CN114497380A - Method for improving performance of perovskite battery through grain boundary passivation - Google Patents
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
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- 125000000565 sulfonamide group Chemical group 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract 2
- 239000002243 precursor Substances 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000010408 film Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- QHOMFOGULKIGBE-UHFFFAOYSA-N 3-ethyl-1,2-benzothiazole 1,1-dioxide Chemical group C1=CC=C2C(CC)=NS(=O)(=O)C2=C1 QHOMFOGULKIGBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 5
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- HFFXLYHRNRKAPM-UHFFFAOYSA-N 2,4,5-trichloro-n-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C(=CC(Cl)=C(Cl)C=2)Cl)=N1 HFFXLYHRNRKAPM-UHFFFAOYSA-N 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- -1 amine ion Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 2
- 125000003375 sulfoxide group Chemical group 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
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- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
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- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to a method for improving the energy conversion efficiency and stability of an organic-inorganic hybrid perovskite solar cell, and mainly comprises ethyl benzo sultam (PSAD for short) containing sulfonamide functional groups and-NH in a perovskite material2And Pb2+And the like passivates crystal defects caused by the two functional groups and cations in the perovskite crystal grains through hydrogen bonds and coordination action respectively. The oxygen atom of the sulfoxide group in PSAD can not only fix the organic amine ion in the perovskite by hydrogen bonding, but it can also react with Pb2+The formation of a coordination bond of Pb … O passivates the defects caused thereby. The method passivates grain boundaries, reduces non-radiative recombination of current carriers, enhances charge transmission of the perovskite thin film, and obviously improves energy conversion efficiency and stability of the perovskite solar cell. The additive PSAD is cheap and easy to obtainAnd provides possibility for realizing industrialization.
Description
Technical Field
The invention belongs to a method for improving the energy conversion efficiency and stability of a lead-based perovskite solar cell, and mainly comprises ethyl benzo sultam (PSAD for short) containing sulfonamide functional groups and-NH in a perovskite material2And Pb2+The defects of perovskite grain boundaries are passivated by combining hydrogen bonds and coordination actions, the non-radiative recombination of current carriers is reduced, the charge transmission of the perovskite thin film is effectively enhanced, and the energy conversion efficiency and the stability of the perovskite solar cell are obviously improved.
Background
The energy conversion efficiency of the perovskite solar cell is 25% breakthrough in a short decade, and the perovskite solar cell is gradually close to the theoretical maximum value, so that the perovskite solar cell has a great development prospect. Perovskite materials have caused a hot tide of research due to their high absorption coefficient and excellent carrier transport properties. However, there are critical problems to be solved, such as device stability and large-area fabrication, in order to realize industrialization. Studies have shown that perovskite thin films inevitably produce unfavorable defects in the interior of crystals, grain boundaries and surfaces during formation, which lead to non-radiative recombination, accelerated corrosion of water and oxygen, and severe reduction in parameters such as current and voltage, thereby reducing device efficiency and long-term stability. Therefore, introducing some effective chemical species to passivate these defects will greatly contribute to the efficiency and stability of the device. Here, we introduce benzosultams into the perovskite precursor solution, thereby passivating the defects of the perovskite grain boundaries to improve the efficiency and stability of the device: the ethyl benzene sultam is dissolved in the perovskite precursor solution, the defects of perovskite grain boundaries are effectively passivated by utilizing the hydrogen bond and atom coordination, and the performance and the long-term stability of the device are improved.
Disclosure of Invention
The invention aims to improve the energy conversion efficiency and stability of a perovskite solar cell through grain boundary passivation.
In order to achieve the purpose, the invention adopts the technical scheme that:
the additive is dissolved in N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) with a certain volume ratio, and then diluted to the optimal concentration according to a certain proportion and added into the perovskite precursor solution. The perovskite thin film doped with the additive can be obtained through operations such as spin coating, annealing and the like.
Wherein the chemical name of the sulfonamide additive is 3-ethyl-benzoisothiazole-1,1-dioxide, PSAD for short.
Preference is given to
Mixing the required components in proportion, taking DMSO/DMF as a solvent, and fully stirring until the components are completely dissolved to obtain a precursor solution. The lead-based perovskite thin film is prepared through an anti-solvent method, the anti-solvent is chlorobenzene, the precursor solution of a control group does not contain an additive, and the additive which is diluted in advance is added into the precursor solution of an experimental group.
The optimal mass concentration of the additive in the precursor solution is 0.5 mg/mL.
The heat treatment temperature of the film is 100 ℃.
The invention has the advantages that:
according to the invention, through introducing sulfonamide organic micromolecules PSAD into the perovskite thin film, oxygen atoms in sulfoxide groups can fix organic amine ions in the perovskite through hydrogen bonds, and the organic amine ions and Pb in the perovskite can be mixed2+The defect that Pb … O coordination bonds passivate grain boundaries is formed. The method reduces the non-radiative recombination of current carriers, effectively enhances the charge transmission of the perovskite thin film, and obviously improves the energy conversion efficiency and stability of the perovskite solar cell.
Meanwhile, the used additive material has low cost and is easy to operate in process.
The process is easy to operate, has good repeatability and is suitable for large-scale production.
Drawings
Fig. 1 is an XRD spectrum of a perovskite thin film prepared before and after PSAD is introduced into a precursor solution provided in an embodiment of the present invention.
FIG. 2 is an SEM photograph of a perovskite thin film prepared before and after PSAD is introduced into a precursor solution provided by an embodiment of the invention; wherein a) is before adding PSAD and b) is after adding 0.4mg/ml PSAD.
FIG. 3 is an NMR spectrum of formamidine iodide (FAI) which is an important component of the precursor provided by the embodiment of the invention and before and after the introduction of PSAD.
Fig. 4 is an XPS spectrum of a perovskite thin film prepared before and after PSAD is introduced into a precursor solution provided in an embodiment of the present invention.
Fig. 5 is an FTIR spectrum of a perovskite cell prepared before and after PSAD is introduced into a precursor solution provided in an embodiment of the present invention.
FIG. 6 is an I-V curve of a perovskite thin film prepared before and after PSAD is introduced into a precursor solution provided by an embodiment of the present invention.
Fig. 7 is an air stability curve of an unpackaged perovskite cell prepared before and after introducing PSAD into a precursor solution provided by an embodiment of the present invention.
Fig. 8 is a PL curve of a perovskite cell prepared before and after the precursor solution provided by the embodiment of the present invention is introduced with PSAD.
Fig. 9 is a TRPL curve of a perovskite battery prepared before and after PSAD is introduced into the precursor solution provided in the embodiment of the present invention.
Fig. 10 is a TPV curve of a perovskite battery prepared before and after introducing PSAD into the precursor solution provided in the embodiment of the present invention.
Detailed Description
1. Device fabrication
(1) Preparation of perovskite precursor solution
228.8mgFAI, 18.2mgCsI, 33.7mgMACl, 705.3mgPbI are accurately weighed2、4.3mgMABr、13.9mgPbBr2The resulting solution was dissolved in a mixed solvent of 1ml DMF and DMSO (volume ratio DMF: DMSO: 9: 1).
(2) Pretreatment of substrates
Cleaning the etched fluorine-doped tin oxide (FTO) glass substrate with a cleaning agent, deionized water, ethanol and isopropanol for 15 minutes in sequence, then blowing the glass substrate with a nitrogen gun, and using O to dry the glass substrate2Plasma treatment was carried out for 500 seconds.
(3) Preparation of the Electron transport layer
Deposition of dense TiO on FTO substrates by Atomic Layer Deposition (ALD)2The layers were then sintered in an air environment at 500 ℃ for 30 minutes. SnO2The colloidal precursor is formed by SnCl4Synthesized by hydrolysis. Based on SnO2Spin casting the electron transport layer on precleaned FTO glass at 3000rpm/s for 30 seconds followed by annealing at 180 ℃ for 30 minutes in an air atmosphere.
(4) Preparation of perovskite thin film
The perovskite precursor solution was spin coated by two-step spin coating method first 10s at 1000rpm and then accelerated to 4000rpm for 30s, 300 μ L of anisole was dropped on the spinning substrate 20 seconds before the end of the second step. In the preparation of the improved device, the PSAD solutions with different concentrations are pre-dissolved in the perovskite precursor solution. And then annealing all the perovskite thin films in air (relative humidity is 20-30%) at 100 ℃ for 40 minutes. After PSAD modification, the intensity of the (110) plane of the main peak is enhanced, and the FWHM of the PSAD modified main peak is also reducedIt is shown that the addition of the additive improves the crystallization properties of the crystals. Represents PbI2Adding PbI after PSAD2The peak of (A) is reduced, indicating that the addition of PSAD can effectively passivate the surface of the substrate with PbI2Resulting in defects that slow the decomposition of the perovskite (see fig. 1). The grain size of the perovskite thin film after adding the PSAD can be seen to be increased in the SEM picture (see figure 2). And the additive is gathered at the grain boundary of the perovskite, so that the quality of the perovskite film is improved.
(5) Preparation of the passivation layer
40 μ L of PTABr at a concentration of 1mg/mL was deposited on the annealed perovskite thin film at 4000rpm for 20 s.
(6) Preparation of hole transport layer
A solution of spiro-OMeTAD in chlorobenzene, 40. mu.L, containing 72.3mg of spiro-OMeTAD, 28.8. mu.L of 4-tert-butylpyridine and 17.5. mu.L of Li-TFSI solution (520mg of Li-TSFI in 1mL of acetonitrile) was drawn up in 1mL and deposited on the perovskite thin film at 4000rpm for 20 seconds.
(7) Preparation of metal electrodes
An 80nm Au electrode was deposited by thermal evaporation under vacuum.
NMR, XPS and FTIR spectra reflect the hydrogen bonds and coordination formed between the additive PSAD and the perovskite, respectively (see fig. 3, 4 and 5). Long-term exposure of perovskite devices to air and heat accelerates film damage, and the rate and extent of film damage can be seen from stability characterization. The I-V performance measurement (see FIG. 6) is carried out under the condition of positive and negative sweep between-0.1V and 1.2V, and the energy conversion efficiency of the device containing the PSAD is obviously improved. The air stability change curve (see fig. 7) is the change of the normalized PCE value of the unencapsulated perovskite device at dark room temperature and a relative humidity of 20 ± 5%, the PCE of the control device is reduced to 30% in 1000 hours, and the initial PCE of the control device is still maintained at 80% after 1300 hours after the PSAD modification, which indicates that the additive PSAD can effectively improve the stability of the perovskite solar cell. From the PL curve (see fig. 8), we can see that the luminescence intensity of the perovskite film modified by PSAD is much higher than that of the original perovskite film, which indicates that the perovskite film modified by PSAD has reduced internal defect states, increased carrier lifetime, and can effectively inhibit non-radiative recombination. Similarly, the carrier lifetime of the perovskite film modified by the PSAD can be obviously prolonged through a TRPL curve (see figure 9), which means that trap-assisted recombination and non-radiative recombination in the particle are effectively inhibited, the trap state is reduced, and the carrier transmission of the perovskite film is enhanced. The carrier lifetime and recombination kinetics of doped and undoped PSAD devices were further understood by making measurements of the transient photovoltage (TPV, see fig. 10). It can be seen from the figure that the decay time of the device doped with the PSAD is obviously longer than that of the control device, and the prolongation of the decay time shows that the carrier life of the device modified by the PSAD is prolonged, and the defect density is reduced, so that the non-radiative recombination is inhibited. And this can lead to an increase in open circuit voltage (Voc) and Fill Factor (FF), consistent with previous characterization PL and TRPL results.
Claims (9)
1. A method for improving energy conversion efficiency and stability of a lead-based perovskite solar cell device by using organic micromolecules containing sulfonamide functional groups is characterized by comprising the following steps of: the additive is added into a lead-based perovskite precursor solution, and the perovskite thin film doped with the additive is obtained by spin coating. Wherein the chemical name of the additive is 3-ethyl-benzoisothiazole-1,1-dioxide, PSAD for short.
2. The method for improving the energy conversion efficiency and stability of the lead-based perovskite solar cell device by utilizing hydrogen bonding and coordination according to claim 1, which is characterized in that: the grain boundary is passivated, the non-radiative recombination of carriers is reduced, the carrier transmission of the perovskite thin film is enhanced, and the energy conversion efficiency and the stability of the perovskite solar cell are obviously improved.
3. The method for improving the energy conversion efficiency and stability of a lead-based perovskite solar cell device according to claim 1 or 2, wherein: the additive is a sulfonamide derivative.
4. The method for improving the energy conversion efficiency and stability of a lead-based perovskite solar cell device as claimed in claim 3, wherein: the structural formula of the adopted additive is as follows: .
5. The method for improving the energy conversion efficiency and stability of a lead-based perovskite solar cell device according to claim 1 or 2, wherein: the optimum concentration of the additive used in the precursor solution is 0.5 mg/ml.
6. The method for improving the energy conversion efficiency and stability of a lead-based perovskite solar cell device according to claim 1 or 2, wherein: the additive is dissolved in N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) with a certain volume ratio, and then diluted to the optimal concentration according to a certain proportion and added into the perovskite precursor solution. The perovskite thin film doped with the additive can be obtained through operations such as spin coating, annealing and the like.
7. The method of improving the energy conversion efficiency and stability of a perovskite solar cell device as claimed in claim 2 wherein: the annealing temperature of the perovskite thin film is 100 ℃.
8. The method for improving the energy conversion efficiency and stability of a lead-based perovskite solar cell device according to claim 1 or 2, wherein: the structural formula of the organic-inorganic perovskite of the prepared perovskite film is ABX3Wherein A is a cation containing methylamine (CH)3NH3(MA)) ion, formamidine (NH)2-CH＝NH2(FA)) ions and cesium (Cs) ions; b is Pb ion; x is I, Br, Cl ion.
9. An improved perovskite solar cell prepared as described in claims 5 and 6, wherein: compared with a reference device, the perovskite solar cell added with the additive has higher energy conversion efficiency and stability.
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| CN116600613A (en) * | 2023-07-17 | 2023-08-15 | 四川京龙光电科技有限公司 | Perovskite flexible display device preparation method and flexible display device |
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| CN116600613A (en) * | 2023-07-17 | 2023-08-15 | 四川京龙光电科技有限公司 | Perovskite flexible display device preparation method and flexible display device |
| CN116600613B (en) * | 2023-07-17 | 2023-09-26 | 四川京龙光电科技有限公司 | Perovskite flexible display device preparation method and flexible display device |
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