CN111162170B - Perovskite thin film doped with ultraviolet absorber, preparation method and solar cell - Google Patents
Perovskite thin film doped with ultraviolet absorber, preparation method and solar cell Download PDFInfo
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- CN111162170B CN111162170B CN201811323212.8A CN201811323212A CN111162170B CN 111162170 B CN111162170 B CN 111162170B CN 201811323212 A CN201811323212 A CN 201811323212A CN 111162170 B CN111162170 B CN 111162170B
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- perovskite
- ultraviolet absorbent
- thin film
- solvent
- ultraviolet
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- 239000010409 thin film Substances 0.000 title claims abstract description 88
- 239000006097 ultraviolet radiation absorber Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002250 absorbent Substances 0.000 claims abstract description 124
- 230000002745 absorbent Effects 0.000 claims abstract description 118
- 238000000034 method Methods 0.000 claims abstract description 43
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- 229960001860 salicylate Drugs 0.000 claims abstract description 17
- 239000012965 benzophenone Substances 0.000 claims abstract description 16
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 16
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 15
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
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- 239000000243 solution Substances 0.000 claims description 60
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- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a perovskite thin film doped with an ultraviolet absorbent, wherein the perovskite thin film is doped with the ultraviolet absorbent, and the ultraviolet absorbent is at least one of benzophenone ultraviolet absorbent, salicylate ultraviolet absorbent, benzotriazole ultraviolet absorbent and p-aminobenzoate ultraviolet absorbent. The ultraviolet absorber is incorporated into the perovskite thin film by a solution mixing method, or a co-evaporation method, or an anti-solvent method, or a lamination method. The invention also discloses a method for preparing the perovskite thin film doped with the ultraviolet absorbent and a solar cell. The invention not only avoids the damage of the perovskite structure caused by the absorption of ultraviolet light by the perovskite, improves the stability of the perovskite solar cell, but also simplifies the preparation process and reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of solar cell preparation, and particularly relates to an ultraviolet absorber doped perovskite thin film, a preparation method thereof and a solar cell.
Background
Perovskite solar cells have attracted attention because of their advantages of simple preparation conditions, low preparation cost, high efficiency, and being flexible. Up to now in 2009, the photoelectric conversion efficiency has been increased from 3.8% to 23% or more, but the stability of perovskite solar cells has been a problem that has been difficult to solve. Factors such as light, water oxygen, temperature, etc., all affect the stability of the perovskite solar cell. The photosensitive material of the perovskite solar cell mainly comprises nitrogen-containing organic halide AX (A is nitrogen-containing organic matter such as methylamine and formamidine; X = Cl, Br, I) and lead halide (BX)2) And (4) forming. The high ultraviolet energy can degrade organic molecules in the perovskite structure and separate metal-anion (such as Pb-I) ionic bonds, thereby destroying the structure of the perovskite solar cell.
In the existing solar cell module, as disclosed in the patent with publication number CN201590420U, an ultraviolet absorbent is usually disposed on the surface of the transparent substrate, and the ultraviolet absorbent layer can effectively shield ultraviolet rays, prevent the ultraviolet rays from passing through the mask film, so that EVA is aged, the temperature of the cell sheet is raised, and the long-term use and the power generation efficiency of the module are affected. Because an ultraviolet absorber layer is added to the solar cell structure, the complexity of the solar cell module manufacturing process is increased, and the manufacturing cost is increased.
Disclosure of Invention
The invention aims to provide a perovskite thin film doped with an ultraviolet absorbent, a preparation method and a solar cell.
The invention is realized in such a way, and provides a perovskite thin film doped with an ultraviolet absorbent, wherein the perovskite thin film is doped with the ultraviolet absorbent, and the ultraviolet absorbent is at least one of benzophenone ultraviolet absorbent, salicylate ultraviolet absorbent, benzotriazole ultraviolet absorbent and p-aminobenzoate ultraviolet absorbent; wherein,
the benzophenone ultraviolet absorbent comprises (2-hydroxy-4-methoxyphenyl) phenyl ketone, 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-n-octoxy benzophenone, and 2,2 '-dihydroxy-4, 4' -dimethoxy benzophenone;
the salicylate ultraviolet absorbent comprises phenyl salicylate, amyl salicylate, p-isopropyl phenyl salicylate, phenyl o-hydroxybenzoate, salicylate (potassium, sodium, triethanolamine), and resorcinol monobenzoate;
benzotriazole ultraviolet absorbers include 2- (2 '-hydroxy-3', 5 '-di-tert-phenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2' - (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) p-cresol, 2- (2' -hydroxy-3 ',5' bis (a, a-dimethylbenzyl) phenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole;
the ultraviolet absorber of p-aminobenzoate refers to a series of p-aminobenzoic acid derivatives, including ethyl p-aminobenzoate and ethyl 4-dimethylaminobenzoate.
Further, the ultraviolet absorber is incorporated into the perovskite thin film by a solution mixing method, or a co-evaporation method, or an anti-solvent method, or a lamination method.
The present invention has been achieved in this way, and further provides a method for preparing the ultraviolet absorber-doped perovskite thin film as described above, wherein the method for preparing the ultraviolet absorber-doped perovskite thin film is a solution mixing method, and comprises the following steps:
step S11, preparing a perovskite solution;
step S12, adding an ultraviolet absorbent into the perovskite solution, and obtaining a mixed solution of the perovskite and the ultraviolet absorbent after the ultraviolet absorbent is completely dissolved;
step S13, coating the mixed solution on a substrate deposited with a transmission layer by any one of spin coating, blade coating, slit type continuous coating or spray coating to form a film containing the mixed solution, and annealing the film to obtain a perovskite film doped with an ultraviolet absorbent to form a perovskite active layer; wherein,
in step S11, the perovskite solution contains at least one precursor BX2At least one reactant AX, at least one solvent additive and at least one main solvent, wherein B is a divalent metal cation of any one of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is an anion of at least one of iodine, bromine, chlorine and astatine, A is a cation of at least one of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidine group and a guanidine nitrogen-containing organic compound, the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GBL), the solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents, alcohol solvents, and/alcohol solvents Ether solvents, aromatic hydrocarbons, such as at least one of DMSO, NMP, 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB), toluene; in the perovskite solution, the perovskite solution is dissolved in the organic solvent,precursor BX2The concentration of the solution is 0.5-2 mol/L, and the molar ratio of the reactant AX is AX: BX2= 0.9-1.1, the volume ratio of the solvent additive to the main solvent is 0-50%;
in step S12, the ultraviolet absorber is at least one of benzophenone, salicylate, benzotriazole, compound, and others; the dosage of the ultraviolet absorbent is precursor BX20.01 to 5% by mole.
The present invention has been achieved in this way, and further provides a method for preparing the ultraviolet absorber-doped perovskite thin film as described above, wherein the method for preparing the ultraviolet absorber-doped perovskite thin film is a solution mixing method, and comprises the following steps:
step S21, adding BX2Adding ultraviolet absorbent into the solution, and dissolving sufficiently to obtain precursor BX containing ultraviolet absorbent2Mixing the solution;
s22, coating the mixed solution on a substrate deposited with a transmission layer by any one of spin coating, blade coating, slit type continuous coating or spray coating to form a film containing the mixed solution, and annealing the film to obtain a precursor BX doped with an ultraviolet absorbent2A thin film layer;
step S23, placing the substrate containing the film layer in a film forming cavity, and controlling the vacuum degree in the film forming cavity to be 10-5 Pa~105Pa;
step S24, heating reactant AX powder which is placed in a film forming cavity in advance at the temperature of 100-200 ℃ to enable precursor BX containing ultraviolet absorbent to be2The film layer is placed in a vapor atmosphere of a reactant AX while heating the substrate at a temperature of 30 to 150 ℃ and a precursor BX containing an ultraviolet absorber2The thin film layer reacts with the reactant AX, the reaction time is controlled to be 10 min-120 min, and the gas molecules of the reactant AX react with the precursor BX in the thin film layer2Carrying out molecular reaction to generate a perovskite thin film doped with an ultraviolet absorbent to form a perovskite active layer; wherein,
in step S21, the front driveObject BX2The solution contains at least one solvent additive and at least one main solvent, wherein B is any one of divalent metal cations of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is at least one anion of iodine, bromine, chlorine and astatine, the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl pyrrolidone (NMP) and gamma-butyrolactone (GBL), the solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, aromatic hydrocarbons such as DMSO, NMP, 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), At least one of Chlorobenzene (CB) and toluene; precursor BX2The concentration of the solution is 0.5-2 mol/L, and the volume ratio of the solvent additive to the main solvent is 0-50%; the ultraviolet absorbent is at least one of benzophenone, salicylate, benzotriazole compounds, compound and other compounds, and the dosage of the ultraviolet absorbent is precursor BX20.01-5% of molar weight;
in step S24, a in the reactant AX is at least one cation of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidino group, or a guanidine nitrogen-containing organic compound, and the perovskite active layer has the following composition ratios: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
The invention is realized in such a way, and also provides a preparation method of the perovskite thin film doped with the ultraviolet absorbent, wherein the preparation method is a co-evaporation method and comprises the following steps:
step S31, placing the substrate deposited with the transmission layer in a film forming cavity, and controlling the vacuum degree in the film forming cavity at 10-5 Pa~105Heating the substrate at the same time under Pa, and controlling the heating temperature of the substrate at 30-150 ℃;
step S32, in the film forming cavity, the precursor BX is put2The reactant AX and the ultraviolet absorbent are respectively put in different evaporation sources for evaporation and reactionThe evaporation rate of the substance AX is 0.1-10A/s, and the precursor BX2Has an evaporation rate of 0.1-10A/s and an evaporation rate of 0.05-5A/s, and an evaporated precursor BX on the surface of a substrate deposited with a transmission layer2Continuously depositing and reacting the steam, the reactant AX steam and the ultraviolet absorbent steam to generate a perovskite thin film doped with the ultraviolet absorbent and form a perovskite active layer; wherein,
in step S32, the precursor BX2In (B) is any one of divalent metal cations of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is at least one anion of iodine, bromine, chlorine, astatine, thiocyanato and acetate, a in the reactant AX is at least one cation of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidine group and a guanidine nitrogen-containing organic compound, and the finally formed perovskite active layer has the component ratio: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
The present invention has been achieved in this way, and further provides a method for preparing the ultraviolet absorber-doped perovskite thin film as described above, which is an anti-solvent method, comprising the steps of:
step S41, dissolving the ultraviolet absorbent in the anti-solvent, and fully dissolving to prepare a mixed solution of the ultraviolet absorbent and the anti-solvent;
step S42, preparing a perovskite solution;
s43, coating the perovskite solution on the substrate deposited with the transmission layer by any one of spin coating, blade coating, slit type continuous coating or spray coating to form a layer of perovskite thin film;
step S44, coating the mixed solution prepared in the step 41 on the perovskite thin film prepared in the step 43 through any one of spin coating, blade coating, slit type continuous coating or spray coating to obtain a mixed thin film containing the mixed solution of the ultraviolet absorbent and the anti-solvent, and annealing the mixed thin film to obtain the perovskite thin film doped with the ultraviolet absorbent to form a perovskite active layer; wherein,
in step S41, the antisolvent is at least one of benzene, toluene, 1, 2-xylene, 1, 3-xylene, 1, 4-xylene, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether, amyl alcohol; the ultraviolet absorbent is at least one of benzophenone, salicylate, benzotriazole compounds, compounds and other compounds, and the concentration of the ultraviolet absorbent in the anti-solvent solution is 0.001-0.1 mol/L;
in step S42, the perovskite solution contains at least one precursor BX2At least one reactant AX, at least one solvent additive and at least one main solvent, wherein B is a divalent metal cation of any one of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is an anion of at least one of iodine, bromine, chlorine and astatine, A is a cation of at least one of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidine group and a guanidine nitrogen-containing organic compound, the main solvent is one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), gamma-butyrolactone (GBL), the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, a ketone solvent, an ether solvent, a ketone solvent, an ether solvent, a gamma-butyrolactone solvent, a hydrocarbon solvent, a halogenated hydrocarbon solvent, a ketone solvent, an ether solvent, a ketone, and a ketone solvent, Aromatic hydrocarbons, such as at least one of DMSO, NMP, 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB), toluene; in the perovskite solution, a precursor BX2The concentration of the solution is 0.5-2 mol/L, and the molar ratio of the reactant AX is AX: BX2= 0.9-1.1, the volume ratio of the solvent additive to the main solvent is 0-50%;
in step S44, the composition ratio of the finally formed perovskite active layer is: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
The present invention has been achieved in this way, and further provides a method for producing the ultraviolet absorber-doped perovskite thin film as described above, the method being a lamination method comprising the steps of:
s51, selecting any one solar cell as a substrate, wherein the solar cell comprises any one of amorphous silicon, polycrystalline silicon, crystalline silicon, copper indium gallium selenide sulfide, copper indium gallium sulfide, copper zinc tin sulfide and cadmium telluride;
step S52, depositing a buffer layer on the substrate;
step S53, preparing a perovskite thin film containing the ultraviolet absorbent on the buffer layer by adopting the preparation method of the perovskite thin film doped with the ultraviolet absorbent to prepare the laminated solar cell; wherein,
in step S52, the buffer layer is composed of at least one layer of single substance or mixture, and has the function of collecting and transporting carriers, and the material for preparing the buffer layer comprises TiO2、ZnO、SnO2、PCBM、PTAA、C60、C70、ITO、AZO、CuSCN、CuGaO2NiOx, WOx, MoOx, and their dopants.
The present invention has been achieved in this way, and provides a solar cell including the above-described ultraviolet absorber-doped perovskite thin film.
The present invention has been achieved in this way, and provides a solar cell including a perovskite thin film produced by the above-described method for producing a perovskite thin film doped with an ultraviolet absorber.
Compared with the prior art, the ultraviolet absorbent doped perovskite thin film, the preparation method and the solar cell have the advantages that the ultraviolet absorbent is doped into the perovskite thin film, and through the introduction of the ultraviolet absorbent, the damage of a perovskite structure caused by ultraviolet absorption of perovskite can be avoided, the internal defects of perovskite can be passivated, and the stability of the perovskite solar cell is improved. Meanwhile, the preparation process can be simplified, and the production cost can be reduced.
Drawings
FIG. 1 is a schematic diagram of a perovskite solar cell structure prepared according to a preferred embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, a preferred embodiment of the ultraviolet absorber doped perovskite thin film of the present invention is doped with an ultraviolet absorber. Therefore, the perovskite solar cell of the present invention comprises, in order from top to bottom, a back electrode layer 1, an upper transport layer 2, a perovskite thin film layer 3 doped with an ultraviolet absorber, a lower transport layer 4, and a transparent conductive layer 5.
Wherein the ultraviolet absorbent is at least one of benzophenone ultraviolet absorbent, salicylate ultraviolet absorbent, benzotriazole ultraviolet absorbent and p-aminobenzoate ultraviolet absorbent. Wherein, the benzophenone ultraviolet absorbent includes but is not limited to (2-hydroxy-4-methoxyphenyl) phenyl ketone, 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-n-octoxy benzophenone, 2 '-dihydroxy-4, 4' -dimethoxy benzophenone; salicylate-based ultraviolet absorbers include, but are not limited to, phenyl salicylate, amyl salicylate, phenyl p-isopropyl salicylate, phenyl o-hydroxybenzoate, salicylates (potassium, sodium, triethanolamine), resorcinol monobenzoate; benzotriazole-based ultraviolet absorbers include, but are not limited to, 2- (2 '-hydroxy-3', 5 '-di-tert-phenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2' - (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) p-cresol, 2- (2' -hydroxy-3 ',5' bis (a, a-dimethylbenzyl) phenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole; the ultraviolet absorber of p-aminobenzoate refers to a series of p-aminobenzoic acid derivatives, including but not limited to ethyl p-aminobenzoate, ethyl 4-dimethylaminobenzoate.
The ultraviolet absorber is incorporated into the perovskite thin film by a solution mixing method, or a co-evaporation method, or an anti-solvent method, or a lamination method.
The invention also discloses a preparation method of the perovskite thin film doped with the ultraviolet absorbent, which is a solution mixing method and comprises the following steps:
and step S11, preparing the perovskite solution.
And step S12, adding an ultraviolet absorbent into the perovskite solution, and obtaining a mixed solution of the perovskite and the ultraviolet absorbent after the ultraviolet absorbent is completely dissolved.
And step S13, coating the mixed solution on the substrate deposited with the transmission layer by any one of spin coating, blade coating, slit continuous coating or spray coating to form a film containing the mixed solution, and annealing the film to obtain the perovskite film doped with the ultraviolet absorbent to form the perovskite active layer.
Wherein, in step S11, the perovskite solution contains at least one precursor BX2At least one reactant AX, at least one solvent additive and at least one main solvent, wherein B is a divalent metal cation of any one of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is an anion of at least one of iodine, bromine, chlorine and astatine, A is a cation of at least one of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidine group and a guanidine nitrogen-containing organic compound, the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and gamma-butyrolactone (GBL), the solvent additive is any one of amide solvents, sulfone/sulfoxide solvents, ester solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents, alcohol solvents, and/alcohol solvents Ether solvents, aromatic hydrocarbons, such as at least one of DMSO, NMP, 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB), toluene; in the perovskite solution, a precursor BX2The concentration of the solution is 0.5-2 mol/L, and the molar ratio of the reactant AX is AX: BX2And = 0.9-1.1, wherein the volume ratio of the solvent additive to the main solvent is 0-50%.
In step S12, the ultraviolet absorber is at least one of benzophenone, salicylate, benzotriazole, compound, and others; the dosage of the ultraviolet absorbent is precursor BX20.01 to 5% by mole.
The invention also discloses a preparation method of the perovskite thin film doped with the ultraviolet absorbent, which is a solution mixing method and comprises the following steps:
step S21, adding BX2Adding ultraviolet absorbent into the solution, and dissolving sufficiently to obtain precursor BX containing ultraviolet absorbent2And (4) mixing the solution.
S22, coating the mixed solution on a substrate deposited with a transmission layer by any one of spin coating, blade coating, slit type continuous coating or spray coating to form a film containing the mixed solution, and annealing the film to obtain a precursor BX doped with an ultraviolet absorbent2A thin film layer.
Step S23, placing the substrate containing the film layer in a film forming cavity, and controlling the vacuum degree in the film forming cavity to be 10-5 Pa~105Pa is between Pa.
Step S24, heating reactant AX powder which is placed in a film forming cavity in advance at the temperature of 100-200 ℃ to enable precursor BX containing ultraviolet absorbent to be2The film layer is placed in a vapor atmosphere of a reactant AX while heating the substrate at a temperature of 30 to 150 ℃ and a precursor BX containing an ultraviolet absorber2The thin film layer reacts with the reactant AX, the reaction time is controlled to be 10 min-120 min, and the gas molecules of the reactant AX react with the precursor BX in the thin film layer2The molecules react to form a perovskite thin film doped with the ultraviolet absorbent to form a perovskite active layer.
Wherein, in step S21, the precursor BX2The solution contains at least one solvent additive and at least one main solvent, wherein B is Pb, Sn, W, Cu, Zn, Ga, Ge, As, Se, Rh, Pd, Ag, Cd, in, Sb, Os, Ir, Pt, Au, Cu, Zn, Cu, Zn, Sn, Ag, Zn, Cu, Sn, Sb,any one of divalent metal cations of mercury, thallium, bismuth and polonium, X is at least one anion of iodine, bromine, chlorine and astatine, the main solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl pyrrolidone (NMP) and gamma-butyrolactone (GBL), and the solvent additive is at least one of amide solvents, sulfones/sulfoxides solvents, ester solvents, hydrocarbons, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents and aromatic hydrocarbons, such as DMSO, NMP, 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB) and toluene; precursor BX2The concentration of the solution is 0.5-2 mol/L, and the volume ratio of the solvent additive to the main solvent is 0-50%; the ultraviolet absorbent is at least one of benzophenone, salicylate, benzotriazole compounds, compound and other compounds, and the dosage of the ultraviolet absorbent is precursor BX20.01 to 5% by mole.
In step S24, a in the reactant AX is at least one cation of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidino group, or a guanidine nitrogen-containing organic compound, and the perovskite active layer has the following composition ratios: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
The invention also discloses a preparation method of the perovskite thin film doped with the ultraviolet absorbent, which is a co-evaporation method and comprises the following steps:
step S31, placing the substrate deposited with the transmission layer in a film forming cavity, and controlling the vacuum degree in the film forming cavity at 10-5 Pa~105Pa, heating the substrate at 30-150 deg.C.
Step S32, in the film forming cavity, the precursor BX is put2The reactant AX and the ultraviolet absorbent are respectively put in different evaporation sources for evaporation, the evaporation rate of the reactant AX is 0.1-10A/s, and the precursor BX2Has an evaporation rate of 0.1-10A/s and an evaporation rate of 0.05-5A/s, and an evaporated precursor BX on the surface of a substrate deposited with a transmission layer2Steam, reactantsThe AX vapor and the ultraviolet absorber vapor are continuously deposited and react with each other to form a perovskite thin film doped with the ultraviolet absorber, thereby forming a perovskite active layer.
Wherein, in step S32, the precursor BX2In (B) is any one of divalent metal cations of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is at least one anion of iodine, bromine, chlorine, astatine, thiocyanato and acetate, a in the reactant AX is at least one cation of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidine group and a guanidine nitrogen-containing organic compound, and the finally formed perovskite active layer has the component ratio: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
The invention also discloses a preparation method of the perovskite thin film doped with the ultraviolet absorbent, which is an anti-solvent method and comprises the following steps:
step S41 is to dissolve the ultraviolet absorber in the anti-solvent and to dissolve it sufficiently to prepare a mixed solution of the ultraviolet absorber and the anti-solvent.
And step S42, preparing the perovskite solution.
And step S43, coating the perovskite solution on the substrate deposited with the transmission layer by any one of spin coating, blade coating, slit type continuous coating or spray coating to form a layer of perovskite thin film.
And step S44, coating the mixed solution prepared in step 41 on the perovskite thin film prepared in step 43 by any one of spin coating, blade coating, slit continuous coating or spray coating to obtain a mixed thin film containing the mixed solution of the ultraviolet absorber and the anti-solvent, and annealing the mixed thin film to obtain the perovskite thin film doped with the ultraviolet absorber and form the perovskite active layer.
Wherein in step S41, the antisolvent is at least one of benzene, toluene, 1, 2-xylene, 1, 3-xylene, 1, 4-xylene, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether, and pentanol; the ultraviolet absorbent is at least one of benzophenone, salicylate, benzotriazole compounds, compounds and other compounds, and the concentration of the ultraviolet absorbent in the anti-solvent solution is 0.001-0.1 mol/L.
In step S42, the perovskite solution contains at least one precursor BX2At least one reactant AX, at least one solvent additive and at least one main solvent, wherein B is a divalent metal cation of any one of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is an anion of at least one of iodine, bromine, chlorine and astatine, A is a cation of at least one of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidine group and a guanidine nitrogen-containing organic compound, the main solvent is one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), gamma-butyrolactone (GBL), the solvent additive is an amide solvent, a sulfone/sulfoxide solvent, an ester solvent, a hydrocarbon, a halogenated hydrocarbon solvent, a ketone solvent, an ether solvent, a ketone solvent, an ether solvent, a gamma-butyrolactone solvent, a hydrocarbon solvent, a halogenated hydrocarbon solvent, a ketone solvent, an ether solvent, a ketone, and a ketone solvent, Aromatic hydrocarbons, such as at least one of DMSO, NMP, 1, 8-Diiodooctane (DIO), N-cyclohexyl-2-pyrrolidone (CHP), Chlorobenzene (CB), toluene; in the perovskite solution, a precursor BX2The concentration of the solution is 0.5-2 mol/L, and the molar ratio of the reactant AX is AX: BX2And = 0.9-1.1, wherein the volume ratio of the solvent additive to the main solvent is 0-50%.
In step S44, the composition ratio of the finally formed perovskite active layer is: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
The invention also provides a preparation method of the perovskite thin film doped with the ultraviolet absorbent, which is a lamination method and comprises the following steps:
and step S51, selecting any one of solar cells as a substrate, wherein the solar cell comprises any one of amorphous silicon, polycrystalline silicon, crystalline silicon, copper indium gallium selenide sulfide, copper indium gallium sulfide, copper zinc tin sulfide and cadmium telluride.
Step S52, depositing a buffer layer on the substrate.
Step S53, preparing a perovskite thin film containing an ultraviolet absorber on the buffer layer by the above-mentioned preparation method of the perovskite thin film doped with an ultraviolet absorber to prepare a tandem solar cell.
Wherein, in step S52, the buffer layer is composed of at least one layer of single substance or mixture, and has the function of collecting and transmitting carriers, and the material for preparing the buffer layer comprises TiO2、ZnO、SnO2、PCBM、PTAA、C60、C70、ITO、AZO、CuSCN、CuGaO2NiOx, WOx, MoOx, and their dopants.
The invention also discloses a solar cell, wherein the solar cell comprises the perovskite thin film doped with the ultraviolet absorbent.
The invention also discloses a solar cell, which contains the perovskite thin film prepared by the preparation method of the perovskite thin film doped with the ultraviolet absorbent.
The preparation process of the present invention will be described with reference to specific examples.
The first embodiment is as follows:
(1) sequentially and ultrasonically cleaning 5 multiplied by 5cm ITO glass sheets by detergent, deionized water, acetone and isopropanol for 30min respectively, and then cleaning by N2And after drying, carrying out UV O-zone treatment for 10 min.
(2) A NiOx film was prepared as a hole transport layer.
(3) 461mg of precursor PbI2(1 mmol) and 11.26mg of ultraviolet absorbent 2- (2H-benzotriazole-2-yl) P-cresol (UV-P) (0.05 mmol) are dissolved in 1mL of DMF solution, 70.9uL of anhydrous DMSO is added, the mixture is heated and stirred for 2H at 60 ℃, and the mixture is completely mixed for standby application to prepare a mixed solution containing the ultraviolet absorbent and a precursor.
(4) Preparing doped PbI on the surface of the hole transport layer by slit coating with the prepared precursor mixed solution2A film.
(5) Will contain doped PbI2The ITO glass sheet of the film is arranged inIn the film forming cavity, the air pressure is controlled at 10 by a vacuum pump-5Pa~105Pa, preliminary supply of the reactant CH3NH3I, heating the powder at 100-200 ℃, heating the ITO glass sheet at 30-150 ℃, and reacting substance CH3NH3I gas molecule and precursor PbI2The reaction produces a perovskite thin film doped with an ultraviolet absorber.
(6) Depositing an electron transport layer PCBM on the perovskite thin film, wherein the thickness is 20 nm-50 nm.
(7) And evaporating the metal conducting layer Ag electrode to obtain the perovskite solar cell doped with the ultraviolet absorbent.
Example two:
(1) sequentially cleaning 5 × 5cm FTO glass sheet with detergent, deionized water, acetone and isopropanol for 30min, and cleaning with N2And after drying, carrying out UV O-zone treatment for 30 min.
(2) Preparation of SnO2The film acts as an electron transport layer.
(3) 461mg of PbI2(1 mmol) and 159mg of methyliodide (1 mmol) were dissolved in 1mL of DMF, 76uL of anhydrous NMP was added, and then the UV absorber (2-hydroxy-4-methoxyphenyl) phenone (BP-3) was added in an amount corresponding to the precursor PbI22% of the molar mass, i.e. 4.565 mg. Heating and stirring for 2h at 60 ℃, completely dissolving, and filtering for later use to prepare the perovskite mixed solution containing the ultraviolet absorbent.
(4) The prepared perovskite mixed solution is coated on the surface of an electron transport layer in a spin mode, and then annealing is carried out for 10 minutes on a heating table at 100 ℃ to form a perovskite crystal thin film.
(5) And a hole transport layer PTAA is spin-coated on the perovskite crystalline film doped with the ultraviolet absorbent, and the thickness is 20 nm-50 nm.
(6) And evaporating a metal conducting layer Ag electrode on the hole transport layer to obtain the perovskite solar cell doped with the ultraviolet absorbent.
Example three:
(1) sequentially and ultrasonically cleaning a flexible transparent conductive substrate PET sheet by using liquid detergent, deionized water, acetone and isopropanol30min, then N is used2And after drying, carrying out UV O-zone treatment for 5 min.
(2) Preparation of Low temperature SnO2The film acts as an electron transport layer.
(3) The PET sheet deposited with the transmission layer is placed in a film forming cavity, and the vacuum degree in the film forming cavity is controlled to be 10-5 Pa-105And heating the PET sheet at the same time under the condition of Pa, wherein the heating temperature is controlled to be 30-150 ℃.
(4) In a film forming cavity, precursor PbI is added2A reactant CH3NH3I. Ultraviolet absorbent UV-326 is respectively arranged in different evaporation sources, CH3NH3The evaporation rate of I is 0.1-10A/s, PbI2The evaporation rate of the organic light-emitting diode is 0.1-10A/s, the evaporation rate of the ultraviolet absorbent UV-326 is 0.005-0.5A/s, and precursor PbI is deposited on the surface of the substrate with the transmission layer2Steam, reactant CH3NH3I, continuously depositing and reacting the steam and the ultraviolet absorbent UV-326 steam to generate the perovskite thin film doped with the ultraviolet absorbent, and forming the perovskite active layer.
(6) And a hole transport layer CuSCN is coated on the perovskite active layer in a scraping way, and the thickness is 50 nm-100 nm.
(7) And performing magnetron sputtering of an ITO electrode on the surface of the hole transport layer to prepare the ultraviolet absorbent doped perovskite solar cell.
Example four:
(1) sequentially cleaning a 5 × 5cm FTO glass plate with detergent, deionized water, acetone and isopropanol for 30min, and then cleaning with N2And after drying, carrying out UV O-zone treatment for 30 min.
(2) A PTAA film was prepared as a hole transport layer.
(3) Preparing a perovskite solution: 415mg of PbI2(0.9 mmol) and 36.7mg of PbBr2(0.1mmol) and 159mg of methyliodiamide (1 mmol) were dissolved in 1mL of a gamma-butyrolactone solution, and 71uL of anhydrous DMSO was added. Heating and stirring for 2h at 60 ℃, completely dissolving, and filtering for later use.
(4) Preparing an anti-solvent mixed solution doped with an ultraviolet absorber: 10.97mg (0.04mmoL L) of ultraviolet absorbent BP-6 (2, 2 '-dihydroxy-4, 4' -dimethoxybenzophenone) was dissolved in 1mL of toluene, heated and stirred at 60 ℃ for 2 hours, and after complete dissolution, it was filtered at a concentration of 0.04 mol/L.
(5) Spin-coating the prepared perovskite solution on the surface of an electron transport layer, quickly dropwise adding an anti-solvent mixed solution in the spin-coating process, placing an FTO glass plate of the perovskite thin film containing the ultraviolet absorbent on a heating table after the spin-coating is finished, and annealing the perovskite thin film containing the ultraviolet absorbent at 100 ℃ for 20 minutes to form the perovskite crystalline thin film.
(6) Depositing an electron transport layer PCBM on the perovskite crystal film, wherein the thickness is 20 nm-50 nm.
(7) And evaporating a metal conducting layer Ag electrode on the electron transport layer to obtain the perovskite solar cell doped with the ultraviolet absorbent.
Example five:
(1) cadmium telluride solar cells were selected as substrates.
(2) Preparation of TiO on a substrate2The film acts as an electron transport layer.
(3) Preparing a perovskite mixed solution containing an ultraviolet absorbent: 461mg of precursor PbI2(1 mmol) and 159mg of methyliodide (1 mmol) were dissolved in 1mL of DMF, 71uL of anhydrous DMSO was added, and then UV absorbent (2-hydroxy-4-methoxyphenyl) phenone (BP-3) was added in an amount corresponding to the precursor PbI22% of the molar mass, i.e. 4.5648 mg. Heating and stirring for 2h at 60 ℃, completely dissolving, and filtering for later use.
(4) The prepared perovskite mixed solution is coated on the surface of an electron transport layer in a spin mode, and then annealing is carried out for 10 minutes on a heating table at 100 ℃ to form a perovskite crystal thin film.
(5) And a hole transport layer PTAA is spin-coated on the perovskite crystal film, and the thickness is 10 nm-50 nm.
(6) And evaporating a metal conducting layer Ag electrode on the hole transport layer to obtain the titanium ore solar cell with the calcium-doped ultraviolet absorbent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The perovskite thin film doped with the ultraviolet absorbent is characterized in that the perovskite thin film is doped with the ultraviolet absorbent, and the ultraviolet absorbent is at least one of benzophenone ultraviolet absorbent, salicylate ultraviolet absorbent, benzotriazole ultraviolet absorbent and p-aminobenzoate ultraviolet absorbent; wherein,
the benzophenone ultraviolet absorbent comprises any one of (2-hydroxy-4-methoxyphenyl) phenyl ketone, 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-n-octoxy benzophenone, and 2,2 '-dihydroxy-4, 4' -dimethoxy benzophenone;
the salicylate ultraviolet absorbent comprises any one of phenyl salicylate, amyl salicylate, p-isopropyl phenyl salicylate, phenyl o-hydroxybenzoate and resorcinol monobenzoate;
the benzotriazole ultraviolet absorber includes any one of 2- (2 '-hydroxy-3', 5 '-di-tert-phenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2' - (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) p-cresol, 2- (2' -hydroxy-3 ',5' bis (a, a-dimethylbenzyl) phenyl) benzotriazole, and 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole;
the ultraviolet absorbent of p-aminobenzoate comprises ethyl p-aminobenzoate or ethyl 4-dimethylaminobenzoate.
2. The ultraviolet absorber-doped perovskite thin film according to claim 1, wherein the ultraviolet absorber is incorporated into the perovskite thin film by a solution mixing method, or a co-evaporation method, or an anti-solvent method, or a lamination method.
3. A method for preparing the ultraviolet absorber-doped perovskite thin film as claimed in claim 1 or 2, wherein the preparation method is a solution mixing method comprising the steps of:
step S11, preparing a perovskite solution;
step S12, adding an ultraviolet absorbent into the perovskite solution, and obtaining a mixed solution of the perovskite and the ultraviolet absorbent after the ultraviolet absorbent is completely dissolved;
step S13, coating the mixed solution on a substrate deposited with a transmission layer by any one of spin coating, blade coating, slit type continuous coating or spray coating to form a film containing the mixed solution, and annealing the film to obtain a perovskite film doped with an ultraviolet absorbent to form a perovskite active layer; wherein,
in step S11, the perovskite solution contains at least one precursor BX2At least one reactant AX, at least one solvent additive and at least one main solvent, wherein B is a divalent metal cation of any one of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is an anion of at least one of iodine, bromine, chlorine and astatine, A is a cation of at least one of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidine group and a guanidine nitrogen-containing organic compound, the main solvent is any one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and gamma-butyrolactone, the solvent additive is at least one of DMSO, NMP, 1, 8-diiodooctane, N-cyclohexyl-2-pyrrolidone, chlorobenzene and toluene; in the perovskite solution, a precursor BX2The concentration of the solution is 0.5-2 mol/L, and the molar ratio of the reactant AX is AX: BX2= 0.9-1.1, the volume ratio of the solvent additive to the main solvent is 0-50%;
in step S12, the ultraviolet absorber is at least one of benzophenones, salicylates, benzotriazoles, and p-aminobenzoates; the dosage of the ultraviolet absorbent is precursor BX20.01 to 5% by mole.
4. A method for preparing the ultraviolet absorber-doped perovskite thin film as claimed in claim 1 or 2, wherein the preparation method is a solution mixing method comprising the steps of:
step S21, adding BX2Adding ultraviolet absorbent into the solution, and dissolving sufficiently to obtain precursor BX containing ultraviolet absorbent2Mixing the solution;
s22, coating the mixed solution on a substrate deposited with a transmission layer by any one of spin coating, blade coating, slit type continuous coating or spray coating to form a film containing the mixed solution, and annealing the film to obtain a precursor BX doped with an ultraviolet absorbent2A thin film layer;
step S23, placing the substrate containing the film layer in a film forming cavity, and controlling the vacuum degree in the film forming cavity to be 10-5 Pa~105Pa;
step S24, heating reactant AX powder which is placed in a film forming cavity in advance, wherein the heating temperature range is 100-200 ℃, simultaneously heating a substrate, the heating temperature of the substrate is controlled to be 30-150 ℃, the reaction time is controlled to be 10-120 min, and the gas molecules of the reactant AX and a precursor BX in the film layer2Carrying out molecular reaction to generate a perovskite thin film doped with an ultraviolet absorbent to form a perovskite active layer; wherein,
in step S21, precursor BX2The solution contains at least one solvent additive and at least one main solvent, wherein B is any one of divalent metal cations of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is at least one anion of iodine, bromine, chlorine and astatine, the main solvent is any one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and gamma-butyrolactone, and the solvent additive is at least one of DMSO, NMP, 1, 8-diiodooctane, N-cyclohexyl-2-pyrrolidone, chlorobenzene and toluene; precursor BX2The concentration of the solution is 0.5-2 mol/L, and the volume ratio of the solvent additive to the main solvent is 0-50%; the ultraviolet ray absorptionThe ultraviolet absorbent is at least one of benzophenone, salicylate, benzotriazole and p-aminobenzoate, and the amount of the ultraviolet absorbent is precursor BX20.01-5% of molar weight;
in step S24, a in the reactant AX is at least one cation of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidino group, or a guanidine nitrogen-containing organic compound, and the perovskite active layer has the following composition ratios: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
5. A method for preparing the ultraviolet absorber-doped perovskite thin film as claimed in claim 1 or 2, wherein the preparation method is a co-evaporation method comprising the steps of:
step S31, placing the substrate deposited with the transmission layer in a film forming cavity, and controlling the vacuum degree in the film forming cavity at 10-5 Pa~105Heating the substrate at the same time under Pa, and controlling the heating temperature of the substrate at 30-150 ℃;
step S32, in the film forming cavity, the precursor BX is put2The reactant AX and the ultraviolet absorbent are respectively put in different evaporation sources for evaporation, the evaporation rate of the reactant AX is 0.1-10A/s, and the precursor BX2Has an evaporation rate of 0.1-10A/s and an evaporation rate of 0.05-5A/s, and an evaporated precursor BX on the surface of a substrate deposited with a transmission layer2Continuously depositing and reacting the steam, the reactant AX steam and the ultraviolet absorbent steam to generate a perovskite thin film doped with the ultraviolet absorbent and form a perovskite active layer; wherein,
in step S32, the precursor BX2B in the reaction is any one of divalent metal cations of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is at least one anion of iodine, bromine, chlorine, astatine, thiocyanato and acetate, A in the reactant AX is at least one cation of lithium, sodium, potassium, cesium, rubidium, amine, amidino and guanidine nitrogen-containing organic compounds, and finally formedThe perovskite active layer comprises the following components in percentage by weight: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
6. A method for preparing the ultraviolet absorber-doped perovskite thin film as claimed in claim 1 or 2, wherein the preparation method is an anti-solvent method comprising the steps of:
step S41, dissolving the ultraviolet absorbent in the anti-solvent, and fully dissolving to prepare a mixed solution of the ultraviolet absorbent and the anti-solvent;
step S42, preparing a perovskite solution;
s43, coating the perovskite solution on the substrate deposited with the transmission layer by any one of spin coating, blade coating, slit type continuous coating or spray coating to form a layer of perovskite thin film;
step S44, coating the mixed solution prepared in the step 41 on the perovskite thin film prepared in the step 43 through any one of spin coating, blade coating, slit type continuous coating or spray coating to obtain a mixed thin film containing the mixed solution of the ultraviolet absorbent and the anti-solvent, and annealing the mixed thin film to obtain the perovskite thin film doped with the ultraviolet absorbent to form a perovskite active layer; wherein,
in step S41, the antisolvent is at least one of benzene, toluene, 1, 2-xylene, 1, 3-xylene, 1, 4-xylene, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether, amyl alcohol; the ultraviolet absorbent is at least one of benzophenone, salicylate, benzotriazole and p-aminobenzoate, and the concentration of the ultraviolet absorbent in the anti-solvent solution is 0.001-0.1 mol/L;
in step S42, the perovskite solution contains at least one precursor BX2At least one reactant AX, at least one solvent additive and at least one main solvent, wherein B is a divalent metal cation of any one of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, and X is iodineAt least one anion selected from the group consisting of bromine, chlorine and astatine, A is at least one cation selected from the group consisting of lithium, sodium, potassium, cesium, rubidium, an amine group, an amidino group and a guanidine nitrogen-containing organic compound, the main solvent is one selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and gamma-butyrolactone, and the solvent additive is at least one selected from the group consisting of DMSO, NMP, 1, 8-diiodooctane, N-cyclohexyl-2-pyrrolidone, chlorobenzene and toluene; in the perovskite solution, a precursor BX2The concentration of the solution is 0.5-2 mol/L, and the molar ratio of the reactant AX is AX: BX2= 0.9-1.1, the volume ratio of the solvent additive to the main solvent is 0-50%;
in step S44, the composition ratio of the finally formed perovskite active layer is: AX: BX2The ultraviolet absorber = 0.9-1.1: 1: 0-0.05.
7. A preparation method of a perovskite thin film doped with an ultraviolet absorbent is characterized by being a lamination method and comprising the following steps:
s51, selecting any one solar cell as a substrate, wherein the solar cell comprises any one of amorphous silicon, polycrystalline silicon, crystalline silicon, copper indium gallium selenide sulfide, copper indium gallium sulfide, copper zinc tin sulfide and cadmium telluride;
step S52, depositing a buffer layer on the substrate;
step S53, preparing a perovskite thin film containing an ultraviolet absorber on the buffer layer by using the preparation method of the ultraviolet absorber-doped perovskite thin film as claimed in any one of claims 3, 4, 5 and 6 to prepare a tandem solar cell; wherein,
in step S52, the buffer layer is composed of at least one layer of single substance or mixture, and has the function of collecting and transporting carriers, and the material for preparing the buffer layer comprises TiO2、ZnO、SnO2、PCBM、PTAA、C60、C70、ITO、AZO、CuSCN、CuGaO2NiOx, WOx, MoOx, and their dopants.
8. A solar cell comprising the ultraviolet absorber-doped perovskite thin film according to claim 1 or 2.
9. A solar cell comprising a perovskite thin film produced by the method for producing a perovskite thin film doped with an ultraviolet absorber according to any one of claims 3 to 7.
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