CN108649124B - High-efficiency inorganic perovskite solar cell and preparation method thereof - Google Patents
High-efficiency inorganic perovskite solar cell and preparation method thereof Download PDFInfo
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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Abstract
The invention discloses a one-step solution method for preparing a high-efficiency planar heterojunction inorganic perovskite solar cell and a preparation method thereof. The preparation method comprises the following steps: preparing, cleaning and treating a substrate; preparing a stannic oxide electron transport layer by using a spin coating mode; preparing a perovskite material precursor solution; preparing the perovskite material film by using a spin coating method, a blade coating method, a printing method and a flash annealing process to obtain a high-quality perovskite material light absorption layer; preparing a 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9 '-spirobifluorene solution and depositing the solution on a perovskite light absorption layer to prepare a 2,2',7,7 '-tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene hole transport layer; the electrodes were prepared by evaporation. The product of the invention has the advantages of high thermal stability, simple process, high efficiency and the like, and has important application prospect.
Description
Technical Field
The invention belongs to the field of photoelectric devices, and particularly relates to a method for preparing a high-efficiency inorganic planar heterojunction CsPbI by a one-step solution method2Br perovskite solar cell and preparation method thereof
Background
Among the various new energy technologies available, photovoltaic power generation is undoubtedly one of the most promising directions. Solar cells refer to photovoltaic devices that are capable of converting solar energy into electrical energy. At present, the traditional solar cell is mainly prepared by inorganic materials, such as monocrystalline silicon, gallium arsenide, copper indium gallium selenide and the like. However, in terms of cost and efficiency, the further development of the solar cell is influenced by the pollution and energy consumption problems in the manufacturing process, so that the research and development of a novel solar cell with high efficiency and low cost are very important.
In recent years, metal halide perovskite semiconductor materials have been used for their high light absorption, low defect state density, and current carryingThe solar photovoltaic cell has the advantages of high mobility, long carrier service life and the like, and is very suitable for being applied to the field of photovoltaic power generation, thereby drawing wide attention of people. The dye-sensitized solar cell is introduced into the dye-sensitized solar cell for the first time from 2009, and achieves an energy conversion efficiency of 3.8%, and the research heat is increasing. To date, the highest energy conversion efficiency of perovskite solar cells has been as high as 22.1%. However, the most widely studied organic-inorganic hybrid perovskite materials have significant thermal instability, leading to decomposition of the perovskite material. Therefore, the substitution of inorganic for organic components in the perovskite structure is a fundamental solution to the thermal instability, such as the substitution of the a site with Cs. As an alternative to organic-inorganic hybrid perovskite photoactive layers, cesium-lead halide perovskites exhibit excellent thermal stability. Wherein CsPbI2Br is a stable and efficient light conversion material, has a proper band gap of 1.91eV, can absorb most visible light, is suitable for solar energy conversion, and has excellent photovoltaic properties.
The invention successfully prepares the smooth and compact cesium halide lead perovskite thin film by using a one-step solution method, obtains excellent thermal stability, prepares a high-efficiency planar heterojunction solar cell by using the thin film as an active layer, and provides important reference for commercialization of perovskite solar cells.
Disclosure of Invention
The invention aims to solve the technical problems of providing a method with simple process for preparing a high-quality lead-halide cesium perovskite thin film and finding a method for preparing a high-performance planar heterojunction perovskite solar cell.
In order to solve the technical problems, the technical scheme provided by the invention is to prepare a high-quality cesium-halide-lead perovskite thin film by a one-step solution method, and prepare a planar heterojunction high-performance perovskite solar cell on the basis of the high-quality cesium-halide-lead perovskite thin film.
According to the plane heterojunction high-performance perovskite solar cell, the substrate is Indium Tin Oxide (ITO).
According to the plane heterojunction high-performance perovskite solar cell, the electron transmission layer is tin dioxide.
According to the planar heterojunction high-performance perovskite solar cell, the perovskite material is CsPbIxBr3-x。
In the planar heterojunction high-performance perovskite solar cell, the hole transport layer is 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene.
According to the plane heterojunction high-performance perovskite solar cell, the electrode layer is made of silver.
Aiming at the planar heterojunction CsPbI with simple preparation process, good thermal stability and high performance2The technical scheme of the invention provides a method for preparing a Br perovskite solar cell by CsPbI2The Br perovskite material is a light absorption layer and 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]The structure of the solar cell with 9,9' -spirobifluorene as a hole transport layer and tin dioxide as an electron transport layer is based on the following ideas and research experiences: the perovskite material is an excellent light absorption material, has good light absorption characteristics in ultraviolet, visible light and near infrared regions, and can be well utilized in the field of solar cells. However, the most widely studied organic-inorganic hybrid perovskite materials have significant thermal instability, leading to decomposition of the perovskite material. As an alternative to organic-inorganic hybrid perovskite photoactive layers, cesium-lead halide perovskites exhibit excellent thermal stability. However, the fabrication of photovoltaic devices based on pure inorganic perovskites remains challenging in view of band gap and phase stability, among other factors. And CsPbI2The Br perovskite has a proper band gap of 1.91eV, can absorb most visible light, is suitable for solar energy conversion, and has excellent photovoltaic properties. A high-quality perovskite thin film is prepared by a one-step solution method or blade coating or printing with a simple process, and a high-efficiency planar heterojunction solar cell is prepared by selecting a proper electron hole transport layer, so that a premise and a basis are provided for the specific implementation of the invention.
As a general technical concept, the present invention mainly provides a CsPbI-based method2BrThe preparation method of the high-performance planar heterojunction solar cell with the perovskite as the active layer comprises the following steps:
(1) preparing, cleaning and treating a substrate;
(2) preparing a stannic oxide electron transport layer based on a solution film forming method;
(3) preparing precursor solution of inorganic perovskite material;
(4) preparing an inorganic perovskite material film by spin coating, blade coating or printing through a one-step solution method, and performing flash annealing treatment to obtain a high-quality perovskite material light absorption layer;
(5) preparing a hole transport layer based on a solution film forming method;
(6) and preparing a top electrode.
In the above preparation method, in the step (1), the substrate preparation, cleaning and treatment includes that the substrate is ultrasonically cleaned for 20 minutes by acetone, detergent/deionized water, deionized water and isopropanol respectively, then is dried by nitrogen, and finally is treated by ultraviolet-ozone for 20 minutes. Organic matters, impurities and the like on the surface of the substrate can be effectively removed through the cleaning steps, so that interface contact is improved, and the preparation of a high-quality perovskite thin film is facilitated; blowing the substrate by using nitrogen to remove solid particles attached to the surface of the substrate; in addition, the ITO work function can be improved by treating the substrate with ultraviolet-ozone, and meanwhile, the wettability of the tin dioxide solution on the surface of the substrate is improved, so that the preparation of the tin dioxide electron transport layer is facilitated.
In the preparation method, in the step (2), the step of preparing the tin dioxide electron transport layer is to prepare the tin dioxide electron transport layer by adopting a spin coating method. The spin coating process comprises the following steps: spin coating at 3000rpm for 30 s. The wet film after spin coating was annealed at a temperature of 150 ℃ for 15 minutes.
In the preparation method, in the step (3), the perovskite precursor solution is CsBr: PbI2Weighing according to the molar ratio of 1:1, dissolving in a mixed solution (volume ratio of 4:1) of N-N dimethylformamide and dimethyl sulfoxide to form a perovskite solution with the molar concentration of 0.5mol/L, and heating and stirring at the temperature of 60-70 ℃ for 12 hours. By adopting the above proportion and through heating and stirringThe materials can be fully dissolved by means of the method, so that the proportion of each component of the film is ensured, the wet film can fully react to form perovskite in the subsequent annealing link, and the residual PbI is reduced2。
In the preparation method, in the step (4), the inorganic perovskite material thin film layer is prepared on the sample on which the electron transport layer is deposited by spin coating or blade coating or printing technology, and then flash annealing is carried out at 220 ℃ to 250 ℃ for 8 seconds to 20 seconds, so that a continuous and compact light absorption layer with the thickness of 200 nanometers to 350 nanometers can be formed.
In the above preparation method, in the step (5), the hole material is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, which is dissolved in chlorobenzene to form a solution with a concentration of 90mg/ml, and 45ul of bis (trifluoromethylsulfonyl) lithium solution (acetonitrile as a solvent with a concentration of 170mg/ml) and 10ul of tributyl phosphate are added, stirred at normal temperature for 12 hours, and a hole transport layer is prepared by depositing on the perovskite light absorption layer by spin coating, and spin coating is performed at 3000rpm for 30 s.
In the above preparation method, in the step (6), the step of preparing the electrode by evaporation is to deposit a silver electrode of 100nm by evaporation.
Compared with the prior art, the invention has the advantages that:
1. the invention prepares CsPbI2The preparation method of the Br perovskite thin film is simple in process, and the high-quality perovskite thin film can be prepared by utilizing spin coating or blade coating or printing technology and providing a flash annealing process, namely flash annealing at the temperature of 220-250 ℃ for 8-20 seconds.
2. With simultaneous use of tin dioxide/CsPbI2Br perovskite/2, 2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]And the perovskite plane heterojunction solar cell with high performance is prepared by the structure of-9, 9' -spirobifluorene. The tin oxide electron transport layer is applied to the lead halide cesium oxide inorganic perovskite solar cell for the first time.
In general, the invention provides a method for preparing CsPbI-based material2The method for preparing the high-efficiency planar heterojunction solar cell of the Br perovskite simplifies the preparation of the lead halideThe process of the cesium perovskite solar cell has important significance for improving the practicability of the perovskite solar cell.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
[ FIG. 1 ] based on CsPbI2And the structural schematic diagram of the planar heterojunction solar cell of the Br perovskite active layer.
FIG. 2 is a scanning electron microscope topography of the surface of the perovskite thin film prepared by flash annealing.
FIG. 3 is an X-ray diffraction spectrum of a perovskite thin film prepared by flash annealing.
FIG. 4 shows the UV-visible absorption spectrum of the perovskite thin film prepared by flash annealing.
FIG. 5 preparation of CsPbI based on spin coating method2The hole layer is a current-voltage curve of a spiral-OMeTAD or NiOx planar heterojunction solar cell; preparation of CsPbI based on knife coating method2Current-voltage curves for planar heterojunction solar cells of the Br perovskite layer.
FIG. 6 is based on CsPbI2And (3) statistically distributing the energy conversion efficiency of the planar heterojunction solar cell with the Br perovskite active layer.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the following specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the cell structure of the embodiment is shown in fig. 1, and comprises five parts, namely a substrate, an electron transport layer, a perovskite material light absorption layer, a hole transport layer and an electrode, wherein the thickness of the perovskite material light absorption layer is about 200 nm. Wherein the hole transport layer is Spiro-OMeTAD.
The preparation method on the Indium Tin Oxide (ITO) substrate in this embodiment includes the following steps:
(1) the Indium Tin Oxide (ITO) glass substrates were ultrasonically cleaned with acetone, detergent/deionized water, isopropanol, respectively, for 20 minutes, then blow-dried with nitrogen, and then uv-ozone treated for 20 minutes.
(2) The tin dioxide solution was taken out of the refrigerator, stirred at room temperature for 20min, and filtered through a 0.45ul organic filter. The substrate was placed well and the filtered tin dioxide solution was dropped into it, accelerated to 3000rpm in 3 seconds and held for 30 seconds. The wet film after spin coating was annealed at a temperature of 150 ℃ for 15 minutes.
(3) Mixing CsBr and PbI2Weighing according to the molar ratio of 1:1, dissolving in a mixed solvent of N-N dimethylformamide and dimethyl sulfoxide (the volume ratio is 4:1), and finally heating and stirring at the temperature of 65 ℃ for 12 hours to obtain 0.5mol/L CsPbI2Br precursor solution.
(4) The light absorbing layer was prepared in a one-step solution process in a glove box. The sample was placed on a spin coater, and CsPbI was dropped2Br precursor solution. The spinning process was accelerated to 2000rpm for 30 seconds in 6 seconds. After the spin coating was completed, the wet film was annealed at 240 degrees for 10 seconds. And after the annealing is finished and the cooling is finished, obtaining the high-quality perovskite film. The scanning electron microscope topography of the perovskite thin film surface is shown in fig. 2, the X-ray diffraction spectrum of the perovskite thin film is shown in fig. 3, and the ultraviolet-visible light absorption spectrum of the perovskite thin film is shown in fig. 4.
(5) 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene was dissolved in chlorobenzene to form a solution having a concentration of 90mg/ml, and 45ul of a bis (trifluoromethylsulfonyl) lithium solution (the solvent was acetonitrile, the concentration was 170mg/ml) and 10ul of tributyl phosphate were added thereto and stirred at normal temperature for 12 hours. And depositing the hole transport layer on the perovskite light absorption layer by using a spin coating mode. The substrate on which the light absorbing layer was deposited was set, and a 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene solution was dropped, and the spin coating process was accelerated to 3000rpm within 6 seconds, and held for 30 seconds.
(6) Preparing a silver electrode by adopting evaporation, and depositing to form the silver electrode with the thickness of 100 nm.
The CsPbI-based material prepared by the steps2The current-voltage curve of the planar heterojunction solar cell with the Br perovskite active layer and the Spiro-OMeTAD as the hole transport layer is shown in FIG. 5, and the statistical distribution graph of the energy conversion efficiency is shown in FIG. 6.
CsPbI-based material of the present example prepared by the above method2The planar heterojunction solar cell with the Br perovskite active layer achieves the energy conversion efficiency of 13.09% and achieves the expected target. The above CsPbI-based2The specific properties of the planar heterojunction solar cell with the Br perovskite active layer are shown in the following table:
example 2:
the battery structure of the embodiment comprises a substrate, an electron transport layer, a perovskite material light absorption layer, a hole transport layer and an electrode, wherein the thickness of the perovskite material light absorption layer is about 200 nm. Wherein the hole transport layer is NiOx.
The preparation method on the Indium Tin Oxide (ITO) substrate in this embodiment includes the following steps:
(1) the Indium Tin Oxide (ITO) glass substrates were ultrasonically cleaned with acetone, detergent/deionized water, isopropanol, respectively, for 20 minutes, then blow-dried with nitrogen, and then uv-ozone treated for 20 minutes.
(2) The NiOx solution was stirred at 90 ℃ for 1h and filtered through a filter head. The substrate was placed well and the filtered nickel oxide solution was dropped into it, accelerated to 3000rpm in 3 seconds and held for 30 seconds. The wet film after spin coating was annealed at a temperature of 300 c for 30 minutes.
(3) Mixing CsBr and PbI2Weighing according to the molar ratio of 1:1, dissolving in a mixed solvent of N-N dimethylformamide and dimethyl sulfoxide (the volume ratio is 4:1), and finally heating and stirring at the temperature of 65 ℃ for 12 hours to obtain 0.5mol/L CsPbI2Br precursor solution.
(4) The light absorbing layer was prepared in a one-step solution process in a glove box. The sample was placed on a spin coater, and CsPbI was dropped2Br precursor solution. The spinning process was accelerated to 2000rpm for 30 seconds in 6 seconds. After the spin coating was completed, the wet film was annealed at 240 degrees for 10 seconds. And after the annealing is finished and the cooling is finished, obtaining the high-quality perovskite film.
(5) PCBM was dissolved in chlorobenzene to give a solution with a concentration of 15mg/ml, and the solution was stirred at 50 ℃ for 12 hours. And depositing and preparing on the perovskite light absorption layer by using a spin coating mode. The substrate on which the light absorbing layer was deposited was placed, and PCBM solution was dropped, and the spin coating process was accelerated to 3000rpm for 6 seconds and held for 30 seconds.
(6) Preparing a silver electrode by adopting evaporation, and depositing to form the silver electrode with the thickness of 100 nm.
The CsPbI-based material prepared by the steps2The current-voltage curve of the Br perovskite active layer and the plane heterojunction solar cell taking NiOx as the hole transport layer is shown in figure 5,
example 3:
the battery structure of the embodiment comprises five parts, namely a substrate, an electron transport layer, a perovskite material light absorption layer, a hole transport layer and an electrode. Wherein the perovskite material light absorption layer is prepared by a blade coating method.
The preparation method on the Indium Tin Oxide (ITO) substrate in this embodiment includes the following steps:
(1) the Indium Tin Oxide (ITO) glass substrates were ultrasonically cleaned with acetone, detergent/deionized water, isopropanol, respectively, for 20 minutes, then blow-dried with nitrogen, and then uv-ozone treated for 20 minutes.
(2) The tin dioxide solution was taken out of the refrigerator, stirred at room temperature for 20min, and filtered through a 0.45ul organic filter. The substrate was placed well and the filtered tin dioxide solution was dropped into it, accelerated to 3000rpm in 3 seconds and held for 30 seconds. The wet film after spin coating was annealed at a temperature of 150 ℃ for 15 minutes.
(3) Mixing CsBr and PbI2Weighing according to the molar ratio of 1:1, dissolving in a mixed solvent of N-N dimethylformamide and dimethyl sulfoxide (the volume ratio is 4:1), and finally heating and stirring at the temperature of 65 ℃ for 12 hours to obtain 0.5mol/L CsPbI2Br precursor solution.
(4) And (3) blade-coating the prepared perovskite precursor solution on a substrate deposited with an electron transport layer by using blade coating equipment, wherein the blade interval is 150 microns, the coating speed is set to be 15 m/min, and the coated substrate is placed on a 240-DEG hot bench to be annealed and dried for 1s to form an active layer film.
(5) 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene was dissolved in chlorobenzene to form a solution having a concentration of 90mg/ml, and 45ul of a bis (trifluoromethylsulfonyl) lithium solution (the solvent was acetonitrile, the concentration was 170mg/ml) and 10ul of tributyl phosphate were added thereto and stirred at normal temperature for 12 hours. And depositing the hole transport layer on the perovskite light absorption layer by using a spin coating mode. The substrate on which the light absorbing layer was deposited was set, and a 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene solution was dropped, and the spin coating process was accelerated to 3000rpm within 6 seconds, and held for 30 seconds.
(6) Preparing a silver electrode by adopting evaporation, and depositing to form the silver electrode with the thickness of 100 nm.
By knife coating CsPbI2The current-voltage curve of the planar heterojunction solar cell prepared by the Br perovskite active layer is shown in figure 5.
Claims (3)
1. The preparation method of the high-efficiency inorganic perovskite solar cell is characterized in that the inorganic perovskite solar cell adopts tin dioxide/CsPbI 2 Br perovskite/2, 2',7,7' -tetra [ N, N-di (4-methoxy group)Phenyl) amino]-9,9' spirobifluorene structure; the preparation method specifically comprises the following steps:
(1) preparing, cleaning and treating a substrate;
(2) preparing a stannic oxide electron transport layer based on a solution film forming method;
(3) preparing precursor solution of inorganic perovskite material;
(4) preparing an inorganic perovskite material film by spin coating, blade coating or printing through a one-step solution method, and performing flash annealing treatment at the temperature of 220-250 ℃ for 8-20 seconds to obtain a high-quality perovskite material light absorption layer;
(5) preparing a hole transport layer based on a solution film forming method;
(6) and preparing a top electrode.
2. The method for preparing a high efficiency inorganic perovskite solar cell as claimed in claim 1, wherein in the step (3), the perovskite precursor solution is formed by CsBr and PbI2Weighing according to a certain molar ratio, dissolving the mixture in a mixed solution of N-N dimethylformamide and dimethyl sulfoxide to form an inorganic perovskite solution with the molar concentration of 0.5mol/L, and heating and stirring the solution at the temperature of between 60 and 70 ℃ for 12 hours; the volume ratio of the N-N dimethylformamide to the dimethyl sulfoxide in the mixed solution is 4: 1.
3. the method according to claim 1, wherein in the step (4), the thin film layer of inorganic perovskite material is formed on the sample on which the electron transport layer is deposited by spin coating, doctor blading or printing technique to form a continuous, dense light absorption layer with a thickness of 200nm to 350 nm.
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