CN111416045A - Preparation method of non-lead perovskite material, material and device - Google Patents

Preparation method of non-lead perovskite material, material and device Download PDF

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CN111416045A
CN111416045A CN201910011989.9A CN201910011989A CN111416045A CN 111416045 A CN111416045 A CN 111416045A CN 201910011989 A CN201910011989 A CN 201910011989A CN 111416045 A CN111416045 A CN 111416045A
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perovskite material
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王建浦
王娜娜
常进
王颖
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Nanjing Tech University
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Abstract

The invention discloses a preparation method of a non-lead perovskite material, a material and a device thereof, wherein a precursor solution of the perovskite material is prepared from SnX2And small-size cationic halide and large-size organic cationic halide are dissolved in a solvent according to a certain proportion and a certain concentration, and are stirred and dissolved. According to the invention, through the introduction of large-size organic cations, the conversion of a perovskite structure from three-dimensional to multi-quantum well is realized, on one hand, the morphology of the film can be improved, the size of perovskite crystal grains is increased, on the other hand, the oxidation of tin perovskite can be inhibited, the fluorescence quantum efficiency and stability of the film are improved, and finally, the high-performance non-lead perovskite light-emitting diode is realized.

Description

Preparation method of non-lead perovskite material, material and device
Technical Field
The invention relates to the technical field of perovskite material light-emitting diodes, in particular to a preparation method of a non-lead perovskite material, a material and a device.
Background
The organic-inorganic hybrid perovskite has the advantages of simple preparation process, adjustable color, high color purity, high luminous efficiency and the like, and has great potential in the field of photoelectricity. However, the conventional perovskite is composed of lead halide and is not friendly to the environment, so that research on the non-lead perovskite is urgently needed. Because the film forming property of the three-dimensional perovskite material is poor, the external quantum efficiency of the current light-emitting diode based on the tin three-dimensional perovskite is only 0.72 percent, and the maximum irradiance is 3.4W sr-1m-2And the device stability is poor, and thus, the Tunable Near-isolated L atomic in Tin Halide Perovskite Devices, J.Phys.chem. L et.7: 2653-2658, 2016. therefore, the development of efficient and stable non-lead Perovskite materials and Devices is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method, a material and a device of a non-lead perovskite material aiming at the defects of the prior art.
The technical scheme of the invention is as follows:
a process for preparing the non-lead perovskite material features that the SnX solution as the precursor of perovskite material2And the small-size cationic halide and the large-size organic cationic halide are dissolved in a solvent at a certain concentration according to a molar ratio of 1-100: 1-100, and are stirred and dissolved.
The preparation method can form a multi-quantum well structure, the structure can effectively improve the film forming quality of the non-lead perovskite film, and can inhibit the oxidation of the tin perovskite.
The preparation method is that the small-size cation is K+，Rb+，Cs+，CH3NH3 +，NH2CHNH2 +，(NH2)2CHNH2 +Any one or more of them.
According to the preparation method, the large-size organic cation is any one or more of aliphatic hydrocarbon ammonium cation with 1-50 carbon atoms, alicyclic hydrocarbon ammonium cation with 5-100 carbon atoms, optionally substituted aryl ammonium cation with 6-100 carbon atoms or five-membered heterocyclic azole (imidazole, thiazole, oxazole, pyrrole and the like) with N in a heterocyclic ring as a connecting site, six-membered heterocyclic ring (pyridine, diazine and the like), five-membered benzo system (benzimidazole, benzothiazole, benzoxazole and the like) and six-membered benzo system (quinoline and the like) cation.
In the preparation method, the solvent is one or more of DMF, DMSO and GB L.
The preparation method is that X comprises I-，Br-，Cl-Any one or a combination of several of them.
In the preparation method, the large-size organic cation adopts Benzimidazole (Benzimidazole, abbreviated as Bmz)+)，BmzI:CsI:SnI2Preparing a precursor solution with the mass fraction of 7-15% according to the molar ratio of 0.5-1.5: 1-1.6: 0.5-1.5, and realizing the multi-quantum well non-lead perovskite under the annealing condition by adopting a hot spin coating preparation method; preferably, a precursor solution with the mass fraction of 7% is prepared by adopting a mixed solvent of DMF and DMSO in a ratio of 4: 1; the preferred method is as follows: heating the substrate coated with the PVK hole transport layer for 5 minutes on a 70 ℃ hot stage by adopting a thermal spin coating preparation method, then spin coating a perovskite precursor solution, and preparing the multi-quantum-well non-lead perovskite under the annealing condition of 70 ℃ for 10 minutes; BmzI CsI SnI2The ratio of (1.4) to (0.6, 0.8, 1.1, 1.2, 1.1) is preferably 1.3: 1; BmzI CsI SnI2The ratio is preferably 1:1.3:1, 0.9:1.3: 1.2.
In the preparation method, the large-size organic cation adopts phenylethylamine (abbreviated as PEA)+)，PEAI:CsI:SnI2Preparing a precursor solution with the mass fraction of 7% -15% according to the molar ratio of 2: 1-5: 1-6, and realizing the multi-quantum-well non-lead perovskite under the annealing condition by adopting a hot spin coating preparation method.
Preferably, a precursor solution with the mass fraction of 7% is prepared by adopting a mixed solvent of DMF and DMSO in a ratio of 4: 1;
the preferred hot spin coating and annealing method is: heating the substrate coated with the PVK hole transport layer on a 70 ℃ hot stage for 5 minutes, then coating perovskite precursor solution in a spinning mode, and preparing the multi-quantum-well non-lead perovskite under the annealing conditions of 70 ℃ and 10 minutes.
The preparation method adopts PEA as large-size organic cation+，PEABr:CsBr:SnBr2:SnF2The molar ratio of 2: 1-5: 1-6: 0.2-2The precursor solution with the fraction of 7-15 percent adopts a spin coating method to realize the multi-quantum well non-lead perovskite under the annealing condition.
The preparation method comprises the steps of preparing a precursor solution with the mass fraction of 5% -20% by adopting a mixed solvent with the volume ratio of DMF to DMSO of 1-10: 1-10, heating a substrate for 3 min-20 min at 50-150 ℃ before preparing a perovskite thin film by spin coating, then spin coating the perovskite thin film on the substrate, and annealing at 70 ℃ for 5 min-30 min to realize the multi-quantum-well non-lead perovskite.
The non-lead perovskite material realized according to any one of the preparation methods.
A non-lead perovskite light emitting diode device prepared according to any one of the non-lead perovskite materials.
By adopting the scheme, the invention obviously improves the film appearance, increases the size of tin perovskite crystal grains, inhibits the oxidation of the tin perovskite and improves the stability by introducing large-size organic cations. On one hand, the fluorescence quantum efficiency of the non-lead perovskite film is improved, and on the other hand, the high-efficiency and stable non-lead perovskite light-emitting diode is realized. The maximum external quantum efficiency of the light-emitting diode based on tin-lead-free perovskite reaches 3.0%, and the maximum irradiance is 41.06W m-2sr-1。
Drawings
FIG. 1 is a schematic diagram of a device structure;
FIG. 2 is a current density-voltage curve for the device of example 1;
FIG. 3 is an external quantum efficiency-current density curve for the device of example 1;
FIG. 4 is an irradiance-current density curve for the device of example 1;
FIG. 5 is a graph of absorption and luminescence spectra of perovskite thin films prepared from precursor solutions of different content of large-sized organic cations according to example 1;
FIG. 6 is an AFM image of perovskite thin films prepared from precursor solutions of different content of large-sized organic cations of example 1;
fig. 7 is a current density-voltage curve of the perovskite light emitting device prepared by using precursor solutions with different contents of CsI in example 2;
fig. 8 is an external quantum efficiency-current density curve of the perovskite light-emitting device prepared by using precursor solutions with different contents of CsI in example 2;
FIG. 9 is an irradiance-current density curve for perovskite light emitting devices of example 2 prepared using precursor solutions of different CsI contents;
FIG. 10 is a current density-voltage curve for perovskite light emitting devices prepared using precursor solutions of different tin content of example 3;
FIG. 11 is the external quantum efficiency-current density curve for perovskite light emitting devices prepared using precursor solutions of different tin contents of example 3;
FIG. 12 is an irradiance-current density curve for perovskite light emitting devices prepared from precursor solutions of different tin content of example 3;
FIG. 13 is a graph of perovskite thin film P L prepared from precursor solutions of different halogens according to example 4;
FIG. 14 is an external quantum efficiency-current density curve of a non-lead perovskite light-emitting device prepared based on phenethylamine iodine (PEAI) of example 5;
FIG. 15 is an irradiance-current density curve for a PEAI-based fabricated non-lead perovskite light emitting device of example 5;
FIG. 16 is a P L plot of perovskite thin films of different values of n prepared based on PEAI for example 6;
FIG. 17 is an absorption plot of perovskite thin films of different values of n prepared based on PEAI of example 6;
FIG. 18 is an SEM image of perovskite thin films of different n-values prepared based on PEAI of example 6;
FIG. 19 is a plot of the fluorescence quantum efficiency of the multi-quantum well perovskite thin film prepared based on PEAI of example 6;
FIG. 20 is a current density-voltage curve for different values of n perovskite light emitting devices prepared based on PEAI of example 6;
FIG. 21 is a graph of external quantum efficiency versus current density for different values of n perovskite light emitting devices prepared based on PEAI of example 6;
FIG. 22 is an XPS plot of multi-quantum well perovskite thin film and three-dimensional tin perovskite thin film prepared based on PEAI of example 7;
FIG. 23 is an XRD of the PEAI-based perovskite thin film of example 7 tested at various times in the glove box;
FIG. 24 is a graph of stability testing of tin perovskite devices prepared based on PEAI of example 7;
FIG. 25 is a current density-voltage curve of a perovskite light-emitting device prepared using precursor solutions of different large-sized organic cations according to example 8;
FIG. 26 is the external quantum efficiency-current density curve of the perovskite device prepared from the precursor solutions of different large-sized organic cations of example 8;
FIG. 27 is an E L spectrum of the red non-lead perovskite light-emitting device of example 9;
fig. 28 is an external quantum efficiency-luminance-current density curve of the red non-lead perovskite light emitting device of example 9.
Detailed Description
The present invention will be described in detail with reference to specific examples.
As shown in fig. 1, the non-lead perovskite light emitting diode device structure comprises a substrate 1, an anode layer 2, a hole transport layer 3, a perovskite layer 4, an electron transport layer 5 and a cathode layer 6, wherein the substrate 1 can be any one of glass, a flexible substrate and a metal sheet, the anode layer 2 is Indium Tin Oxide (ITO), the hole transport layer 3 is Poly (9, 9-dioctylfluorene-co-fluorenone) (TFB), Poly [ bis (4-phenyl) (4-butylphenyl) amine ] (Poly-TPD), [ N, N '- (4-N-butylphenyl) -N, N' -diphenyl-p-phenylenediamine ] - [9, 9-di-N-octylfluorene-2, 7-diyl ] copolymer (PFB), Poly (9, 9-dioctylfluorene (F8), 2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino ] -9,9 '-spirobifluorene (Spiro-mead), or carboamine, aromatic diamine or star-triphenylamine compound, and the aromatic diamine compound can be prepared by a process of 1, 2, 3' -biphenyl-2-o-mead, 5-triphenylamine (pvia-1, 3-biphenyl-1, 5-2-naphthalene-2-diamine) or a triphenylamine compound (p-phenylene-1, 3-phenylene-1, 2-biphenyl-diamine) or a triphenylamine) compound (p-phenylene-triphenylamine) is prepared by a triphenylamine) process, 2-triphenylamine) or a triphenylamine compound.
The process comprises the following steps:
1) solution preparation
The perovskite precursor solution is prepared from SnX2Small size cationic halides (mainly FAX, MAX, CsX and GAX) and large size organic cationic halides are dissolved in a certain proportion and concentration in a solvent (DMF, DMSO, GB L), and stirred for dissolution.
2) Device fabrication
a) And ultrasonically cleaning the transparent conductive substrate ITO glass twice by using acetone and ethanol solutions respectively, drying the transparent conductive substrate ITO glass by using nitrogen after treatment, transferring the ITO glass into an oxygen plasma cleaning machine, and cleaning the transparent conductive substrate ITO glass by using oxygen plasma under a vacuum condition.
b) The hole transport layers were prepared by spin coating and thermal annealing was performed, respectively.
c) A perovskite layer is prepared by a solution spin coating method and is thermally annealed.
d) The electron transport layer is prepared by a solution spin coating method or a thermal evaporation method.
e) L iF and Al were deposited on the surface of the electron transport layer using thermal evaporation.
Example 1
Introducing large-size organic cations into a three-dimensional non-lead perovskite material, preparing a precursor solution with the mass fraction of 7% by adopting a mixed solvent of DMF and DMSO in a ratio of 4:1, and regulating and controlling BmzI, CsI and SnI of the precursor solution2The molar ratio of BmzI (0.6, 0.8, 1.1, 1.2 and 1.4):1.3:1) is prepared by heating the substrate coated with the PVK hole transport layer on a hot stage at 70 ℃ for 5 minutes, then coating perovskite precursor solution by spin coating, and preparing the multi-quantum well non-lead perovskite under the annealing condition of 70 ℃ and 10 minutes. The performance of the device is obviously improved compared with that of a three-dimensional tin perovskite device, and the addition of benzimidazole reduces the leakage current of the device as shown by a J-V curve shown in figure 2And current can be injected well; in FIG. 3 BmzI CsI SnI2The proportion of the medium BmzI is 0.6, 0.8 and 1.1 respectively, and from the external quantum efficiency-current density curve of figure 3, the addition of large-size organic cations improves the efficiency of the luminescent device on one hand (the efficiency of the three-dimensional non-lead perovskite luminescent device is less than 0.01%); on the other hand, the brightness of the device is improved (figure 4), and the brightness is improved by 1-2 orders of magnitude compared with that of the three-dimensional non-lead perovskite. In conclusion, the addition of a proper amount of benzimidazole greatly improves the luminous efficiency of the device, and the tin perovskite luminous device recorded with the highest efficiency is realized, and the external quantum efficiency reaches 0.99%.
Referring to fig. 5, a large-sized organic cation benzimidazole iodine is added to a three-dimensional perovskite precursor solution. In the figure, 1:1 and 1.3:1 are CsI: SnI2The rest is BmzI, CsI and SnI2Molar ratio. It can be seen that with the addition of large-size organic cations, characteristic peaks of two-dimensional perovskite appear on the absorption spectrum, and with the increase of the content of large-size organic cations, the characteristic absorption peaks become stronger; from the luminescence spectrum, it can be seen that weak luminescence peaks appear at 700nm and 520nm with the addition of large-sized organic cations. The perovskite thin film prepared is a mixture of quantum wells with different band gaps, and a multi-quantum well structure of the lead-free perovskite can be further confirmed.
Referring to FIG. 6, 1:1 and 1.3:1 are two different CsI: SnI2The rest is BmzI, CsI and SnI2In a molar ratio of (a). As can be seen from the surface topography of the film, with the introduction of large-size organic cations, the size of the tin perovskite crystal grains is increased, the film has better crystallinity, and the topography is improved.
Example 2
Regulates and controls BmzI CsI SnI2The ratio of middle CsI is shown in FIGS. 7, 8 and 9. FIG. 7 is a current density-voltage curve for perovskite light emitting devices prepared from precursor solutions of different CsI contents; FIG. 8 is a curve of external quantum efficiency versus current density for perovskite light-emitting devices prepared from precursor solutions of different CsI contents; fig. 9 is an irradiance-current density curve for perovskite light emitting devices prepared from precursor solutions of different CsI content. CsI content visualization can be seenDevice performance is affected. When BmzI, CsI, SnI2When the ratio is 1:1.3:1, the maximum external quantum efficiency of the device is 0.63%, and the maximum irradiance is 5.0W m-2sr-1。
Example 3
Regulates and controls BmzI CsI SnI2Middle SnI2Fig. 10 is a graph of current density versus voltage for perovskite light emitting devices prepared from precursor solutions of different tin contents, as shown in fig. 10, 11, and 12; FIG. 11 is a graph of external quantum efficiency versus current density for perovskite light-emitting devices prepared from precursor solutions of different tin contents; fig. 12 is an irradiance-current density curve for perovskite light emitting devices prepared from precursor solutions of different tin contents. It can be seen that the tin content has a significant effect on device performance. When BmzI, CsI, SnI2At a ratio of 0.9:1.3:1.2, the maximum external quantum efficiency of the device is 0.78%, and the maximum irradiance is 11.7W m- 2sr-1。
Example 4
By regulating and controlling the components of the perovskite precursor solution, the non-lead perovskite with different luminous wavelengths can be realized, for example, BmzBr, CsBr and SnBr2As shown in fig. 13, 1:1:1 as the precursor solution can realize light emission from 920nm to 656 nm.
Example 5
The preparation of the non-lead perovskite light-emitting diode by replacing large-size organic ammonium salt BmzI with phenethylamine iodine (PEAI) realizes the device efficiency of 3.0 percent, 41.06W m-2sr-1Irradiance of (c). The overall device performance was superior to benzimidazole and the device performance is shown in figures 14 and 15.
Example 6
Based on PEAI, according to PEAI: CsI: SnI2The perovskite thin films prepared into different multi-quantum well structures in the ratio of 2:0:1, 2:1:2, 2:2:3, 2:3:4, 2:4:5 and 2:5:6 are subjected to photoluminescence (P L) and absorption spectrum tests, and the test results are shown in FIGS. 16 and 17. from the absorption diagram, the 2:0:1 thin film has an obvious exciton absorption peak with n being 1 at 605nm, the 2:1:2 thin film has a new exciton absorption peak with n being 2 at 657nm and also has an absorption peak with n being 1 at the same time, and so on, when the ratio of small-size cations is increased,the same conclusion can be drawn from the P L graph that the 2:0:1 thin film has a characteristic luminescence peak where n is 1, the luminescence peak is closer to the three-dimensional perovskite as the proportion of small-sized cations increases, and thus it can be concluded that we have formed tin perovskite thin films with a multiple quantum well structure.
FIG. 18 is a graph of the difference PEAI: CsI: SnI2SEM images of the proportional perovskite thin film show that the crystallinity and the surface coverage of the thin film are improved as the proportion of small-size cations is increased. And the overall performance of the device is superior to that of benzimidazole-based devices. In addition, as shown in fig. 19, compared to the three-dimensional tin perovskite, the defect state density of the multi-quantum well perovskite thin film (2:5:6) is significantly reduced after adding phenylethylamine iodine, and the fluorescence quantum efficiency of the thin film is improved. As can be seen from the voltage-current density curve of fig. 20, the leakage current of the device becomes small, and as can be seen from the external quantum efficiency-current density curve of fig. 21, the improvement of the device efficiency is significant.
Example 7
The prepared thin film was subjected to XPS test, as shown in FIG. 22, and Sn was contained in the pure three-dimensional perovskite thin film4+Dominant, peak area Sn in the d3/2 orbital2+/Sn4+0.15, and peak area Sn in the corresponding orbitals of our multi-quantum well thin film2+/Sn4+Is 2.68. It can be seen that the addition of the large size organic ammonium salt slows the oxidation of the stannous tin, making the film more stable. When the tin perovskite thin film of 0.8:1.1:1 prepared based on PEAI is placed in a glove box to be tested for XRD, as shown in figure 23, the thin film has better crystallinity, and the thin film does not have obvious 'deterioration' (diffraction peaks of other substances) after being placed for 265 hours, thereby also indicating that the multi-quantum well lead-free perovskite thin film is very stable. In addition, the tin perovskite thin film with a multi-quantum well structure prepared on the basis of PEAI is prepared into a device at 10mA/cm2The stability was tested at the current of (1). As shown in fig. 24, when the device efficiency is reduced to half of the initial efficiency, the lifetime is more than 150 minutes, which is the longest lifetime of the non-lead perovskite light emitting device reported in the literature at present, and is far higher than that of the three-dimensional perovskite light emitting device by only 5 minutes.
Example 8
The same effect as that of BmzI and PEAI non-lead perovskite can be realized by changing large-size organic ammonium salt in the perovskite precursor solution, and the device performance is obviously improved compared with that of the three-dimensional non-lead perovskite, for example, when 3-bromobenzaminomethane iodine (3-BrPEMAI), naphthylmethylamine iodine (NMAI), 4-fluorophenylethylamine bromine (4-FPEABr) and 4-fluorophenylethylamine iodine (4-FPEAI) are adopted, as shown in fig. 25 and 26.
Example 9
By regulating and controlling the components of the perovskite precursor solution according to the proportion of PEABr, CsBr and SnBr2:SnF2The ratio is 2:5:6:1.8, as shown in FIG. 27, the visible light non-lead perovskite L ED. with the light emitting wavelength of 667nm is realized for the first time, as shown in FIG. 28, the EQE of the device is 0.026%, and the luminance is 44cd m-2。
By adding large-size organic cations into the non-lead perovskite precursor solution, on one hand, the perovskite structure is converted from three dimensions to a multi-quantum well, and the non-lead perovskite film with high fluorescence quantum efficiency and high stability is obtained; on the other hand, the high-efficiency and stable non-lead perovskite light-emitting diode is realized. Based on the tin non-lead perovskite light-emitting diode, the maximum external quantum efficiency of the device reaches 3.0 percent, and the maximum irradiance is 41.06W m-2sr-1。
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.

Claims (10)

1. A preparation method of a non-lead perovskite material for a light-emitting diode is characterized in that a precursor solution of the perovskite material is SnX2And the small-size cationic halide and the large-size organic cationic halide are dissolved in a solvent at a certain concentration according to a molar ratio of 1-100: 1-100, and are stirred and dissolved.
2. The method for producing a non-lead perovskite material as claimed in claim 1, wherein a multiple quantum well structure is formed, which is effective for improving the film formation quality of the non-lead perovskite thin film and for suppressing oxidation of tin perovskite.
3. The method of producing the non-lead perovskite material as claimed in claim 1, wherein the small-size cation is K+，Rb+，Cs+，CH3NH3 +，NH2CHNH2 +，(NH2)2CHNH2 +Any one or more of them.
4. The method for preparing a non-lead perovskite material according to claim 1, wherein the large-size organic cation is any one or more of aliphatic hydrocarbon ammonium cations having 1 to 50 carbon atoms, alicyclic hydrocarbon ammonium cations having 5 to 100 carbon atoms, optionally substituted aryl ammonium cations having 6 to 100 carbon atoms, or five-membered heterocyclic azoles (imidazole, thiazole, oxazole, pyrrole, etc.), six-membered heterocycles (pyridine, diazine, etc.), five-membered benzo systems (benzimidazole, benzothiazole, benzoxazole, etc.), six-membered benzo systems (quinoline, etc.) cations having N in the heterocycle as a linking site.
5. The method of producing a non-lead perovskite material as claimed in claim 1, wherein X comprises I-，Br-，Cl-Any one or a combination of several of them.
6. The method for producing the non-lead perovskite material as claimed in claim 1, wherein BmzI CsI SnI2Preparing a precursor solution with the mass fraction of 7-15% according to the molar ratio of 0.5-1.5: 1-1.6: 0.5-1.5, and realizing the multi-quantum-well non-lead perovskite under the annealing condition by adopting a hot spin coating preparation method.
7. The method of claim 1, wherein the lead-free perovskite material is produced according to PEAI CsI SnI2The molar ratio is 2: 1-5: 1-6, and the mass fraction is prepared7-15% of precursor solution, adopting a hot spin coating preparation method, and realizing the multi-quantum-well non-lead perovskite under the annealing condition.
8. The method of claim 1, wherein the lead-free perovskite material is prepared according to the formula PEABr CsBr SnBr2:SnF2Preparing a precursor solution with the mass fraction of 7% -15% according to the molar ratio of 2: 1-5: 1-6: 0.2-2, and realizing the multi-quantum-well non-lead perovskite under the annealing condition by adopting a spin coating method; PEABr CsBr SnBr2:SnF2The ratio is preferably 2:5:6: 1.8.
9. The non-lead perovskite material prepared by the method according to any one of claims 1 to 8, which has good film crystallinity, high surface coverage, high fluorescence quantum efficiency, good stability and adjustable luminescence wavelength.
10. The non-lead perovskite light emitting diode prepared from the non-lead perovskite material of claim 9, having high external quantum efficiency and high stability.
CN201910011989.9A 2019-01-07 2019-01-07 Preparation method of non-lead perovskite material, material and device Pending CN111416045A (en)

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CN112794864A (en) * 2020-12-17 2021-05-14 湖北大学 Layered double-element perovskite structure luminescent material and preparation method thereof
CN114141950A (en) * 2021-11-29 2022-03-04 四川大学 Tin-based perovskite solar cell and preparation method thereof
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