CN115835753A - Perovskite thin film and preparation method thereof, perovskite solar cell and preparation method thereof - Google Patents
Perovskite thin film and preparation method thereof, perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of solar cells, and particularly relates to a perovskite thin film and a preparation method thereof, and a perovskite solar cell and a preparation method thereof. The preparation method provided by the invention comprises the following steps: coating an interface treatment solution on the surface of the hole transport layer, wherein the interface treatment solution comprises polyelectrolyte, organic ammonium salt and an organic solvent; and annealing the obtained interface treatment coating, and coating the perovskite precursor solution on the surface of the obtained interface layer to prepare the perovskite layer. According to the invention, the interface is only required to be treated before the perovskite layer is prepared, the perovskite film with compact structure and few crystal boundaries can be obtained, and the non-radiative recombination of the perovskite film is also obviously inhibited; the photoelectric conversion efficiency and stability of the perovskite solar cell are effectively improved.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a perovskite thin film and a preparation method thereof, and a perovskite solar cell and a preparation method thereof.
Background
At present, organic-inorganic hybrid Perovskite Solar Cells (PSCs) are one of the most promising photovoltaic candidate materials due to the advantages of low cost and excellent photoelectric properties of solution method preparation, and the photoelectric conversion efficiency of the PSCs is improved from 3.8% to more than 25% in the last decade, which has attracted great interest of researchers in practical application.
Due to the sensitivity of perovskites to light, heat and humidity, improving the efficiency and stability of PSCs is challenging to commercialize. The preparation of high-quality perovskite thin films is an important basis for realizing high-efficiency stable perovskite solar cells. Meanwhile, as the defects of the perovskite thin film are generally enriched at the interface and the grain boundary, in order to prepare the perovskite thin film with low defect density and good crystallinity, passivation molecules are often required to be introduced into the perovskite precursor solution, and meanwhile, passivation treatment is respectively carried out on the top interface and the bottom interface of the perovskite thin film in the perovskite solar cell structure, so that the complexity of preparing PSCs is greatly improved, and the prepared perovskite solar cell has poor photoelectric conversion performance.
Disclosure of Invention
The invention aims to provide a perovskite thin film and a preparation method thereof, and a perovskite solar cell and a preparation method thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a perovskite thin film, which comprises the following steps:
coating an interface treatment solution on the surface of the hole transport layer to obtain an interface treatment coating; the interface treatment solution comprises polyelectrolyte, organic ammonium salt and organic solvent;
annealing the interface treatment coating to obtain the interface layer;
coating a perovskite precursor solution on the surface of the interface layer to prepare a perovskite layer to obtain the perovskite film, wherein a solvent in the perovskite precursor solution is a solvent capable of dissolving the polyelectrolyte and the organic ammonium salt; and obtaining the perovskite thin film formed on the surface of the hole transport layer, wherein the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked.
Preferably, the polyelectrolyte preferably comprises one or more of poly (9,9-bis (3 '- (N, N-dimethyl) -N-ethylaminopropyl-2,7-fluorene) -alt-2,7- (9,9-dioctylfluorene)) dibromide (PFN-Br), poly (9,9-bis (3' - (N, N-dimethyl) -N-ethylaminopropyl-2,7-fluorene) -alt-2,7- (9,9-dioctylfluorene)) diiodide (PFN-I), a compound of the structure shown in chemical formula 1 (PEIE), and a compound of the structure shown in chemical formula 2 (P3 CT-K);
preferably, the organic ammonium salt includes one or more of phenethylamine iodide (PEAI), ethyltrimethylammonium bromide (HTAB), butanediamine iodide (BDADI), octylamine chloride (OACl), tert-butylamine hydroiodide (t-BAI), tert-butyl ammonium chloride (t-BACl), phenethylammonium chloride (PEACl), 1,4-phenylenediamine hydroiodide (PhDADI), benzyl amine iodide (PMAI), 1,4-xylylenediamine iodide, guanidinium hydrobromide (GABr), and guanidinium thiocyanate (GuSCN).
Preferably, in the interface treatment solution, the mass ratio of the polyelectrolyte to the organic ammonium salt is 1 (1-20).
Preferably, the annealing temperature is between room temperature and 150 ℃, and the annealing heat preservation time is between 5 and 10min.
Preferably, the coating is replaced by the following steps:
first coating a first interface treatment solution on the surface of the hole transport layer to obtain a first interface treatment coating; the first interfacial treatment solution comprises the polyelectrolyte and an organic solvent;
secondly coating a second interface treatment solution on the surface of the first interface treatment coating to obtain a second interface treatment coating; the second interface treatment solution comprises an organic ammonium salt and an organic solvent;
the first interface treatment coating and the second interface treatment coating which are arranged in a stacked mode form the interface treatment coating.
The invention provides the perovskite thin film prepared by the preparation method in the technical scheme, and the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked.
Preferably, the thicknesses of the organic ammonium salt buried interface layer and the polyelectrolyte interface surface layer are independently 0.5-30 nm.
The invention provides a perovskite solar cell which comprises a conductive substrate, and a hole transport layer, a perovskite thin film, an electron transport layer, an interface buffer layer and an electrode which are sequentially stacked on the surface of the conductive substrate, wherein the perovskite thin film is the perovskite thin film in the technical scheme.
The invention provides a preparation method of a perovskite solar cell, which comprises the following steps:
preparing a hole transport layer on the surface of the conductive substrate;
preparing a perovskite thin film on the surface of the hole transport layer according to the method of the technical scheme;
preparing an electron transport layer on the surface of the perovskite thin film;
preparing an interface buffer layer on the surface of the electron transport layer;
and preparing an electrode on the surface of the interface buffer layer to obtain the perovskite solar cell.
The invention provides a preparation method of a perovskite thin film, which comprises the following steps: coating an interface treatment solution on the surface of the hole transport layer to obtain an interface treatment coating; the interface treatment solution comprises polyelectrolyte, organic ammonium salt and organic solvent; annealing the interface treatment coating to obtain the interface layer; coating a perovskite precursor solution on the surface of the interface layer to prepare a perovskite layer to obtain the perovskite film, wherein a solvent in the perovskite precursor solution is a solvent capable of dissolving the polyelectrolyte and the organic ammonium salt; and obtaining the perovskite thin film formed on the surface of the hole transport layer, wherein the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked. Before a perovskite layer is prepared on the surface of a hole transport layer, an interface treatment solution is adopted to treat the surface of the hole transport layer to prepare an interface layer, and then after a perovskite precursor solution is coated, polyelectrolyte in the interface layer, metal salt in the perovskite precursor solution and a solvent in the perovskite precursor solution form an intermediate ligand phase to assist the perovskite precursor solution in obtaining the compact perovskite layer with few crystal boundaries and holes; meanwhile, the density of the polyelectrolyte is low, the polyelectrolyte can spontaneously enrich on the upper surface of the perovskite layer to form a polyelectrolyte interface surface layer, functional groups contained in the polyelectrolyte can passivate the surface defects of the perovskite layer, and the hydrophobic aliphatic chain structure of the polyelectrolyte can protect the perovskite, so that the stability of the perovskite solar cell is improved; the organic amine salt is spontaneously enriched on the bottom interface of the perovskite layer to form an organic ammonium salt buried interface layer, thereby passivating the defects of the bottom interface of the perovskite layer, forming an energy band arrangement structure which is more favorable for transporting current carriers on the interface where the perovskite is in contact with the hole transport layer, and reducing the recombination of the current carriers at the interface where the perovskite is in contact with the hole transport layer. Therefore, the preparation method provided by the invention only needs to process the interface before the perovskite layer is prepared, the perovskite film with compact structure and few crystal boundaries can be obtained, and the non-radiative recombination of the perovskite film is also obviously inhibited; the photoelectric conversion efficiency and stability of the perovskite solar cell are effectively improved.
The invention provides the perovskite thin film prepared by the preparation method in the technical scheme, and the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked. According to the invention, a polyelectrolyte interface surface layer is formed on the upper surface of the perovskite, and a buried interface layer is formed on the lower surface of the perovskite, so that the defect of a perovskite thin layer is reduced, the photoelectric conversion efficiency of the perovskite solar cell is more than 23%, and the stability of the device is obviously improved.
Drawings
FIG. 1 is a scanning electron microscope image of a perovskite thin film prepared in example 1 of the present invention, a perovskite thin film prepared in comparative example 1, and a perovskite thin film prepared in comparative example 2;
FIG. 2 is a time-of-flight secondary mass spectrum characterization chart of the perovskite thin film prepared in example 1 of the present invention;
FIG. 3 is a graph showing transient fluorescence spectra and time-resolved fluorescence spectra of the perovskite thin film prepared in example 1 of the present invention, the perovskite thin film prepared in comparative example 1, and the perovskite thin film prepared in comparative example 2;
FIG. 4 is a graph showing the performance characteristics of the perovskite solar cell fabricated in example 1 of the present invention, the perovskite solar cell fabricated in comparative example 1, and the perovskite solar cell fabricated in comparative example 2;
FIG. 5 is a graph comparing the performance of the perovskite solar cell (denoted as Target device) prepared in example 4 of the present invention and the perovskite solar cell (denoted as Control device) prepared in comparative example 3;
fig. 6 is a graph comparing the performance of the perovskite thin-film solar cell prepared in example 2 of the present invention and the perovskite solar cell prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of a perovskite thin film, which comprises the following steps:
coating an interface treatment solution on the surface of the hole transport layer to obtain an interface treatment coating; the interface treatment solution comprises polyelectrolyte, organic ammonium salt and organic solvent;
annealing the interface treatment coating to obtain the interface layer;
coating a perovskite precursor solution on the surface of the interface layer to prepare a perovskite layer to obtain the perovskite film, wherein a solvent in the perovskite precursor solution is a solvent capable of dissolving the polyelectrolyte and the organic ammonium salt; and obtaining the perovskite thin film formed on the surface of the hole transport layer, wherein the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked.
In the present invention, all the preparation starting materials/components are commercially available products well known to those skilled in the art, unless otherwise specified.
Coating an interface treatment solution on the surface of the hole transport layer to obtain an interface treatment coating; the interfacial treatment solution includes a polyelectrolyte, an organic ammonium salt, and an organic solvent.
In the present invention, the polyelectrolyte preferably includes one or more of PFN-Br, PFN-I, a compound of the structure represented by chemical formula 1, and a compound of the structure represented by chemical formula 2;
in the present invention, the compound of the structure represented by chemical formula 1 has the english name: polyethylene, abbreviated as PEIE. X, y and z in chemical formula 1 represent the degree of polymerization.
In the present invention, the compound of the structure represented by chemical formula 2 has the english name: potasssium poly [3- (4-carboxylatebutyl) thiophene, abbreviated as P3CT-K. N in chemical formula 2 represents the degree of polymerization.
In the present invention, the polyelectrolyte is more preferably PFN-Br and/or PFN-I, and further preferably PFN-Br.
In the present invention, the organic ammonium salt preferably comprises one or more of PEAI, HTAB, BDADI, OACl, t-BAI, t-BACl, PEACl, phDADI, PMAI, 1,4-xylylenediamine iodine, GABr and GuSCN, more preferably phenethylamine iodine (PEAI) and/or ethyltrimethylammonium bromide (HTAB), and still more preferably PEAI.
In the present invention, in the interfacial treatment solution, the mass ratio of the polyelectrolyte to the organic ammonium salt is preferably 1 (1 to 20), more preferably 1.
In the present invention, the organic solvent is particularly preferably methanol or isopropanol.
In the present invention, the mass concentration of the polyelectrolyte in the interface treatment solution is preferably 1mg/mL.
In the present invention, the mass concentration of the organic ammonium salt in the interface treatment solution is preferably 10mg/mL.
In the present invention, the temperature of the interfacial treatment solution is preferably 50 ℃ at the time of the coating.
In the present invention, the coating is preferably spin coating, slit coating, blade coating, screen printing, or ink jet printing. In the present invention, when the coating is spin coating, the rotation speed of the spin coating is preferably 2000 to 5000rpm. The time for the spin coating is preferably 30s.
As one or more embodiments of the invention, the coating is replaced by the following steps:
first coating a first interface treatment solution on the surface of the hole transport layer to obtain a first interface treatment coating; the first interfacial treatment solution comprises the polyelectrolyte and an organic solvent;
secondly coating a second interface treatment solution on the surface of the first interface treatment coating to obtain a second interface treatment coating; the second interface treatment solution comprises an organic ammonium salt and an organic solvent;
the first interface treatment coating and the second interface treatment coating which are arranged in a stacked manner form the interface layer.
Firstly coating a first interface treatment solution on the surface of the hole transport layer to obtain a first interface treatment coating; the first interfacial treatment solution includes the polyelectrolyte and an organic solvent. In the present invention, the organic solvent is preferably methanol; the mass concentration of the polyelectrolyte in the first interface treatment solution is preferably 1mg/mL. In the present invention, the temperature of the first interface treatment solution at the time of the first coating is preferably 50 ℃. In the present invention, the first coating is preferably spin coating, and the rotation speed of the spin coating is preferably 2000 to 5000rpm. The time for the spin coating is preferably 30s.
After the first interface treatment coating is obtained, secondly coating a second interface treatment solution on the surface of the first interface treatment coating to obtain a second interface treatment coating; the second interfacial treatment solution includes an organic ammonium salt and an organic solvent. In the present invention, the organic solvent is preferably methanol, and in the present invention, the mass concentration of the organic ammonium salt in the second interface treatment solution is preferably 10mg/mL. In the present invention, the temperature of the second interface treatment solution at the time of the second coating is preferably 50 ℃. In the present invention, the second coating is preferably spin coating, and the rotation speed of the spin coating is preferably 2000 to 5000rpm. The time for the spin coating is preferably 30s.
In the present invention, the first interface treatment coating layer and the second interface treatment coating layer which are arranged in a stack form the interface layer.
After the interface treatment coating is obtained, the interface treatment coating is annealed to obtain the interface layer.
In the present invention, the annealing temperature is preferably room temperature to 150 ℃, more preferably 100 ℃, and the annealing holding time is preferably 5 to 10min, more preferably 5min.
After the interface layer is obtained, coating a perovskite precursor solution on the surface of the interface layer to prepare a perovskite layer to obtain the perovskite film, wherein a solvent in the perovskite precursor solution is a solvent capable of dissolving the polyelectrolyte and the organic ammonium salt; and obtaining the perovskite thin film formed on the surface of the hole transport layer, wherein the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked.
In the present invention, the method for preparing the perovskite layer preferably includes a two-step method and a one-step method.
In the present invention, the two-step process is preferably prepared with reference to the method for preparing perovskite layers described in "Surface coating of Perovskite Film for Efficient Solar Cells" (Qi Jiang, yang ZHao, xingwang Zhang, xiaolei Yang, yong Chen1, zema Chu, qiufengye, xingxing Li, zhigangyin and Jungbiyou. Nat. Photonics 2019,13,460-466.). The one-step process is preferably carried out with reference to a method for producing a layer of titanium by "Surface Reaction for affected and Stable incorporated Perovskite Solar cells" (Jiang, Q.; tong, J.; xian, Y.; kerner, R.A.; dunfield, S.P.; xiao, C.; scheidt, R.A.; kuciaskas, D.; wang, X.; hautzinger, M.P.; tirawat, R.; beard, M.C.; fenning, D.P.; berry, J.J.; larson, B.W.; yan Y.; zhu K.; surface Reaction for affected and Stable incorporated Perurve cell 2022.DOI: 8978/4178-41022 3).
When the perovskite layer is prepared by adopting a two-step method, the perovskite precursor solution comprises PbI 2 The solution and a mixed solution of formamidine iodide (FAI), methylamine chloride (MACl) and methylamine chloride (MAI).
In the present invention, the two-step process particularly preferably comprises the following steps:
will PbI 2 Coating the solution on the surface of the interface layer to obtain PbI 2 A solution layer;
coating the mixed solution of FAI, MACl and MAI on the PbI 2 And (4) carrying out annealing treatment on the surface of the solution layer to obtain the perovskite layer.
The invention combines PbI 2 Coating the solution on the surface of the interface layer to obtain PbI 2 And (4) solution layer. In the present invention, the PbI is 2 The solvent in the solution is preferably N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) with a volume ratio of DMF to DMSO of 9:1, and the PbI is 2 The mass concentration of the solution is preferably 691.5mg/mL. The coating method is preferably spin coating, the rotating speed of the spin coating is preferably 5000-15000 rpm, and the time of the spin coating is preferably 30s. Then, the plate was placed on a hot stage at 70 ℃ and annealed for 1min.
To obtain PbI 2 After the solution layer, the mixed solution of FAI, MAI and MACl is coated on the PbI 2 And (3) annealing the surface of the solution layer to obtain a mixed solution of FAI, MAI and MACl, so as to obtain the perovskite layer. In the present invention, the solvent in the mixed solution of FAI, MAI and MACl is preferably isopropyl alcohol (IPA). The mass concentration of FAI in the mixed solution of FAI, MAI and MACl is preferably 90mg/mL, the mass concentration of MAI is preferably 6.39mg/mL, and the mass concentration of MACl is preferably 9mg/mL. The coating is preferably spin coating, the rotation speed of the spin coating is preferably 2000-5000 rpm, and the time of the spin coating is preferably 30s. The temperature of the annealing treatment is preferably 150 ℃, and the heat preservation of the annealing treatmentThe temperature time is preferably 15min, and the annealing is required to be carried out outdoors in the step, wherein the outdoor humidity is required to be 20-40% Relative Humidity (RH).
In the present invention, the interface layer is coated with the PbI 2 Obtaining PbI from the solution 2 After solution layer, the PbI 2 The solvent in the solution layer dissolves the polyelectrolyte in the interface layer, the polyelectrolyte and the PbI 2 DMSO forms an intermediate ligand phase which assists in reacting with FAI, MAI and MACl to obtain a compact perovskite layer with few holes, and in the formation process of the perovskite layer, the polyelectrolyte is gradually enriched on the surface of the perovskite layer to form a polyelectrolyte interface surface layer; the organic ammonium salt is positioned on the bottom surface of the perovskite layer to form an organic ammonium salt buried interface layer.
When the perovskite layer is prepared by adopting a one-step method, the perovskite precursor solution comprises CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 The solution was mixed. In the present invention, the one-step method particularly preferably includes the steps of:
mixing CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 Coating the mixed solution on the surface of the interface layer to obtain CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 Mixing the solution layer, adding the CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 And annealing the mixed solution layer to obtain the perovskite layer.
In the present invention, the FAI, MAI and PbI 2 The solvent in the mixed solution is preferably DMF and DMSO blending solvent (volume ratio DMF: DMSO = 4:1). The CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 The mass concentration of CsI in the mixed solution is preferably 19.5mg/mL, the mass concentration of RbI is preferably 15.9mg/mL, the mass concentration of MABr is preferably 8.4mg/mL, the mass concentration of FAI is preferably 219.5mg/mL, and PbI 2 The mass concentration is preferably 656.9mg/mL, pbBr 2 The mass concentration is preferably 27.5mg/mL. The coating is preferably spin coating, the rotation speed of the spin coating is preferably 1000rpm 10s, the second step of the spin coating is 3000rpm 30s, 150 mu L of anti-solvent Chlorobenzene (CB) is dripped in the second step of the spin coating process, the temperature of the annealing treatment is preferably 100 ℃, and the annealing treatment is preferably carried outThe holding time for the fire treatment is preferably 10min.
In the invention, the CsI, rbI, MABr, FAI and PbI are coated on the interface layer 2 And PbBr 2 After mixing the solution, the CsI, rbI, MABr, FAI, pbI 2 And PbBr 2 Dissolving polyelectrolyte in the interface layer by using a solvent in a perovskite precursor mixed solution, wherein the polyelectrolyte, perovskite precursor components and a DMSO solvent form an intermediate ligand phase to obtain a compact perovskite layer with few holes, and in the formation process of the perovskite layer, the polyelectrolyte is gradually enriched on the surface of the perovskite layer to form a polyelectrolyte interface surface layer; the organic ammonium salt is positioned on the bottom surface of the perovskite layer to form an organic ammonium salt buried interface layer.
The invention provides the perovskite thin film prepared by the preparation method in the technical scheme, and the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked.
In the invention, the thickness of the organic ammonium salt buried interface layer is preferably 3-30 nm.
In the present invention, the thickness of the polyelectrolyte interface surface layer is preferably 3 to 30nm.
In the present invention, the thickness of the perovskite layer is preferably 600 to 1000nm.
The invention provides a perovskite solar cell which comprises a conductive substrate, and a hole transport layer, a perovskite thin film, an electron transport layer, an interface buffer layer and an electrode which are sequentially stacked on the surface of the conductive substrate, wherein the perovskite thin film is the perovskite thin film in the technical scheme.
In the present invention, the conductive substrate is particularly preferably Indium Tin Oxide (ITO).
In the present invention, the material of the hole transport layer is preferably poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ] (PTAA), self-assembled monolayer [2- (3,6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid (MeO-2 PACz), or nickel oxide (NiOx).
In the present invention, the thickness of the hole transport layer is preferably 5 to 10nm.
In the present invention, the material of the electron transport layer is preferably (6,6) -phenyl-C61 methyl butyrate (PCBM) or C 60 。
In the present invention, the thickness of the electron transport layer is preferably 25 to 50nm.
In the present invention, the interface buffer layer is preferably Bathocuproine (BCP) in particular.
In the present invention, the thickness of the interfacial buffer layer is preferably 5 to 10nm.
In the present invention, the material of the electrode is particularly preferably copper.
In the present invention, the thickness of the electrode is preferably 100nm.
The invention provides a preparation method of a perovskite solar cell, which comprises the following steps:
preparing a hole transport layer on the surface of the conductive substrate;
preparing a perovskite thin film on the surface of the hole transport layer according to the method of the technical scheme to form a perovskite layer;
preparing an electron transport layer on the surface of the perovskite layer;
preparing an interface buffer layer on the surface of the electron transport layer;
and preparing an electrode on the surface of the interface buffer layer to obtain the perovskite solar cell.
The invention prepares the hole transport layer on the surface of the conductive substrate.
The present invention preferably sequentially performs cleaning and ultraviolet-ozone (UV-O) on the conductive substrate before preparing the hole transport layer 3 ) And (6) processing.
In the present invention, the washing preferably comprises the steps of: and sequentially carrying out ultrasonic cleaning on the conductive substrate by adopting a cleaning agent, ultrasonic cleaning on deionized water, ultrasonic cleaning on acetone and ultrasonic cleaning on isopropanol. The time for ultrasonic cleaning by the cleaning agent is preferably 15min, the time for ultrasonic cleaning by deionized water is preferably 15min, the time for ultrasonic cleaning by acetone is preferably 15min, and the time for ultrasonic cleaning by isopropanol is preferably 15min.
In the present invention, the UV-O 3 The treatment time was 15min. The invention is directed to the UV-O 3 The specific implementation of the treatment is not particularly critical. The invention preferably passes through the UV-O 3 The treatment removes residual organic matter on the surface of the conductive substrate and improves work function.
In the present invention, the method for producing the hole transport layer preferably includes the steps of:
dissolving a hole transport layer material in an organic solvent to obtain a hole transport layer precursor solution; coating the hole transport layer precursor solution on the surface of the conductive substrate to obtain a hole transport layer precursor solution layer; and preferably, annealing the hole transport layer precursor solution layer to obtain the hole transport layer.
In the present invention, the hole transport layer material is particularly preferably PTAA, meO-2PACz or NiOx. In the present invention, toluene is particularly preferable as the PTAA hole transport layer solvent, and the mass concentration is preferably 2mg/mL; the MeO-2PACz hole transport layer solvent is preferably isopropanol, the mass concentration is preferably 0.5mg/mL, and in the invention, the coating is preferably spin coating, the rotation speed of the spin coating is preferably 2000-5000 rpm, and the time of the spin coating is preferably 30s.
After the hole transport layer precursor solution layer is obtained, the hole transport layer precursor solution layer is preferably subjected to annealing treatment to obtain the hole transport layer. The temperature of the annealing treatment is preferably 120 ℃, and the heat preservation time of the annealing treatment is preferably 10min.
After the hole transport layer is obtained, the perovskite thin film is prepared on the surface of the hole transport layer according to the preparation method of the perovskite thin film of the technical method.
According to the invention, the hole transport layer is made of PTAA, the PTAA has a hydrophobic property, the interface layer is prepared on the surface of the hole transport layer through the technical scheme, and then the perovskite layer is prepared on the surface of the interface layer, so that the wettability of the perovskite layer on the surface of the hole transport layer can be effectively improved.
The perovskite thin film is obtained, and the electron transport layer is prepared on the surface of the perovskite thin film.
In the present invention, the method for preparing the electron transport layer preferably includes the steps of:
dissolving PCBM in an organic solvent to obtain an electron transport layer precursor solution; and coating the electron transport layer precursor solution on the surface of the perovskite layer and then carrying out annealing treatment. In the present invention, the organic solvent is particularly preferably chlorobenzene. The mass concentration of the electron transport layer precursor solution is preferably 20mg/mL. In the present invention, the coating is preferably spin coating, the rotation speed of the spin coating is preferably 1000 to 5000rpm, and the time of the spin coating is preferably 30s. Or depositing C by vacuum deposition 60 The electron transport layer preferably has a thickness of 25 to 50nm and a vapor deposition rate of
Thermal annealing is not used after deposition.
After the electron transport layer is obtained, the interface buffer layer is prepared on the surface of the electron transport layer.
In the present invention, the method for preparing the interfacial buffer layer preferably includes the steps of:
dissolving BCP in an organic solvent to obtain an interface buffer layer precursor solution; and coating the interface buffer layer precursor solution on the surface of the electron transport layer and then carrying out annealing treatment. In the present invention, the organic solvent is particularly preferably ethanol. The mass concentration of the interface buffer layer precursor solution is preferably 1mg/mL. In the present invention, the coating is preferably spin coating, the spin speed is preferably 2000 to 5000rpm, and the spin time is preferably 30 seconds. Simultaneously, a BCP interface buffer layer can be deposited in a vacuum deposition mode, the thickness is 5-10nm, and the evaporation rate is
Thermal annealing is not used after deposition.
After the interface buffer layer is obtained, preparing an electrode on the surface of the interface buffer layer to obtain the perovskite solar cell.
In the present invention, the method for producing the electrode is preferably vacuum evaporation. The invention has no special requirements on the specific implementation process of the vacuum evaporation. The vacuum evaporation is preferably performed in a vacuum evaporation apparatus.
In order to further illustrate the present invention, the following detailed description of the technical solutions provided by the present invention is made with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Cleaning the ITO transparent conductive substrate, and respectively ultrasonically cleaning the ITO transparent conductive substrate for 15min by using a glass cleaning agent, deionized water, acetone and isopropanol;
carrying out UV-O on the cleaned ITO transparent conductive substrate 3 Treating for 15min to remove residual organic matters on the surface of the ITO transparent conductive substrate and improve the work function;
dissolving PTAA in toluene to obtain a hole transport layer precursor solution with the mass concentration of 2mg/mL, spin-coating the hole transport layer precursor solution on the surface of an ITO (indium tin oxide) transparent conductive substrate at the rotation speed of 5000rpm for 30s to obtain a hole transport layer precursor solution layer, and then annealing at 120 ℃ for 10min; obtaining a hole transport layer;
dissolving PFN-Br and phenethyl ammonium iodide (PEAI) in methanol according to the mass ratio of 1; obtaining an interface layer;
will PbI 2 Dissolving in DMF and DMSO to obtain PbI 2 Solution, pbI 2 The mass concentration of the solution is preferably 691.5mg/mL, and the solvent is DMF and DMSO blended solution (volume ratio DMF: DMSO = 9:1); will PbI 2 The solution is coated on the surface of the interface layer in a spinning way, the rotating speed of the spinning is 1500rpm, and the solution is coated on the surface of the interface layer in the spinning wayWith a time of 30s, followed by annealing in a hot stage at 70 ℃ for 1min to obtain PbI 2 Coating;
and blending and dissolving FAI, MAI and MACl to obtain a solvent in the mixed solution of FAI, MAI and MACl, wherein the solvent is preferably isopropanol, the mass concentration of FAI in the mixed solution of FAI, MAI and MACl is preferably 90mg/mL, the mass concentration of MAI is preferably 6.39mg/mL, and the mass concentration of MACl is preferably 9mg/mL. Spin coating FAI, MAI and MACl solution on PbI 2 The surface of the solution layer is spin-coated at 2500rpm for 30s, and then annealed on a 150 deg.C hot bench outside a glove box for 15min, taking care that the air humidity needs to be controlled to 20-40% Relative Humidity (RH); and obtaining the perovskite thin film, wherein the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked on the surface of the substrate, so as to obtain the perovskite layer.
Dissolving PCBM in chlorobenzene to obtain an electron transport layer precursor solution, wherein the mass concentration of the electron transport layer precursor solution is 20mg/mL, and spin-coating the electron transport layer precursor solution on the surface of the perovskite layer at the rotation speed of 1000rpm for 30s to obtain an electron transport layer; simultaneously, a C60 electron transmission layer can be deposited by a vacuum deposition mode, the thickness is 25-50nm, and the evaporation rate is
Thermal annealing is not used after deposition.
And then preparing a BCP interface buffer layer, wherein the BCP interface buffer layer can be prepared by a solution method or a vacuum evaporation method. For the specific process of preparing the BCP layer by the solution method, firstly, dissolving BCP in ethanol to obtain an interface buffer layer precursor solution, wherein the mass concentration of the interface buffer layer precursor solution is 1mg/mL, spin-coating the interface buffer layer precursor solution on the surface of an electron transport layer at the rotation speed of 5000rpm for 30s to obtain the BCP interface buffer layer; for the specific process of preparing the BCP layer by the vacuum evaporation method, the chamber pressure is 4 multiplied by 10 -4 pa is 5-10nm in thickness and the evaporation rate is
After the deposition is finished, do notThermal annealing is used.
And finally, carrying out vacuum evaporation on the surface of the BCP interface buffer layer to form a copper electrode with the thickness of 100nm to obtain the perovskite solar cell.
Example 2
Cleaning the ITO transparent conductive substrate, and respectively ultrasonically cleaning the ITO transparent conductive substrate for 15min by using a glass cleaning agent, deionized water, acetone and isopropanol;
carrying out UV-O on the cleaned ITO transparent conductive substrate 3 Treating for 15min to remove residual organic matters on the surface of the transparent ITO conductive substrate and improve the work function;
dissolving PTAA in toluene to obtain a hole transport layer precursor solution with the mass concentration of 2mg/mL, spin-coating the hole transport layer precursor solution on the surface of an ITO (indium tin oxide) transparent conductive substrate at the rotation speed of 5000rpm for 30s to obtain a hole transport layer precursor solution layer, and then annealing at 120 ℃ for 10min; obtaining a hole transport layer;
dissolving PFN-Br and hexyltrimethylammonium bromide (HTAB) in methanol according to a mass ratio of 1; obtaining an interface layer;
will PbI 2 Dissolving in DMF and DMSO to obtain PbI 2 Solution, pbI 2 The mass concentration of the solution is preferably 691.5mg/mL, and the solvent is DMF and DMSO blending solution (volume ratio DMF: DMSO = 9:1); will PbI 2 Spin-coating the solution on the surface of the interface layer at 1500rpm for 30s, and annealing at 70 deg.C for 1min to obtain PbI 2 Coating;
and blending and dissolving FAI, MAI and MACl to obtain a solvent in the mixed solution of FAI, MAI and MACl, wherein the solvent is preferably isopropanol, the mass concentration of FAI in the mixed solution of FAI, MAI and MACl is preferably 90mg/mL, the mass concentration of MAI is preferably 6.39mg/mL, and the mass concentration of MACl is preferably 9mg/mL. To obtain FAI, MAIAnd MACl solution spin-coated on PbI 2 The surface of the solution layer is spin-coated at 2500rpm for 30s, and then annealed on a hot bench at 150 ℃ outside a glove box for 15min, taking care that the air humidity needs to be controlled to 20-40% Relative Humidity (RH); and obtaining the perovskite film, wherein the perovskite film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked on the surface of the substrate, so as to obtain the perovskite layer.
Dissolving PCBM in chlorobenzene to obtain an electron transport layer precursor solution, wherein the mass concentration of the electron transport layer precursor solution is 20mg/mL, and spin-coating the electron transport layer precursor solution on the surface of the perovskite layer at the rotation speed of 1000rpm for 30s to obtain an electron transport layer; simultaneously, a C60 electron transmission layer can be deposited by a vacuum deposition mode, the thickness is 25-50nm, and the evaporation rate is
Thermal annealing is not used after deposition.
And then preparing a BCP interface buffer layer, wherein the BCP interface buffer layer can be prepared by a solution method or a vacuum evaporation method. For the specific process of preparing the BCP layer by the solution method, firstly, dissolving BCP in ethanol to obtain an interface buffer layer precursor solution, wherein the mass concentration of the interface buffer layer precursor solution is 1mg/mL, spin-coating the interface buffer layer precursor solution on the surface of an electron transport layer at the rotation speed of 5000rpm for 30s to obtain the BCP interface buffer layer; for the specific process of preparing the BCP layer by the vacuum evaporation method, the chamber pressure is 4 multiplied by 10 -4 pa is 5-10nm in thickness and the evaporation rate is
Thermal annealing is not used after deposition.
And finally, carrying out vacuum evaporation on the surface of the BCP interface buffer layer to form a copper electrode with the thickness of 100nm to obtain the perovskite solar cell.
Example 3
Cleaning the ITO transparent conductive substrate, and respectively ultrasonically cleaning the ITO transparent conductive substrate for 15min by using a glass cleaning agent, deionized water, acetone and isopropanol;
carrying out UV-O on the cleaned ITO transparent conductive substrate 3 Treating for 15min to remove residual organic matters on the surface of the transparent ITO conductive substrate and improve the work function;
dissolving PTAA in toluene to obtain a hole transport layer precursor solution with the mass concentration of 2mg/mL, spin-coating the hole transport layer precursor solution on the surface of an ITO transparent conductive substrate at the rotation speed of 5000rpm for 30s to obtain a hole transport layer precursor solution layer, and then annealing at 120 ℃ for 10min; obtaining a hole transport layer;
dissolving PFN-Br in methanol to obtain a first interface treatment solution, wherein the mass concentration of PFN-Br in the first interface treatment solution is 1mg/mL, stirring and heating the first interface treatment solution on a 50 ℃ hot bench, and then spin-coating the first interface treatment solution on the surface of a hole transport layer at the spin-coating rotation speed of 5000rpm for 30s to obtain a first interface treatment solution layer;
dissolving phenethyl ammonium iodide (PEAI) in methanol to obtain a second interface treatment solution, wherein the mass concentration of the PEAI in the second interface treatment solution is 10mg/mL, spin-coating the second interface treatment solution on the surface of the first interface treatment solution layer at the rotation speed of 5000rpm for 30s to obtain a second interface treatment solution layer, and then annealing at 100 ℃ for 5min; obtaining an interface layer;
will PbI 2 Dissolving in DMF and DMSO to obtain PbI 2 Solution, pbI 2 The mass concentration of the solution is preferably 691.5mg/mL, and the solvent is a DMF and DMSO blended solution (DMF: DMSO = 9:1); will PbI 2 Spin-coating the solution on the surface of the interface layer at 1500rpm for 30s, and annealing at 70 deg.C for 1min to obtain PbI 2 Coating;
and blending and dissolving FAI, MAI and MACl to obtain a solvent in the mixed solution of FAI, MAI and MACl, wherein the solvent is Isopropanol (IPA), the mass concentration of FAI in the mixed solution of FAI, MAI and MACl is 90mg/mL, the mass concentration of MAI is 6.39mg/mL, and the mass concentration of MACl is 9mg/mL. Spin coating FAI, MAI and MACl solution on PbI 2 The surface of the solution layer is spin-coated at 2500rpmCoating time is 30s, then annealing for 15min on a hot bench outside the glove box at 150 ℃, taking care that the air humidity needs to be controlled to 20-40% Relative Humidity (RH); and obtaining the perovskite film, wherein the perovskite film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked on the surface of the substrate, so as to obtain the perovskite layer.
Dissolving PCBM in chlorobenzene to obtain an electron transport layer precursor solution, wherein the mass concentration of the electron transport layer precursor solution is 20mg/mL, and spin-coating the electron transport layer precursor solution on the surface of the perovskite layer at the rotation speed of 1000rpm for 30s to obtain an electron transport layer; simultaneously, a C60 electron transmission layer can be deposited by a vacuum deposition mode, the thickness is 25-50nm, and the evaporation rate is
Thermal annealing is not used after the deposition is finished.
And then preparing a BCP interface buffer layer, wherein the BCP interface buffer layer can be prepared by a solution method or a vacuum evaporation method. For the specific process of preparing the BCP layer by the solution method, firstly, dissolving the BCP in ethanol to obtain an interface buffer layer precursor solution, wherein the mass concentration of the interface buffer layer precursor solution is 1mg/mL, spin-coating the interface buffer layer precursor solution on the surface of an electron transport layer at the rotation speed of 5000rpm for 30s to obtain the BCP interface buffer layer; for the specific process of preparing the BCP layer by the vacuum evaporation method, the chamber pressure is 4 multiplied by 10 -4 pa is 5-10nm in thickness and the evaporation rate is
Thermal annealing is not used after deposition.
Finally, plating copper electrodes on the surface of the BCP interface buffer layer in a vacuum evaporation mode, wherein the thickness of the copper electrodes is 100nm, and obtaining the perovskite solar cell
Example 4
Cleaning the ITO transparent conductive substrate, and respectively ultrasonically cleaning the ITO transparent conductive substrate for 15min by using a glass cleaning agent, deionized water, acetone and isopropanol;
carrying out UV-O on the cleaned ITO transparent conductive substrate 3 Treating for 15min to remove residual organic matters on the surface of the transparent ITO conductive substrate and improve the work function;
dissolving self-assembled monomolecular layer [2- (3,6-dimethoxy-9H-carbazole-9-yl) ethyl ] phosphonic acid (MeO-2 PACz) in isopropanol to obtain a hole transport layer precursor solution with the mass concentration of 0.5mg/mL, spin-coating the hole transport layer precursor solution on the surface of an ITO (indium tin oxide) transparent conductive substrate at the spin-coating rotation speed of 3000rpm for 30s to obtain a hole transport layer precursor solution layer, and then annealing at 100 ℃ for 10min; obtaining a hole transport layer;
dissolving PFN-Br and phenethyl ammonium iodide (PEAI) in methanol according to the mass ratio of 1; obtaining an interface layer;
mixing CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 Coating the mixed solution on the surface of the interface layer to obtain CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 Mixing the solution layer, adding the CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 Annealing the mixed solution layer to obtain the perovskite layer;
in the invention, the CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 The solvent in the mixed solution is preferably DMF and DMSO blending solvent (volume ratio DMF: DMSO = 4:1), the CsI, rbI, MABr, FAI, pbI 2 And PbBr 2 The mass concentration of CsI in the mixed solution is preferably 19.5mg/mL, the mass concentration of RbI is preferably 15.9mg/mL, the mass concentration of MABr is preferably 8.4mg/mL, FAI219.5mg/mL and PbI 2 The mass concentration is preferably 656.9mg/mL, pbBr 2 The mass concentration is preferably 27.5mg/mL. The coating is preferably spin coating, the rotation speed of the spin coating is preferably 1000rpm 10s, 3000rpm,30s in the first step, 150 mu L of anti-solvent chlorobenzene is dripped in the 15 th s in the second step, the temperature of the annealing treatment is preferably 100 ℃, and the annealing position is preferablyThe heat preservation time is preferably 10min;
dissolving PCBM in chlorobenzene to obtain an electron transport layer precursor solution, wherein the mass concentration of the electron transport layer precursor solution is 20mg/mL, and spin-coating the electron transport layer precursor solution on the surface of the perovskite layer at the rotation speed of 1000rpm for 30s to obtain an electron transport layer; simultaneously, a C60 electron transmission layer can be deposited by a vacuum deposition mode, the thickness is 25-50nm, and the evaporation rate is
Thermal annealing is not used after deposition.
And then preparing a BCP interface buffer layer, wherein the BCP interface buffer layer can be prepared by a solution method or a vacuum evaporation method. For the specific process of preparing the BCP layer by the solution method, firstly, dissolving BCP in ethanol to obtain an interface buffer layer precursor solution, wherein the mass concentration of the interface buffer layer precursor solution is 1mg/mL, spin-coating the interface buffer layer precursor solution on the surface of an electron transport layer at the rotation speed of 5000rpm for 30s to obtain the BCP interface buffer layer; for the specific process of preparing the BCP layer by the vacuum evaporation method, the chamber pressure is 4 multiplied by 10 -4 pa is 5-10nm in thickness and the evaporation rate is
Thermal annealing is not used after deposition.
Finally, plating copper electrodes on the surface of the BCP interface buffer layer in a vacuum evaporation mode, wherein the thickness of the copper electrodes is 100nm, and obtaining the perovskite solar cell
Comparative example 1
Cleaning the ITO transparent conductive substrate, and respectively ultrasonically cleaning the ITO transparent conductive substrate for 15min by using a glass cleaning agent, deionized water, acetone and isopropanol;
carrying out UV-O on the cleaned ITO transparent conductive substrate 3 Treating for 15min to remove residual organic matters on the surface of the ITO transparent conductive substrate and improve the work function;
dissolving PTAA in toluene to obtain a hole transport layer precursor solution with the mass concentration of 2mg/mL, spin-coating the hole transport layer precursor solution on the surface of an ITO (indium tin oxide) transparent conductive substrate at the rotation speed of 5000rpm for 30s to obtain a hole transport layer precursor solution layer, and then annealing at 120 ℃ for 10min; obtaining a hole transport layer;
dissolving PFN-Br in methanol to obtain an interface treatment solution, wherein the mass concentration of PFN-Br in the interface treatment solution is 1mg/mL, stirring and heating the interface treatment solution on a 50 ℃ hot bench, spin-coating the interface treatment solution on the surface of a hole transport layer at the rotation speed of 5000rpm for 30s to obtain an interface treatment solution layer, and then annealing at 100 ℃ for 5min; obtaining an interface layer;
will PbI 2 Dissolving in DMF and DMSO to obtain PbI 2 Solution, pbI 2 The mass concentration of the solution is preferably 691.5mg/mL, and the solvent is DMF and DMSO blended solution (volume ratio DMF: DMSO = 9:1); will PbI 2 Spin-coating the solution on the surface of the interface layer at 1500rpm for 30s, and annealing at 70 deg.C for 1min to obtain PbI 2 Coating;
blending and dissolving FAI, MAI and MACl to obtain a solvent in the mixed solution of FAI, MAI and MACl, wherein the solvent is preferably Isopropanol (IPA), the mass concentration of FAI in the mixed solution of FAI, MAI and MACl is preferably 90mg/mL, the mass concentration of MAI is preferably 6.39mg/mL, and the mass concentration of MACl is preferably 9mg/mL. Spin coating FAI, MAI and MACl solution on PbI 2 The surface of the solution layer is spin-coated at 2500rpm for 30s, and then annealed on a hot bench at 150 ℃ outside a glove box for 15min, taking care that the air humidity needs to be controlled to 20-40% Relative Humidity (RH); and obtaining the perovskite film, wherein the perovskite film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked on the surface of the substrate, so as to obtain the perovskite layer.
Dissolving PCBM in chlorobenzene to obtain an electron transport layer precursor solution, wherein the mass concentration of the electron transport layer precursor solution is 20mg/mL, and spin-coating the electron transport layer precursor solution on the surface of the perovskite layer at the rotating speed of 1000rpm for 30s to obtain an electron transport layer; simultaneously, a C60 electron transmission layer can be deposited by a vacuum deposition mode, the thickness is 25-50nm, and the evaporation rate is
Thermal annealing is not used after the deposition is finished.
And then preparing a BCP interface buffer layer, wherein the BCP interface buffer layer can be prepared by a solution method or a vacuum evaporation method. For the specific process of preparing the BCP layer by the solution method, firstly, dissolving BCP in ethanol to obtain an interface buffer layer precursor solution, wherein the mass concentration of the interface buffer layer precursor solution is 1mg/mL, spin-coating the interface buffer layer precursor solution on the surface of an electron transport layer at the rotation speed of 5000rpm for 30s to obtain the BCP interface buffer layer; for the specific process of preparing the BCP layer by the vacuum evaporation method, the chamber pressure is 4 multiplied by 10 -4 pa is 5-10nm in thickness and the evaporation rate is
Thermal annealing is not used after the deposition is finished.
Finally, copper electrodes are evaporated on the surface of the BCP interface buffer layer in vacuum with the thickness of 100nm to obtain the perovskite solar cell
Comparative example 2
Cleaning the ITO transparent conductive substrate, and respectively ultrasonically cleaning the ITO transparent conductive substrate for 15min by using a glass cleaning agent, deionized water, acetone and isopropanol;
carrying out UV-O on the cleaned ITO transparent conductive substrate 3 Treating for 15min to remove residual organic matters on the surface of the transparent ITO conductive substrate and improve the work function;
dissolving PTAA in toluene to obtain a hole transport layer precursor solution with the mass concentration of 2mg/mL, spin-coating the hole transport layer precursor solution on the surface of an ITO (indium tin oxide) transparent conductive substrate at the rotation speed of 5000rpm for 30s to obtain a hole transport layer precursor solution layer, and then annealing at 120 ℃ for 10min; obtaining a hole transport layer;
dissolving PEAI in methanol to obtain an interface treatment solution, wherein the mass concentration of PEAI in the interface treatment solution is 10mg/mL, oscillating at normal temperature to rapidly dissolve the PEAI, spin-coating the interface treatment solution on the surface of the hole transport layer at the rotation speed of 5000rpm for 30s to obtain an interface treatment solution layer, and then annealing at 100 ℃ for 5min; obtaining an interface layer;
will PbI 2 Dissolving in DMF and DMSO to obtain PbI 2 Solution, pbI 2 The mass concentration of the solution is preferably 691.5mg/mL, and the solvent is DMF and DMSO blended solution (volume ratio DMF: DMSO = 9:1); will PbI 2 Spin-coating the solution on the surface of the interface layer at 1500rpm for 30s, and annealing at 70 deg.C for 1min to obtain PbI 2 Coating;
blending and dissolving FAI, MAI and MACl to obtain a solvent in the mixed solution of FAI, MAI and MACl, wherein the solvent is preferably Isopropanol (IPA), the mass concentration of FAI in the mixed solution of FAI, MAI and MACl is preferably 90mg/mL, the mass concentration of MAI is preferably 6.39mg/mL, and the mass concentration of MACl is preferably 9mg/mL. Spin coating FAI, MAI and MACl solution on PbI 2 The surface of the solution layer is spin-coated at 2500rpm for 30s, and then annealed on a 150 deg.C hot bench outside a glove box for 15min, taking care that the air humidity needs to be controlled to 20-40% Relative Humidity (RH); and obtaining the perovskite film, wherein the perovskite film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked on the surface of the substrate, so as to obtain the perovskite layer.
Dissolving PCBM in chlorobenzene to obtain an electron transport layer precursor solution, wherein the mass concentration of the electron transport layer precursor solution is 20mg/mL, and spin-coating the electron transport layer precursor solution on the surface of the perovskite layer at the rotation speed of 1000rpm for 30s to obtain an electron transport layer; simultaneously, a C60 electron transmission layer can be deposited by a vacuum deposition mode, the thickness is 25-50nm, and the evaporation rate is
Thermal annealing is not used after deposition.
And then preparing a BCP interface buffer layer, wherein the BCP interface buffer layer can be prepared by a solution method or a vacuum evaporation method. For the specific process of preparing the BCP layer by the solution method, firstly, the BCP is dissolved in ethanol to obtain an interface buffer layer precursor solution, and the mass concentration of the interface buffer layer precursor solution is 1mg/mL, spin-coating the precursor solution of the interface buffer layer on the surface of the electron transport layer at the rotation speed of 5000rpm for 30s to obtain the bathocuproine interface buffer layer; for the specific process of preparing the BCP layer by the vacuum evaporation method, the chamber pressure is 4 multiplied by 10 -4 pa is 5-10nm in thickness and the evaporation rate is
Thermal annealing is not used after deposition.
And finally, carrying out vacuum evaporation on the surface of the bathocuproine interface buffer layer to form a copper electrode with the thickness of 100nm to obtain the perovskite solar cell.
Comparative example 3
Cleaning the ITO transparent conductive substrate, and respectively carrying out ultrasonic cleaning for 15min by using a glass cleaning agent, deionized water, acetone and isopropanol;
carrying out UV-O on the cleaned ITO transparent conductive substrate 3 Treating for 15min to remove residual organic matters on the surface of the ITO transparent conductive substrate and improve the work function;
dissolving a self-assembled monomolecular layer [2- (3,6-dimethoxy-9H-carbazole-9-yl) ethyl ] phosphonic acid (MeO-2 PACz) in isopropanol to obtain a hole transport layer precursor solution with the mass concentration of 0.5mg/mL, spin-coating the hole transport layer precursor solution on the surface of an ITO (indium tin oxide) transparent conductive substrate at the rotating speed of 3000rpm for 30s to obtain a hole transport layer precursor solution layer, and then annealing at 100 ℃ for 10min; obtaining a hole transport layer;
mixing CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 Coating the mixed solution on the surface of the interface layer to obtain CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 Mixing the solution layer, adding the CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 And annealing the mixed solution layer to obtain the perovskite layer.
In the invention, the CsI, rbI, MABr, FAI and PbI 2 And PbBr 2 The solvent in the mixed solution is preferably a mixed solvent of DMF and DMSO (volume ratio DMF: DMSO = 4:1), and CsI, rbI, MABr, FAI, pbI 2 And PbBr 2 MixingThe mass concentration of CsI in the solution is preferably 19.5mg/mL, the mass concentration of RbI is preferably 15.9mg/mL, the mass concentration of MABr is preferably 8.4mg/mL, the mass concentration of FAI is preferably 219.5mg/mL, and PbI 2 The mass concentration is preferably 656.9mg/mL, pbBr 2 The mass concentration is preferably 27.5mg/mL. The coating is preferably spin coating, the rotation speed of the spin coating is preferably 1000rpm,10s, 3000rpm and 30s in the first step, 150 mu L of anti-solvent chlorobenzene is dripped in the 15 th step, the temperature of the annealing treatment is preferably 100 ℃, and the holding time of the annealing treatment is preferably 10min.
Dissolving PCBM in chlorobenzene to obtain an electron transport layer precursor solution, wherein the mass concentration of the electron transport layer precursor solution is 20mg/mL, and spin-coating the electron transport layer precursor solution on the surface of the perovskite layer at the rotation speed of 1000rpm for 30s to obtain an electron transport layer; simultaneously, a C60 electron transmission layer can be deposited by a vacuum deposition mode, the thickness is 25-50nm, and the evaporation rate is
Thermal annealing is not used after deposition.
And then preparing a BCP interface buffer layer, wherein the BCP interface buffer layer can be prepared by a solution method or a vacuum evaporation method. For the specific process of preparing the BCP layer by the solution method, firstly, dissolving BCP in ethanol to obtain an interface buffer layer precursor solution, wherein the mass concentration of the interface buffer layer precursor solution is 1mg/mL, spin-coating the interface buffer layer precursor solution on the surface of an electron transport layer at the rotation speed of 5000rpm for 30s to obtain the BCP interface buffer layer; for the specific process of preparing BCP layer by vacuum evaporation method, the chamber pressure is 4 x 10 -4 pa is 5-10nm in thickness and the evaporation rate is
Thermal annealing is not used after deposition.
And finally, carrying out vacuum evaporation on the surface of the BCP interface buffer layer to form a copper electrode with the thickness of 100nm to obtain the perovskite solar cell.
Test example 1
FIG. 1 is a scanning electron microscope image of a perovskite thin film prepared in example 1 of the present invention, a perovskite thin film prepared in comparative example 1, and a perovskite thin film prepared in comparative example 2; the left side of fig. 1 is a scanning electron microscope image of the perovskite thin film prepared in comparative example 1, the middle of fig. 1 is a scanning electron microscope image of the perovskite thin film prepared in comparative example 2, and the right side of fig. 1 is a scanning electron microscope image of the perovskite thin film prepared in example 1. FIG. 2 is a graph showing the secondary primitive representation of the time-of-flight of the perovskite thin film prepared in example 1 of the present invention.
From fig. 1 and 2, it can be seen that: in the perovskite thin film, polyelectrolyte can be spontaneously enriched on the upper surface of a perovskite layer, energy groups contained in PFN-Br can passivate the surface defects of the perovskite layer, and meanwhile, hydrophobic fatty chains contained in PFN-Br can be used as a protective layer to improve the stability of a device; the organic amine salt PEAI can be spontaneously enriched on a buried interface of the perovskite layer to passivate the defect of the buried interface, and meanwhile, an energy band arrangement structure which is more favorable for carrier transportation is formed on the buried interface, so that the recombination of carriers at the interface is reduced.
Test example 2
Fig. 3 is a characterization diagram of the transient fluorescence spectrum and the time-resolved fluorescence spectrum of the perovskite thin film prepared in example 1 of the present invention, the perovskite thin film prepared in comparative example 1, and the perovskite thin film prepared in comparative example 2, and it can be seen from fig. 3 that the transient fluorescence spectrum and the time-resolved fluorescence spectrum of the perovskite thin film prepared in example 1 of the present invention are significantly improved compared with the perovskite thin films prepared in comparative examples 1 and 2, which indicates that the perovskite thin film prepared in example 1 (example 1) has the least defect content and the non-radiative recombination is also significantly suppressed.
Test example 3
Fig. 4 is a graph showing the performance characteristics of the perovskite solar cell prepared in example 1 of the present invention, the perovskite solar cell prepared in comparative example 1, and the perovskite solar cell prepared in comparative example 2. The performance test conditions for aging of the product in the right graph in fig. 4 are: heating at 85 deg.C under nitrogen atmosphere, and irradiating with indoor light for 500 hr.
From the right graph of fig. 4, it can be seen that the co-treatment of PFN-Br and PEAI achieves a photoelectric conversion performance of more than 23%, and the stability of the device is also significantly improved.
Test example 4
FIG. 5 is a graph comparing the performance of the perovskite solar cell (denoted as Target device) prepared in example 4 of the present invention and the perovskite solar cell (denoted as Control device) prepared in comparative example 3; from fig. 5, it can be seen that: the preparation method provided by the invention has good universality, is not only used for preparing the perovskite thin film by the two-step method in the embodiment 1, but also is compatible with the method for preparing the perovskite thin film by the one-step method.
Fig. 6 is a graph comparing the performance of the perovskite thin-film solar cell prepared in example 2 of the present invention and the perovskite solar cell prepared in comparative example 1. From fig. 6, it can be derived that: the method provided by the invention is not limited to the use of PEAI ammonium salt, and can also play a role in improving the photoelectric conversion performance of the perovskite solar cell by adopting the blending treatment of HTAB and PFN-Br.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The preparation method of the perovskite thin film is characterized by comprising the following steps:
coating an interface treatment solution on the surface of the hole transport layer to obtain an interface treatment coating; the interface treatment solution comprises polyelectrolyte, organic ammonium salt and organic solvent;
annealing the interface treatment coating to obtain the interface layer;
coating a perovskite precursor solution on the surface of the interface layer to prepare a perovskite layer to obtain the perovskite film, wherein a solvent in the perovskite precursor solution is a solvent capable of dissolving the polyelectrolyte and the organic ammonium salt; and obtaining the perovskite thin film formed on the surface of the hole transport layer, wherein the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked.
2. The method of claim 1, wherein the polyelectrolyte comprises one or more of poly (9,9-bis (3 '- (N, N-dimethyl) -N-ethylaminopropyl-2,7-fluorene) -alt-2,7- (9,9-dioctylfluorene)) dibromide, poly (9,9-bis (3' - (N, N-dimethyl) -N-ethylaminopropyl-2,7-fluorene) -alt-2,7- (9,9-dioctylfluorene)) diiodide, a compound of formula 1, and a compound of formula 2;
3. the method of claim 1, wherein the organic ammonium salt comprises one or more of phenethylamine iodide, ethyltrimethylammonium bromide, butanediamine iodide, octylamine chloride, tert-butylamine hydroiodide, tert-butylammonium chloride, phenethylammonium chloride, 1,4-phenylenediamine hydroiodide, benzyl amine iodide, 1,4-xylylenediamine iodide, guanidinium hydrobromide, and guanidinium thiocyanate.
4. The production method according to any one of claims 1 to 3, wherein the mass ratio of the polyelectrolyte to the organic ammonium salt in the interfacial treatment solution is 1 (1 to 20).
5. The method according to claim 1, wherein the annealing temperature is between room temperature and 150 ℃, and the annealing holding time is between 5 and 10min.
6. The method of claim 1, wherein the coating is replaced with the steps of:
first coating a first interface treatment solution on the surface of the hole transport layer to obtain a first interface treatment coating; the first interfacial treatment solution comprises the polyelectrolyte and an organic solvent;
secondly coating a second interface treatment solution on the surface of the first interface treatment coating to obtain a second interface treatment coating; the second interface treatment solution comprises an organic ammonium salt and an organic solvent;
the first interface treatment coating and the second interface treatment coating which are arranged in a stacked mode form the interface treatment coating.
7. The perovskite thin film prepared by the preparation method according to any one of claims 1 to 6, wherein the perovskite thin film comprises an organic ammonium salt buried interface layer, a perovskite layer and a polyelectrolyte interface surface layer which are sequentially stacked.
8. The perovskite thin film of claim 7, wherein the thickness of the organoammonium salt buried interface layer and the polyelectrolyte interface surface layer are independently 0.5 to 30nm.
9. A perovskite solar cell comprising a conductive substrate and a hole transport layer, a perovskite thin film, an electron transport layer, an interfacial buffer layer and an electrode which are sequentially stacked on the surface of the conductive substrate, wherein the perovskite thin film is the perovskite thin film according to claim 7 or 8.
10. The method of fabricating the perovskite solar cell as claimed in claim 9, comprising the steps of:
preparing a hole transport layer on the surface of the conductive substrate;
preparing a perovskite thin film on the surface of the hole transport layer according to the method of any one of claims 1 to 6;
preparing an electron transport layer on the surface of the perovskite thin film;
preparing an interface buffer layer on the surface of the electron transport layer;
and preparing an electrode on the surface of the interface buffer layer to obtain the perovskite solar cell.
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| CN116507185B (en) * | 2023-06-30 | 2023-10-20 | 长江三峡集团实业发展(北京)有限公司 | Formamidine perovskite solar cell and preparation method thereof |
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