CN110886017A - Preparation method of all-inorganic cesium-lead halogen perovskite nanocrystalline film - Google Patents

Preparation method of all-inorganic cesium-lead halogen perovskite nanocrystalline film Download PDF

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CN110886017A
CN110886017A CN201911204679.5A CN201911204679A CN110886017A CN 110886017 A CN110886017 A CN 110886017A CN 201911204679 A CN201911204679 A CN 201911204679A CN 110886017 A CN110886017 A CN 110886017A
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thin film
film
perovskite nanocrystalline
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张灿云
彭小改
陈进
王凤超
孔晋芳
杨波波
李澜
刘启龙
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Shanghai Institute of Technology
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    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution

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Abstract

The invention relates to a preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film, which comprises the following steps: 1) uniformly mixing DMF, oleic acid and oleylamine to obtain a mixed solution; 2) CsX and PbY2Respectively adding the mixed solution obtained in the step 1), and sequentially stirring, standing and centrifuging to obtain a precursor solution; 3) cleaning, drying and heating the film substrate in sequence, and then spraying the precursor solution on the film substrate while the precursor solution is hot to obtain the all-inorganic cesium-lead halogen perovskite nanocrystalline film; wherein, X and Y are respectively one or more of Cl, Br and I. Compared with the prior art, the method can realize quick one-time film formation, and has the advantages of simple operation, low cost,The prepared nanocrystalline film has the advantages of uniform distribution, high crystallization quality and good luminescence performance, and shows wide application prospect.

Description

Preparation method of all-inorganic cesium-lead halogen perovskite nanocrystalline film
Technical Field
The invention belongs to the technical field of materials science, and relates to a preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film.
Background
All-inorganic cesium-lead halide compound CsPbX3The (X ═ Cl, Br, I) perovskite material has excellent optical properties, including high fluorescence quantum yield (90%), narrow emission peak half-peak width (12-42 nm), emission spectrum covering the whole visible light wavelength (410-700 nm), and the emission wavelength can be adjusted freely. In addition, the material also has better thermal stability and biocompatibility. Therefore, in recent years, the compound has attracted attention in the field of light-emitting materials.
Currently, CsPbX is limited3The problems of the application of (X ═ Cl, Br, I) materials in the field of photoelectric devices are mainly that the stability of the materials is insufficient, and the CsPbX prepared by a chemical solution method has high quantum luminous efficiency3The (X ═ Cl, Br, I) materials are limited to gram-scale, and mass production is difficult to achieve. Perovskite CsPbX3The (X ═ Cl, Br, I) nanocrystalline film can be used as an active layer of photoelectron and photoelectric devices, and the main film forming modes include evaporation and spin coating. However, the evaporation method requires preparation conditions such as a high vacuum environment and a high evaporation temperature, and is not favorable for the large-scale production of the inorganic perovskite thin film. The preparation of the perovskite film by the spin-coating method also comprises different preparation processes, such as the preparation of the prepared perovskite CsPbX3(X ═ Cl, Br, I) nanocrystals were spin coated or dropped onto the sublayer, which is limited by the gram scale of nanocrystals prepared by solution methods, and it is also difficult to achieve commercial production; and another by spin-coating PbX2The film forming method by the in-situ reaction of the film and CsX (X ═ Cl, Br, I) solution has high requirements on preparation operation,it is difficult to popularize.
Therefore, the research and development of the perovskite CsPbX which is simple to operate, low in cost and easy to produce in large area3The preparation method of the (X ═ Cl, Br, I) nanocrystalline film has positive practical significance for promoting the application of the (X ═ Cl, Br, I) nanocrystalline film in the field of photoelectric devices.
Chinese patent CN109904315A discloses a method for preparing perovskite nanocrystalline thin film by spraying, wherein a precursor solution is sprayed on a substrate to form a liquid film; the precursor solution comprises a solvent and a perovskite material dissolved in the solvent; heating the substrate to form a semi-dry film on the liquid film; spraying an anti-solvent on the semi-dry film to crystallize the semi-dry film; the perovskite nanocrystalline film is prepared by a spraying method: filling the perovskite nanocrystalline dispersion liquid into a spray bottle, installing the spray bottle on a spray gun, and adjusting the distance between the spray gun and a substrate, the liquid output amount of the spray gun and the air pressure; and then heating the substrate, spraying, and annealing to obtain the perovskite nanocrystalline film. Although the method has the advantages of uniform and compact film, stable substrate, good photocatalytic performance and the like, the method also has the following defects:
1) the method belongs to a multi-step film forming method, namely a liquid film (spraying of precursor liquid), a semi-dry film (heating a substrate), a crystallization film (spraying of anti-solvent), a finished film (annealing/tempering), multiple process steps, more factors influencing the quality of the film and more complex operation;
2) dispersing the generated perovskite nanocrystalline in a solution, filling the solution into a spray bottle, and then spraying the solution on a heated substrate to form a film, wherein the large-area deposition of the film is directly limited by the magnitude of the generated perovskite nanocrystalline;
3) the substrate is selected more singly.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of an all-inorganic cesium-lead-halogen perovskite nanocrystalline film, which has the advantages of simple and convenient operation, low cost, no selectivity to a substrate and easy large-area film formation, and the perovskite nanocrystalline film obtained by the method has the characteristics of good uniformity, high crystallization quality, strong visible light emission and high stability at room temperature and in atmospheric environment.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film comprises the following steps:
1) uniformly mixing N, N-Dimethylformamide (DMF), oleic acid and oleylamine to obtain a mixed solution;
2) CsX and PbY2Respectively adding the mixed solution obtained in the step 1), and sequentially stirring, standing and centrifuging to obtain a clear solution, thus obtaining a precursor solution;
3) cleaning, drying and heating the film substrate in sequence, and then spraying the precursor solution in the step 2) on the film substrate while the precursor solution is hot to obtain the all-inorganic cesium-lead halide perovskite nanocrystalline film;
wherein CsX is one or more of CsCl, CsBr and CsI, PbY2Is PbCl2、PbBr2And PbI2One or more than one of them.
Further, in the step 1), the volume ratio of DMF, oleic acid and oleylamine is 10 (0.5-1.5) to (0.05-0.2).
Further, in the step 2), the stirring time is 10-20 min.
Further, in the step 2), the standing time is 25-35 min.
Further, in the step 2), the precursor solution is an oily system containing oleic acid and oleylamine, and the concentration of CsX in the oily system is 0.01-0.1mol/L, PbY2The concentration of (A) is 0.01-0.1 mol/L.
X in the precursor solution-And Y-The ratio can be prepared according to the composition of a target product and is controlled by controlling the I in the precursor solution-、Cl-、Br-The concentration of the perovskite nano-crystal film can adjust the emission wavelength of the product nano-crystal film, so that the perovskite nano-crystal film material which can emit light in the full wave band within the visible light range is prepared.
Further, in the step 3), the thin film substrate is one of common glass, ITO glass, FTO glass, a monocrystalline silicon wafer, or a sapphire substrate.
Further, in the step 3), the cleaning process specifically includes firstly cleaning the film substrate with ethanol, and then ultrasonically cleaning the film substrate.
Further, in the step 3), in the spraying process, the distance between the spray gun and the film substrate is 15-20cm, and the spraying time is 2-5 min.
Spraying the clear oily precursor solution at high speed by a high-pressure spray gun, wherein the spraying area is changed along with the distance between the spray gun and the substrate, when the distance between the substrate and the spray gun is 15cm, taking 20ml of precursor solution, spraying the film to micrometer level in thickness, and the spraying area can reach at least 100cm2Therefore, the method is suitable for forming a large-area film.
Further, in step 3), the heating temperature of the thin film substrate is 160-250 ℃, and within the temperature range, Cs is present+、Pb2 +And X-Under the assistance of stabilizing agent oleic acid and oleylamine, the ions react rapidly to generate nano-crystals with quantum size effect, and meanwhile, the nano-crystals are deposited on the surface of the thin film substrate to form a film.
In addition, the perovskite nanocrystalline thin film prepared by the method has the advantages that the organic solvent residue in the thin film is reduced along with the increase of the substrate temperature, the solidification degree of the thin film is improved, and therefore the stability of the nanocrystalline is improved. The CsPbBr prepared at 220 ℃ in the substrate temperature range adopted by the method, namely between 160 ℃ and 250 DEG C3The film can maintain higher luminescence performance within three months without any passivation treatment.
The invention adds oleic acid and oleylamine into a common solvent DMF to stabilize Cs+、Pb2+And X-Thereby obtaining the precursor solution with higher concentration. Then, the precursor solution is directly sprayed on a substrate by a high-pressure spray gun, and the substrate is heated to a boiling point (153 ℃) of DMF (dimethyl formamide) in advance to enable Cs to be dissolved+、Pb2+And X-Rapidly react under the assistance of stabilizing agent oleic acid and oleylamine to generate nanocrystalline with quantum size effect, and simultaneously, the spray gun has small size of sprayed liquid drop, high consistency and spraying areaLarge, so that the perovskite nanocrystalline film which is uniformly distributed in a large area and has extremely strong visible luminescence peaks under the wrapping of the stabilizer can be obtained.
Compared with the prior art, the invention has the following characteristics:
1) the precursor solution contains Cs+、Pb2+And X-DMF, oleic acid and oleylamine systems, Cs compared to the solution systems without oleic acid oleylamine+、Pb2+And X-The solubility is higher, which is beneficial to rapid one-time film formation and simplifies the operation;
2) the precursor solution used in the spraying process is in a transparent and clear state after being stirred, kept stand and centrifuged, so that the mixing uniformity of various ions required by the formation of a target perovskite material is ensured, but perovskite nanocrystals are not formed at the moment, and only when the precursor solution is sprayed on a substrate heated above the boiling point of a solvent, the solvent is evaporated, various ions are combined to form the perovskite nanocrystals, so that the sufficiency of ionic reaction and the utilization rate of raw materials are ensured, therefore, the large-area deposition of a film only needs to amplify the magnitude of the precursor solution in proportion, namely, the method disclosed by the invention is more beneficial to the large-area deposition of the film, has a wider industrial application prospect and is suitable for large-scale industrial production;
3) in the forming process of the nanocrystalline film, oleic acid and oleylamine are used as stabilizing agents to wrap the surface of generated nanocrystals, namely the nanocrystals are wrapped by the stabilizing agents while being generated, so that the size of the nanocrystals is effectively controlled, the nanocrystals are prevented from growing too fast, and the nanocrystals keep higher quantum size effect;
4) in the traditional spin coating process, generated nanocrystalline particles are coated on a substrate through a spin coater at a high rotating speed, a considerable part of precursor solution material splashes out of the substrate under the action of centrifugal force in the high-speed spin coating process, the utilization rate of the material is low, and a large amount of waste is caused, so that the limitation of the large-scale application of the quantum dot preparation process which is originally limited to gram-order is further aggravated, and when the substrate is heated to be above the boiling point of DMF (dimethyl formamide), Cs sprayed on the substrate is heated to be above the boiling point of DMF (dimethyl formamide)+、Pb2 +And X-The solvent DMF is evaporated to quickly react to generate nano crystal grains and separate out, so that all the nano crystal in the solution sprayed on the substrate is deposited, and the material utilization rate is greatly improved;
5) the method belongs to a one-step film forming method, namely, a precursor solution is sprayed on a heated substrate, nanocrystalline is separated out when a solvent is evaporated, a film is formed, anti-solvent and annealing/tempering treatment are not needed, and the process is simple and practical;
6) the substrate in the invention has wide applicability, and theoretically, the solid substrate material with no obvious change in physical property and chemical property can be used as the substrate within the temperature range of 160-250 ℃, namely, the substrate material in the invention has larger selection flexibility;
7) the preparation condition of the precursor solution is normal temperature and normal pressure, the temperature and air pressure condition are not required to be controlled, the precursor solution is directly sprayed on a substrate heated to a specific temperature by a high-pressure spray gun in the film deposition process, and the method is simple and easy to implement, can realize quick film formation at one time, is simple to operate, has low cost and has wide application prospect.
Drawings
FIG. 1 shows CsPbBr prepared in example 13Scanning electron micrographs of the perovskite nanocrystalline thin film;
FIG. 2 shows CsPbBr prepared in example 13Photoluminescence spectra of the perovskite nanocrystalline thin film;
FIG. 3 shows CsPbBr prepared in example 21.2I1.8Scanning electron micrographs of the perovskite nanocrystalline thin film;
FIG. 4 shows CsPbBr prepared in example 21.2I1.8Photoluminescence spectra of perovskite nanocrystalline thin films.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
a preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film specifically comprises the following steps:
(1) a precursor solution preparation step, taking 20mL of N, N-Dimethylformamide (DMF), 2mL of oleic acid and 0.3mL of oleylamine, wherein the volume ratio of the three reagents is 10:1: 0.15, mixing DMF, oleic acid and oleylamine at room temperature for later use; according to the following steps: 1 CsBr and PbBr of analytically pure purity were weighed2Adding 1.6mmol of the powder into a mixed solution of DMF, oleic acid and oleylamine, stirring for 15min, standing for 30min, and centrifuging to obtain a clear solution, namely a precursor solution required for preparing the perovskite nanocrystalline film;
(2) the preparation method comprises the steps of taking common glass as a film substrate, cleaning the substrate with ethanol, then cleaning with ultrasonic waves, and finally drying for later use; heating the substrate to 180 ℃, spraying the precursor solution onto the cleaned substrate by a spray gun while the substrate is hot, wherein the distance between the spray gun and the substrate is 15cm, the spraying time is 3min, and Cs is+、Pb2+And Br-The nano-crystalline with quantum size effect is rapidly generated by reaction under the assistance of stabilizing agent oleic acid and oleylamine, and simultaneously, a film is deposited on the surface of the substrate, and the thickness of the film is about 1 mu m.
The perovskite nanocrystalline thin film obtained by the preparation method is irradiated by a xenon lamp with the wavelength of 365nm, and the thin film is observed to emit bright and uniform green light, and no obvious particles or holes are formed on the surface of the thin film.
As shown in FIG. 1, the surface morphology of the film observed by a scanning electron microscope shows that the film is formed by stacking closely arranged square particles, and the Energy Dispersive Spectroscopy (EDS) analysis of a single particle shows that the atomic contents of Cs, Pb and Br in the particles are 16.85%, 19.29% and 63.86%, respectively, which are close to 1:1: 3.
The perovskite nanocrystalline thin film obtained by the method is tested by a fluorescence spectrometer, the result is shown in figure 2, a green luminous peak with extremely strong and symmetrical peak shape can be observed near 520nm of the thin film, the half-height width of an emission peak is about 20nm,the film is proved to have high crystallization quality and strong quantum size effect, that is, the green luminescent CsPbBr with good uniformity, higher crystallization quality and strong quantum size effect can be obtained by the preparation method3Perovskite nanocrystalline thin film material.
Example 2:
a preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film specifically comprises the following steps:
(1) preparing a precursor solution by taking 20mL of DMF, 2mL of oleic acid and 0.3mL of oleylamine, wherein the volume ratio of the three reagents is 10:1: 0.15, mixing DMF, oleic acid and oleylamine at room temperature for later use; according to the following steps: 0.1: 0.9 ratio CsBr and PbBr with analytical purity2And PbI2Adding 1.6mmol, 0.16mmol and 1.44mmol of the powder into a mixed solution of DMF, oleic acid and oleylamine, stirring for 15min, standing for 30min, and centrifuging to obtain a clear solution, namely a precursor solution required for preparing the perovskite nanocrystalline film;
(2) preparing a perovskite nanocrystalline film, using ITO glass as a film substrate, cleaning the substrate with ethanol, then cleaning with ultrasonic waves, and finally drying for later use; heating the substrate to 180 ℃, spraying the precursor solution onto the cleaned substrate by a high-pressure spray gun while the substrate is hot, wherein the distance between the spray gun and the substrate is 15cm, the spraying time is 3min, and Cs is+、Pb2+、Br-And I-The nano-crystalline with quantum size effect is rapidly generated by reaction under the assistance of stabilizing agent oleic acid and oleylamine, and simultaneously, a film is deposited on the surface of the substrate, and the thickness of the film is about 1 mu m.
The CsPbBr obtained by the preparation method is irradiated by a xenon lamp with the wavelength of 365nm1.2I1.8The perovskite nanocrystalline thin film is observed to emit uniform red light, and particles and holes are obvious on the surface of the thin film.
The surface morphology of the film observed with a scanning electron microscope is shown in fig. 3, where it can be seen that the film is built up from a large number of dispersedly arranged, small number of middle thin, strand-like particles scattered at both ends, and Energy Dispersive Spectroscopy (EDS) analysis of individual particles shows that the atomic proportions of Cs, Pb, Br and I in the particles are 13.49%, 20.88%, 29.77% and 35.85%, respectively, indicating that the concentration of Pb ions in the particles is slightly higher than that of Cs ions, and the ratio of Br to I is 1.2:1.45, slightly higher than the nominal ratio of Br to I in the precursor solution, 1.2: 1.8.
The perovskite nanocrystalline thin film is tested by a fluorescence spectrometer, and the result is shown in fig. 4, and the thin film has a strong basically symmetrical red luminescence peak near 610nm as shown in fig. 4, and the half-height width of an emission peak is about 50 nm. I prepared by the method-Partial replacement of Br-In the perovskite nanocrystalline thin film, the stability of the nanocrystalline is improved along with the rise of the substrate temperature, the stability time of the luminous performance of the perovskite nanocrystalline thin film is at most about one week, and the perovskite nanocrystalline thin film is similar to CsPbBr3The stability time of the luminescence property of the film is much shorter, and a subsequent passivation treatment is still needed to improve the stability.
Example 3:
a preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film comprises the following steps:
1) uniformly mixing DMF, oleic acid and oleylamine in a volume ratio of 10:0.5:0.05 to obtain a mixed solution;
2) mixing CsCl, CsI and PbBr2Respectively adding the mixed solution in the step 1) in a molar ratio of 0.5:0.5:1, stirring for 10min, standing for 25min, centrifuging, and collecting clear solution to obtain CsCl and CsI with concentration of 0.005mol/L and PbBr2The concentration of (a) is 0.01 mol/L;
3) cleaning the FTO glass with ethanol, ultrasonically cleaning, drying, heating to 160 ℃, and then spraying the precursor solution in the step 2) on a film substrate by a high-pressure spray gun while the precursor solution is hot to obtain an all-inorganic cesium-lead halogen perovskite nanocrystalline film;
wherein, in the spraying process in the step 3), the distance between the spray gun and the film substrate is 18cm, and the spraying time is 5 min.
Example 4:
a preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film comprises the following steps:
1) uniformly mixing DMF, oleic acid and oleylamine in a volume ratio of 10:1.5:0.2 to obtain a mixed solution;
2) CsBr and PbBr2、PbI2And PbCl2Adding the mixed solution obtained in the step 1) into the mixed solution respectively according to a molar ratio of 1:0.2:0.3:0.5, stirring for 20min, standing for 35min, centrifuging, and taking a clear solution to obtain CsBr with the concentration of 0.1mol/L, PbBr2Has a concentration of 0.02mol/L, PbI2Has a concentration of 0.03mol/L, PbCl2The concentration of (a) is 0.05 mol/L;
3) cleaning a monocrystalline silicon wafer with ethanol, cleaning with ultrasonic waves, drying, heating to 250 ℃, and then spraying the precursor solution obtained in the step 2) on a film substrate by a high-pressure spray gun while the precursor solution is hot to obtain an all-inorganic cesium-lead halogen perovskite nanocrystalline film;
wherein, in the spraying process in the step 3), the distance between the spray gun and the film substrate is 20cm, and the spraying time is 5 min.
Example 5:
a preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film comprises the following steps:
1) uniformly mixing DMF, oleic acid and oleylamine in a volume ratio of 10:1:0.1 to obtain a mixed solution;
2) CsBr and PbBr2Respectively adding the mixed solution obtained in the step 1) into the mixed solution, sequentially stirring for 15min, standing for 30min, centrifuging, and taking a clear solution to obtain CsBr with the concentration of 0.05mol/L, PbBr2The concentration of (a) is 0.05 mol/L;
3) sequentially cleaning a sapphire substrate with ethanol, ultrasonically cleaning, drying and heating to 220 ℃, and then spraying the precursor solution in the step 2) on a film substrate by a high-pressure spray gun while the precursor solution is hot to obtain an all-inorganic cesium-lead halogen perovskite nanocrystalline film;
wherein, in the spraying process in the step 3), the distance between the spray gun and the film substrate is 15cm, and the spraying time is 4 min.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (9)

1. A preparation method of an all-inorganic cesium-lead halogen perovskite nanocrystalline film is characterized by comprising the following steps:
1) uniformly mixing DMF, oleic acid and oleylamine to obtain a mixed solution;
2) CsX and PbY2Respectively adding the mixed solution obtained in the step 1), and sequentially stirring, standing and centrifuging to obtain a precursor solution;
3) cleaning, drying and heating the film substrate in sequence, and then spraying the precursor solution in the step 2) on the film substrate while the precursor solution is hot to obtain the all-inorganic cesium-lead halide perovskite nanocrystalline film;
wherein CsX is one or more of CsCl, CsBr and CsI, PbY2Is PbCl2、PbBr2And PbI2One or more than one of them.
2. The method for preparing an all-inorganic cesium lead halide perovskite nanocrystalline thin film according to claim 1, wherein in the step 1), the volume ratio of DMF, oleic acid and oleylamine is 10 (0.5-1.5) to (0.05-0.2).
3. The method for preparing an all-inorganic cesium lead halide perovskite nanocrystalline thin film according to claim 1, wherein in the step 2), the stirring time is 10-20 min.
4. The method for preparing an all-inorganic cesium lead halide perovskite nanocrystalline thin film according to claim 1, wherein in the step 2), the standing time is 25-35 min.
5. The method for preparing an all-inorganic cesium lead halide perovskite nanocrystalline thin film according to claim 1, wherein in the step 2), CsX concentration in the precursor solution is 0.01-0.1mol/L, PbY mol/L2The concentration of (A) is 0.01-0.1 mol/L.
6. The method for preparing an all-inorganic cesium lead halide perovskite nanocrystalline thin film according to claim 1, wherein in the step 3), the thin film substrate is one of common glass, ITO glass, FTO glass, monocrystalline silicon wafer or sapphire substrate.
7. The method for preparing an all-inorganic cesium lead halide perovskite nanocrystalline thin film according to claim 1, wherein in the step 3), the cleaning process is specifically to clean the thin film substrate with ethanol, and then perform ultrasonic cleaning on the thin film substrate.
8. The method for preparing an all-inorganic cesium lead halide perovskite nanocrystalline thin film according to claim 1, wherein in the step 3), the distance between a spray gun and a thin film substrate is 15-20cm during spraying, and the spraying time is 2-5 min.
9. The method for preparing an all-inorganic cesium lead halide perovskite nanocrystalline thin film according to claim 1, wherein the heating temperature in step 3) is 160-250 ℃.
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