention relates to the field of battery technology, and in particular to a perovskite solar cell and a preparation method thereof. Background Art

[0002] Perovskite solar cells have the advantages of simple manufacturing process, low cost, and high light absorption coefficient, but the free diffusion distance of carriers is only micrometers, and the thickness of the perovskite light absorption layer is less than 1μm, which leads to a decrease in the light absorption of the perovskite light absorption layer. The cut-off absorption wavelength of the perovskite light absorption layer with a conventional bandgap suitable for perovskite cells is about 800nm, and the cut-off absorption wavelength of the perovskite light absorption layer with a wide bandgap suitable for stacked cells is about 720nm, resulting in some solar light not being fully utilized.

[0003] At present, the main ways to improve the efficiency of perovskite cells are concentrated on additive engineering and interface engineering. Through the interface passivation and body passivation of perovskite solar cells, high-voltage perovskite solar cells are obtained to achieve efficiency improvement. By matching the interface capacity and optimizing the functional layer to reduce the series resistance, improve the carrier collection capacity of the electrode, improve the fill factor and current of the perovskite cell, and improve the efficiency of the perovskite cell. However, the improvement of the current density of perovskite cells has encountered a big bottleneck. The current of wide-bandgap perovskite cells is difficult to exceed 21.5mA / cm 2 According to the report, the current of normal bandgap perovskite cells is difficult to exceed 26.5 mA / cm 2 It is of great significance to find new methods and ideas to further improve the current.

[0004] In view of this, this invention is proposed. Summary of the invention

[0005] The first object of the present invention is to provide a perovskite solar cell, which improves the absorption efficiency and current density of the perovskite solar cell to the solar spectrum.

[0006] The second object of the present invention is to provide a method for preparing a perovskite solar cell, which has simple steps and is suitable for large-scale industrial production.

[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0008] In a first aspect, the present invention provides a perovskite solar cell, the perovskite solar cell comprising a substrate, a transparent conductive film, a functional layer and an electrode layer stacked in sequence;

[0009] The perovskite solar cell further comprises an up-conversion material layer;

[0010] The up-conversion material layer is disposed between the substrate and the transparent conductive film; or, the up-conversion material layer is disposed on a side of the substrate away from the transparent conductive film; or, the up-conversion material layer is disposed on a side of the electrode layer away from the functional layer.

[0011] In the perovskite solar cell of the present invention, the upconversion material layer can improve the light utilization rate of the perovskite solar cell, and convert the light in the infrared band that cannot be absorbed by the cell into visible light through the upconversion material layer, thereby broadening the usable band of sunlight, increasing the efficiency of sunlight utilization, and thus improving the current density of the perovskite solar cell.

[0012] In a second aspect, the present invention further provides a method for preparing a perovskite solar cell, comprising the following steps:

[0013] Depositing the material of the up-conversion material layer on the surface of the substrate to obtain the up-conversion material layer; then depositing the material of the transparent conductive film, the material of the functional layer and the material of the electrode layer in sequence on the surface of the up-conversion material layer;

[0014] Alternatively, after depositing the material of the transparent conductive film, the material of the functional layer and the material of the electrode layer in sequence on the surface of one side of the substrate, the material of the up-conversion material layer is deposited on the surface of the other side of the substrate;

[0015] Alternatively, a transparent conductive film material, a functional layer material, and an electrode layer material are sequentially deposited on the surface of one side of the substrate, so that a transparent conductive film, a functional layer, and an electrode layer are sequentially formed on the substrate surface; and then the material of the conversion material layer is deposited on the surface of the electrode layer.

[0016] The preparation method of the perovskite solar cell of the present invention has simple steps. By depositing a layer of up-conversion material in the perovskite solar cell, the light in the infrared band of sunlight is converted into visible light, which increases the absorption and utilization of the full spectrum of sunlight by the perovskite, and realizes the preparation of a perovskite solar cell with a high current density. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 It is a schematic structural diagram of the perovskite solar cell of the present invention.

[0019] Figure 2 Another schematic diagram of the structure of the perovskite solar cell of the present invention.

[0020] Figure 3 It is another structural schematic diagram of the perovskite solar cell of the present invention. DETAILED DESCRIPTION

[0021] The technical scheme of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0022] A perovskite solar cell and a preparation method thereof according to an embodiment of the present invention are described in detail below.

[0023] See also Figure 1 , Figure 2 and Figure 3 , in some embodiments of the present invention, a perovskite solar cell is provided, comprising: a substrate, a transparent conductive film, a functional layer, an electrode layer and an upconversion material layer;

[0024] The substrate, the transparent conductive film, the functional layer and the electrode layer are stacked in sequence;

[0025] The up-conversion material layer is arranged between the substrate and the transparent conductive film; or, the up-conversion material layer is arranged on the side of the substrate away from the transparent conductive film; or, the up-conversion material layer is arranged on the side of the electrode layer away from the functional layer.

[0026] The perovskite solar cell of the present invention improves the light utilization rate of the cell by providing an upconversion material layer, converts light in the infrared band that cannot be absorbed by the cell into visible light through the upconversion material layer, converts the long-wavelength spectrum that accounts for more than 50% of the sunlight into visible light, increases the absorption and utilization of the full spectrum of sunlight by the perovskite, thereby broadening the usable band of sunlight, increasing the utilization efficiency of sunlight, and thus improving the current density of the perovskite solar cell.

[0027] The up-conversion material layer of the present invention is formed into a separate film, thereby avoiding the negative impact on the original film layer. The present invention is more conducive to improving stability by arranging the up-conversion material layer between the glass and the transparent conductive film.

[0028] In some embodiments of the present invention, the substrate comprises glass and / or a flexible substrate.

[0029] In some embodiments of the present invention, the upconversion material layer includes at least one of a hot-band absorption (HBA) upconversion material, a lanthanide-based upconversion nanoparticle (Ln-UCNPs) material, and a triplet-triplet annihilation (TTA) upconversion material.

[0030] The up-conversion material layer of the present invention adopts the above-mentioned material to have the up-conversion property of converting light in the 800-1200nm band into visible light, and the excitation energy is less than 100mW / cm 2 , and the transmittance of the upconversion material layer to visible light is maintained above 95%, which is beneficial to improving the performance of perovskite solar cells.

[0031] In some embodiments of the present invention, the up-conversion material layer includes at least one of the following tropical absorption up-conversion materials: rhodamine, oxazine compounds and fluorescein derivatives.

[0032] The tropical absorption up-conversion material of the present invention has high-efficiency energy conversion and excellent light stability, and is beneficial to improving the photoelectric conversion efficiency.

[0033] In some embodiments of the present invention, the chemical structural formula of rhodamine is: The chemical structure of oxazine compounds is: The chemical structure of fluorescein derivatives is:

[0034] In the formula, R1, R2, R3 and R4 are each independently H, Any of; In the formula, n is an integer between 0 and 10.

[0035] In some embodiments of the present invention, the upconversion material layer includes at least one of the following lanthanide-based upconversion nanoparticle materials: Ln-UCNPs@silica core-shell structure material, Ln-UCNPs@NaLuF4 material, doped Ln-UCNPs@CaF2 material and doped Ln-UCNPs@NaYF4 material; the doping elements in the doped Ln-UCNPs@CaF2 material and the doped Ln-UCNPs@NaYF4 material each independently include at least one of Er, Tm, Ho and Yb.

[0036] The lanthanide-based upconversion nanoparticle material of the present invention can absorb low-energy near-infrared light and emit high-energy visible light or ultraviolet light, and has excellent photostability, and can convert the long-wavelength spectrum in sunlight into visible light, thereby increasing the absorption and utilization of the full spectrum of sunlight by perovskite.

[0037] In some embodiments of the present invention, the upconversion material layer includes the following triplet-triplet annihilation upconversion materials: a photoreceptor and a luminescent body; the photoreceptor includes at least one of Pt-TPBP (platinum (II) tetraphenyltetrabenzoporphyrin), PdOEP ((2,3,7,8,12,13,17,18-octaethylporphyrinato)palladium (II)) and Ir(ppy)3 (Ir(III)-(2-phenylpyridin)3); the luminescent body includes at least one of DPA (9,10-diphenylanthracene), rubrene (Rubrene) and BODIPY (boron-dipyrromethene).

[0038] The triplet-triplet annihilation up-conversion material of the present invention can be effectively excited at a relatively low excitation light energy and can realize an effective up-conversion process.

[0039] In some embodiments of the present invention, the chemical formula of Pt-TPBP is: The chemical structure of PdOEP is: The chemical structure of Ir(ppy)3 is

[0040] In some embodiments of the present invention, the chemical structural formula of DPA is: The chemical structure of rubrene is The chemical structure of BODIPY is: In the formula, R1, R2 and R3 are each independently bromine (Br), iodine (I), hydrogen (H), phenyl (Ph), carboxyl (COOH), cyano (CN) and Any of; In the formula, n is an integer between 0 and 10.

[0041] In some embodiments of the present invention, the thickness of the up-conversion material layer is 5 to 100 nm; typically but not limitatively, for example, the thickness of the up-conversion material layer can be 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm or a range of any two thereof.

[0042] The up-conversion material layer of the present invention is within the range of 5 to 100 nm, which can keep the transmittance of the up-conversion material layer to visible light above 95%. If the thickness of the up-conversion material layer is too thick, the transmittance of visible light will be reduced, and if it is too thin, its quality cannot be guaranteed.

[0043] In some embodiments of the present invention, the functional layer includes a first carrier transport layer, a perovskite light absorption layer, a second carrier transport layer and a buffer layer stacked in sequence; the first carrier transport layer is in contact with the transparent conductive film; and the buffer layer is in contact with the electrode.

[0044] In perovskite solar cells, the carrier transport layer, perovskite light absorption layer and buffer layer each play a key role; the carrier transport layer has excellent charge transfer performance, which is beneficial to improving the light conversion efficiency of the cell; the perovskite light absorption layer can absorb sunlight and generate photogenerated electrons and holes to achieve photoelectric conversion; the buffer layer is beneficial to improving battery stability and life.

[0045] In some embodiments of the present invention, the functional layer further includes a passivation layer, and the passivation layer is disposed between the perovskite light absorbing layer and the second carrier transport layer.

[0046] The passivation layer of the present invention can improve the interface contact between the light absorbing layer and the carrier transport layer, improve the stability of the perovskite light absorbing layer, and improve the photoelectric conversion efficiency.

[0047] In some specific embodiments of the present invention, the structure of the perovskite solar cell can be any one of the following three structures;

[0048] A perovskite solar cell comprises: glass, an upconversion material layer, a transparent conductive film, a first carrier transport layer, a perovskite light absorption layer, a passivation layer, a second carrier transport layer, a buffer layer and an electrode layer which are stacked in sequence;

[0049] Alternatively, a perovskite solar cell comprises: an up-conversion material layer, glass, a transparent conductive film, a first carrier transport layer, a perovskite light absorption layer, a passivation layer, a second carrier transport layer, a buffer layer and an electrode layer which are stacked in sequence;

[0050] Alternatively, a perovskite solar cell comprises: glass, a transparent conductive film, a first carrier transport layer, a perovskite light absorption layer, a passivation layer, a second carrier transport layer, a buffer layer, an electrode layer and an upconversion material layer stacked in sequence.

[0051] In some embodiments of the present invention, the transparent conductive film includes at least one of ITO (indium tin oxide), FTO (fluorine-doped SnO2), IZO (indium zinc oxide), LTO (lithium titanate) and VTTO (vertical target tin oxide).

[0052] In some embodiments of the present invention, the thickness of the transparent conductive film is 30 to 80 nm; typically but not limiting, for example, the thickness of the transparent conductive film can be 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm or a range of any two thereof.

[0053] The transparent conductive film of the present invention has excellent conductive and optical properties, low resistivity and high visible light transmittance, and is useful for improving the photoelectric conversion efficiency when used in perovskite solar cells. The use of the transparent conductive film in the above-mentioned thickness range can ensure that the passage of photons is not affected and that the square resistance of the transparent conductive film is reasonable.

[0054] In some embodiments of the present invention, the band gap energy (Eg) of the perovskite light absorbing layer is greater than 1.63 eV, or the band gap energy (Eg) of the perovskite light absorbing layer is less than 1.59 eV.

[0055] If the band gap of the perovskite light-absorbing layer is smaller, it will have a higher photoelectric conversion efficiency, but the open-circuit voltage will also be lower; if the band gap is larger, it will have a lower photoelectric conversion efficiency, but the open-circuit voltage will also be higher.

[0056] In some embodiments of the present invention, the thickness of the perovskite light absorbing layer is 300 to 900 nm; typically but not limiting, for example, the thickness of the perovskite light absorbing layer can be 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm or a range of any two thereof.

[0057] The perovskite light absorbing layer of the present invention has efficient light absorption performance and can absorb most of the photons in the ultraviolet-near infrared spectrum range; the use of the perovskite light absorbing layer with the above thickness can ensure that the material of the perovskite light absorbing layer can fully absorb incident photons to achieve efficient photoelectric conversion efficiency.

[0058] In some embodiments of the present invention, the passivation layer includes, but is not limited to, phenylethylamine hydroiodide.

[0059] In some embodiments of the present invention, the thickness of the passivation layer is 1 to 10 nm, preferably 2 to 5 nm.

[0060] The present invention adopts phenylethylamine hydroiodide as the passivation layer, which can effectively passivate the defects in the perovskite layer and improve the quality of the perovskite light-absorbing layer.

[0061] In some embodiments of the present invention, the buffer layer includes, but is not limited to, tin oxide.

[0062] In some embodiments of the present invention, the thickness of the buffer layer is 10-50 nm; typically but not limiting, for example, the thickness of the buffer layer can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm or a range of any two thereof.

[0063] The tin oxide buffer layer has excellent physical and chemical stability and good charge transport properties, which is beneficial to improving the performance of battery devices.

[0064] In some embodiments of the present invention, the electrode layer includes at least one of Ag, ITO, FTO, IZO, LTO, and VTTO.

[0065] In some embodiments of the present invention, the thickness of the electrode layer is 30 to 120 nm, typically but not limiting. For example, the thickness of the electrode layer can be 30 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm or a range of any two thereof.

[0066] The transparent electrode layer in the above thickness range in perovskite solar cells has high transmittance, excellent conductivity, good chemical stability and physical and mechanical properties, which is beneficial to improving battery performance.

[0067] In some embodiments of the present invention, the first carrier transport layer is a hole transport layer, and the second carrier transport layer is an electron transport layer; or, the first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer.

[0068] In some embodiments of the present invention, the electron transport layer includes, but is not limited to, C60.

[0069] In some embodiments of the present invention, the thickness of the electron transport layer is 10 to 50 nm; typically but not limiting, for example, the thickness of the electron transport layer can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm or a range of any two thereof.

[0070] The electron transport layer within the above thickness range of the present invention ensures that the perovskite solar cell has efficient electron transport performance and excellent stability, can improve the photoelectric conversion efficiency of the battery, ensures good light transmittance and can passivate defects and protect the perovskite layer, thereby improving the stability and life of the battery.

[0071] In some embodiments of the present invention, the hole transport layer includes but is not limited to a nickel oxide layer and a PACz ([2-(9H-carbazole-9-yl)ethyl]phosphonic acid) monolayer; preferably, the nickel oxide layer is close to the glass side and the PACz monolayer is close to the electrode layer side.

[0072] In some embodiments of the present invention, the thickness of the nickel oxide layer is 1 to 20 nm; typically but not limiting, for example, the thickness of the nickel oxide layer can be 1 nm, 5 nm, 10 nm, 15 nm, 20 nm or a range of any two thereof.

[0073] The hole transport layer within the above thickness range of the present invention can effectively transport holes and reduce the loss of holes during the transmission process. It not only plays a blocking role but also matches with other film layers to ensure that photons can pass through, thereby improving the photoelectric conversion efficiency.

[0074] In some embodiments of the present invention, the perovskite solar cell includes at least one of a formal perovskite cell and an inverted perovskite cell.

[0075] The up-conversion material layer of the present invention can be used in regular perovskite cells and inverted perovskite cells, and can increase the efficiency of the cells in utilizing sunlight and improve the current density of the cells.

[0076] In some embodiments of the present invention, in a formal perovskite cell, the first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer.

[0077] In some embodiments of the present invention, in the inverse perovskite cell, the first carrier transport layer is a hole transport layer, and the second carrier transport layer is an electron transport layer.

[0078] In some embodiments of the present invention, a method for preparing the above-mentioned perovskite solar cell is also provided, comprising the following steps:

[0079] Depositing the material of the up-conversion material layer, the material of the transparent conductive film, the material of the functional layer and the material of the electrode layer in sequence on one side surface of the substrate;

[0080] Alternatively, after depositing the material of the transparent conductive film, the material of the functional layer and the material of the electrode layer in sequence on the surface of one side of the substrate, the material of the up-conversion material layer is deposited on the surface of the other side of the substrate;

[0081] Alternatively, the material of the transparent conductive film, the material of the functional layer, the material of the electrode layer and the material of the up-conversion material layer are sequentially deposited on one surface of the substrate.

[0082] The preparation method of the perovskite solar cell of the present invention has simple steps. By depositing a layer of up-conversion material in the perovskite solar cell, the long-wavelength spectrum of sunlight is converted into visible light, thereby increasing the absorption and utilization of the full spectrum of sunlight by the perovskite, and realizing the preparation of a perovskite solar cell with a high current density.

[0083] In some embodiments of the present invention, the deposition method includes at least one of a sputtering deposition method, a coating method, an evaporation method, and an atomic layer deposition method.

[0084] The present invention adopts deposition technology, has a fast film forming speed, a smooth surface, and the prepared film layer has excellent uniformity.

[0085] In some embodiments of the present invention, depositing the material of the functional layer includes: depositing the material of the first carrier transport layer, depositing the material of the perovskite light absorption layer, and after annealing, depositing the material of the second carrier transport layer, and depositing the material of the buffer layer.

[0086] In some embodiments of the present invention, annealing includes: annealing at 130-180° C. for 5-20 min.

[0087] In some embodiments of the present invention, after annealing, the process further includes depositing a material for a passivation layer.

[0088] In some embodiments of the present invention, the deposition method of the material of the up-conversion material layer includes but is not limited to evaporation and / or solution coating.

[0089] In some embodiments of the present invention, the deposition method of the material of the transparent conductive film includes but is not limited to a sputtering deposition method.

[0090] In some embodiments of the present invention, the deposition method of the material of the hole transport layer includes but is not limited to a sputtering deposition method and / or a solution coating method.

[0091] In some embodiments of the present invention, the deposition method of the material of the perovskite light absorbing layer includes but is not limited to evaporation and / or solution coating.

[0092] In some embodiments of the present invention, the deposition method of the material of the passivation layer includes but is not limited to a coating method.

[0093] In some embodiments of the present invention, the deposition method of the material of the electron transport layer includes but is not limited to evaporation.

[0094] In some embodiments of the present invention, the deposition method of the material of the buffer layer includes but is not limited to atomic layer deposition (ALD).

[0095] In some embodiments of the present invention, the deposition method of the material of the electrode layer includes but is not limited to sputtering deposition or evaporation.

[0096] In some specific embodiments of the present invention, when the perovskite cell is a formal perovskite cell, the materials for depositing the functional layers include: materials for depositing the electron transport layer, materials for depositing the perovskite light absorbing layer, and after annealing, materials for depositing the passivation layer, materials for depositing the hole transport layer, and materials for depositing the buffer layer.

[0097] In some specific embodiments of the present invention, when the perovskite cell is an inverted perovskite cell, the material for depositing the functional layer includes: the material for depositing the hole transport layer, the material for depositing the perovskite light absorbing layer, and after annealing, the material for depositing the passivation layer, the material for depositing the electron transport layer, and the material for depositing the buffer layer.

[0098] Example 1

[0099] The preparation method of the perovskite solar cell provided in this embodiment has a cell structure of an inverted perovskite solar cell structure, which comprises, from the light incident surface, a high-transmittance glass, an upconversion luminescent material Rodanmine, a transparent conductive film (ITO layer), a hole transport layer, a perovskite light absorbing layer, a passivation layer, an electron transport material, a buffer layer material and an electrode layer; specifically comprises the following steps:

[0100] Step 1: Deposit a layer of upper conversion luminescent material Rodanmine on the surface of high-transmittance glass with a thickness of 50nm;

[0101] Step 2: Deposit a layer of ITO with a thickness of 60 nm on the surface of the upconversion luminescent material Rodanmine by sputtering deposition;

[0102] Step 3: Pre-treat the high-transmittance glass after ITO deposition; the specific steps are as follows: clean the high-transmittance glass after ITO deposition to remove surface impurities; use glass cleaning agent and deionized water to ultrasonically treat the high-transmittance glass after ITO deposition for 15 minutes, then blow dry with dry air, and then treat with ozone for 20 minutes;

[0103] Step 4: Using a spin coating process, a nickel oxide layer with a thickness of 20 nm is deposited on the surface of the ITO layer as a hole transport layer. In the solution for forming the hole transport layer, the solvent is ethanol, the solute is nickel oxide, and the concentration of the solute is 20 mg / ml;

[0104] Step 5: Spin-coat a 0.008 mol / L [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (PACz) IPA (isopropyl alcohol) solution on the hole transport layer away from the ITO layer at a rotation speed of 5000 rpm to obtain a monolayer organic hole layer;

[0105] Step 6: Vacuum evaporation is used to deposit a 400nm thick inorganic salt layer on the organic hole layer PACz. The deposition rate of the inorganic salt layer is The types of inorganic salts are PbI2, PbBr2 and CsI, and the molar ratio is PbI2:PbBr2:CsI=5:2:1;

[0106] Step 7: Spin-coat a layer of organic salt on the inorganic salt layer using a spin coating process, including a 4 mol / L solution of methylammonium iodide (FAI), methylammonium chloride (MACl) and methylammonium bromide (MABr), with a molar ratio of FAI:MACl:MABr=3:0.1:1;

[0107] Step 8: Annealing at 150°C for 10 min to obtain a perovskite light absorption layer with a thickness of 800 nm;

[0108] Step 9: Spin-coat a passivation layer material with a thickness of 3 nm on the perovskite light-absorbing layer, wherein the passivation layer material is phenylethylamine hydroiodide;

[0109] Step 10: Vapor-deposit a C60 electron transport layer material with a thickness of 20 nm on the passivation layer;

[0110] Step 11: depositing a 20 nm thick tin oxide buffer layer material on the electron transport layer material by ALD to obtain a buffer layer;

[0111] Step 12: Evaporate a layer of metal Ag with a thickness of 30nm on the buffer layer to obtain an electrode layer.

[0112] Example 2

[0113] This embodiment provides a method for preparing a perovskite solar cell with reference to Embodiment 1, except that the upconversion luminescent material Rodanmine is replaced by Ln-UCNPs@NaLuF4.

[0114] Example 3

[0115] This embodiment provides a method for preparing a perovskite solar cell with reference to Embodiment 1, except that the upconversion luminescent material Rodanmine is replaced by Ir(ppy)3.

[0116] Example 4

[0117] The present embodiment provides a method for preparing a perovskite solar cell with reference to Example 1, except that the cell structure is an inverted perovskite solar cell structure, which includes, from the light incident surface, a high-transmittance glass, a transparent conductive film (ITO layer), a hole transport layer, a perovskite light absorbing layer, a passivation layer, an electron transport material, a buffer layer, an electrode layer and an up-conversion luminescent material Rodanmine; the ITO conductive glass is pretreated; the specific steps are as follows: the ITO conductive glass (the high-transmittance glass and the ITO layer are arranged in sequence) is cleaned to remove impurities on the surface; the ITO conductive glass is ultrasonically treated with a glass cleaning agent and deionized water for 15 minutes in sequence, the ITO conductive glass is blown dry with dry air, and then treated with ozone for 20 minutes; a spin coating process is used to directly deposit nickel oxide with a thickness of 20 nm on the surface of the ITO layer of the ozone-treated ITO conductive glass as a hole transport layer; a layer of up-conversion luminescent material Rodanmine with a thickness of 50 nm is deposited on the surface of the electrode layer.

[0118] Example 5

[0119] This embodiment provides a method for preparing a perovskite solar cell with reference to Example 4, except that the upconversion luminescent material Rodanmine is replaced by Ln-UCNPs@NaLuF4.

[0120] Example 6

[0121] This embodiment provides a method for preparing a perovskite solar cell with reference to Embodiment 4, except that the up-conversion luminescent material Rodanmine is replaced by Ir(ppy)3.

[0122] Example 7

[0123] The present embodiment provides a method for preparing a perovskite solar cell with reference to Example 1, except that the cell structure is an inverted perovskite solar cell structure, which includes, from the light incident surface, an up-conversion luminescent material Rodanmine, a high-transmittance glass, a transparent conductive film (ITO layer), a hole transport layer, a perovskite light absorption layer, a passivation layer, an electron transport material, a buffer layer, and an electrode layer; the ITO conductive glass is pretreated; the specific steps are as follows: the ITO conductive glass (the high-transmittance glass and the ITO layer are arranged in sequence) is cleaned to remove impurities on the surface; the ITO conductive glass is ultrasonically treated with a glass cleaning agent and deionized water for 15 minutes in sequence, the ITO conductive glass is blown dry with dry air, and then treated with ozone for 20 minutes; a spin coating process is used to directly deposit nickel oxide with a thickness of 20 nm on the surface of the ITO layer of the ozone-treated ITO conductive glass as a hole transport layer; after obtaining the electrode layer, a layer of up-conversion luminescent material Rodanmine with a thickness of 50 nm is deposited on the high-transmittance glass surface of the ITO conductive glass.

[0124] Example 8

[0125] This embodiment provides a method for preparing a perovskite solar cell with reference to Example 7, except that the upconversion luminescent material Rodanmine is replaced with Ln-UCNPs@NaLuF4.

[0126] Example 9

[0127] This embodiment provides a method for preparing a perovskite solar cell with reference to Embodiment 7, except that the upconversion luminescent material Rodanmine is replaced by Ir(ppy)3.

[0128] Comparative Example 1

[0129] The present embodiment provides a method for preparing a perovskite solar cell with reference to Example 1, except that there is no up-conversion luminescent material Rodanmine; from the light incident surface, there are high-transmittance glass, transparent conductive film (ITO layer), hole transport layer, perovskite light absorption layer, passivation layer, electron transport material, buffer layer and electrode layer; the ITO conductive glass is pretreated; the specific steps are as follows: the ITO conductive glass (high-transmittance glass and ITO layer arranged in sequence) is cleaned to remove surface impurities; the ITO conductive glass is ultrasonically treated with glass cleaning agent and deionized water for 15 minutes in sequence, the ITO conductive glass is blown dry with dry air, and then treated with ozone for 20 minutes; a spin coating process is used to directly deposit nickel oxide with a thickness of 20 nm on the surface of the ITO layer of the ITO conductive glass after ozone treatment as a hole transport layer.

[0130] Test example

[0131] IV tests were performed on the batteries of Examples 1 to 9 and Comparative Example 1, and the results are shown in Table 1.

[0132] The active area of ​​the battery device is 4mm 2 , using a xenon lamp solar simulator, the test light source intensity is AM1.5G, 100mW / cm 2 The JV performance curve of the battery was tested under light, and the following parameters were obtained: open circuit voltage (Voc), short circuit current density (Jsc), fill factor (FF), and photoelectric conversion efficiency (PCE) for testing.

[0133] Table 1

[0134] Upconversion materials Location Voc(V) <![CDATA[Jsc(mA / cm 2 )]]> FF(%) PCE(%) Example 1 Rodanmine Between glass and ITO 1.17 21.12 80.15 19.79 Example 2 <![CDATA[Ln-UCNPs@NaLuF4]]> Between glass and ITO 1.18 21.06 80.42 20.14 Example 3 <![CDATA[Ir(ppy)3]]> Between glass and ITO 1.19 21.23 81.67 19.88 Example 4 Rodanmine Electrode layer 1.15 20.89 80.18 20.03 Example 5 <![CDATA[Ln-UCNPs@NaLuF4]]> Electrode layer 1.17 19.95 79.81 20.15 Example 6 <![CDATA[Ir(ppy)3]]> Electrode layer 1.18 20.74 78.24 18.86 Example 7 Rodanmine Glass back 1.17 19.89 80.38 21.47 Example 8 <![CDATA[Ln-UCNPs@NaLuF4]]> Glass back 1.16 20.75 79.15 20.14 Example 9 <![CDATA[Ir(ppy)3]]> Glass back 1.15 19.74 80.24 19.52 Comparative Example 1 none - 1.12 18.12 78.15 16.25

[0135] As can be seen from Table 1, the perovskite solar cell of the present invention broadens the usable wavelength band of sunlight, increases the efficiency of sunlight utilization, and improves the current density of the perovskite solar cell.

[0136] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A perovskite solar cell, characterized in that: include: Substrate, transparent conductive film, functional layer, electrode layer and up-conversion material layer; The substrate, the transparent conductive film, the functional layer and the electrode layer are stacked in sequence; The up-conversion material layer is arranged between the substrate and the transparent conductive film; or, the up-conversion material layer is arranged on a side of the substrate away from the transparent conductive film; or, the up-conversion material layer is arranged on a side of the electrode layer away from the functional layer.

2. The perovskite solar cell according to claim 1, characterized in that Also includes at least one of the following features: (1) The substrate comprises glass and / or a flexible substrate; (2) the up-conversion material layer comprises at least one of a tropical absorption up-conversion material, an up-conversion nanoparticle material based on lanthanide elements, and a triplet-triplet annihilation up-conversion material; (3) the up-conversion material layer comprises at least one of the following tropical absorption up-conversion materials: rhodamine, oxazine compounds and fluorescein derivatives; (4) The upconversion material layer includes at least one of the following lanthanide-based upconversion nanoparticle materials: Ln-UCNPs@silica core-shell structure material, Ln-UCNPs@NaLuF4 material, doped Ln-UCNPs@CaF2 material and doped Ln-UCNPs@NaYF4 material; the doping elements in the doped Ln-UCNPs@CaF2 material and the doped Ln-UCNPs@NaYF4 material each independently include at least one of Er, Tm, Ho and Yb; (5) The up-conversion material layer includes the following triplet-triplet annihilation up-conversion materials: a photoreceptor and a luminophore; the photoreceptor includes at least one of Pt-TPBP, PdOEP and Ir(ppy)3; the luminophore includes at least one of DPA, rubrene and BODIPY; (6) The thickness of the up-conversion material layer is 5 to 100 nm.

3. The perovskite solar cell according to claim 2, characterized in that: The functional layer includes a first carrier transport layer, a perovskite light absorption layer, a second carrier transport layer and a buffer layer which are stacked in sequence; the first carrier transport layer is in contact with the transparent conductive film; and the buffer layer is in contact with the electrode layer.

4. The perovskite solar cell according to claim 3, characterized in that: Includes at least one of the following features: (1) The transparent conductive film includes at least one of ITO, FTO, IZO, LTO and VTTO; (2) The thickness of the transparent conductive film is 30 to 80 nm; (3) The band gap energy of the perovskite light absorbing layer is greater than 1.63 eV, or the band gap energy of the perovskite light absorbing layer is less than 1.59 eV; (4) The thickness of the perovskite light absorbing layer is 300 to 900 nm; (5) The buffer layer comprises tin oxide; (6) The thickness of the buffer layer is 10 to 50 nm; (7) The electrode layer includes at least one of Ag, ITO, FTO, IZO, LTO and VTTO; (8) The thickness of the electrode layer is 30 to 120 nm.

5. The perovskite solar cell according to claim 3, characterized in that: The first carrier transport layer is a hole transport layer, and the second carrier transport layer is an electron transport layer; or, the first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer.

6. The perovskite solar cell according to claim 5, characterized in that: Includes at least one of the following features: (1) The electron transport layer comprises C60; (2) The thickness of the electron transport layer is 10 to 50 nm; (3) The hole transport layer includes a nickel oxide layer and a PACz monolayer.

7. The perovskite solar cell according to claim 6, characterized in that: The thickness of the nickel oxide layer is 1-20 nm.

8. The method for preparing a perovskite solar cell according to any one of claims 1 to 7, characterized in that: The steps include: Depositing the material of the up-conversion material layer, the material of the transparent conductive film, the material of the functional layer and the material of the electrode layer in sequence on one side surface of the substrate; Alternatively, after depositing the material of the transparent conductive film, the material of the functional layer and the material of the electrode layer in sequence on the surface of one side of the substrate, the material of the up-conversion material layer is deposited on the surface of the other side of the substrate; Alternatively, the material of the transparent conductive film, the material of the functional layer, the material of the electrode layer and the material of the up-conversion material layer are sequentially deposited on one surface of the substrate.

9. The method for preparing a perovskite solar cell according to claim 8, characterized in that: The deposition method includes at least one of a sputtering deposition method, a coating method, an evaporation method and an atomic layer deposition method; And / or, depositing the material of the functional layer includes: depositing the material of the first carrier transport layer, depositing the material of the perovskite light absorption layer, and after annealing, depositing the material of the second carrier transport layer, and depositing the material of the buffer layer.

10. The method for preparing a perovskite solar cell according to claim 9, characterized in that: The annealing comprises: annealing at 130-180° C. for 5-20 minutes.

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