CN117711950A - Alpha-phase CsPbI 3 Film and method for producing the same - Google Patents

Alpha-phase CsPbI 3 Film and method for producing the same Download PDF

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CN117711950A
CN117711950A CN202410164804.9A CN202410164804A CN117711950A CN 117711950 A CN117711950 A CN 117711950A CN 202410164804 A CN202410164804 A CN 202410164804A CN 117711950 A CN117711950 A CN 117711950A
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cspbi
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CN117711950B (en
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李欣怡
毕海
张钰
董美秋
郭扬武
于紫薇
王魁
杨兴龙
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Ji Hua Laboratory
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Abstract

The application relates to the field of perovskite thin films, and mainly relates to an alpha-phase CsPbI 3 A film and a method for preparing the same. The method comprises the following steps of: (1) CsI and PbI 2 Dissolving in solvent to obtain CsPbI 3 A precursor solution; (2) CsPbI 3 Spin-coating the precursor solution on the surface of a substrate, standing for the first time, dripping diphenyl phosphinoyl chloride solution on the substrate, standing for the second time until the color of the surface of the substrate changes from yellow to black, and rotating the substrate; (3) Annealing the substrate to obtain the alpha phase CsPbI 3 A film. Alpha phase CsPbI of the present application 3 The preparation method of the film has the advantages of convenient operation, low cost, good film forming property, easy achievement of conditions and convenient mass production of factories. Alpha-phase CsPbI prepared by the method 3 Thin film crystallizationThe surface is compact and smooth, the phase stability is high, and the method has great significance for the expandable production of the photovoltaic material.

Description

Alpha-phase CsPbI 3 Film and method for producing the same
Technical Field
The application relates to the field of perovskite thin films, and mainly relates to an alpha-phase CsPbI 3 A film and a method for preparing the same.
Background
CsPbI 3 The material has the characteristics of inorganic property, low-temperature synthesis, proper band gap and the like, and is an ideal high-performance photovoltaic material. CsPbI 3 The material has a cubic phase (alpha-CsPbI) 3 Phase), tetragonal phase (beta-CsPbI 3 Phase), quadrature phase (delta-CsPbI 3 Phase) of the three common phases, the cubic phase has the smallest optical band gap and the best electron transport capacity. However, csPbI is prepared at normal temperature 3 delta-CsPbI, mostly generated as yellow 3 Phase, even after formation of black alpha-CsPbI by annealing process 3 The phase is also difficult to stably exist under the condition of normal temperature air, and is easy to be formed by black alpha-CsPbI 3 delta-CsPbI phase-converted to yellow 3 And (3) phase (C). alpha-CsPbI 3 The phases present a large nucleation energy barrier during unassisted natural crystallization and phase transitions are slower, resulting in scalable production of their photovoltaics still being challenging.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present application to provide an alpha-phase CsPbI 3 Film and preparation method thereof, which aims at solving the problem of CsPbI prepared at normal temperature in the prior art 3 The film is difficult to keep black alpha-CsPbI 3 Phase problems.
The technical scheme of the application is as follows:
in a first aspect, the present application provides an alpha phase CsPbI 3 A method for producing a film, wherein,the method comprises the following steps:
(1) CsI and PbI 2 Dissolving in solvent to obtain CsPbI 3 A precursor solution;
(2) CsPbI is processed by 3 Spin-coating the precursor solution on the surface of a substrate, standing for the first time, dripping diphenyl phosphinoyl chloride solution on the substrate, standing for the second time until the color of the surface of the substrate changes from yellow to black, and rotating the substrate;
(3) Annealing the substrate to obtain the alpha phase CsPbI on the substrate 3 A film.
Alpha phase CsPbI of the present application 3 The preparation method of the film has the advantages of convenient operation, low cost, good film forming property, easy achievement of conditions and convenient mass production of factories. Alpha-phase CsPbI prepared by the method 3 The film has good crystallinity, compact and smooth surface and high phase stability, and has important significance for the expandable production of photovoltaic materials.
Further, the substrate is one of glass, a quartz plate, a silicon wafer or a silicon dioxide plate;
the substrate is subjected to pretreatment, and the pretreatment comprises the following steps:
ultrasonically cleaning the substrate by using detergent, deionized water, isopropanol and ethanol for 5-40 minutes respectively and drying by using nitrogen;
and then cleaning the mixture for 5 to 30 minutes by using an oxygen plasma cleaner.
Further, in step (1), the CsPbI 3 CsPbI in precursor solution 3 The concentration of (2) is 0.5mol/L-5mol/L;
the solvent is DMF solution, DMSO solution or a mixed solution of the DMF solution and the DMSO solution.
Further, in step (1), the CsPbI 3 The precursor solution comprises cesium valerate, and the concentration of the cesium valerate is CsPbI 3 The concentration is 5% -20%.
Further, in step (2), the CsPbI 3 The spin coating amount of the precursor solution is 10-30ul/cm 2 The spin coating speed is 3000-6000rpm, and the spin coating time is 20-60s.
Further, in the step (2), the time of the first standing is 1-10min, and the time of the second standing is 1-20min.
Further, in the step (2), the diphenylphosphinoyl chloride solution is prepared by dropwise adding 0.5 to 10ul of diphenylphosphinoyl chloride to 1ml of chlorobenzene, and the dropwise adding amount of the diphenylphosphinoyl chloride solution on the substrate is 50 to 400ul.
Further, in the step (2), the rotation speed of the substrate is 3000-6000rpm, and the rotation time is 20-60s.
Further, in the step (3), the annealing treatment is performed at a temperature of 30-80 ℃ for 2-20min.
In a second aspect, the present application also provides an alpha phase CsPbI 3 A film wherein CsPbI is formed by the alpha phase as described in the first aspect 3 The film is prepared by a preparation method.
The beneficial effects are that: alpha phase CsPbI provided herein 3 The preparation method of the film has convenient operation, easy achievement of conditions and lower cost, and can be used for preparing the film from yellow delta phase CsPbI at normal temperature 3 Conversion of film to alpha phase CsPbI 3 Film, alpha-phase CsPbI prepared by the preparation method 3 The film has the characteristics of good crystallinity, compact and smooth surface, high phase stability, good film forming property and the like, and is convenient for industrial mass production.
Drawings
FIG. 1 is a CsPbI prepared in example 2 of the present application 3 Phase change process of the film.
Fig. 2 is a CsPbI prepared in example 2, blank and comparative examples of the present application 3 XRD diffraction pattern of the film.
Fig. 3 is a CsPbI prepared in example 2 and comparative example of the present application 3 XRD diffraction patterns of the films before and after 72h of standing in air.
Fig. 4 is a CsPbI prepared in example 2 of the present application 3 Optical micrograph of film after 72h of air.
Fig. 5 is a CsPbI prepared in comparative example of the present application 3 Optical micrograph of film after 72h of air.
FIG. 6 is a practical example of the present applicationCsPbI prepared in example 1 3 Scanning electron microscope photograph of the central region of the film.
Fig. 7 is a CsPbI prepared in example 2 of the present application 3 Scanning electron microscope photograph of the central region of the film.
Fig. 8 is a CsPbI prepared in example 3 of the present application 3 Scanning electron microscope photograph of the central region of the film.
Fig. 9 is a CsPbI prepared in example 4 of the present application 3 Scanning electron microscope photograph of the central region of the film.
Detailed Description
The present application provides an alpha phase CsPbI 3 The film and the preparation method thereof are used for making the purposes, technical schemes and effects of the application clearer and more definite, and the application is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In the prior art, csPbI is prepared at normal temperature 3 Delta phase CsPbI, mostly generated as yellow 3 Even if black alpha phase CsPbI is generated by a high temperature annealing process in the later stage 3 Is difficult to stably exist under the condition of normal temperature air, and is easy to be formed by black alpha-phase CsPbI 3 Delta phase CsPbI converted to yellow 3 。
In response to this problem, the present application provides an alpha phase CsPbI 3 The preparation method of the film can realize the preparation of alpha-phase CsPbI at normal temperature 3 A film, comprising in particular the steps of:
s1, preparing perovskite precursor solution: csI and PbI 2 Dissolving in solvent to obtain CsPbI 3 A precursor solution;
s2, spin coating: csPbI 3 Spin-coating the precursor solution on the surface of a substrate, performing first standing, dropwise adding diphenyl phosphinoyl chloride solution on the substrate, performing second standing, turning the color of the surface of the substrate from yellow to black, and rotating the substrate to remove the solvent;
s3, low-temperature treatment: annealing the substrate to obtain alpha-phase CsPbI 3 A film.
Alpha phase CsPbI of the present application 3 Method for producing filmThe operation is convenient, the cost is low, the film forming property is good, the condition is easy to achieve, and the large-scale production of factories is convenient. Alpha-phase CsPbI prepared by the method 3 The film has good crystallinity, compact and smooth surface and high phase stability, and has important significance for the expandable production of photovoltaic materials.
Further, the substrate is one of glass, quartz plate, silicon wafer or silicon dioxide plate.
Further, the substrate is subjected to a pretreatment comprising the steps of:
ultrasonically cleaning a substrate by using detergent, deionized water, isopropanol and ethanol for 5-40 minutes respectively and drying by using nitrogen; and then cleaning the mixture for 5 to 30 minutes by using an oxygen plasma cleaner.
The impurities and organic matters on the surface of the substrate are removed by multiple times of cleaning, so that the surface energy of the substrate is increased, and the CsPbI is improved 3 Crystallinity of the film.
Further, csPbI 3 CsPbI in precursor solution 3 The concentration is 0.5mol/L-5mol/L; the solvent is DMF solution, DMSO solution or a mixed solution of the two. The DMF solution and the DMSO solution which are selected are good solvents for each other, are mainly used for dissolving perovskite raw materials, and can be mixed in any proportion. The solvent used in the present application was easily obtained, and commercially available DMF solution and DMSO solution having a purity of 99.8% were used.
Further, in step (1), csPbI 3 The precursor solution also comprises cesium valerate with the concentration of CsPbI 3 The concentration of (2) is 5% -20%, preferably 10%. Wherein, cesium valerate can be prepared by completely dissolving 1mmol of cesium carbonate in ethanol at 70 ℃, then adding 2mmol of n-valeric acid, and evaporating to dryness to obtain cesium valerate powder. In the application, the CsPbI is improved by adding a certain amount of cesium valerate into the perovskite precursor solution in proportion 3 Crystallinity of thin film, csPbI is improved 3 Film quality of the film as a whole.
Further, in step (2), csPbI 3 The spin coating amount of the precursor solution is 10-30ul/cm 2 The spin coating speed is 3000-6000rpm, and the spin coating time is 20-60s. CsPbI by spin coating 3 Precursor(s)Coating a bulk solution on a substrate to form CsPbI 3 Films, as used herein, generally have a substrate area in the range of 1-5cm 2 。
Due to CsPbI 3 Cs in (3) + The ion radius is smaller, and the [ PbI ] cannot be limited effectively 6 ] 4- Octahedral tilt, resulting in severe lattice distortion. In practical use, the CsPbI is embodied at normal temperature 3 The perovskite tends to spontaneously transition from a black phase (α) to a non-perovskite yellow phase (δ), and the process will further accelerate under the action of a humid environment. This results in a low temperature prepared CsPbI 3 Thin films are often limited by phase stability problems in solar cell applications.
In order to solve the problem, the method can prepare alpha-phase CsPbI at normal temperature by dripping diphenyl phosphinyl chloride solution 3 Film, alpha phase CsPbI produced 3 The film also has good stability and can be maintained for a period of time for subsequent application preparation.
Further, in the step (2), the diphenylphosphinoyl chloride solution is prepared by dropping 0.5 to 10ul of diphenylphosphinoyl chloride in 1ml of chlorobenzene, and the dropping amount of the diphenylphosphinoyl chloride solution on the substrate is 50 to 400ul. In the specific examples herein, the diphenylphosphinoyl chloride solution was prepared by dropping 1ul of diphenylphosphinoyl chloride in 1ml of chlorobenzene, and the dropping amount of the diphenylphosphinoyl chloride solution on the substrate was 100ul.
In the film forming process, the solution containing diphenyl phosphinyl chloride and chlorobenzene is added dropwise to help the alpha-phase CsPbI at normal temperature 3 The stability of the film is improved. In CsPbI 3 In the film, black phase CsPbI 3 The crystal structure of (a) is a co-angular octahedron, and a yellow phase CsPbI 3 Are edge octahedra, so octahedral rotation occurs during the black-to-yellow phase transition. Cl is introduced by dropwise adding diphenyl phosphinyl chloride solution - Ion doping, wherein the phosphate groups have passivation effect and can be bonded with strong ions on the surface to block [ PbI ] 6 ] 4- Octahedral rotation at the surface, thereby preventing phase transition from black to yellow, helping to promote alpha-phase CsPbI 3 Perovskite thinStability of the film. Wherein Cl is introduced into - The ions are uniformly distributed in CsPbI 3 The near-surface film layer of the film not only passivates Iodine Vacancies (IV) and improves the energy band alignment structure, but also promotes carrier extraction and transport, contributing to CsPbI 3 The stability and photoelectric performance of the film are improved. Pb in phosphate group and perovskite material 2+ The CsPbI in the precursor solution is effectively increased by the strong chemical action between P and Pb 3 Cluster size, csPbI is achieved 3 The growth of large grains can improve the quality of the film. At the same time phosphate groups promote [ PbI ] 6 ] 4- Binding of octahedral framework to cesium cations increases [ PbI 6 ] 4- The energy barrier of the octahedral rotation avoids the disturbance of crystal orientation caused by the octahedral rotation to a certain extent, and the stability of the lattice structure is enhanced. Overall, the added diphenylphosphinoyl chloride increased [ PbI 6 ] 4- Octahedral rotation barrier and allows CsPbI to be prepared 3 The moisture resistance and light resistance of the film are remarkably improved, and the film can maintain long-time stability at normal temperature.
In the film forming process, the crystal grain size of perovskite can be effectively regulated within a certain range by dripping chlorobenzene solution containing diphenylphosphinoyl chloride, and partial perovskite crystal grains are enabled to be smaller, so that a thin CsPbI can be formed on the surface of the film 3 The perovskite type nano crystal has high specific surface area, can reduce the phase transition temperature from non-perovskite phase to perovskite phase, and is favorable for realizing CsPbI at normal temperature 3 Transition of the delta phase to the alpha phase of the film. At the same time a part of CsPbI 3 The nanocrystals are used as nucleation centers, so that the compactness of the active layer film can be improved; on the other hand, csPbI with partial dissociation 3 The nanocrystals fill the ion vacancy defects in the active layer, playing a role in passivation of the defects. CsPbI 3 The nanocrystalline promotes grain growth in the perovskite crystallization process, induces large-size perovskite grains, simultaneously passivates ion vacancy defects and repairs grain boundary defects, effectively improves film quality, and is not easy to be subjected to water or waterThe influence of oxygen is also beneficial to improving the prepared alpha-phase CsPbI 3 Stability of the film.
However, the action process of the diphenylphosphinoyl chloride has a certain time limit, and when the chlorobenzene solution containing the diphenylphosphinoyl chloride stays on the surface of the perovskite film for a long time, the quality and stability of the film are reduced, so that the standing time of the film needs to be strictly controlled.
Further, in the step (2), the time of the first standing is 1-10min, and the time of the second standing is 1-20min. In the present application, csPbI can be improved by performing two standing 3 Film formation quality of the film. In the first standing of the application, the growth of the perovskite film is controlled by the solvent through standing for a certain period of time, DMF or DMSO in the solvent is not easy to overflow from the precursor film completely due to higher boiling point of DMF or DMSO, and the residual DMF or DMSO in the solvent can promote CsPbI 3 Mass transfer and diffusion in the precursor solution, thereby improving the film quality.
In the second rest of the present application, csPbI 3 The film can generate phase change, and the phase change process is particularly from yellow CsPbI as a whole 3 The outer periphery of the film was progressively blackened toward the central region, with the yellow being the delta phase CsPbI 3 Black is alpha phase CsPbI 3 . Wherein the second standing time is required to be kept within a certain range and is equal to CsPbI 3 The surface of the film forms a crystal with small size, which is equivalent to forming a CsPbI layer 3 Nanocrystalline thin film on CsPbI 3 The surface of the film is enabled to prepare alpha phase CsPbI 3 The film has better stability. Wherein the second standing time is too short, csPbI 3 The phase change process of the film does not occur or the phase change is incomplete, and the formed CsPbI 3 Nanocrystalline action is also incomplete; the second standing time is too long to ensure the completion of the phase change process, but as the chlorobenzene solution containing diphenylphosphinoyl chloride is also added, the chlorobenzene solution containing diphenylphosphinoyl chloride stays at CsPbI for a long time 3 The surface of the film still dissolves a part of perovskite film, which damages the appearance of the film, so that the surface of the film generatesLarger pores, rather poor film quality, increased risk of being affected by water or oxygen and impact CsPbI 3 The stability of the film, so in this application it is necessary to keep the second rest time between 1 and 20 minutes.
Further, in the step (2), the rotation speed of the substrate is 3000-6000rpm, and the rotation time is 20-60s. The solvent on the surface of the substrate is removed by rotating the substrate.
In this application, the spin operation is employed primarily to remove solvent from the substrate surface, including solvent in the precursor solution and solvent in the diphenylphosphinoyl chloride solution. The diphenyl phosphinyl chloride solution dropwise added in the application is prepared by taking chlorobenzene as a solvent, and the diphenyl phosphinyl chloride solution stays on the surface of the CsPbI3 film for too long, so that the surface of the CsPbI3 film is damaged. In addition, chlorobenzene is an anti-solvent of perovskite, and still has certain solubility to perovskite, and the long-time retention of the solvent still can damage the surface of the perovskite film and affect the stability and photoelectric property of the perovskite film, so that the solvent on the surface of the substrate needs to be removed by rotating the substrate in time after the phase change is complete and stable, thereby ensuring CsPbI 3 Film quality and stability of the film.
Further, in the step (3), the annealing treatment temperature is 30-80 ℃ and the annealing treatment time is 2-20min. Can remove residual organic solvent after annealing treatment, and can also improve the prepared alpha-phase CsPbI 3 The phase stability of the film is favorable for CsPbI 3 And (3) maintaining the alpha phase of the film.
The prior art often requires high temperatures to ensure the black phase CsPbI 3 Perovskite phase, which causes severe tensile strain on the perovskite film surface, is known as CsPbI 3 The morphology of the thin film is affected, thereby seriously affecting the photoelectric performance of the perovskite device. And the perovskite film prepared by the method has poor stability, is easily changed from black delta phase to yellow alpha phase under the influence of temperature and humidity in the atmosphere, so that the perovskite device is often required to be carried out under the severe conditions of vacuum or nitrogen protection and the like in the subsequent assembly process.
According to the preparation method, during the crystallization process of the perovskite, the chlorobenzene anti-solvent enables the crystal grains of the perovskite to be moreMicro-scale, forming a thin CsPbI layer on the surface of the film 3 The perovskite type nano crystal has high specific surface area, can reduce the phase transition temperature from a non-perovskite phase to a perovskite phase, can realize phase transition under the normal temperature condition, and avoids the influence of high temperature treatment on good film performance and optical activity. The prepared CsPbI 3 The film can stably maintain CsPbI in black 3 Besides no high-temperature treatment, the perovskite phase can be kept in normal-temperature air for at least 3 days, has good stability, and provides great convenience for the subsequent assembly process of perovskite devices.
The application also provides an alpha-phase CsPbI 3 A film wherein CsPbI is an alpha phase as described above 3 The film is prepared by a preparation method.
Further description will be given below by way of specific examples.
Alpha-phase CsPbI of examples 1-4 of the present application 3 The preparation method of the film comprises the following steps:
selecting a silicon wafer as a substrate, respectively and sequentially ultrasonically cleaning the silicon wafer with detergent, deionized water, isopropanol and ethanol for 15 minutes, and drying the silicon wafer with nitrogen; cleaning for 10 minutes by using an oxygen plasma cleaner, and removing impurities and organic matters on the surface of the substrate;
CsI and PbI 2 CsPbI with concentration A was prepared by dissolving in DMSO solution with purity of 99.8% 3 Precursor solution, and in CsPbI 3 Adding cesium valerate into the precursor solution to enable the cesium valerate to be in CsPbI 3 The concentration of CsPbI in the precursor solution 3 B ratio of the concentration of (a);
CsPbI was spun at 3000rpm 3 Coating the precursor solution on a substrate, wherein the spin coating amount is 20ul/cm 2 Spin coating for 45s, standing the coated substrate for a period of time C for the first time, dripping a certain volume D of diphenyl phosphinoyl chloride solution (1 ul of diphenyl phosphinoyl chloride is dissolved in 1ml of chlorobenzene) into the substrate, standing for a period of time E for the second time, rotating the substrate for 45s at a rotating speed of 3000rpm after the color of the surface of the substrate changes from yellow to black, and throwing out the solvent on the surface of the substrate.
Annealing at temperature F for G time to remove excessive solvent and obtain stable alpha phase CsPbI 3 A film.
Wherein, the alpha phase CsPbI of examples 1-4 3 The detailed data of the concentration a, the proportion B, the first standing time C, the volume D, the second standing time E, the temperature F and the time G of the film preparation method are shown in table 1:
examples A(mol/L) B(%) C(min) D(ul) E(min) F(℃) G(min)
1 0.8 10 5 100 2 60 5
2 0.8 10 5 100 6 60 5
3 0.8 10 5 100 12 60 5
4 0.8 10 5 100 18 60 5
；
Blank examples
Selecting a silicon wafer substrate subjected to the same cleaning treatment as the example, and obtaining CsI and PbI from the same source as the example 2 Dissolved in DMSO solution to prepare CsPbI with the same concentration as the embodiment 3 A precursor solution; for the CsPbI 3 The precursor solution was not subjected to any treatment, csPbI was applied at a spin-coating speed of 3000rpm 3 Coating the precursor solution on a substrate, wherein the spin coating amount is 20ul/cm 2 Spin coating for 45s, standing the coated substrate for 5min, rotating the substrate at 3000rpm for 45s, and throwing out solvent on the substrate surface to obtain yellow color at room temperatureDelta phase CsPbI of (C) 3 A film.
Comparative example
In comparison, the comparative example was operated substantially the same as the blank example, except that a delta phase CsPbI exhibiting a yellow color was obtained on the surface of the substrate 3 The film is then annealed at 360 ℃ to form yellow delta phase CsPbI 3 Alpha phase CsPbI with conversion of film to black 3 A film.
Performance testing
(1) Example 2 phase CsPbI from yellow delta at ambient temperature 3 Alpha phase CsPbI with black film 3 The film, during this transition, the corresponding starting and final states are as shown in FIG. 1, as can be seen from FIG. 1, from CsPbI 3 There is a significant phase change process from edge to center of the film.
Alpha phase CsPbI prepared in example 2 3 Film and alpha-phase CsPbI prepared in comparative example 3 The films were placed in air and the morphology and XRD data changes before and after 72h of placement in air were compared.
Wherein, the comparative example is alpha-phase CsPbI obtained after annealing treatment at 360 DEG C 3 The film, after 5min in air, changed from black to yellow completely.
CsPbI for example 2, comparative example and blank example 3 XRD testing of the films gave XRD data as shown in FIG. 2. As can be seen from FIG. 2, the XRD data of example 2 and comparative example are consistent, demonstrating that the alpha phase CsPbI produced by the preparation method provided herein 3 The film achieves the same effect as the comparative example through high temperature annealing treatment. And the XRD diffraction pattern of example 2 shows that the XRD pattern has sharp peak shape and high intensity, and the obtained alpha phase CsPbI has high ordered out-of-plane stacking 3 The film has good crystallinity. XRD patterns of the blank example are then compared with the yellow delta phase CsPbI 3 XRD data of the thin film corresponds.
Alpha phase CsPbI of example 2 3 Film and comparative alpha phase CsPbI 3 XRD results of the film when left in air for 72h are shown in FIG. 3. As can be seen from FIG. 3 by comparison, the XRD data of the film of example 2 does not change significantly before and after placement, whereas the film of the comparative exampleIs evident from the XRD data of alpha phase CsPbI 3 The film becomes delta phase CsPbI 3 。
Alpha phase CsPbI of example 2 3 An optical micrograph of the film in air for 72h is shown in FIG. 4, with the alpha phase CsPbI of the comparative example 3 An optical micrograph of the film in air for 72 hours is shown in figure 5. CsPbI by comparative example 2 and comparative example 3 The morphology of the film can be found for CsPbI in example 2 3 The film quality of (C) is significantly better than that of CsPbI of the comparative example 3 A film.
(2) For the alpha phase CsPbI prepared in examples 1-4 3 SEM test of films, examples 1-4 gave alpha-CsPbI 3 SEM results of the film center region are shown in FIGS. 6-9, respectively, and the phase change process is performed from CsPbI 3 The film quality is more representative in the central region, where the film periphery proceeds toward the central region, as can be seen by comparing FIGS. 6-9, with CsPbI extending the second rest time 3 The stronger the surface crystallinity of the film, the larger the crystals and the larger the gaps between the crystals. CsPbI when the standing time is 6 min 3 The film has good surface crystallinity, small crystal size and small gap, and is more beneficial to alpha-phase CsPbI 3 And (3) stabilizing the film. This is because a crystal layer of small size is formed on the surface of the film, as opposed to CsPbI 3 The quantum dot film is arranged on the surface of the film, so that alpha-phase CsPbI is prepared 3 The film has better stability. The standing time is prolonged, and the chlorobenzene as an organic solvent can lead to CsPbI of alpha phase 3 The film is broken. As the film forming process proceeds, large-sized perovskite crystal grains are formed, but at the same time, a part of the crystals are dissolved by the organic solvent chlorobenzene, which causes large pores to appear in the film, and conversely causes deterioration of the film quality.
Alpha phase CsPbI of the present application 3 The preparation method of the film has the advantages of convenient operation, low cost, good film forming property, easy achievement of conditions and convenient mass production of factories. Alpha-phase CsPbI prepared by the method 3 The film has good crystallinity, compact and smooth surface and high phase stability, and has important significance for the expandable production of photovoltaic materials.
It will be understood that the application of the present application is not limited to the examples described above, but that modifications and variations can be made by those skilled in the art in light of the above description, all of which are intended to be within the scope of the present application.

Claims (10)

1. Alpha-phase CsPbI 3 The preparation method of the film is characterized by comprising the following steps:
(1) CsI and PbI 2 Dissolving in solvent to obtain CsPbI 3 A precursor solution;
(2) CsPbI is processed by 3 Spin-coating the precursor solution on the surface of a substrate, standing for the first time, dripping diphenyl phosphinoyl chloride solution on the substrate, standing for the second time until the color of the surface of the substrate changes from yellow to black, and rotating the substrate;
(3) Annealing the substrate to obtain the alpha phase CsPbI on the substrate 3 A film.
2. Alpha phase CsPbI according to claim 1 3 The preparation method of the film is characterized in that the substrate is one of glass, quartz plate, silicon wafer or silicon dioxide plate;
the substrate is subjected to pretreatment, and the pretreatment comprises the following steps:
ultrasonically cleaning the substrate by using detergent, deionized water, isopropanol and ethanol for 5-40 minutes respectively and drying by using nitrogen;
and then cleaning the mixture for 5 to 30 minutes by using an oxygen plasma cleaner.
3. Alpha phase CsPbI according to claim 1 3 A method for producing a film, characterized in that in step (1), the CsPbI 3 CsPbI in precursor solution 3 The concentration of (2) is 0.5mol/L-5mol/L;
the solvent is DMF solution, DMSO solution or a mixed solution of the DMF solution and the DMSO solution.
4. An alpha phase CsPbI according to claim 3 3 A method for producing a film, characterized by comprisingIn step (1), the CsPbI 3 The precursor solution comprises cesium valerate, and the concentration of the cesium valerate is CsPbI 3 The concentration is 5% -20%.
5. Alpha phase CsPbI according to claim 1 3 A method for producing a film, characterized in that in step (2), the CsPbI 3 The spin coating amount of the precursor solution is 10-30ul/cm 2 The spin coating speed is 3000-6000rpm, and the spin coating time is 20-60s.
6. Alpha phase CsPbI according to claim 1 3 The preparation method of the film is characterized in that in the step (2), the first standing time is 1-10min, and the second standing time is 1-20min.
7. Alpha phase CsPbI according to claim 1 3 The method for preparing the film is characterized in that in the step (2), the diphenyl phosphinic chloride solution is prepared by dripping 0.5-10ul of diphenyl phosphinic chloride into 1ml of chlorobenzene, and the dripping amount of the diphenyl phosphinic chloride solution on a substrate is 50-400ul.
8. Alpha phase CsPbI according to claim 1 3 The preparation method of the film is characterized in that in the step (2), the rotation speed of the substrate is 3000-6000rpm, and the rotation time is 20-60s.
9. Alpha phase CsPbI according to claim 1 3 The preparation method of the film is characterized in that in the step (3), the annealing treatment temperature is 30-80 ℃ and the annealing treatment time is 2-20min.
10. Alpha-phase CsPbI 3 A film characterized by being produced by the alpha-phase CsPbI of any one of claims 1 to 9 3 The film is prepared by a preparation method.
CN202410164804.9A 2024-02-05 2024-02-05 Alpha-phase CsPbI3Film and method for producing the same Active CN117711950B (en)

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