CN112071994B - Method for preparing large-size crystal grain perovskite film by blade coating method - Google Patents

Method for preparing large-size crystal grain perovskite film by blade coating method Download PDF

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CN112071994B
CN112071994B CN202010911585.8A CN202010911585A CN112071994B CN 112071994 B CN112071994 B CN 112071994B CN 202010911585 A CN202010911585 A CN 202010911585A CN 112071994 B CN112071994 B CN 112071994B
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陈永华
陈畅顺
黄维
宋霖
冉晨鑫
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Northwestern Polytechnical University
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Abstract

The invention relates to a method for preparing a large-size crystal grain perovskite film by a blade coating method, which comprises the steps of firstly preparing an ionic liquid perovskite blade coating precursor, dragging a scraper to move at a constant speed from one end of a substrate to the other end, and then leaving a layer of wet perovskite film on the substrate; annealing for 20 +/-5 seconds on a blade coating coater, then transferring the perovskite thin film which is completely transformed into the phase to a heating table at 110 +/-10 ℃ and then annealing for 10 minutes to obtain the fully-deposited large-size crystal grain perovskite thin film. Has the advantages that: the preparation of the perovskite thin film with large-size crystal grains is carried out in the air, and no special protective atmosphere requirement exists; parameters of the perovskite thin film can be adjusted according to actual requirements by adjusting the blade coating rate, the gap spacing and the like; the knife coating coater has simple equipment structure, easy operation and lower instrument cost, and is suitable for large-scale production; the perovskite thin film with large-size crystal grains can be applied to solar cells, and can also be applied to other fields such as light emitting diodes, photoelectric detectors and the like.

Description

Method for preparing large-size crystal grain perovskite film by blade coating method
Technical Field
The invention belongs to a method for preparing a perovskite film, and relates to a method for preparing a large-size crystal grain perovskite film by a blade coating method.
Background
With the rapid development of society and the rapid increase of population, the demand for developing green energy without environmental pollution is increasingly outstanding, and the significant problems of energy crisis, environmental pollution and the like faced by human beings can be solved by fully utilizing solar energy. The titanium ore solar cell as a new generation solar cell has the advantages of low cost, proper band gap width, long carrier service life, long diffusion distance and the like, is a high-efficiency metal halide semiconductor material, has the photoelectric conversion efficiency exceeding 25 percent in short years, and is close to the highest efficiency record of a monocrystalline silicon cell. At present, the preparation method of the perovskite light absorption layer with high efficiency is mainly a spin coating method, however, the preparation process of the spin coating method is long in time consumption and difficult to produce on a large scale, and further application of the perovskite solar cell is limited. According to past experience, non-radiative coincidence caused by charge defects is an important reason influencing low photoelectric conversion efficiency of perovskite, the defects are closely related to crystal lattice vacancies, crystal boundary traps and the like, and internal defects of the perovskite are mainly shallow defects and have small influence on device performance. The key point of preparing the perovskite thin film with large-size crystal grains is to control the crystal nucleation process of the perovskite, the crystal nucleation process of the perovskite thin film is influenced by a preparation process, solvent composition, solution components and other factors, the preparation method of the perovskite thin film mainly adopts a spin-coating method, but the thin film prepared by the spin-coating method has the problems of small crystal grain size, dense crystal boundary, more defects and the like, so that the carrier mobility of the perovskite thin film is seriously reduced, and the service life of the perovskite thin film is prolonged. Therefore, in order to solve the problems of low performance of perovskite devices caused by excessive grain boundary defects, research on preparation of large-sized crystal perovskite thin films is attracting much attention. The perovskite device with large-size crystal grains has better damp-heat stability and higher device efficiency, and is an important research direction for the industrial application of the perovskite solar device.
At present, in order to reduce grain boundaries, improve crystal order and improve carrier mobility, the following methods are used for preparing large-grain perovskite thin films:
printing a large-size crystal grain perovskite film by using a meniscus auxiliary solvent:calcium titaniumThe ore precursor solution forms a meniscus with a certain radian at the edge of the scraper, and due to the coffee ring effect, the solvent in the perovskite precursor solution at the edge of the scraper is volatilized rapidly, so that the perovskite solution locally reaches a supersaturated state, and the method is favorable forCalcium titaniumNucleation and growth of mineral crystals.
High-temperature gas-phase assisted growth of a large-size crystal grain perovskite film: a method for forming large-size crystal perovskite thin film by spin-coating a layer of Isopropanol (IPA) solution for dissolving organic ammonium salt on a uniform inorganic ammonium salt thin film, transferring the spin-coated thin film to the atmosphere of saturated organic ammonium salt steam, and inhibiting the organic ammonium salt from sublimating from the perovskite transition state.
Preparing a large-size crystal grain perovskite film by solvent engineering regulation: the solvent with high dielectric constant is beneficial to preparing the absorption layer with coarse crystal grains and less crystal boundaries, can inhibit the carrier recombination of the perovskite, and is a method more suitable for preparing the high-efficiency planar perovskite solar cell.
The existing preparation method of the large-size crystal grain perovskite thin film mainly has the following defects:
1) in order to grow perovskite grains with a preferred tendency at low temperatures, the process of preparing perovskite thin films by meniscus assisted solvent printing requires very slow substrate movement, typically at a rate of 10-20 μm/s, which reduces the speed of perovskite device fabrication.
2) The gas-solid interface reaction of the gas-phase auxiliary deposition method is very limited, the compact perovskite thin film can be obtained only by generally needing higher temperature (more than or equal to 200 ℃) or prolonging the reaction time (for a plurality of hours), and the size of the perovskite crystal grain prepared by the method is still to be improved.
3) The traditional organic solvent for preparing the perovskite precursor has high toxicity, cannot achieve environment-friendly preparation, has high consumption and is easy to damage the air environment and human health.
Reference documents:
(1)Deng,Y.；Peng,E.；Shao,Y.；Xiao,Z.；Dong,Q.；Huang,J.,Scalable fabrication of efficient organolead trihalide perovskite solar cells with doctor-bladed active layers.Energy&Environmental Science 2015,8(5),1544-1550.
(2)Liu,Y.；Yang,Z.；Cui,D.；Ren,X.；Sun,J.；Liu,X.；Zhang,J.；Wei,Q.；Fan,H.；Yu,F.；Zhang,X.；Zhao,C.；Liu,S.F.,Two-Inch-Sized Perovskite CH3 NH3 PbX3(X＝Cl,Br,I)Crystals:Growth and Characterization.Adv Mater 2015,27(35),5176-83.
(3)Liu,Y.；Sun,J.；Yang,Z.；Yang,D.；Ren,X.；Xu,H.；Yang,Z.；Liu,S.F.,20-mm-Large Single-Crystalline Formamidinium-Perovskite Wafer for Mass Production of Integrated Photodetectors.Advanced Optical Materials 2016,4(11),1829-1837.
(4)Becker,M.；Wark,M.,Controlling the crystallization and grain size of sequentially deposited planar perovskite films via the permittivity of the conversion solution.Organic Electronics 2017,50,87-93.
(5)He,M.；Li,B.；Cui,X.；Jiang,B.；He,Y.；Chen,Y.；O'Neil,D.；Szymanski,P.；Ei-Sayed,M.A.；Huang,J.；Lin,Z.,Meniscus-assisted solution printing of large-grained perovskite films for high-efficiency solar cells.Nat Commun 2017,8,16045.
(6)Ma,T.；Zhang,Q.；Tadaki,D.；Hirano-Iwata,A.；Niwano,M.,Fabrication and Characterization of High-Quality Perovskite Films with Large Crystal Grains.J Phys Chem Lett 2017,8(4),720-726.
(7)Zhang,L.；Zhang,X.；Yu,Y.；Xu,X.；Tang,J.；He,X.；Wu,J.；Lan,Z.,Efficient planar perovskite solar cells based on high-quality perovskite films with smooth surface and large crystal grains fabricated in ambient air conditions.Solar Energy 2017,155,942-950.
(8)Li,P.；Liang,C.；Bao,B.；Li,Y.；Hu,X.；Wang,Y.；Zhang,Y.；Li,F.；Shao,G.；Song,Y.,Inkjet manipulated homogeneous large size perovskite grains for efficient and large-area perovskite solar cells.Nano Energy 2018,46,203-211.
(9)Biewald,A.；Giesbrecht,N.；Bein,T.；Docampo,P.；Hartschuh,A.；Ciesielski,R.,Temperature-Dependent Ambipolar Charge Carrier Mobility in Large-Crystal Hybrid Halide Perovskite Thin Films.ACS Appl Mater Interfaces 2019,11(23),20838-20844.
(10)Lian,X.；Chen,J.；Qin,M.；Zhang,Y.；Tian,S.；Lu,X.；Wu,G.；Chen,H.,The Second Spacer Cation Assisted Growth of a 2D Perovskite Film with Oriented Large Grain for Highly Efficient and Stable Solar Cells.Angew Chem Int Ed Engl 2019,58(28),9409-9413.
(11)Mathur,S.,Protic ionic liquid assisted solution processing of lead halide perovskites with water,alcohols and acetonitrile.Nano Energy 2018,51,632-638.
(12)Chao,L.；Xia,Y.；Li,B.；Xing,G.；Chen,Y.；Huang,W.,Room-Temperature Molten Salt for Facile Fabrication of Efficient and Stable Perovskite Solar Cells in Ambient Air.Chem 2019,5(4),995-1006.
disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for preparing a large-size crystal grain perovskite film by a blade coating method, which avoids using an environmentally-friendly organic solvent, prepares the large-size crystal grain perovskite film and simplifies the post-treatment process of the film.
Technical scheme
A method for preparing a large-size crystal grain perovskite film by a blade coating method is characterized by comprising the following steps:
step 1, preparing an ionic liquid perovskite blade coating precursor: mixing inorganic halide YX2Adding the organic halide and the organic halide into a proton type ionic liquid according to a molar ratio of 1: 1, heating the mixture at 55 ℃ in an inert gas atmosphere, stirring the mixture for 6 to 9 hours, and then transferring the perovskite precursor solution into an air environment; the organic halide is MAI or MAI and FAI;
step 2, cleaning the FTO fluorine-doped tin dioxide coating glass substrate by adopting alkali liquor, an active detergent, deionized water and ethanol:
and step 3: preheating a substrate for 10 +/-5 minutes at the temperature of 100 +/-10 ℃, adjusting the distance between a coating scraper and the substrate to be 0.2 +/-0.1 mm, and then sucking 10 +/-5 mu L of perovskite precursor solution by using a liquid-transferring gun and transferring the perovskite precursor solution into a slit between the scraper and the substrate;
and 4, step 4: dragging the scraper to move from one end of the substrate to the other end at a constant speed, and then leaving a layer of wet perovskite thin film on the substrate; annealing for 20 +/-5 seconds on a blade coating coater, then transferring the perovskite thin film which is completely transformed into the phase to a heating table at 110 +/-10 ℃ and then annealing for 10 minutes to obtain the fully-deposited large-size crystal grain perovskite thin film.
The proton type ionic liquid is one or a mixture of more of MAAc methylamine acetate, MAP methylamine propionate and MABa methylamine butyrate.
And 4, dragging the scraper at a speed of 1-30 mm/s.
Advantageous effects
The invention provides a method for preparing a large-size crystal grain perovskite film by a blade coating method, which is used for preparing a perovskite blade coating precursor dissolved with inorganic halide and organic halide based on ionic liquid, and realizes non-toxicity and simple preparation. Secondly, the perovskite thin film with large-size crystal grains is prepared by utilizing the advantage that the coating parameters can be accurately adjusted by a blade coating method.
Has the advantages that: the perovskite blade coating precursor based on the proton type ionic liquid can be used for replacing a perovskite precursor prepared by a traditional organic solvent, and the non-toxic operation is realized; the preparation of the perovskite thin film with large-size crystal grains is carried out in the air, and no special protective atmosphere requirement exists; the preparation speed of the perovskite film can reach dozens of millimeters per second, and parameters of the perovskite film can be adjusted according to actual requirements by adjusting the blade coating speed, the gap distance and the like; the knife coating coater has simple equipment structure, easy operation and lower instrument cost, and is suitable for large-scale production; the perovskite thin film with large-size crystal grains can be applied to solar cells, and can also be applied to other fields such as light emitting diodes, photoelectric detectors and the like.
Drawings
FIG. 1: preparation of ionic liquid perovskite blade coating precursor
FIG. 2: preparation of perovskite thin film by adopting blade coating method
FIG. 3: compact graphical representation of perovskite thin film distribution prepared based on ionic liquid MAAc
FIG. 4: XRD test result of perovskite film prepared by the invention
FIG. 5: XRD test result of perovskite thin film prepared by spin-coating method in prior art
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
preparing an ionic liquid perovskite blade coating precursor:
as shown in FIG. 1Inorganic halide (YX)2) And an organic halide (MAI or MAI and FAI) in a molar ratio of 1: 1 is added into a proton type ionic liquid. The ionic liquid is used as a solvent of the perovskite precursor. Heating to 55 ℃ in an inert gas atmosphere, stirring for 6-9 hours, and transferring the perovskite precursor solution into an air environment for blade coating to prepare the perovskite thin film. The active ingredient of the proton type ionic liquid is one or a mixture of more of MAAc (methylamine acetate), MAP (methylamine propionate) and MABa (methylamine butyrate).
Preparing a perovskite film by a knife coating method:
firstly, cleaning an FTO (fluorine-doped tin dioxide) coated glass substrate by adopting alkali liquor, an active detergent, deionized water and ethanol. The FTO coated glass is cleaned by ultrasonic wave in alkali liquor, active detergent, deionized water and ethanol for 15 minutes respectively in sequence, and then exposed for 15 minutes in an ultraviolet ozone environment.
The perovskite film is prepared by adopting a blade coating method. As shown in fig. 2, the substrate is preheated at 100 ± 10 ℃ for 10 ± 5 minutes, the distance between the coating scraper and the substrate is adjusted to be 0.2 ± 0.1mm, then 10 ± 5 μ L of the perovskite precursor solution is sucked by a liquid-transferring gun and transferred to a slit between the scraper and the substrate, and the scraper is dragged to leave a layer of wet perovskite thin film on the substrate. The doctor blade is not in contact with the substrate all the time during the doctor-blade process. The film forming quality of the perovskite is influenced by factors such as the blade coating speed, the gap distance between the blade and the substrate, the preheating temperature of the substrate, the constant blade coating temperature and the like, and is also related to the precision and the quality of the blade coating machine.
Heat treatment of the wet perovskite thin film:
during the blade coating process, the substrate is always on a blade coating machine with the temperature of 100 +/-10 ℃, and the phase change of the perovskite is carried out at the same time. After the scraper moves from one end of the substrate to the other end at a constant speed, annealing is carried out on the scraper coater for 20 +/-5 seconds, then the perovskite thin film which is completely transformed into the phase is transferred to a heating table at the temperature of 110 +/-10 ℃ and then is annealed for 10 minutes, and finally the fully deposited large-size crystal grain perovskite thin film is obtained.
Example 1:
the embodiment provides a method for preparing a perovskite thin film by blade coating, which comprises the following specific steps:
the method comprises the following steps: mixing a mixture of 1: 1 MAI (methylamine hydroiodide) and PbI2(lead iodide) was mixed with 1mL of an ionic liquid MAAc, MAI and PbI2The mass was 102mg and 298mg, respectively, and the mixture was stirred under heating at 55 ℃ for 9 hours for use.
Step two: will spin on c-TiO2The substrate of (2) was preheated at 100 ℃ for 5 minutes, the gap between the coating blade and the substrate was adjusted to 0.1mm, and then 10. mu.L of the perovskite precursor solution was sucked by a pipette and transferred into a slit between the blade and the substrate.
Step three: and dragging the scraper at the speed of 30mm/s to obtain a wet perovskite thin film, wherein the wet thin film gradually turns black and undergoes phase change. And after the blade coating is finished, annealing for 20 seconds on a blade coating machine, and then transferring the phase-changed perovskite thin film to a heating table at 110 ℃ for annealing for 10 minutes to obtain a compact perovskite thin film.
Step four: the surface SEM test of the prepared perovskite thin film is carried out, the surface SEM test result of the perovskite thin film is shown in figure 3, and it can be seen from figure 3 that the perovskite thin film prepared based on the ionic liquid MAAc is tightly distributed, and the perovskite grain size averagely reaches 7-8 μm.
Example 2:
the embodiment provides a method for preparing a perovskite thin film by blade coating, which comprises the following specific steps:
the method comprises the following steps: mixing the components in a molar ratio of 0.5: 0.5: 1 MAI, FAI and PbI2Mixing with 1mL of ionic liquid MAAc, MAI, FAI and PbI2The mass is 50.8mg, 54.9mg and 294.3mg respectively, and the mixture is heated to 55 ℃ and stirred for 9 hours for standby.
Step two: will spin on c-TiO2The substrate of (2) was preheated at 100 ℃ for 5 minutes, the gap between the coating blade and the substrate was adjusted to 0.1mm, and then 10. mu.L of the perovskite precursor solution was sucked by a pipette and transferred into a slit between the blade and the substrate.
Step three: and dragging the scraper at the speed of 30mm/s to obtain a wet perovskite thin film, wherein the wet thin film gradually turns black and undergoes phase change. After the end of the doctor blade coating, the phase-changed perovskite thin film was annealed for 20 seconds on a doctor blade coater, and then transferred to a heating stage at 110 ℃ and further annealed for 10 minutes, to obtain a perovskite thin film 1 prepared under the doctor blade coating condition.
Step four: the prepared perovskite thin film is subjected to XRD test, and the XRD test result of the perovskite thin film is shown in figure 4.
Comparative example 1:
the embodiment provides a method for preparing a perovskite thin film by spin coating, which comprises the following specific steps:
the method comprises the following steps: mixing the components in a molar ratio of 0.5: 0.5: 1 MAI, FAI and PbI2Mixing with 1mL of ionic liquid MAAc, MAI, FAI and PbI2The mass is 50.8mg, 54.9mg and 294.3mg respectively, and the mixture is heated to 55 ℃ and stirred for 9 hours for standby.
Step two: will spin on c-TiO2The substrate is preheated for 5 minutes at 100 ℃, a liquid-transferring gun is used for sucking 80 mu L of perovskite precursor solution, the solution is titrated on the preheated substrate, the perovskite precursor solution is coated for 30 seconds in a rotating mode at the rotating speed of 4000 rpm, then the phase-changed perovskite thin film is transferred to a heating table at 110 ℃ and is annealed for 10 minutes, and the perovskite thin film 2 prepared under the spin-coating condition is obtained.
Step three: the prepared perovskite thin film 2 was subjected to XRD testing, and the XRD testing result of the perovskite thin film 2 is shown in fig. 5. The XRD diffraction peak of film 1 is compared with that of film 2, the peak positions corresponding to the (001) and (002) crystal planes are the same, but the full width at half maximum (FWHM) of film 1 in the crystal plane (002) is almost half of that of film 2 in the crystal plane (002), which indicates that the blade coating method is used for preparing the perovskite film with larger crystal grains.
Example 3:
the embodiment provides a method for preparing a perovskite thin film by blade coating, which comprises the following specific steps:
the method comprises the following steps: mixing a mixture of 1: 1 MAI and PbI2Mixing with 1mL of ionic liquid MAAc, MAI and PbI2The mass is 102mg and 298mg respectively, and the mixture is heated to 55 ℃ and stirred for 9 hours for standby.
Step two: will spin on c-TiO2The substrate is preheated for 5 minutes at the temperature of 100 ℃, and the coating scraper and the substrate are adjustedThe spacing therebetween was 0.1mm, and then 10 μ L of the perovskite precursor solution was sucked up with a pipette gun and transferred into a slit between a doctor blade and a substrate.
Step three: and dragging the scraper at the speed of 1mm/s to obtain a wet perovskite film, wherein the wet film gradually turns black and undergoes phase change. And after the blade coating is finished, annealing for 20 seconds on a blade coating machine, and then transferring the phase-changed perovskite thin film to a heating table at 110 ℃ for annealing for 10 minutes to obtain a compact perovskite thin film.
Step four: and performing surface SEM test on the prepared perovskite film, wherein the perovskite film prepared based on the ionic liquid MAAc has compact crystal grain distribution, and the average size of the perovskite crystal grains reaches 500 nm.
Example 4:
the embodiment provides a method for preparing a perovskite thin film by blade coating, which comprises the following specific steps:
the method comprises the following steps: mixing a mixture of 1: 1 MAI and PbI2Mixing with 1mL of ionic liquid MAAc, MAI and PbI2The mass is 102mg and 298mg respectively, and the mixture is heated to 55 ℃ and stirred for 9 hours for standby.
Step two: will spin on c-TiO2The glass substrate is preheated for 5 minutes at the temperature of 100 ℃, the distance between the coating scraper and the substrate is adjusted to be 0.1mm, and then 10 mu L of the perovskite precursor solution is sucked by a liquid transfer gun and transferred into a slit between the scraper and the substrate.
Step three: and dragging the scraper at the speed of 5mm/s to obtain a wet perovskite film, wherein the wet film gradually turns black and undergoes phase change. And after the blade coating is finished, annealing for 20 seconds on a blade coating machine, and then transferring the phase-changed perovskite thin film to a heating table at 110 ℃ for annealing for 10 minutes to obtain a compact perovskite thin film.
Step four: and performing surface SEM test on the prepared perovskite film, wherein the perovskite film prepared based on the ionic liquid MAAc has compact crystal grain distribution, and the average size of the perovskite crystal grains reaches 3 mu m.

Claims (3)

1. A method for preparing a large-size crystal grain perovskite film by a blade coating method is characterized by comprising the following steps:
step 1, preparing an ionic liquid perovskite blade coating precursor: mixing inorganic halide YX2Adding the organic halide and the organic halide into a proton type ionic liquid according to a molar ratio of 1: 1, heating the mixture at 55 ℃ in an inert gas atmosphere, stirring the mixture for 6 to 9 hours, and then transferring the perovskite precursor solution into an air environment; the organic halide is MAI or MAI and FAI;
step 2, cleaning the FTO fluorine-doped tin dioxide coating glass substrate by adopting alkali liquor, an active detergent, deionized water and ethanol:
and step 3: preheating a substrate for 10 +/-5 minutes at the temperature of 100 +/-10 ℃, adjusting the distance between a coating scraper and the substrate to be 0.2 +/-0.1 mm, and then sucking 10 +/-5 mu L of perovskite precursor solution by using a liquid-transferring gun and transferring the perovskite precursor solution into a slit between the scraper and the substrate;
and 4, step 4: dragging the scraper to move from one end of the substrate to the other end at a constant speed, and then leaving a layer of wet perovskite thin film on the substrate; annealing for 20 +/-5 seconds on a blade coating coater, then transferring the perovskite thin film which is completely transformed into the phase to a heating table at 110 +/-10 ℃ and then annealing for 10 minutes to obtain the fully-deposited large-size crystal grain perovskite thin film.
2. The blade coating method for preparing large-size grain perovskite thin film according to claim 1, characterized in that: the proton type ionic liquid is one or a mixture of more of MAAc methylamine acetate, MAP methylamine propionate and MABa methylamine butyrate.
3. The blade coating method for preparing large-size grain perovskite thin film according to claim 1, characterized in that: and 4, dragging the scraper at a speed of 1-30 mm/s.
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Publication number Priority date Publication date Assignee Title
CN110224069A (en) * 2019-06-13 2019-09-10 天合光能股份有限公司 Perovskite solar cell with waterproof function and preparation method thereof
CN110854274A (en) * 2019-11-22 2020-02-28 中南大学 Regulating and controlling method for perovskite nucleation process and preparation method for perovskite thin film based solar cell

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112015028867B1 (en) * 2013-05-17 2022-02-01 Exeger Operations Ab Dye-sensitized solar cell and dye-sensitized solar cell manufacturing method
CN108417722A (en) * 2018-03-31 2018-08-17 南开大学 A kind of preparation method of the perovskite solar cell based on ion solution additive
CN109461821A (en) * 2018-10-15 2019-03-12 北京曜能科技有限公司 A kind of preparation method of hybrid inorganic-organic perovskite thin film
GB201819380D0 (en) * 2018-11-28 2019-01-09 Univ Oxford Innovation Ltd Long-term stable optoelectronic device
CN111162140B (en) * 2019-12-19 2022-04-29 中国海洋大学 Ionic liquid interface modification CsPbBr3Perovskite solar cell preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110224069A (en) * 2019-06-13 2019-09-10 天合光能股份有限公司 Perovskite solar cell with waterproof function and preparation method thereof
CN110854274A (en) * 2019-11-22 2020-02-28 中南大学 Regulating and controlling method for perovskite nucleation process and preparation method for perovskite thin film based solar cell

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