CN110808335A - Preparation method and application of tin-lead binary perovskite film with preferred orientation growth - Google Patents

Preparation method and application of tin-lead binary perovskite film with preferred orientation growth Download PDF

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CN110808335A
CN110808335A CN201911066280.5A CN201911066280A CN110808335A CN 110808335 A CN110808335 A CN 110808335A CN 201911066280 A CN201911066280 A CN 201911066280A CN 110808335 A CN110808335 A CN 110808335A
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perovskite
tin
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CN110808335B (en
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杨丽丽
孙岩森
王奉友
孙云飞
范琳
庞振宇
杨景海
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Jilin Normal University
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Abstract

The invention relates to a preparation method of a tin-lead binary perovskite film with preferred orientation growth, which combines additive engineering and ultrasonic external force to process a precursor solution in the process of preparing the tin-lead binary perovskite film by a one-step spin coating method. By adding tartaric acid as a solid additive into the precursor solution, the crystallization speed can be delayed while the perovskite crystal structure is stabilized, and further ultrasonic treatment is adopted, so that the controllable preferential growth of different crystal faces can be realized in the growth process of the film crystal, and the crystallization quality of the tin-lead binary perovskite polycrystalline film is improved. The prepared tin-lead binary perovskite thin film with (224) preferred orientation is used for preparing an inverted structure perovskite solar cell, and the cell structure is ITO/PEDOT: PSS/MA0.9Cs0.1Pb0.75Sn0.25I3/PCBM/Ag. The photoelectric conversion efficiency of the perovskite solar cell is obviously improved. The preparation process for realizing the growth dynamics regulation and control of the tin-lead binary absorption layer thin film crystal has the characteristics of simple operation, safety, environmental protection and high repeatability.

Description

Preparation method and application of tin-lead binary perovskite film with preferred orientation growth
Technical Field
The invention belongs to the technical field of nano functional materials, and particularly relates to a preparation method of a preferred orientation growth tin-lead binary perovskite thin film, which is characterized by regulating and controlling the growth process of a low-toxicity tin-lead binary perovskite absorption layer, realizing controllable preferred orientation growth from a (110) crystal face to a (224) crystal face and constructing a corresponding perovskite solar cell.
Background
Due to the excellent photoelectric properties of the polycrystalline perovskite material, such as higher bulk mobility, micron-sized diffusion length, larger absorption coefficient and the like, the polycrystalline perovskite material can be widely applied to the emerging fields of solar cells, light emitting diodes, quantum dots and the like. To date, perovskite solar cells have attracted extensive attention from numerous researchers with continuous breakthrough photovoltaic characteristics at low manufacturing costs. In order to further realize the preparation of high-performance devices, researchers find that the improvement of the quality of an absorption layer, the optimization of a charge transport layer material, the interface characteristics and the like are important means for promoting the continuous improvement of the photovoltaic performance of the high-performance devices. In addition, realizing the preferential growth of different crystal faces of the perovskite polycrystalline film also becomes one of the important research directions for improving the photoelectric properties of the absorption layer. Therefore, effective measures are taken to regulate and control the preferred orientation of the crystal face, and the photovoltaic characteristics of the device are expected to be further improved. Meanwhile, in order to accelerate the commercialization process, the development of a novel low-toxicity/non-toxic perovskite material system is also very meaningful.
At present, tin is one of the most promising materials for replacing a toxic substance lead to realize the preparation of a high-performance perovskite absorption layer. However, studies have shown that Sn is present even in the case of very low oxygen contents2+Is still easily oxidized into Sn4+Can be brokenStructure of bad perovskite, in addition, solutes MAI and SnI2The combination of the two components leads to an excessively fast crystallization rate, and finally limits the improvement of the photovoltaic performance of the tin-based and tin-lead binary device. That is, how to overcome or suppress the adverse effects of the above phenomena to achieve the production of high-quality absorption layers and high-performance photovoltaic devices is one of the technical problems facing the present time. Through analysis, researchers find that compared with the traditional lead-based perovskite material system, for a system with an abnormally rapid crystallization speed, such as a tin-based and tin-lead binary perovskite absorption layer, in the process of preparing the absorption layer thin film by utilizing a one-step spin coating process, the regulation of crystal growth kinetics by controlling the spin coating process is almost impossible, and the quality optimization of the absorption layer thin film is difficult to further realize. In contrast, the crystal growth kinetics of the polycrystalline thin film is expected to be changed by adopting effective means to regulate and control the state and the characteristics of the perovskite precursor solution. Particularly for perovskite polycrystalline materials, the different degrees of preferred orientation of crystal planes greatly influence the transmission and separation of carriers in the thin film. It is known that in the preparation process of the polycrystalline perovskite thin film, the intermediate is adjusted and external force is applied by accurately controlling the thermal temperature gradient, so that the method is an important method which is expected to realize the preferential growth of different crystal faces of the perovskite polycrystalline material. For the perovskite system, the perovskite structure can be stabilized while the quality of the film is improved to a certain extent by adding a proper amount of complexing agent to a precursor solution to regulate the formation of an intermediate. However, how to further realize controllable preferred orientation growth of different crystal planes while ensuring the quality of the absorption layer film so as to further improve the photoelectric properties of the perovskite absorption layer is another technical problem currently faced. At present, a few exploratory works such as element doping, additive engineering and the like are carried out in a lead perovskite system and realize the preferential growth of different crystal faces, but the controllable preferential growth of different crystal faces is still difficult to realize, that is, the realization of the controllable preferential growth of crystals is expected to further improve the photovoltaic performance of devices of the devices on the premise of not sacrificing the quality of films. Therefore, it is urgently needed to adopt an effective measure to realize the controllability of the tin-lead binary absorption layer filmThe preferred growth of the silicon nitride layer provides a reliable preparation scheme for further improving the performance of the device.
Disclosure of Invention
Aiming at the problems of poor photoelectric characteristics of a film and a large amount of Sn caused by the over-high crystallization speed of the conventional tin-lead low-toxicity binary perovskite polycrystalline material system2+Is oxidized to Sn4+The performance improvement of the perovskite photovoltaic device is greatly limited by the problems that the three-dimensional perovskite structure can be seriously damaged and the like. Therefore, the invention provides a preparation method of a tin-lead binary perovskite thin film with preferred orientation growth, which realizes controllable preferred orientation growth from a (110) crystal face to a (224) crystal face and is used for further improving the photoelectric property of the thin film so as to improve the photovoltaic performance of a device.
The technical scheme adopted by the invention is as follows: a preparation method of a tin-lead binary perovskite film with preferred orientation growth is provided, the method improves the physical and chemical properties of an absorption layer film by using a functional additive tartaric acid and combining the use of ultrasonic external force, and further improves the photovoltaic characteristics of a device, and comprises the following steps:
1. PSS preparation: carrying out ultraviolet ozone treatment on the clean ITO transparent conductive glass for 20 minutes to improve the surface wettability and remove functional groups such as-OH on the surface of the ITO transparent conductive glass, dripping 80 mu of LPEDOT (AI4083) original solution on the ITO surface after the ITO is cooled to room temperature, standing for 5-15s, then carrying out low-speed spin coating for 10s at 500rpm and high-speed spin coating for 60s at 4000rpm, then heating the material on a baking table at 140 ℃ for 10 minutes to finish the preparation of a hole transport layer PEDOT (PSS), finally carrying out ultraviolet ozone treatment on the prepared PEDOT (PSS) film for 20 minutes, cooling to room temperature, and then moving to a glove box for later use.
2. MA containing tartaric acid as a solid additive0.9Cs0.1Pb0.75Sn0.25I3Preparing a tin-lead binary perovskite precursor solution: 1.105mmol of lead iodide and 1.1mmol of methyl ammonium iodide are respectively weighed in a glove box with the oxygen content of 5.3ppm and the water vapor content of 4.3ppm and dissolved in a mixed solvent containing 700 mu LN, N-dimethylformamide and 300 mu L of dimethyl sulfoxide to prepare 1.1M MAPbI3Perovskite solution A1, title1.1M MASnI was prepared by dissolving 1.1mmol of methylammonium iodide and 1.105mmol of stannous iodide in a mixed solvent of 800. mu.L of N, N-dimethylformamide and 200. mu.L of dimethyl sulfoxide3Perovskite solution B1, 1.1mmol of cesium iodide and 1.105mmol of stannous iodide were similarly weighed and dissolved in a mixed solvent of 800. mu.L of LN, N-dimethylformamide and 200. mu.L of dimethyl sulfoxide to prepare 1.1M CsSnI3Perovskite solution C1, adding 5-15% mmol of solid additive tartaric acid into the prepared B1 and C1 solutions respectively to prepare MASnI containing tartaric acid3Perovskite solution B2 and CsSnI3The perovskite solution C2, then respectively stirring the prepared A1, B2 and C2 perovskite solutions for 30 minutes at room temperature, mixing 750 mu LA1,150 mu L B2 and 100 mu LC2 perovskite solutions after the solute is fully dissolved to prepare 1mL of MA containing a solid additive tartaric acid0.9Cs0.1Pb0.75Sn0.25I3The tin-lead binary perovskite precursor solution.
3. Precursor ultrasonic treatment: the MA prepared in the step 2 and containing the solid additive tartaric acid0.9Cs0.1Pb0.75Sn0.25I3The tin-lead binary perovskite precursor solution is placed in a bottle, the bottle mouth is tightly sealed, then the bottle is moved out of a glove box and further subjected to ultrasonic treatment, the ultrasonic frequency of an ultrasonic machine is set to be 45KHz, the ultrasonic power is 60%, the temperature of water in the ultrasonic machine is controlled to be 20-35 ℃ in the ultrasonic process, and the tin-lead binary perovskite precursor solution is subjected to ultrasonic treatment for 5-25 minutes. In the ultrasonic treatment process in the step 3, when the ultrasonic time is 10 minutes, the preferential growth of the crystal face (110) still dominates, but the growth condition of the crystal face (224) is improved, and when the ultrasonic time is controlled to 15 minutes, the complete preferential growth of the crystal face (224) is facilitated.
4. Preparing a tin-lead binary perovskite thin film: preparing a tin-lead binary perovskite film on a PEDOT (patterned sapphire substrate) PSS (patterned sapphire substrate) film by adopting a one-step spin-coating process, and extracting 75 mu L of MA (maleic anhydride) containing tartaric acid after ultrasonic treatment in the step 30.9Cs0.1Pb0.75Sn0.25I3Dripping the tin-lead binary perovskite precursor solution on the PEDOT (PSS) film prepared in the step 1, standing for 0-10s, and then firstlySpin coating at 500rpm for 3s, spin coating at 4000rpm for 30s, adding 400 μ L chlorobenzene dropwise 15s before the end of the procedure, and heating on a 120 deg.C baking table for 10 min to obtain MA0.9Cs0.1Pb0.75Sn0.25I3Perovskite absorption layer film.
The thickness of the PEDOT/PSS hole transport layer is 40-80 nm.
The MA is0.9Cs0.1Pb0.75Sn0.25I3The thickness of the perovskite layer is 400-600 nm.
The invention has the beneficial effects that:
1. according to the Lewis acid-base theory, in the kinetics of crystal nucleation, Lewis base with a melting/boiling point higher than that of liquid dimethyl sulfoxide (the boiling point is 189 ℃) is added into a precursor solution to retard the crystallization rate of a perovskite polycrystalline thin film and improve the film forming quality of the perovskite thin film to a certain extent, therefore, the inventor introduces tartaric acid (the melting point is 204-2/SnI2TA and PbI2/SnI2And the crystal quality of the tin-lead binary perovskite absorption layer is further regulated and controlled in the form of DMSO two intermediates, the surface appearance of the tin-lead binary perovskite film is improved, and the crystal structure of the tin-lead binary perovskite is stabilized. Furthermore, the introduction of tartaric acid avoids SnF-like behavior compared to the commonly used solid additive stannous fluoride2In this way, the surface appearance of the film can be improved due to the phase separation phenomenon caused by introducing an additional tin source, and meanwhile, the inventor also utilizes ultrasonic external force to carry out ultrasonic treatment on the tin-lead binary perovskite precursor solution to ensure that the chelating agent tartaric acid and the solute PbI2/SnI2The interaction between the two is more sufficient. The combined use of the two modes can change PbI2/SnI2The growth sites influence the subsequent formation mode of the perovskite crystal, and induce the formation energy of different crystal planes to change in the crystal growth process, so that the conversion of preferred growth orientation of each crystal plane is realized, and the effect of improving the photoelectric property of the coefficient layer film is achieved.
2. Compared with the prior art, the multifunctional chelating agent tartaric acid and the ultrasonic external force combination strategy can effectively regulate and control the crystal growth kinetics of the tin-lead binary perovskite polycrystalline material system, stabilize the tin-lead binary perovskite crystal structure and improve the crystallization quality of a film thereof, and simultaneously realize effective regulation and control of preferential growth of crystal faces from (110) to (224) of a tin-lead binary perovskite absorption layer by regulating and controlling ultrasonic frequency, ultrasonic power, ultrasonic time and water temperature in an ultrasonic machine, thereby improving the transmission characteristic of carriers in the tin-lead binary perovskite film. In addition, the tartaric acid has low toxicity, low price and stable self-attribute in the air, so that the tartaric acid becomes an ideal additive with high cost performance, and meanwhile, the ultrasonic technology is safe to use, convenient to operate and low in cost, and the mode of combining the ultrasonic technology and the ultrasonic technology is favorable for accelerating the large-scale production process of the high-performance low-toxicity tin-lead binary perovskite photovoltaic device.
3. The method selects Tartaric Acid (TA) with chelation and oxidation resistance as an additive. The additive can react with solute SnI2/PbI2Additional intermediates are formed. Since solid tartaric acid has a higher melting point than DMSO, PbI2/SnI2The TA intermediate exists for a longer time, and can further improve the growth kinetics of the crystal. In addition, Sn in solution2+Is oxidized to Sn4+The degree of the perovskite thin film is inhibited, the defect state density in the thin film is reduced, the perovskite crystal structure is stabilized, and the photoelectric property of the perovskite thin film is further improved. When the addition amount of tartaric acid as a solid additive is 10% mmol, the oxidation resistance state of the precursor solution can be effectively guaranteed, and the prepared MA cannot be caused0.9Cs0.1Pb0.75Sn0.25I3Phase separation of the film. The tartaric acid additive engineering strategy has the characteristics of simple operation, environmental protection, safety, low cost and the like.
4. The invention further applies external force to MA0.9Cs0.1Pb0.75Sn0.25I3Performing ultrasonic treatment on the perovskite precursor solution to ensure that the chelating agent tartaric acid and the solute PbI2/SnI2The effect between the two is more sufficient to change PbI2/SnI2The crystal nucleus forming mode changes the formation of different crystal faces in the crystal growth process, and the preferential growth of each crystal face can be realized. Meanwhile, ultrasonic conditions are controlled and optimized, and when the ultrasonic frequency is 45KHz, the ultrasonic power is 60 percent, the water temperature is 25 ℃, and the ultrasonic time reaches 15 minutes, the MA is realized on the ITO/PEDOT/PSS substrate0.9Cs0.1Pb0.75Sn0.25I3Complete conversion of the preferred orientation of the film from the (110) crystal plane to the (224) crystal plane.
5. The invention is in MA0.9Cs0.1Pb0.75Sn0.25I3Tartaric acid additive is added into the precursor solution, and the precursor solution is subjected to ultrasonic treatment, so that MA is realized0.9Cs0.1Pb0.75Sn0.25I3The preferential orientation of the crystal face (110) to the crystal face (224) of the perovskite absorption layer film is changed, so that the photoelectric conversion efficiency of the perovskite solar cell photovoltaic device is not changed from the original MA0.9Cs0.1Pb0.75Sn0.25I3The 12.44% of the precursor solution added with any additive and subjected to ultrasonic treatment is increased to 15.59%, the hysteresis phenomenon of the device is inhibited, and the long-term stability of the device is improved. The preparation process of the polycrystalline perovskite thin film and the photovoltaic device is simple and controllable, green and environment-friendly, and provides technical support for controllable preferential growth of low-toxicity polycrystalline perovskite thin film crystals.
Drawings
FIG. 1 is an XRD spectrum of a perovskite thin film prepared by the invention on an ITO/PEDOT: PSS substrate.
FIG. 2 is a scanning graph of the plane and cross-section of the perovskite thin film prepared by the present invention on a PEDOT: PSS thin film.
FIG. 3 shows ITO/PEDOT: PSS/MA prepared according to the invention0.9Cs0.1Pb0.75Sn0.25I3the/PCBM/Ag structure is prepared into a device structure diagram of a device.
FIG. 4 shows ITO/PEDOT: PSS/MA prepared according to the invention0.9Cs0.1Pb0.75Sn0.25I3And preparing the IV pattern of the device by the/PCBM/Ag structure.
FIG. 5 is a graph of the efficiency decay of an unpackaged device tested in an atmospheric environment with a humidity of 40 + -5% RH and a temperature of 25 deg.C for one month for perovskite devices prepared according to the present invention.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
A method for preparing a tin-lead binary perovskite film with preferred orientation growth comprises the following steps:
1. PSS preparation: carrying out ultraviolet ozone treatment on the cleaned ITO transparent conductive glass for 20 minutes to improve the surface wettability and remove functional groups such as-OH on the surface of the ITO transparent conductive glass, dripping 80 mu LPEDOT (AI4083) original solution on the ITO surface after the ITO is cooled to room temperature, standing for 5-15s, then carrying out low-speed spin coating at 500rpm for 10s and high-speed spin coating at 4000rpm for 60s, and then heating the material on a scorching table at 140 ℃ for 10 minutes. And carrying out ultraviolet ozone treatment on the prepared PEDOT/PSS film for 20 minutes, cooling to room temperature, and then transferring to a glove box for later use.
2. MA containing tartaric acid as a solid additive0.9Cs0.1Pb0.75Sn0.25I3Preparing a tin-lead binary perovskite precursor solution: 1.105mmol of lead iodide and 1.1mmol of methyl ammonium iodide are respectively weighed in a glove box with the oxygen content of 5.3ppm and the water vapor content of 4.3ppm and dissolved in a mixed solvent containing 700 mu LN, N-dimethylformamide and 300 mu L of dimethyl sulfoxide to prepare 1.1M MAPbI3Perovskite solution A1, 1.1mmol of methyl ammonium iodide and 1.105mmol of stannous iodide were weighed and dissolved in a mixed solvent of 800. mu.L of LN, N-dimethylformamide and 200. mu.L of dimethyl sulfoxide to prepare 1.1M of MASnI3Perovskite solution B1, 1.1mmol of cesium iodide and 1.105mmol of stannous iodide were similarly weighed and dissolved in a mixed solvent of 800. mu.L of LN, N-dimethylformamide and 200. mu.L of dimethyl sulfoxide to prepare 1.1M CsSnI3Perovskite solution C1, adding 10% mmol solid additive tartaric acid into the above prepared perovskite solutions B1 and C1 respectively to obtain MASnI containing tartaric acid3Perovskite solution B2 and CsSnI3The perovskite solution C2, then respectively stirring the prepared A1, B2 and C2 perovskite solutions for 30 minutes at room temperature, mixing 750 mu LA1,150 mu L B2 and 100 mu LC2 perovskite solutions after the solute is fully dissolved to prepare 1mL of MA containing a solid additive tartaric acid0.9Cs0.1Pb0.75Sn0.25I3The tin-lead binary perovskite precursor solution.
3. Precursor ultrasonic treatment: and (3) placing the prepared tin-lead binary perovskite precursor solution containing tartaric acid in the step (2) into a bottle, sealing and tightly sealing the bottle opening, moving out of the glove box, and further performing ultrasonic treatment, wherein the ultrasonic frequency of an ultrasonic machine is set to be 45KHz, the ultrasonic power is 60%, the temperature of water in the ultrasonic machine is controlled to be 25 ℃ in the ultrasonic process, and the temperature of water in the ultrasonic machine is controlled to be 25 ℃ in the ultrasonic process, so that the tin-lead binary perovskite precursor solution is subjected to ultrasonic treatment for 15 minutes.
4. Preparing a tin-lead binary perovskite thin film: preparing a tin-lead binary perovskite thin film on a PEDOT (PSS) thin film by adopting a one-step spin coating process, extracting 75 mu L of solution prepared in the step 3, dripping the solution on the PEDOT (PSS) thin film prepared in the step 1, standing for 0-10s, firstly spin-coating at a low speed of 500rpm for 3s, then spin-coating at a high speed of 4000rpm for 30s, dripping 400 mu L of chlorobenzene 15s before the procedure is finished, and finally heating on a scorching table at 120 ℃ for 10 min to obtain MA (methyl methacrylate)0.9Cs0.1Pb0.75Sn0.25I3Perovskite absorption layer film.
5、MA0.9Cs0.1Pb0.75Sn0.25I3The application of the perovskite absorption layer thin film in a photovoltaic device.
①, binary tin-lead perovskite MA0.9Cs0.1Pb0.75Sn0.25I3The perovskite photovoltaic device is prepared by dissolving 20mgPCBM powder in 1mL chlorobenzene in a glove box to prepare PCBM solution, taking out 65 mu LPCBM solution, and dripping the solution with the geometric structure of ITO/PEDOT: PSS/MA in step 40.9Cs0.1Pb0.75Sn0.25I3After the perovskite thin film substrate is kept still for 5s, the low-speed spin coating is carried out at 500rpm for 3s, and the high-speed spin coating is carried out at 2000rpmAnd (4) coating for 30s to complete the preparation of the electron transport layer, and finally evaporating a 150nm silver metal electrode under the thermal evaporation condition.
②, preparing a tin-lead binary perovskite coefficient layer film comparison sample without additives and a photovoltaic device comparison sample thereof, keeping the preparation process in the step 1 unchanged, and carrying out comparison on MAPbI in the step 23，CsSnI3Solutions and MASnI3The ratio of perovskite solution preparation is kept constant, but by adding CsSnI3And MASnI3And (3) completing the preparation of a comparison sample solution without adding any additive into the solution, keeping the rest processes in the step 2 unchanged, then carrying out ozone treatment on the PEDOT/PSS base material prepared in the step 1 for 20 minutes, cooling to room temperature, and then moving to a glove box. By utilizing a one-step spin coating preparation process, 75 mu L of perovskite precursor solution obtained in the step 2 is extracted from a PEDOT (PSS) film as a substrate, stands for 5s, then is spin-coated at a low speed of 500rpm for 3s, then is spin-coated at a high speed of 4000rpm for 30s for treatment, 400 mu L of chlorobenzene is dropwise added 15s before the procedure is finished, and finally, the mixture is heated on a 120 ℃ baking table for 10 minutes to finish the MA (methyl methacrylate) without additives or containing stannous fluoride0.9Cs0.1Pb0.75Sn0.25I3And (4) preparing the perovskite absorption layer thin film, and preparing a comparison device without changing the preparation process in the step (4).
③, preparing a stannous fluoride tin lead binary perovskite coefficient layer film comparison sample containing a solid additive and a photovoltaic device comparison sample thereof, keeping the preparation process in the step 1 unchanged, and carrying out comparison on MAPbI in the step 23，CsSnI3Solutions and MASnI3The ratio of perovskite solution preparation is kept constant, but by adding CsSnI3And MASnI3And (3) adding 10% mmol of solid additive stannous fluoride into the solution to complete the preparation of the comparison sample solution, keeping the rest processes in the step (2) unchanged, then carrying out ozone treatment on the PEDOT (PSS) substrate material prepared in the step (1) for 20 minutes, cooling to room temperature, and then transferring to a glove box. By utilizing a one-step spin coating preparation process, 75 mu L of perovskite precursor solution obtained in the step 2 is extracted from a PEDOT (PSS) film substrate, stands for 5s, is spin-coated at a low speed of 500rpm for 3s, is spin-coated at a high speed of 4000rpm for 30s, is treated, is dropwise added with 400 mu L of chlorobenzene 15s before the procedure is finished, and is finally baked on a 120 ℃ scorching tableHeating for 10 min to complete additive-free/stannous fluoride-containing MA0.9Cs0.1Pb0.75Sn0.25I3And (4) preparing the perovskite absorption layer thin film, and preparing a comparison device without changing the preparation process in the step (4).
④ MA containing additive tartaric acid with different ultrasonic time0.9Cs0.1Pb0.75Sn0.25I3Preparation of perovskite absorption layer thin film comparative sample: keeping the preparation processes in the step 1 and the step 2 unchanged, regulating and controlling the ultrasonic time to 10 minutes in the step 3, and keeping the other processes unchanged to prepare the MA containing the tartaric acid solid additive for different ultrasonic times0.9Cs0.1Pb0.75Sn0.25I3Preparation of perovskite absorber layer thin film comparative sample.
Effect verification
The XRD pattern of the above films on an ITO/PEDOT: PSS substrate is shown in FIG. 1, and it can be seen in the left image that stannous fluoride (SnF) was added with the solid additive in step 5 ③, as compared to the control sample without any additive in step 5 ②2) And Tartaric Acid (TA) in step 2 at MA0.9Cs0.1Pb0.75Sn0.25I3The introduction of the perovskite precursor solution improves the peak intensity of each crystal face diffraction peak of the XRD spectrum of the corresponding tin-lead binary perovskite film to different degrees, which can show that the Sn is inhibited2+Is oxidized to Sn4+The degree of (2) can play a role in improving the crystal quality of the thin film, but the peak intensity of each crystal plane diffraction peak of the tin-lead binary perovskite thin film containing tartaric acid in the step 2 is stronger, and simultaneously, the tin-lead binary perovskite thin film is compared with the control in the step 5 ② and the SnF in the step 5 ③2For the sample film, the diffraction peak intensities of the (112) crystal plane and the (224) crystal plane of the TA sample in step 2 are also improved to some extent, which can indicate that PbI2/SnI2The formation of TA intermediate can further influence the growth kinetics of the crystal and can improve the crystallization quality of the film, and the phenomenon also indirectly shows that the use of the chelating agent tartaric acid can greatly reduce the formation energy of the (112) crystal face and the (224) crystal face, and promote the growth of several crystals along the crystal faceIn the right graph, the peak intensity of the diffraction peaks of the crystal face (110) and the crystal face (220) of the prepared film is reduced when ultrasonic waves are introduced in the step 5 ④ to process the precursor solution containing tartaric acid for 10 minutes, the peak intensity of the diffraction peaks of the crystal face (112) and the crystal face (224) is gradually enhanced, and the preferential orientation of the diffraction peaks of the crystal face (224) is generated when the ultrasonic time is regulated to 15 minutes in the step 3.
FIG. 2 shows the plan and cross-sectional scan patterns of the PEDOT PSS films obtained from the films described above, from which it can be seen that MA, when no additives were added for step 5 ②0.9Cs0.1Pb0.75Sn0.25I3The film prepared from the perovskite precursor solution has more pores on the surface and poor morphology, as shown in (a) and (b) of FIG. 2, MA added with stannous fluoride for step 5 ③0.9Cs0.1Pb0.75Sn0.25I3For the sample prepared from the perovskite precursor solution, as shown in (d) and (e) of fig. 2, the number of holes existing on the surface of the film is reduced, but the surface appearance of the rough film is not obviously improved, and the absorption layer film with large fluctuation and serious roughness is formed. For step 2, MA tartaric acid was added0.9Cs0.1Pb0.75Sn0.25I3For the samples prepared from the perovskite precursor solution, as shown in FIG. 2 (g) (h), the above problems are all well improved, and accompanied by the phenomenon of increased grain size, when for MA with tartaric acid added, in step 30.9Cs0.1Pb0.75Sn0.25I3When the perovskite precursor solution is further subjected to ultrasonic treatment for 15 minutes, the grain size of the prepared film is further increased, and the surface morphology is also improved to a certain extent, as shown in (j) and (k) in fig. 2. Additives and ultrasound can be seen in the cross-sectional viewThe use of external force makes the tendency of crystal grains to grow in the vertical direction more obvious as shown in (i) and (l) in fig. 2, and facilitates the transport of carriers.
Shown in FIG. 3 is a graph of ITO/PEDOT: PSS/MA0.9Cs0.1Pb0.75Sn0.25I3The structure of the device is prepared from a/PCBM/Ag structure, wherein/PEDOT, PSS is a hole transport layer, PCBM is an electron transport layer, and PEDOT, PSS and PCBM respectively adopt the same preparation process for samples which are not added with any additive and contain stannous fluoride and tartaric acid so as to compare MA of different additives0.9Cs0.1Pb0.75Sn0.25I3The photoelectric property of the absorption layer film and the photovoltaic performance of the device.
FIG. 4 shows a graph of ITO/PEDOT: PSS/MA0.9Cs0.1Pb0.75Sn0.25I3IV pattern of device prepared from/PCBM/Ag structure, the upper left figure is IV pattern of device prepared from control perovskite thin film in step 5 ②, and the upper right figure is IV pattern of device prepared from step 5 ③ containing SnF2The reason why the photoelectric conversion efficiency of the devices IV prepared from the perovskite thin film, the lower left graph is the device IV prepared from the TA-containing perovskite thin film in the step 2, and the lower right graph is the device IV prepared from the thin film obtained by subjecting the TA solution to ultrasonic treatment for 15 minutes in the step 3 is that the photoelectric conversion efficiency of the devices is gradually increased from the upper left, upper right, lower left to lower right graphs, is that when MA is used0.9Cs0.1Pb0.75Sn0.25I3SnF is introduced into perovskite precursor solution2And TA, the presence of these functional additives can affect the MA, a binary perovskite0.9Cs0.1Pb0.75Sn0.25I3State of precursor solution due to SnF2The reducibility of TA improves the film forming quality of the absorption layer film, and suppresses Sn2+Oxidation to Sn4+Besides, the chelating property of TA also improves the surface appearance of the film, which improves the interface characteristic between a PEDOT (PSS) hole transport layer and a perovskite layer, and further influences the improvement of open-circuit voltage Voc, short-circuit current density Jsc and filling factor FFThe introduction of the TA film causes the change of the preferred orientation of each crystal face of the TA film, which affects the transmission characteristics of carriers, further affects the photovoltaic characteristics of the device, and affects the collection of the carriers, which affects the hysteresis phenomenon of the device to a certain extent.
As shown in FIG. 5, which is a graph of the efficiency decay of unpackaged devices over one month of the devices tested in an atmospheric environment with a humidity of 40 + -5% RH at 25 deg.C to characterize the stability of the devices, SnF in step 5 ③2And the use of TA in the perovskite precursor solution in the step 2 and the further treatment of the perovskite precursor solution containing TA after ultrasonic treatment for 15 minutes in the step 3 can lead to the gradual reduction of the efficiency attenuation speed of the device, which shows that the improvement of the quality of the thin film of the absorption layer, the increase of the grain size, the reduction of the defect state density and the preferential growth of the (224) crystal face all improve the stability of the device to different degrees.

Claims (6)

1. A method for preparing a tin-lead binary perovskite film with preferred orientation growth is characterized by comprising the following steps: the method comprises the following steps:
(1) and preparing a substrate material PEDOT: carrying out ultraviolet ozone treatment on the clean ITO transparent conductive glass for 20 minutes to improve the surface wettability and remove functional groups such as-OH on the surface of the ITO transparent conductive glass, dripping 80 mu LPEDOT (AI4083) original solution on the ITO surface and standing for 5-15s after the ITO is cooled to room temperature, then carrying out low-speed spin coating for 10s at 500rpm and high-speed spin coating for 60s at 4000rpm, then heating the material on a baking table at 140 ℃ for 10 minutes to finish the preparation of a hole transport layer PEDOT (PSS), finally carrying out ultraviolet ozone treatment on the prepared PEDOT (PSS) film for 20 minutes, cooling to room temperature and then transferring to a glove box for later use;
(2) MA containing tartaric acid as a solid additive0.9Cs0.1Pb0.75Sn0.25I3Preparing a tin-lead binary perovskite precursor solution: 1.105mmol of lead iodide and 1.1mmol of methyl ammonium iodide are respectively weighed and dissolved in a glove box with the oxygen content of 5.3ppm and the water vapor content of 4.3ppm to form a solution containing 700 mu LN, N-dimethylformamide and 300 muPreparing 1.1M MAPbI in mixed solvent of L dimethyl sulfoxide3Perovskite solution A1, 1.1mmol of methyl ammonium iodide and 1.105mmol of stannous iodide were weighed and dissolved in a mixed solvent of 800. mu.L of LN, N-dimethylformamide and 200. mu.L of dimethyl sulfoxide to prepare 1.1M of MASnI3Perovskite solution B1, 1.1mmol of cesium iodide and 1.105mmol of stannous iodide were similarly weighed and dissolved in a mixed solvent of 800. mu.L of LN, N-dimethylformamide and 200. mu.L of dimethyl sulfoxide to prepare 1.1M CsSnI3Perovskite solution C1, adding 5-15% mmol of solid additive tartaric acid into the prepared B1 and C1 solutions respectively to prepare MASnI containing tartaric acid3Perovskite solution B2 and CsSnI3The perovskite solution C2, then respectively stirring the prepared A1, B2 and C2 perovskite solutions for 30 minutes at room temperature, mixing 750 mu LA1,150 mu L B2 and 100 mu L C2 perovskite solutions after the solute is fully dissolved to prepare 1mL of MA containing a solid additive tartaric acid0.9Cs0.1Pb0.75Sn0.25I3The tin-lead binary perovskite precursor solution;
(3) and precursor ultrasonic treatment: the MA prepared in the step 2 and containing the solid additive tartaric acid0.9Cs0.1Pb0.75Sn0.25I3The tin-lead binary perovskite precursor solution is placed in a bottle, the bottle mouth is tightly sealed, then the bottle is moved out of a glove box and further subjected to ultrasonic treatment, the ultrasonic frequency of an ultrasonic machine is set to be 45KHz, the ultrasonic power is 60%, the temperature of water in the ultrasonic machine is controlled to be 20-35 ℃ in the ultrasonic process, and the tin-lead binary perovskite precursor solution is subjected to ultrasonic treatment for 5-25 minutes;
(4) preparing a tin-lead binary perovskite film: preparing a tin-lead binary perovskite film on a PEDOT (patterned sapphire substrate) PSS (patterned sapphire substrate) film by adopting a one-step spin-coating process, and extracting 75 mu L of MA (maleic anhydride) containing tartaric acid after ultrasonic treatment in the step 30.9Cs0.1Pb0.75Sn0.25I3Dropping the tin-lead binary perovskite precursor solution on the PEDOT (PSS) film prepared in the step 1, standing for 0-10s, spin-coating at a low speed of 500rpm for 3s, then spin-coating at a high speed of 4000rpm for 30s, dropping 400 mu L of chlorobenzene 15s before the procedure is finished, and finally heating on a 120 ℃ scorching table for 10 minClock, obtain MA0.9Cs0.1Pb0.75Sn0.25I3Perovskite absorption layer film.
2. The method for preparing a tin-lead binary perovskite thin film with preferred orientation growth according to claim 1, which is characterized in that: when the addition amount of the solid additive tartaric acid in the tin-based precursor solution prepared in the step 2 is preferably 10% mmol, the optimal antioxidant effect can be obtained, and phase separation is not caused.
3. The method for preparing a tin-lead binary perovskite thin film with preferred orientation growth according to claim 1, which is characterized in that: the ultrasonic time in the step 3 is preferably 15 minutes, so that MA can be completely realized0.9Cs0.1Pb0.75Sn0.25I3The preferential growth of the crystal face of the perovskite thin film (224).
4. The method for preparing a tin-lead binary perovskite thin film with preferred orientation growth according to claim 1, which is characterized in that: the thickness of the PEDOT/PSS hole transport layer is 40-80 nm.
5. The method for preparing a tin-lead binary perovskite thin film with preferred orientation growth according to claim 1, which is characterized in that: the MA is0.9Cs0.1Pb0.75Sn0.25I3The thickness of the perovskite thin film is 400-600 nm.
6. MA with preferential growth according to claim 10.9Cs0.1Pb0.75Sn0.25I3The perovskite absorption layer film is used on a photovoltaic device, and can improve the photoelectric property of the absorption layer and the photovoltaic performance and stability of the device.
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