CN113130678B - All-inorganic tin-lead binary perovskite absorbing material and preparation method thereof - Google Patents

All-inorganic tin-lead binary perovskite absorbing material and preparation method thereof Download PDF

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CN113130678B
CN113130678B CN202110273280.3A CN202110273280A CN113130678B CN 113130678 B CN113130678 B CN 113130678B CN 202110273280 A CN202110273280 A CN 202110273280A CN 113130678 B CN113130678 B CN 113130678B
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张懿强
陈刚树
宋延林
李鹏伟
马家乐
金泽
雷诺
郭峰
吴振华
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Abstract

The invention belongs to the technical field of perovskite absorbing materials, and discloses an all-inorganic tin-lead binary perovskite absorbing material and a preparation method thereof. The molecular formula is CsPb 1‑x Sn x I 2 Br、CsPb 1‑ x Sn x I 2 Br-CsCl or CsPb 1‑x Sn x I 2 Br-CsCl-S,0 < x < 1. (1) Synthesis of CsPb 1‑x Sn x I 2 Br precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving into organic mixed solvent according to the molar ratio of 2: 1-x: 0.1, stirring and reacting for 10-12h at room temperature to obtain CsPb 1‑x Sn x I 2 Br precursor solution; (2) And preparation of CsPb 1‑x Sn x I 2 Br film: csPb obtained in the step (1) 1‑x Sn x I 2 Filtering Br precursor solution, depositing the Br precursor solution on a substrate in an inert atmosphere by a solution deposition technology, dropwise adding ethyl acetate in the last deposited 5-10 s, and annealing the substrate with a deposited film at the temperature of more than or equal to 60 ℃ for more than or equal to 40s to obtain CsPb 1‑x Sn x I 2 A Br film. The invention obtains the high-quality film through a simple process; the energy bands of the materials are more matched by regulating the proportion of the tin-lead alloy elements, and the light absorption edge of the perovskite thin film is expanded.

Description

All-inorganic tin-lead binary perovskite absorbing material and preparation method thereof
Technical Field
The invention belongs to the technical field of perovskite absorbing materials, and particularly relates to an all-inorganic tin-lead binary perovskite absorbing material and a preparation method thereof.
Background
Since the 21 st century, due to the need of industrial development and the explosion of population pressure, the serious greenhouse effect is formed, and the serious problems of global warming and the like are caused, so that a new energy source with high efficiency and low pollution is urgently needed by human beings for the present and future needs. In recent years, perovskite solar cells have attracted much attention due to their advantages such as excellent photoelectric conversion performance and low-cost solution processing, and are considered to be an outstanding representative of a new generation of thin-film solar cell technology. At present, the photoelectric conversion efficiency of perovskite solar cells has been rapidly improved from 3.81% reported in 2009 to 25.5% at present, and energy conversion efficiency (PCE) comparable to that of traditional commercial silicon-based solar cells is obtained, which is considered as the most promising photoelectric thin-film cell device for realizing low-cost power generation.
Organic-inorganic hybrid perovskite solar cells are the keepers of the current highest record of photoelectric conversion efficiency, but due to the instability of organic cations methylamine and formamidine, thermal contact and light irradiation can cause severe decomposition of perovskite, which greatly limits the development of organic-inorganic hybrid perovskite solar cells. One possible strategy to improve stability is to replace the organic cations with inorganic cations to form an all-inorganic perovskite, thereby improving the photo-thermal stability of the perovskite. However, the optical forbidden bandwidth of the all-inorganic pure-lead perovskite material is large, and sufficient sunlight cannot be absorbed, so that the energy conversion efficiency of the correspondingly prepared perovskite solar cell is low. By utilizing alloy engineering of introducing metal Sn cations, the formed all-inorganic Sn-Pb binary perovskite has the characteristics of narrow band gap, low toxicity and high carrier mobility, has better photovoltaic performance, but is easy to be converted into orthorhombic from a cubic crystal system in atmospheric environmentSn in crystal system and Sn-based perovskite 2+ Is easily oxidized into Sn in the air 4+ This can lead to severe autodoping effects in the perovskite, which severely impair the energy conversion efficiency and device stability of the device, which hinders its commercialization progress. Meanwhile, the synthesis temperature of the all-inorganic Sn-Pb binary perovskite material is higher>100 o C) Low-temperature production cannot be achieved.
Disclosure of Invention
Aiming at the problems that the existing perovskite absorbing material is unstable and cannot be prepared at low temperature and the like, the invention aims to provide an all-inorganic tin-lead binary perovskite light absorbing material which can obtain excellent stability and has a high-efficiency device and a preparation method thereof.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
an all-inorganic Sn-Pb binary perovskite absorbing material with a molecular formula of CsPb 1-x Sn x I 2 Br、CsPb 1- x Sn x I 2 Br-CsCl or CsPb 1-x Sn x I 2 Br-CsCl-S，0﹤x﹤1。
When the molecular formula of the all-inorganic tin-lead binary perovskite absorption material is CsPb 1-x Sn x I 2 Br, the preparation steps are as follows:
(1) Synthesis of CsPb 1-x Sn x I 2 Br precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving into organic mixed solvent according to the molar ratio of 2: 1-x: 0.1, stirring and reacting for 10-12h at room temperature to obtain CsPb 1-x Sn x I 2 Br precursor solution; the organic mixed solvent consists of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) in a volume ratio of (5-7) to (3-5), and the sum of the volumes of the dimethyl sulfoxide (DMSO) and the N, N-Dimethylformamide (DMF) is 10;
(2) And preparation of CsPb 1-x Sn x I 2 Br film: csPb obtained in the step (1) 1-x Sn x I 2 Filtering Br precursor solution, and depositing in inert atmosphereDepositing the film on a substrate, dripping ethyl acetate into the film for 5 to 10 seconds after final deposition, and annealing the substrate with the deposited film at the temperature of more than or equal to 60 ℃ for more than or equal to 40 seconds to obtain the all-inorganic tin-lead binary perovskite absorbing material CsPb 1-x Sn x I 2 A Br film.
When the molecular formula of the all-inorganic tin-lead binary perovskite absorption material is CsPb 1-x Sn x I 2 Br-CsCl, the preparation steps are as follows:
(1) Synthesis of CsPb 1-x Sn x I 2 Br-CsCl precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving into organic mixed solvent according to the molar ratio of 2: 1-x: 0.1, and stirring and reacting for 10-12h at room temperature; adding cesium chloride CsCl into the solution, wherein the addition amount of the cesium chloride CsCl is CsI and PbI 2 、PbBr 2 、SnI 2 、SnBr 2 、SnF 2 Stirring and reacting for 1-2 h to obtain CsPb, wherein the mass percent of the CsPb is 1-10 wt% 1-x Sn x I 2 Br-CsCl precursor solution; the organic mixed solvent consists of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) in a volume ratio of (5-7) to (3-5), and the sum of the volumes of the dimethyl sulfoxide (DMSO) and the N, N-Dimethylformamide (DMF) is 10;
(2) And preparation of CsPb 1-x Sn x I 2 Br-CsCl film: csPb obtained in the step (1) 1-x Sn x I 2 Filtering a Br-CsCl precursor solution, depositing the Br-CsCl precursor solution on a substrate in an inert atmosphere by a solution deposition technology, dripping ethyl acetate into the substrate for 5 to 10 seconds of final deposition, and annealing the substrate with a deposited film at the temperature of more than or equal to 60 ℃ for more than or equal to 40 seconds to obtain the all-inorganic tin-lead binary perovskite absorbing material CsPb 1-x Sn x I 2 Br-CsCl film.
When the molecular formula of the all-inorganic tin-lead binary perovskite absorption material is CsPb 1-x Sn x I 2 Br-CsCl-S, the preparation steps are as follows:
(1) Synthesis of CsPb 1-x Sn x I 2 Br-CsCl precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving into organic mixed solvent according to the molar ratio of 2: 1-x: 0.1, and stirring and reacting for 10-12h at room temperature; adding cesium chloride CsCl into the solution, wherein the addition amount of the cesium chloride CsCl is CsI and PbI 2 、PbBr 2 、SnI 2 、SnBr 2 、SnF 2 Stirring and reacting for 1-2 h to obtain CsPb, wherein the mass percent of the CsPb is 1-10 wt% 1-x Sn x I 2 Br-CsCl precursor solution; the organic mixed solvent consists of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) in a volume ratio of (5-7) to (3-5), and the sum of the volumes of the dimethyl sulfoxide (DMSO) and the N, N-Dimethylformamide (DMF) is 10;
(2) And preparation of CsPb 1-x Sn x I 2 Br-CsCl film: csPb obtained in the step (1) 1-x Sn x I 2 Filtering a Br-CsCl precursor solution, depositing the Br-CsCl precursor solution on a substrate in an inert atmosphere by a solution deposition technology, dropwise adding ethyl acetate into the finally deposited substrate for 5 to 10 seconds, and annealing the substrate with a deposited film at the temperature of more than or equal to 60 ℃ for more than or equal to 40 seconds to obtain CsPb 1-x Sn x I 2 A Br-CsCl film;
(3) And passivating the surface of the film: 1-4 mmol/mL methylamine sulfate Isopropylamine (IPA) solution is added into CsPb obtained in the step (2) 1-x Sn x I 2 Spreading the Br-CsCl film for 10-30 s, then spin-coating, dripping toluene in the spin-coating process to remove excessive unreacted methylamine sulfate, and finally obtaining the all-inorganic tin-lead binary perovskite absorbing material-CsPb 1-x Sn x I 2 Br-CsCl-S film.
Preferably, in step (2), the substrate on which the film is deposited is annealed at 60-70 ℃ for 2-3 min, then at 90-100 ℃ for 2-3 min, and then at 140-150 ℃ for 10-15 min.
Preferably, in step (2), 50 to 100. Mu.L of ethyl acetate is added dropwise per square centimeter of substrate.
Preferably, in the step (2), the solution deposition technique is spin coating, slit coating or blade coating.
Preferably, the spin coating method comprises the following specific steps: the precursor solution is spin-coated on the substrate for 10-30 s at the speed of 1000-2000 rpm, and then spin-coated for 30-60 s at the speed of 3000-5000 rpm.
Preferably, in step (3), 100 to 300. Mu.L of toluene is added dropwise per square centimeter of substrate.
Preferably, in step (3), spin coating is carried out at 5000-8000 rpm for 30-60 s.
Has the advantages that: the invention prepares a new all-inorganic tin-lead binary alloy perovskite absorption material, and obtains a high-quality film by a simple spin coating process; the energy bands are more matched by regulating the proportion of tin-lead alloy elements, and the light absorption edge of the perovskite film is enlarged; by doping inorganic ions CsCl, larger grain size and lower vacancy concentration are obtained, and the photoelectric property of the device is improved; by interfacial passivation, etc., a hydrophobic barrier layer is formed to inhibit iodine migration and prevent Sn 2+ Oxidation is beneficial to resisting attack of oxygen/moisture, and the stability of the device is greatly improved; the invention optimizes the formula of the precursor components and adds SnF 2 Inhibition of Sn 2+ Thereby reducing nucleation barrier of the all-inorganic tin-lead binary perovskite material and realizing 60 o The synthesis of the all-inorganic Sn-Pb perovskite material under C provides a feasible process route for the preparation of the flexible all-inorganic Sn-Pb binary perovskite solar cell. In conclusion, the technology can be used for manufacturing high-performance perovskite films and preparing photoelectric devices.
Drawings
FIG. 1: ultraviolet-visible absorption spectra of all-inorganic tin-lead binary perovskite thin films based on different Sn-Pb ratios.
FIG. 2: and (3) a Tauc diagram of the all-inorganic tin-lead binary perovskite thin film based on different Sn-Pb ratios.
FIG. 3: csPb obtained in example 1 0.90 Sn 0.10 I 2 XRD pattern of Br film.
FIG. 4: csPb obtained in example 1 0.90 Sn 0.10 I 2 XPS spectra of Br film, (a) XPS survey, (b) high-precision XPS spectra of Pb 4f, and (c) high-precision XPS spectra of Sn 3dSpectra.
FIG. 5: csPb obtained in example 1 0.55 Sn 0.45 I 2 XRD pattern of Br film.
FIG. 6: csPb obtained in example 1 0.55 Sn 0.45 I 2 XPS spectra of Br films, (a) XPS survey spectra, (b) high-precision XPS spectra of Pb 4f, and (c) high-precision XPS spectra of Sn 3 d.
FIG. 7: J-V curves of all-inorganic tin-lead binary alloy perovskite solar cells based on different Sn-Pb ratios.
FIG. 8: csPb obtained in example 3 0.55 Sn 0.45 I 2 Time-of-flight secondary ion mass spectrometry image of Br-CsCl-S film: left panel represents SO 4 2- Map image, right image represents Cl - The image is mapped.
FIG. 9: csPb obtained in example 3 0.55 Sn 0.45 I 2 XRD pattern of Br-CsCl-S thin film.
FIG. 10: all-inorganic tin-lead binary perovskite thin films CsPb prepared in examples 1, 2 and 3 0.55 Sn 0.45 I 2 Br、CsPb 0.55 Sn 0.45 I 2 Br-CsCl、CsPb 0.55 Sn 0.45 I 2 Surface topography of Br-CsCl-S: the left panel represents CsPb prepared in example 3 0.55 Sn 0.45 I 2 Br-CsCl-S film, middle panel representing CsPb prepared in example 1 0.55 Sn 0.45 I 2 Br film (no more CsCl added for bulk doping and no surface passivation), right panel represents CsPb prepared in example 2 0.55 Sn 0.45 I 2 Br-CsCl film (no surface passivation treatment).
FIG. 11: all-inorganic tin-lead binary perovskite thin films CsPb prepared in examples 1, 2 and 3 0.55 Sn 0.45 I 2 Br、CsPb 0.55 Sn 0.45 I 2 Br-CsCl、CsPb 0.55 Sn 0.45 I 2 Comparison of the static contact Angle of Br-CsCl-S: the left panel represents CsPb prepared in example 1 0.55 Sn 0.45 I 2 Br film (without CsCl addition for bulk doping and without further doping)Line surface passivation treatment), the middle panel represents CsPb prepared in example 2 0.55 Sn 0.45 I 2 Br-CsCl film (without surface passivation) and the right panel represents CsPb prepared in example 3 0.55 Sn 0.45 I 2 Br-CsCl-S film.
FIG. 12: application examples 1-3 are based on CsPb 0.55 Sn 0.45 I 2 Br、CsPb 0.55 Sn 0.45 I 2 Br-CsCl、CsPb 0.55 Sn 0.45 I 2 The J-V curve of the Br-CsCl-S full-inorganic tin-lead binary alloy perovskite solar cell.
FIG. 13: application example 1 is based on CsPb 0.55 Sn 0.45 I 2 The efficiency attenuation spectrum of the all-inorganic tin-lead binary perovskite solar cell of Br is 2000h in work.
FIG. 14: application example 2 based on CsPb 0.55 Sn 0.45 I 2 And the efficiency attenuation spectrum of the all-inorganic tin-lead binary perovskite solar cell of Br-CsCl is 2000h after the solar cell works.
FIG. 15: application example 3 is based on CsPb 0.55 Sn 0.45 I 2 And the efficiency attenuation spectrum of the all-inorganic tin-lead binary perovskite solar cell of Br-CsCl-S is 2000h after working.
FIG. 16: 60. CsPb obtained at different annealing time under different temperature 0.55 Sn 0.45 I 2 Photograph of Br film.
FIG. 17: csPb obtained by step annealing 0.55 Sn 0.45 I 2 XRD pattern of Br film.
FIG. 18: comparative application example 1 (without addition of SnF) 2 ) And the J-V curve of the obtained all-inorganic tin-lead binary alloy perovskite solar cell.
Detailed Description
In order to make the invention clearer and clearer, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Full-inorganic tin-lead binary perovskite absorption material CsPb 1-x Sn x I 2 The preparation method of Br comprises the following steps:
(1) Synthesis of CsPb 1-x Sn x I 2 Br precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving the mixture into an organic mixed solvent consisting of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) according to the molar ratio of 2: 1-x: 0.1 (x is equal to 0.10,0.15,0.30,0.45,0.60 and 0.80 in sequence), stirring and reacting for 12 hours at room temperature to obtain CsPb 1-x Sn x I 2 Br precursor solution;
(2) And preparation of CsPb 1-x Sn x I 2 Br film: filtering CsPb obtained in the step (1) by using a 0.22 mu m microporous polytetrafluoroethylene filter 1-x Sn x I 2 Br precursor solution, coating the precursor solution by a spin method, depositing a perovskite layer on the substrate: spin-coating 10s and 3000 rpm for 30s in a nitrogen glove box at 1000 rpm respectively, and dropping 100 μ L of ethyl acetate on each square centimeter of substrate at the last 5s of the second step to process the perovskite thin film, and then annealing the thin film at 60 deg.C for 40s to obtain the all-inorganic Sn-Pb binary perovskite absorbing material-CsPb 1-x Sn x I 2 Br film and when x is in the order 0.1,0.15,0.3,0.45,0.6,0.8, the resulting product is marked CsPb in the order 0.90 Sn 0.10 I 2 Br，CsPb 0.85 Sn 0.15 I 2 Br，CsPb 0.70 Sn 0.30 I 2 Br，CsPb 0.55 Sn 0.45 I 2 Br，CsPb 0.40 Sn 0.60 I 2 Br，CsPb 0.20 Sn 0.80 I 2 Br。
The ultraviolet-visible absorption spectrum of the all-inorganic tin-lead binary perovskite thin film based on different Sn-Pb ratios is shown in figure 1, and the Tauc diagram is shown in figure 2 (the spectrum is converted based on the ultraviolet-visible absorption spectrum of figure 1, and the optical forbidden bandwidth of a semiconductor can be accurately determined). As can be seen from fig. 1 and 2: by regulating the Sn-Pb ratio, the optical absorption edge of the obtained perovskite thin film material is regulated (725-900 nm), so that the optical semiconductor forbidden band width is well regulated (1.71-1.59 eV).
CsPb 0.90 Sn 0.10 I 2 XRD pattern of Br film is shown in FIG. 3, and XPS is shown in FIG. 4. As can be seen from fig. 3: diffraction peaks at 14.84 ° and 29.72 ° correspond to the (100) and (200) crystal planes, and the obtained thin film belongs to an α -cubic phase perovskite, and no unwanted impurity diffraction peaks appear. The XPS data is suitable for semi-quantitatively analyzing the element content of a substance, but has certain errors, and as can be seen from FIG. 4, the atomic ratio data of the elements are shown in Table 1, the ratio of Cs: pb: sn: I: br is approximately equal to CsPb 0.90 Sn 0.10 I 2 Br match, equal to about 1: 0.9: 0.1: 2: 1.
Figure 143830DEST_PATH_IMAGE001
CsPb 0.55 Sn 0.45 I 2 XRD pattern of Br film is shown in FIG. 5, XPS is shown in FIG. 6. As can be seen from fig. 5: diffraction peaks at 14.90 ° and 29.65 ° correspond to the (100) and (200) crystal planes, and the obtained thin film belongs to an α -cubic phase perovskite, and no excessive impurity diffraction peaks appear. As can be seen from FIG. 6, the atomic ratio data for the elements are shown in Table 2, where the ratio of Cs: pb: sn: I: br is approximately equal to CsPb 0.55 Sn 0.45 I 2 Br was matched approximately to 1: 0.55: 0.45: 2: 1.
Figure 200036DEST_PATH_IMAGE002
Application example 1
All-inorganic tin-lead binary alloy perovskite solar cell ITO/PEDOT: PSS/CsPb 1-x Sn x I 2 Br/PC 61 The preparation method of BM/BCP/Ag comprises the following steps:
step S1, preparing a PEDOT: PSS film by adopting a spin coating process:
s1.1, sequentially carrying out ultrasonic cleaning on the ITO conductive glass for 20min by using deionized water, acetone, absolute ethyl alcohol and isopropanol respectively;
s1.2, airing the cleaned ITO conductive glass in the air, and then carrying out ultraviolet ozone cleaning agent treatment for 15min;
s1.3, spin-coating poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS, clevios, hewley, germany) on ITO conductive glass for 30S at the speed of 4000 rpm;
s1.4, annealing the ITO conductive glass in the air at 140 ℃ for 20min to prepare a PEDOT: PSS film on the ITO conductive glass;
step S2- -preparation of perovskite thin film (light absorption layer): using the method of example 1, csPb was prepared on the basis of the PEDOT: PSS film prepared in step S1 1-x Sn x I 2 A Br film;
step S3, adopting a spin coating process to prepare the PCBM electronic transmission layer:
s3.1, mixing [6, 6 ]]-phenyl-C61-butyric acid methyl ester (PC) 61 BM) (20 mg) was dissolved in 1mL of Chlorobenzene (CB) solution;
s3.2, spin-coating the solution on the perovskite film for 30S at the speed of 2500 rpm;
s3.3, coating 70 mu L of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) (0.5 mg/mL in IPA) for 30S at the speed of 4000 rpm;
s4, preparing the metal electrode silver on the electron transmission layer by adopting a vacuum thermal evaporation process, wherein the specific parameters are as follows: initial air pressure 4.5X 10 -5 Torr, deposition rate 0.2A/s, and deposition thickness 80 nm.
The J-V curves of the all-inorganic tin-lead binary alloy perovskite solar cells based on different Sn-Pb ratios are shown in fig. 7, and the corresponding data are shown in table 3. As can be seen from Table 3: with the increase of the alloy proportion of Sn, the energy conversion efficiency of the solar cell is gradually improved; when Pb and Sn are 0.55 to 0.45, the corresponding solar cell obtains the highest energy conversion efficiency; further increasing the alloy ratio of Sn results in a decrease in device efficiency.
Figure 397799DEST_PATH_IMAGE003
Example 2
Full-inorganic tin-lead binary perovskite absorption material CsPb 0.55 Sn 0.45 I 2 The preparation method of Br-CsCl comprises the following steps:
(1) Synthesis of CsPb 0.55 Sn 0.45 I 2 Br-CsCl precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving the mixture into an organic mixed solvent consisting of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) according to the molar ratio of 2: 0.55: 0.45: 0.1, and stirring the mixture at room temperature for reaction for 12 hours; adding cesium chloride (CsCl) into the solution, wherein the addition amount of the cesium chloride CsCl is CsI and PbI 2 、PbBr 2 、SnI 2 、SnBr 2 、SnF 2 Stirring and reacting for 2h to finally obtain CsPb, wherein the mass percent of the CsPb is 1 percent of the total mass 0.55 Sn 0.45 I 2 Br-CsCl precursor solution;
(2) And preparation of CsPb 0.55 Sn 0.45 I 2 Br-CsCl film: filtering CsPb obtained in the step (1) by using a 0.22 mu m microporous polytetrafluoroethylene filter 1-x Sn x I 2 A Br-CsCl precursor solution, coating the precursor solution by a spin method, depositing a perovskite layer on a substrate: spin-coating 10s and 3000 rpm for 30s in a nitrogen glove box at 1000 rpm respectively, and drop-coating 100 μ L of ethyl acetate on each square centimeter of substrate for the last 5s of the second spin-coating to process the perovskite thin film, and then annealing the thin film at 60 deg.C for 40s to obtain the all-inorganic tin-lead binary perovskite absorbing material-CsPb 0.55 Sn 0.45 I 2 Br-CsCl film.
Application example 2
All-inorganic tin-lead binary alloy perovskite solar cell ITO/PEDOT: PSS/CsPb 0.55 Sn 0.45 I 2 Br-CsCl/PC 61 The preparation method of BM/BCP/Ag is different from the application example 1 in that: in step S2, csPb was continuously prepared on the basis of the PEDOT: PSS film prepared in step S1 by the method of example 2 0.55 Sn 0.45 I 2 Br-CsCl thin film, the same as in application example 1.
Example 3
Full-inorganic tin-lead binary perovskite absorption material CsPb 0.55 Sn 0.45 I 2 The preparation method of Br-CsCl-S comprises the following steps:
(1) Synthesis of CsPb 0.55 Sn 0.45 I 2 Br-CsCl precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving the mixture into an organic mixed solvent consisting of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) according to the molar ratio of 2: 0.55: 0.45: 0.1, and stirring the mixture at room temperature for reaction for 12 hours; adding cesium chloride (CsCl) to the solution, wherein the CsI and PbI are added to the solution 2 、PbBr 2 、SnI 2 、SnBr 2 、SnF 2 1 wt% of the mass, stirring and reacting for 2h to finally obtain CsPb 0.55 Sn 0.45 I 2 Br-CsCl precursor solution;
(2) And preparation of CsPb 0.55 Sn 0.45 I 2 Br-CsCl film: filtering CsPb obtained in the step (1) by using a 0.22 mu m microporous polytetrafluoroethylene filter 1-x Sn x I 2 Br-CsCl precursor solution, coating the precursor solution by spin coating, depositing a perovskite layer on the substrate: spin-coating 10s and 3000 rpm for 30s in a nitrogen glove box at 1000 rpm, respectively, and dropping 100. Mu.L of ethyl acetate for the last 5s of the second spin-coating to treat the perovskite thin film, followed by annealing the thin film at 60 ℃ for 40s to obtain CsPb 0.55 Sn 0.45 I 2 A Br-CsCl film;
(3) And passivating the surface of the film: dissolving methylamine sulfate in Isopropylamine (IPA) at a concentration of 3 mmol/mL, dissolving methylamine sulfate solution in CsPb 0.55 Sn 0.45 I 2 Spreading on Br-CsCl film for 10s, spin-coating at 5000 rpm for 30s, and adding 200 μ L toluene per square centimeter of substrate to remove excessive unreacted methylamine sulfate during spin-coating process to obtain CsPb 0.55 Sn 0.45 I 2 Br-CsCl-S film.
FIG. 8 is CsPb 0.55 Sn 0.45 I 2 Time-of-flight secondary ion mass spectrometry image of Br-CsCl-S film: left panel represents SO 4 2- Map image, right image represents Cl - The image is mapped. As can be seen from the figure: SO was detected in the material prepared 4 2- With Cl - And are uniformly distributed in the perovskite thin film.
FIG. 9 is CsPb 0.55 Sn 0.45 I 2 XRD pattern of Br-CsCl-S thin film. It can be seen that: standard PbSO 4 Peaks matched well with the corresponding XRD pattern, but no SnSO 4 Peak, indicating Pb in the surface coordination process of sulfuric acid 2+ +SO 4 2- →PbSO 4 By the method without SnSO 4 。
FIG. 10 shows CsPb of all-inorganic tin-lead binary perovskite thin films prepared in examples 1, 2 and 3 0.55 Sn 0.45 I 2 Br、CsPb 0.55 Sn 0.45 I 2 Br-CsCl、CsPb 0.55 Sn 0.45 I 2 Surface topography of Br-CsCl-S: the left panel represents CsPb prepared in example 3 0.55 Sn 0.45 I 2 Br-CsCl-S film, middle panel representing CsPb prepared in example 1 0.55 Sn 0.45 I 2 Br film (no more CsCl for bulk doping and no surface passivation), the right panel represents CsPb prepared in example 2 0.55 Sn 0.45 I 2 Br-CsCl film (no surface passivation treatment). As can be seen from fig. 10: "CsPb 0.55 Sn 0.45 I 2 Br-CsCl-S film "comparable to" CsPb 0.55 Sn 0.45 I 2 Br film of "and" CsPb 0.55 Sn 0.45 I 2 The Br-CsCl film has larger grain size, larger grain boundary density and less defects, and can be regarded as Cl - The doping and the coordination of the surface sulfate are beneficial to improving the crystallization process and the surface structure morphology of the inorganic perovskite film.
FIG. 11 shows CsPb of the all-inorganic tin-lead binary perovskite thin films prepared in examples 1, 2 and 3 0.55 Sn 0.45 I 2 Br、CsPb 0.55 Sn 0.45 I 2 Br-CsCl、CsPb 0.55 Sn 0.45 I 2 Static contact Angle of Br-CsCl-S. Therefore, the following steps are carried out: contact angle from initial CsPb 0.55 Sn 0.45 I 2 57.2 ℃ increase to CsPb for Br films 0.55 Sn 0.45 I 2 80.5 ℃ for Br-CsCl-S film, further confirming Cl - The doping and the coordination of the surface sulfate greatly increase the environmental tolerance and the bulk stability of the film, and the hydrophobicity of the film after the composite functionalization treatment is obviously improved.
Application example 3
All-inorganic tin-lead binary alloy perovskite solar cell ITO/PEDOT: PSS/CsPb 0.55 Sn 0.45 I 2 Br-CsCl-S/PC 61 The preparation method of BM/BCP/Ag is different from the application example 1 in that: in step S2, csPb was continuously prepared on the basis of the PEDOT: PSS film prepared in step S1 by the method of example 3 0.55 Sn 0.45 I 2 Br-CsCl-S film in the same manner as in application example 1.
Application examples 1-3 are based on CsPb 0.55 Sn 0.45 I 2 Br、CsPb 0.55 Sn 0.45 I 2 Br-CsCl、CsPb 0.55 Sn 0.45 I 2 The J-V curve of the all-inorganic tin-lead binary alloy perovskite solar cell of Br-CsCl-S is shown in a figure 12, and the corresponding data are shown in a table 4. As can be seen from Table 4: based on CsPb 0.55 Sn 0.45 I 2 The solar cell of Br-CsCl-S has the highest energy conversion efficiency of 10.39%. And is based on CsPb 0.55 Sn 0.45 I 2 Br、CsPb 0.55 Sn 0.45 I 2 Open circuit voltage (V) of Br-CsCl solar cell oc ) And the Fill Factor (FF) were both significantly improved, indicating that defects at the surface interface were effectively filled and energy loss was effectively suppressed by CsCl doping and sulfate passivation.
Figure 148717DEST_PATH_IMAGE004
Application examples 1-3 are based on CsPb 0.55 Sn 0.45 I 2 B、CsPb 0.55 Sn 0.45 I 2 Br-CsCl、CsPb 0.55 Sn 0.45 I 2 The efficiency attenuation spectra of the all-inorganic tin-lead binary perovskite solar cell of Br-CsCl-S are sequentially shown in figures 13-15 when the cell works for 2000 hours. As can be seen from fig. 13-15: based on CsPb 0.55 Sn 0.45 I 2 The Br solar cell still keeps over 72.6 percent of initial efficiency after 2000 hours of work, and the CsPb based solar cell is based on CsPb 0.55 Sn 0.45 I 2 The initial efficiency of more than 85 percent is still kept after the solar cell of Br-CsCl-S works for 2000 hours, and the CsPb is based on CsPb 0.55 Sn 0.45 I 2 The initial efficiency of the Br-CsCl-S solar cell is still kept above 92.5% after the Br-CsCl-S solar cell works for 2000 hours, which shows that the stability of the device is greatly improved by doping inorganic ions CsCl and passivating an interface.
Example 4
Full-inorganic tin-lead binary perovskite absorbing material CsPb 0.55 Sn 0.45 I 2 Br was prepared differently from example 1 in that: in the step (2), the annealing time 40s was changed to 0s, 10s, 20s, 30s, 50s, 60s, 90s, and 120s in this order, and the other steps were the same as in example 1.
60. CsPb obtained at different annealing time under different temperature 0.55 Sn 0.45 I 2 The photograph of the Br film is shown in FIG. 16. As can be seen from fig. 16: the deposited film was completely blackened after annealing at 60 ℃ for 40s, indicating the formation of a perovskite phase.
Example 5
Full-inorganic tin-lead binary perovskite absorbing material CsPb 0.55 Sn 0.45 I 2 Br preparation, which differs from example 1 in that: in the step (2), annealing at 60 ℃ for 40s is changed into step annealing: the same procedure as in example 1 was followed, except that annealing was performed at 60 ℃ for 2min, then at 100 ℃ for 2min, and then at 150 ℃ for 10 min.
CsPb obtained by annealing step by step 0.55 Sn 0.45 I 2 The XRD pattern of the Br film is shown in FIG. 17. As can be seen from fig. 17: the perovskite phase CsPb can still be formed after the step annealing 0.55 Sn 0.45 I 2 Br and the crystal form is greatly improved.
Comparative example 1
Full-inorganic tin-lead binary perovskite absorbing material CsPb 0.55 Sn 0.45 I 2 Br was prepared differently from example 1 in that: in the step (1), snF is not added any more 2 Otherwise, the same procedure as in example 1 was repeated.
Comparative application example 1
All-inorganic tin-lead binary alloy perovskite solar cell ITO/PEDOT: PSS/CsPb 0.55 Sn 0.45 I 2 Br/PC 61 The preparation method of BM/BCP/Ag is different from the application example 1 in that: in step S2, csPb was continuously prepared on the basis of the PEDOT: PSS film prepared in step S1 by the method of comparative example 1 0.55 Sn 0.45 I 2 Br film, the same as in application example 1.
The J-V curve of the obtained all-inorganic tin-lead binary alloy perovskite solar cell is shown in figure 18. Therefore, the following steps are carried out: the highest photoelectric conversion efficiency of the cell is 0.89%, which is far lower than that of the application example 1 based on CsPb 0.55 Sn 0.45 I 2 Br solar cell efficiency of 5.44%, indicating SnF 2 Is beneficial to inhibiting Sn in the all-inorganic tin-lead binary perovskite material 2+ Oxidation and device efficiency improvement.

Claims (7)

1. A preparation method of an all-inorganic tin-lead binary perovskite absorption material is characterized by comprising the following steps: the molecular formula is CsPb 1- x Sn x I 2 Br,0 < x < 1; the preparation steps are as follows:
(1) Synthesis of CsPb 1-x Sn x I 2 Br precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving into organic mixed solvent according to the molar ratio of 2: 1-x: 0.1, stirring and reacting for 10-12h at room temperature to obtain CsPb 1- x Sn x I 2 Br precursor solution; the organic mixed solvent consists of dimethyl sulfoxide and N, N-dimethylformamide in a volume ratio of (5-7) to (3-5), and the sum of the volumes of the dimethyl sulfoxide and the N, N-dimethylformamide is 10;
(2) Preparation CsPb 1-x Sn x I 2 Br film: csPb obtained in the step (1) 1-x Sn x I 2 Filtering Br precursor solution, depositing onto a substrate in inert atmosphere by solution deposition technology, dripping 50-100 μ L ethyl acetate onto the substrate deposited at last for 5-10 s per square centimeter, and annealing the substrate at 60 deg.C or higher for 40s or more to obtain the final product 1-x Sn x I 2 A Br film.
2. A preparation method of an all-inorganic tin-lead binary perovskite absorption material is characterized by comprising the following steps: the molecular formula is CsPb 1- x Sn x I 2 Br-CsCl,0 < x < 1; the preparation steps are as follows:
(1) Synthesis of CsPb 1-x Sn x I 2 Br-CsCl precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving the mixture into an organic mixed solvent according to the molar ratio of 2: 1-x: 0.1, and stirring the mixture at room temperature for reaction for 10 to 12 hours; adding cesium chloride CsCl into the solution, wherein the addition amount of the cesium chloride CsCl is CsI and PbI 2 、PbBr 2 、SnI 2 、SnBr 2 、SnF 2 Stirring and reacting for 1-2 h to obtain CsPb, wherein the mass percent of the CsPb is 1-10 wt% 1-x Sn x I 2 Br-CsCl precursor solution; the organic mixed solvent consists of dimethyl sulfoxide and N, N-dimethylformamide in a volume ratio of (5-7) to (3-5), and the sum of the volumes of the dimethyl sulfoxide and the N, N-dimethylformamide is 10;
(2) And preparation of CsPb 1-x Sn x I 2 Br-CsCl film: csPb obtained in the step (1) 1-x Sn x I 2 Filtering a Br-CsCl precursor solution, depositing the Br-CsCl precursor solution on a substrate in an inert atmosphere by a solution deposition technology, dripping 50-100 mu L of ethyl acetate on the substrate per square centimeter for 5-10 s deposited finally, and annealing the substrate deposited with a film at the temperature of more than or equal to 60 ℃ for more than or equal to 40s to obtain the all-inorganic tin-lead binary perovskite absorbing material CsPb 1-x Sn x I 2 Br-CsCl film.
3. A preparation method of an all-inorganic tin-lead binary perovskite absorption material is characterized by comprising the following steps: the molecular formula is CsPb 1- x Sn x I 2 Br-CsCl-S,0 < x < 1; the preparation steps are as follows:
(1) Synthesis of CsPb 1-x Sn x I 2 Br-CsCl precursor solution: mixing CsI with PbI 2 ∶PbBr 2 ∶SnI 2 ∶SnBr 2 ∶SnF 2 Dissolving the mixture into an organic mixed solvent according to the molar ratio of 2: 1-x: 0.1, and stirring the mixture at room temperature for reaction for 10 to 12 hours; adding cesium chloride CsCl into the solution, wherein the addition amount of the cesium chloride CsCl is CsI and PbI 2 、PbBr 2 、SnI 2 、SnBr 2 、SnF 2 Stirring and reacting for 1-2 h to obtain CsPb, wherein the mass percent of the CsPb is 1-10 wt% 1-x Sn x I 2 Br-CsCl precursor solution; the organic mixed solvent consists of dimethyl sulfoxide and N, N-dimethylformamide in a volume ratio of (5-7) to (3-5), and the sum of the volumes of the dimethyl sulfoxide and the N, N-dimethylformamide is 10;
(2) And preparation of CsPb 1-x Sn x I 2 Br-CsCl film: csPb obtained in the step (1) 1-x Sn x I 2 Filtering a Br-CsCl precursor solution, depositing the Br-CsCl precursor solution on a substrate in an inert atmosphere by a solution deposition technology, dripping 50-100 mu L of ethyl acetate on each square centimeter of the substrate for 5-10 s of final deposition, and annealing the substrate with a deposited film at the temperature of more than or equal to 60 ℃ for more than or equal to 40s to obtain CsPb 1-x Sn x I 2 A Br-CsCl film;
(3) And passivating the surface of the film: 1-4 mmol/mL methylamine sulfate isopropylamine solution obtained in step (2) is added with CsPb 1-x Sn x I 2 Spreading the Br-CsCl film for 10-30 s, then spin-coating, dripping toluene in the spin-coating process to remove excessive unreacted methylamine sulfate, and finally obtaining the all-inorganic tin-lead binary perovskite absorbing material-CsPb 1-x Sn x I 2 Br-CsCl-S film.
4. A method for preparing an all-inorganic tin-lead binary perovskite absorbing material as claimed in any one of claims 1 to 3, wherein: in the step (2), the solution deposition technology is a spin coating method, a slit coating method or a blade coating method.
5. The preparation method of the all-inorganic tin-lead binary perovskite absorption material as claimed in claim 4, wherein the spin coating method comprises the following specific steps: the precursor solution is spin-coated on the substrate for 10-30 s at the speed of 1000-2000 rpm, and then spin-coated for 30-60 s at the speed of 3000-5000 rpm.
6. The method for preparing the all-inorganic tin-lead binary perovskite absorption material as claimed in claim 3, wherein the method comprises the following steps: in the step (3), 100-300. Mu.L of toluene is dropped per square centimeter of substrate.
7. The method for preparing the all-inorganic tin-lead binary perovskite absorption material as claimed in claim 3, wherein the method comprises the following steps: in the step (3), spin coating is carried out for 30-60 s at 5000-8000 rpm.
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