CN111106248A - Novel perovskite organic-inorganic hybrid film and preparation method thereof - Google Patents
Novel perovskite organic-inorganic hybrid film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel perovskite organic-inorganic hybrid film and a preparation method thereof. The material composition of the hybrid film is (4-Br-C)6H4C2H4NH3)2(CH3NH3)n‑1PbnI3n+1Wherein n is 1,2,3,4,5, 6. The method has simple process and low cost, the obtained film has smooth and flat surface and high crystallinity, and is applied to the light absorption layer of the perovskite solar cell, the forbidden bandwidth changes along with the change of the number n of inorganic layers, so that the solar cell prototype device with excellent and stable performance is obtained, and the commercialization process of the perovskite solar cell is promoted; the organic-inorganic hybrid film prepared by the invention can be widely applied to photovoltaic cells and hairPhotodiode, field effect transistor, etc.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a novel perovskite organic-inorganic hybrid film and a preparation method thereof.
Background
Perovskite solar cells have high efficiency and low cost, and have attracted wide attention in recent years; since the first report of perovskite solar cells by japanese scientist Miyasaka in 2009, the photoelectric conversion efficiency of perovskite solar cells rises from 3.8% to 24.2% reported in the literature in a short period of several years, which is much higher than the development speed of other types of solar cells at the same time.
Although perovskite solar cells have achieved promising achievements, the most widely studied and superior-performance perovskite solar cell light-absorbing layer materials are mainly such as methylamine lead iodide (MAPbI)3，MA＝CH3NH3 +) And formamidine lead iodide [ FAPBI3,FA＝HC(NH2)2 +]The perovskite material with the three-dimensional structure is poor in humidity stability, and when the device is placed in humid air, the perovskite is irreversibly decomposed due to the combined action of moisture and oxygen, so that the photoelectric property of the device is adversely affected; therefore, the development of a perovskite light-absorbing layer material with higher stability to replace the perovskite light-absorbing layer material with the traditional three-dimensional structure has important significance for promoting the commercialization process of perovskite solar cells.
On the basis of exploring how to solve the long-term stability of the perovskite solar cell, researchers find that Two-Dimensional (2D) perovskites have more excellent humidity stability than three-Dimensional perovskites, and the Two-Dimensional perovskites are gradually developed; the general formula of the two-dimensional layered perovskite material is (A')2An-1BnX3n+1(wherein A' ═ C6H5C2H4NH3 +、iso-C4H9NH3 +Etc., A ═ MA+、FA+orCs+,B＝Pb+or Sn+,X＝Cl—、Br—orI—) Compared with a three-dimensional perovskite material, the two-dimensional perovskite material is formed by introducing long-chain organic spacing cations A' into the three-dimensional perovskite3 +The invasion of water molecules can be slowed down, so that the two-dimensional perovskite has better humidity stability than the three-dimensional perovskite; currently, the research on organic substances applied to the A' site of two-dimensional perovskite is mainly focused on C6H5C2H4NH2(PEA) and n-C4H9NH2(n-BA), researchers have also been working on other organic cations such as n-C continuously in recent years6H13NH3 +，n-CH3(CH2)2NH3 +，iso-C4H9NH3 +Meanwhile, researches show that the selection of organic cations has obvious influence on the structure and the performance of the perovskite; therefore, the application of other kinds of organic materials in perovskite solar cells needs to be continuously explored.
Disclosure of Invention
The invention aims to provide a novel organic-inorganic hybrid (4-Br-C)6H4C2H4NH3)2(CH3NH3)n- 1PbnI3n+1The film and the preparation method thereof have the advantages of simple preparation process and low cost, and the obtained film has smooth and flat surface and high crystallinity.
In order to achieve the purpose, the technical scheme is as follows:
a perovskite organic-inorganic hybrid film comprises (4-Br-C)6H4C2H4NH3)2(CH3NH3)n- 1PbnI3n+1Wherein n is 1,2,3,4,5, 6.
The preparation method of the perovskite organic-inorganic hybrid film comprises the following steps:
1) preparing a precursor solution:
4-Br-C6H4C2H4NH3I powder crystals, CH3NH3I and PbI2Preparing N according to a molar ratio of 2 (N-1), wherein N is 1,2,3,4,5 and 6, using N, N-Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) as a solvent, shaking for uniform dissolution, and filtering to obtain a perovskite precursor solution;
2) preparation of organic-inorganic hybrid film:
preheating the substrate in a glove box, spin-coating the perovskite precursor solution obtained in the step 1 on the surface, and annealing to obtain the (4-Br-C) with the thickness of 100-2000 nm on the surface of the substrate6H4C2H4NH3)2(CH3NH3)n-1PbnI3n+1A film.
According to the scheme, the 4-Br-C6H4C2H4NH3I is prepared in the following way:
slowly and dropwise adding 47-58 wt.% hydriodic acid aqueous solution into the absolute ethyl alcohol solution of p-bromophenylethylamine under the ice-water bath condition, and stirring for 1-2 hours, wherein the molar ratio of hydriodic acid to p-bromophenylethylamine is 1: 1.
Then, the mixed solution obtained by the reaction is subjected to rotary evaporation to dryness, and is repeatedly washed by anhydrous ether, a white crystal is obtained by suction filtration, and the white crystal is dried in vacuum for 5-12 hours at the temperature of 50-100 ℃ to obtain 4-Br-C6H4C2H4NH3And I, powder crystal.
According to the scheme, the concentration of the precursor solution obtained in the step 1 is 0.05-0.2 mol/L.
According to the scheme, the substrate in the step 2 is clean FTO, ITO or FTO/TiO2Or FTO/SnO2。
According to the scheme, the preheating temperature of the substrate in the step 2 is 80-200 ℃, and the preheating time is 10-25 min.
According to the scheme, the spin coating in the step 2 has the following technological parameters: and (3) coating 25-70 mu L of precursor solution on the surface of the substrate, wherein the spin coating speed is 2000-4000 rpm, and the spin coating time is 20-60 s.
According to the scheme, the annealing temperature in the step 2 is 60-120 ℃, and the annealing time is 10-30 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention synthesizes a novel organic ammonium salt (4-Br-C)6H4C2H4NH3I)；
2. The invention prepares a novel organic-inorganic hybrid (4-Br-C) by a one-step solution spin coating hot casting method6H4C2H4NH3)2(CH3NH3)n-1PbnI3n+1The film is simple in preparation process and low in cost, the obtained film is smooth and flat in surface and high in crystallinity, the forbidden bandwidth of the film is changed along with the change of the number n of inorganic layers when the film is applied to a light absorption layer of the perovskite solar cell, the light absorption layer of the prepared organic-inorganic hybrid film is good in stability and absorption, and finally the solar cell prototype device with excellent and stable performance is obtained, so that the commercialization process of the perovskite solar cell is promoted.
3. According to the invention, the influence of different solvent ratios on the performance of the perovskite solar cell is researched, the photoelectric conversion efficiency, the short-circuit current density and the filling factor of the finally obtained perovskite solar cell are obviously improved by adjusting the solvent ratio of the precursor solution, the photoelectric conversion efficiency of the prepared perovskite solar cell reaches 11.61%, and the performance of the cell in the air is stable.
Drawings
FIG. 1 shows 4-Br-C synthesized by the present invention6H4C2H4NH3I powder crystal X-ray diffraction pattern;
FIG. 2 is an X-ray diffraction contrast diagram of the organic-inorganic hybrid thin films prepared in examples 1 to 4;
FIG. 3 is a graph showing UV-VIS absorption spectra of organic-inorganic hybrid films prepared in examples 1 to 4;
FIG. 4 is an SEM photograph of organic-inorganic hybrid films prepared in examples 1-4(ii) a Wherein, the figure (a) is (4-Br-PEA)2(MA)2Pb3I10SEM picture of (n-3) thin film, and (b) is (4-Br-PEA)2(MA)3Pb4I13SEM picture of (n-4) thin film, and (c) is (4-Br-PEA)2(MA)4Pb5I16SEM picture of (n-5) thin film, and (d) is (4-Br-PEA)2(MA)5Pb6I19SEM image of (n ═ 6) thin film;
FIG. 5 is a J-V plot of perovskite solar cells prepared in examples 1-4;
FIG. 6 is a J-V plot of perovskite solar cells prepared in examples 3, 5 and 6;
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the organic-inorganic hybrid (4-Br-C) prepared below6H4C2H4NH3)2(CH3NH3)n-1PbnI3n+1The application of the thin film to the light-absorbing layer of a perovskite solar cell and the further detailed description of the present invention with reference to the accompanying drawings, the specific material ratios, process conditions and results thereof described in the examples are only illustrative of the present invention and should not be taken as limiting the invention as detailed in the claims.
Inventive 4-Br-C6H4C2H4NH3I, synthesis of powder crystal:
slowly dropwise adding a hydriodic acid aqueous solution (47-58 wt.%) into an absolute ethyl alcohol solution of p-bromophenylethylamine under the ice-water bath condition, stirring for 2 hours, wherein the molar ratio of hydriodic acid to p-bromophenylethylamine is 1:1, then carrying out rotary evaporation on a mixed solution obtained after reaction, repeatedly washing with anhydrous ether, carrying out suction filtration to obtain a white crystal, and carrying out vacuum drying on the white crystal at 60 ℃ for 12 hours to obtain 4-Br-C6H4C2H4NH3And I, powder crystal.
FIG. 1 shows 4-Br-C synthesized6H4C2H4NH3The X-ray diffraction pattern of the I powder crystal shows that the product isThe width of the diffraction peak is small, the intensity of the diffraction peak is large, which shows that the crystallinity of the product is high, and the figure is a group of X-ray diffraction peaks with equal spacing, which shows that 4-Br-C6H4C2H4NH3The powder crystal I is of a layered structure.
The invention provides a preparation method of an organic-inorganic hybrid film, which is a hot casting method, namely, a substrate is preheated for a period of time at a certain temperature before a precursor solution is spin-coated; wherein:
the suitable substrate is FTO, ITO, FTO/TiO2Or FTO/SnO2；
The precursor solution is 4-Br-C6H4C2H4NH3I powder crystals, MAI and PbI2Preparing N according to the molar ratio of 2 (N-1), wherein N is 3,4,5 and 6, using N, N-Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) as a solvent, shaking to dissolve uniformly, and filtering to obtain a required perovskite precursor solution; the concentration of the precursor solution is 0.2mol/L, and the volume ratio of the N-dimethylformamide to the dimethyl sulfoxide is 1:0, 1:1 or 0: 1;
the heating treatment and spin coating parameters are specifically as follows: and (3) preheating the proper substrate at 140 ℃ for 20min, then spin-coating the perovskite precursor solution, and finally annealing the substrate on a heating table at 100 ℃ for 10min, wherein the spin-coating speed is 4000rpm, and the spin-coating time is 30 s.
The hole transport layer thin film described in the step (5) of the following example was specifically prepared by preparing the organic-inorganic hybrid (4-Br-PEA) obtained in the step (4)2(MA)2Pb3I10Spin-coating a precursor solution of a Spiro-OMeTAD hole transport layer on a light absorption layer of the (n-3) thin film; the specific preparation process of the precursor solution of the hole transport layer comprises the following steps: 0.0416g of Spiro-OMeTAD was dissolved in 500. mu.L of Chlorobenzene (CBZ), and 17. mu.L of 4-tert-butylpyridinium (TBP), 8. mu.L of lithium salt (Li-TFSI, 500mg/mL solvent is acetonitrile), 7. mu.L of cobalt salt (FK 209Co (III) TFSIsalt, 200mg/mL solvent is acetonitrile) were added thereto and dissolved by shaking uniformly; the spin coating speed was 3000rpm, during the spin coatingThe time is 30 s;
the vacuum thermal evaporation method in step (6) in the following examples includes the steps of: at 2.5X 10-4And (5) heating, melting, evaporating and depositing gold on the hole transport layer film prepared in the step (5) under the vacuum degree of Pa.
Example 1
(1) Substrate preparation: sequentially and respectively ultrasonically cleaning the FTO transparent conductive glass for 20min by using deionized water, acetone and absolute ethyl alcohol, and then treating for 15min by using ultraviolet ozone to obtain clean FTO transparent conductive glass;
(2) compact TiO 22Preparation of an electron transport layer: the treated transparent conductive glass substrate was dipped into 0.05M TiCl with the front side facing up4Sealing in the solution, heating at 70 deg.C for 40min, washing the substrate with ultrapure water, blow-drying, annealing at 450 deg.C for 30min to obtain a layer of compact TiO on FTO transparent conductive glass substrate2An electron transport layer;
(3) preparation (4-Br-PEA)2(MA)2Pb3I10(n ═ 3) perovskite precursor solution: 4-Br-C6H4C2H4NH3I. MAI and PbI2The molar ratio of the raw materials is 2:2:3, 0.1312g of Br-PEAI, 0.0636g of MAI and 0.2766g of PbI are accurately weighed2Dissolving the powder crystal in 1mL of N, N-Dimethylformamide (DMF), shaking for uniform dissolution, and filtering to obtain a precursor solution with a concentration of 0.2 mol/L;
(4) the FTO/TiO obtained in the step (2)2Preheating the substrate at 140 deg.C for 20min, spin-coating the perovskite precursor solution prepared in step (3) at 4000rpm, and annealing at 100 deg.C for 10min2Spin coating the surface of the substrate to obtain an organic-inorganic hybrid (4-Br-PEA)2(MA)2Pb3I10(n-3) a light-absorbing layer of the film;
(5) the organic-inorganic hybrid (4-Br-PEA) prepared in step (4)2(MA)2Pb3I10Preparing a Spiro-OMeTAD hole transport layer film on the (n-3) film in a spin coating manner;
(6) preparing a metal electrode: and (5) evaporating a layer of gold electrode on the surface of the hole transport layer material in the step (5) by using a vacuum thermal evaporation method, and finally obtaining the perovskite solar cell, wherein the thickness of the gold electrode is 80 nm.
FIG. 4(a) shows (4-Br-PEA) prepared in this example2(MA)2Pb3I10The surface topography (SEM) of the perovskite film can be seen, the surface quality of the film is poor, the surface has more holes, and the grain size is about 0.75 mu m;
fig. 5(n ═ 3) is a J-V curve of the perovskite solar cell prepared in this example, and table 1 lists the relevant properties of the perovskite solar cell prepared in this example, with a photoelectric conversion efficiency of 4.63%.
Example 2
The preparation method of the perovskite solar cell comprises the following steps:
(1) same as in example 1, step (1);
(2) same as in step (2) of example 1;
(3) preparation (4-Br-PEA)2(MA)3Pb4I13(n ═ 4) perovskite precursor solution: 4-Br-C6H4C2H4NH3I. MAI and PbI2The molar ratio of the raw materials is 2:3:4, 0.1312g of Br-PEAI, 0.0954g of MAI and 0.3688g of PbI are accurately weighed2Dissolving the powder crystal in 1mL of N, N-Dimethylformamide (DMF), shaking for uniform dissolution, and filtering to obtain a precursor solution with a concentration of 0.2 mol/L;
(4) the FTO/TiO obtained in the step (2)2Preheating the substrate at 140 deg.C for 20min, spin-coating the perovskite precursor solution prepared in step (3) at 4000rpm, and annealing at 100 deg.C for 10min2Spin coating the surface of the substrate to obtain an organic-inorganic hybrid (4-Br-PEA)2(MA)3Pb4I13(n-4) a light-absorbing layer of the film;
(5) the organic-inorganic hybrid (4-Br-PEA) prepared in step (4)2(MA)3Pb4I13Preparing a Spiro-OMeTAD hole transport layer film on the (n-4) film in a spin coating manner;
(6) preparing a metal electrode: and (5) evaporating a layer of gold electrode on the surface of the hole transport layer material in the step (5) by using a vacuum thermal evaporation method, and finally obtaining the perovskite solar cell, wherein the thickness of the gold electrode is 80 nm.
FIG. 4(b) shows (4-Br-PEA) prepared in this example2(MA)3Pb4I13Surface topography (SEM) of the perovskite thin film, it can be seen that the surface quality of the thin film prepared in this example is improved compared to that of the thin film of example 1, and the surface pores are reduced by a grain size of about 1.75 μm;
fig. 5(n ═ 4) is a J-V curve of the perovskite solar cell prepared in this example, and table 1 lists the relevant properties of the perovskite solar cell prepared in this example, with a photoelectric conversion efficiency of 5.90%.
Example 3
The preparation method of the perovskite solar cell comprises the following steps:
(1) same as in example 1, step (1);
(2) same as in step (2) of example 1;
(3) preparation (4-Br-PEA)2(MA)4Pb5I16(n ═ 5) perovskite precursor solution: 4-Br-C6H4C2H4NH3I. MAI and PbI2The molar ratio of the components is 2:4:5, 0.1312g of Br-PEAI, 0.1272g of MAI and 0.461g of PbI are accurately weighed2And dissolving the powder crystal in 1mL of N, N-Dimethylformamide (DMF), shaking for uniform dissolution, and filtering to obtain a precursor solution with the concentration of 0.2 mol/L.
(4) The FTO/TiO obtained in the step (2)2Preheating the substrate at 140 deg.C for 20min, spin-coating the perovskite precursor solution prepared in step (3) at 4000rpm, and annealing at 100 deg.C for 10min2Spin coating the surface of the substrate to obtain an organic-inorganic hybrid (4-Br-PEA)2(MA)4Pb5I16(n-5) a light-absorbing layer of the film;
(5) the organic-inorganic hybrid (4-Br-PEA) prepared in step (4)2(MA)4Pb5I16Spin coating (n ═ 5) on the film to prepare a Spiro-OMeTAD hole transport layer film;
(6) preparing a metal electrode: and (5) evaporating a layer of gold electrode on the surface of the hole transport layer material in the step (5) by using a vacuum thermal evaporation method, and finally obtaining the perovskite solar cell, wherein the thickness of the gold electrode is 80 nm.
FIG. 4(c) shows (4-Br-PEA) prepared in this example2(MA)4Pb5I16As can be seen from the surface topography (SEM) of the perovskite thin film, the thin film prepared by the embodiment has good surface quality, almost no holes on the surface, smoothness and flatness, and the grain size is about 3.2 μm;
fig. 5(n ═ 5) is a J-V curve of the perovskite solar cell prepared in this example, and table 1 shows the relevant properties of the perovskite solar cell prepared in this example, and it can be seen that the open-circuit voltage is 0.933V and the short-circuit current density is 16.87mA · cm-2The fill factor was 0.538, and the photoelectric conversion efficiency was 8.46%.
Example 4
The preparation method of the perovskite solar cell comprises the following steps:
(1) same as in example 1, step (1);
(2) same as in step (2) of example 1;
(3) preparation (4-Br-PEA)2(MA)5Pb6I19(n ═ 6) perovskite precursor solution: 4-Br-C6H4C2H4NH3I. MAI and PbI2The molar ratio of the components is 2:5:6, 0.1312g of Br-PEAI, 0.159g of MAI and 0.5532g of PbI are accurately weighed2Dissolving the powder crystal in 1mL of N, N-Dimethylformamide (DMF), shaking for uniform dissolution, and filtering to obtain a precursor solution with a concentration of 0.2 mol/L;
(4) the FTO/TiO obtained in the step (2)2Placing the substrate at 140 ℃ for preheating treatment for 20min, and then spin-coating the perovskite precursor prepared in the step (3) at 4000rpmFinally placing the solution on a heating table at 100 ℃ for annealing treatment for 10min to obtain the FTO/TiO2Spin coating the surface of the substrate to obtain an organic-inorganic hybrid (4-Br-PEA)2(MA)5Pb6I19(n-6) a light-absorbing layer of the film;
(5) the organic-inorganic hybrid (4-Br-PEA) prepared in step (4)2(MA)5Pb6I19Spin coating (n ═ 6) on the film to prepare a Spiro-OMeTAD hole transport layer film;
(6) preparing a metal electrode: and (5) evaporating a layer of gold electrode on the surface of the hole transport layer material in the step (5) by using a vacuum thermal evaporation method, and finally obtaining the perovskite solar cell, wherein the thickness of the gold electrode is 80 nm.
FIG. 4(c) shows (4-Br-PEA) prepared in this example2(MA)5Pb6I19As can be seen from the surface topography (SEM) of the perovskite thin film, the surface quality of the thin film prepared in this example is inferior to that of the thin film obtained in example 3, the grain size of the thin film prepared in this example is about 2.2 μm, and the surface of the thin film has a few holes and is uneven, which is not favorable for the transmission of carriers in the perovskite solar cell and affects the performance of the device;
fig. 5(n ═ 6) is a J-V curve of the perovskite solar cell prepared in this example, and table 1 (example 4) lists the relevant properties of the perovskite solar cell prepared in this example, with a photoelectric conversion efficiency of 7.87%.
Example 5
The preparation method of the perovskite solar cell comprises the following steps:
(1) same as in example 1, step (1);
(2) same as in step (2) of example 1;
(3) preparing (4-Br-PEA)2(MA)4Pb5I16 (n-5) perovskite precursor solution: 4-Br-C6H4C2H4NH3I. MAI and PbI2The molar ratio of the components is 2:4:5, 0.1312g of Br-PEAI, 0.1272g of MAI and 0.461g of PbI are accurately weighed2The powder crystals were dissolved in a solution of 500ml of N-Dimethylformamide (DMF) andin 500mL of mixed solution of dimethyl sulfoxide (DMSO), namely the volume ratio of a solvent DMF to DMSO is 1:1, shaking and dissolving uniformly, and filtering to obtain a precursor solution with the concentration of 0.2 mol/L;
(4) the FTO/TiO obtained in the step (2)2Preheating the substrate at 140 deg.C for 20min, spin-coating the perovskite precursor solution prepared in step (3) at 4000rpm, and annealing at 100 deg.C for 10min2Spin coating the surface of the substrate to obtain an organic-inorganic hybrid (4-Br-PEA)2(MA)4Pb5I16(n-5) a light-absorbing layer of the film;
(5) the organic-inorganic hybrid (4-Br-PEA) prepared in step (4)2(MA)4Pb5I16Spin coating (n ═ 5) on the film to prepare a Spiro-OMeTAD hole transport layer film;
(6) preparing a metal electrode: and (5) evaporating a layer of gold electrode on the surface of the hole transport layer material in the step (5) by using a vacuum thermal evaporation method, and finally obtaining the perovskite solar cell, wherein the thickness of the gold electrode is 80 nm.
FIG. 6(FO11) is a J-V curve of the perovskite solar cell fabricated in this example, and the perovskite solar cell fabricated in this example has the relevant properties shown in Table 2, and it can be seen that the open-circuit voltage is 0.923V and the short-circuit current density is 20.95mA · cm-2The fill factor is 0.601, the photoelectric conversion efficiency is 11.61%, and compared with example 3, the short-circuit current density, the fill factor and the photoelectric conversion efficiency of the perovskite solar cell prepared in the embodiment are greatly improved.
Example 6
The preparation method of the perovskite solar cell comprises the following steps:
(1) same as in example 1, step (1);
(2) same as in step (2) of example 1;
(3) preparation (4-Br-PEA)2(MA)4Pb5I16(n ═ 5) perovskite precursor solution: 4-Br-C6H4C2H4NH3I. MAI andPbI2the molar ratio of the components is 2:4:5, 0.1312g of Br-PEAI, 0.1272g of MAI and 0.461g of PbI are accurately weighed2Dissolving the powder crystal in 1mL of dimethyl sulfoxide (DMSO), shaking to dissolve uniformly, and filtering to obtain a precursor solution with the concentration of 0.2 mol/L;
(4) the FTO/TiO obtained in the step (2)2Preheating the substrate at 140 deg.C for 20min, spin-coating the perovskite precursor solution prepared in step (3) at 4000rpm, and annealing at 100 deg.C for 10min2Spin coating the surface of the substrate to obtain an organic-inorganic hybrid (4-Br-PEA)2(MA)4Pb5I16(n-5) a light-absorbing layer of the film;
(5) the organic-inorganic hybrid (4-Br-PEA) prepared in step (4)2(MA)4Pb5I16Spin coating (n ═ 5) on the film to prepare a Spiro-OMeTAD hole transport layer film;
(6) preparing a metal electrode: and (5) evaporating a layer of gold electrode on the surface of the hole transport layer material in the step (5) by using a vacuum thermal evaporation method, and finally obtaining the perovskite solar cell, wherein the thickness of the gold electrode is 80 nm.
FIG. 6(FO01) is a J-V curve of the perovskite solar cell fabricated in this example, and the relevant properties of the perovskite solar cell fabricated in this example are shown in Table 2, and it can be seen that the open-circuit voltage is 0.799V and the short-circuit current density is 19.70mA · cm-2The fill factor was 0.555, and the photoelectric conversion efficiency was 8.74%.
FIG. 2 shows perovskite thin films (4-Br-PEA) prepared in examples 1 to 42(MA)n-1PbnI3n+1As seen from the X-ray diffraction pattern on the left side of the X-ray diffraction peak contrast chart of (3, 4,5,6), the smaller the n value, the higher the crystallinity of the obtained perovskite thin film; as can be seen from the partial enlarged view of the (111) crystal plane diffraction peak on the right side of fig. 2, as the n value increases, the perovskite thin film (111) crystal plane diffraction peak shifts to a small angle direction;
FIG. 3 shows perovskite thin films (4-Br-PEA) prepared in examples 1 to 42(MA)n-1PbnI3n+1(n-3, 4,5,6) in the ultraviolet-visible absorption spectrum, and it can be seen from the ultraviolet-visible absorption spectrum that the perovskite thin film (4-Br-PEA) prepared in example 4 was obtained2(MA)5Pb6I19The scattering phenomenon of (n-6) is more obvious, which indicates that the surface roughness of the film is larger, and the perovskite film prepared in example 3 has better light absorption capacity;
the performance of the device is further improved by adjusting the solvent ratio of the precursor solution, and table 2 shows the relevant performance of the perovskite solar cells prepared in the embodiments 3, 5 and 6, and table 2 shows that the short-circuit current, the fill factor and the photoelectric conversion efficiency of the perovskite solar cell prepared by the mixed solvent DMF/DMSO are improved compared with those of the perovskite solar cell prepared by a single solvent, and when the volume ratio of the mixed solvent DMF to DMSO is 1:1, the performance of the device is optimal, and the photoelectric conversion efficiency can reach 11.61%;
table 3 shows the unencapsulated (4-Br-PEA) prepared in example 52(MA)4Pb5I16(n-5) based perovskite solar cells exhibit a change in photovoltaic performance at a relative humidity of 40% to 60%; as can be seen from table 3, after the unpackaged cell device is placed for about 720 hours under the environmental condition that the relative humidity is 40% -60%, the efficiency of the device is reduced due to the erosion effect of water and oxygen in the air on the thin film when the device is unpackaged, but the efficiency can still be maintained at 72.5% of the original photoelectric conversion efficiency, which indicates that the device has a certain humidity stability.
TABLE 1
TABLE 2
TABLE 3
Claims (8)
1. A perovskite organic-inorganic hybrid film is characterized in that the component is (4-Br-C)6H4C2H4NH3)2(CH3NH3)n-1PbnI3n+1Wherein n is 1,2,3,4,5, 6.
2. A method of preparing a thin film of the perovskite organic-inorganic hybrid described in claim 1, comprising the steps of:
1) preparing a precursor solution:
4-Br-C6H4C2H4NH3I powder crystals, CH3NH3I and PbI2Preparing N according to a molar ratio of 2 (N-1), wherein N is 1,2,3,4,5 and 6, using N, N-Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) as a solvent, shaking for uniform dissolution, and filtering to obtain a perovskite precursor solution;
2) preparation of organic-inorganic hybrid film:
preheating the substrate in a glove box, spin-coating the perovskite precursor solution obtained in the step 1 on the surface, and annealing to obtain the (4-Br-C) with the thickness of 100-2000 nm on the surface of the substrate6H4C2H4NH3)2(CH3NH3)n-1PbnI3n+1A film.
3. The process for preparing the perovskite organic-inorganic hybrid thin film as claimed in claim 2, wherein the 4-Br-C is6H4C2H4NH3I is prepared in the following way:
slowly dropwise adding 47-58 wt.% hydriodic acid aqueous solution into an absolute ethyl alcohol solution of p-bromophenylethylamine under the ice-water bath condition, and stirring for 1-2 hours, wherein the molar ratio of hydriodic acid to p-bromophenylethylamine is 1: 1;
then, the mixed solution obtained by the reaction is subjected to rotary evaporation to dryness, and is repeatedly washed by anhydrous ether, a white crystal is obtained by suction filtration, and the white crystal is dried in vacuum for 5-12 hours at the temperature of 50-100 ℃ to obtain 4-Br-C6H4C2H4NH3And I, powder crystal.
4. The method for producing a perovskite organic-inorganic hybrid thin film as claimed in claim 2, wherein the concentration of the precursor solution obtained in step 1 is 0.05 to 0.2 mol/L.
5. The method of making the perovskite organic-inorganic hybrid thin film as claimed in claim 2, wherein the substrate of step 2 is FTO, ITO, FTO/TiO clean2Or FTO/SnO2。
6. The method for producing a perovskite organic-inorganic hybrid thin film according to claim 2, wherein the preheating temperature of the substrate in the step 2 is 80 to 200 ℃ and the preheating time is 10 to 25 min.
7. The method of preparing the perovskite organic-inorganic hybrid thin film as claimed in claim 2, wherein the spin coating in step 2 has process parameters of: and (3) coating 25-70 mu L of precursor solution on the surface of the substrate, wherein the spin coating speed is 2000-4000 rpm, and the spin coating time is 20-60 s.
8. The method for producing a perovskite organic-inorganic hybrid thin film according to claim 2, wherein the annealing temperature in step 2 is 60 to 120 ℃ and the annealing time is 10 to 30 min.
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