Preparation method of three-dimensional perovskite blue light film in air environment
By using polyvinylpyrrolidone to modify the substrate and specific precursor solutions in an air environment, a three-dimensional perovskite blue light film was prepared through spin coating heating technology, which solved the problem of difficulty in large-scale production of perovskite luminescent materials in an air environment and low blue light luminescence efficiency, and achieved efficient and excellent blue light film preparation.
Patent Information
- Application Number
- CN202510092319.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-21
- Publication Date
- 2025-05-30
AI Technical Summary
Existing perovskite luminescent materials are difficult to produce on a large scale in air environments, and the luminescent efficiency of blue light perovskite materials is relatively low.
A three-dimensional perovskite blue light film was prepared by spin-coating and heating in an air environment by spin-coating and heating by disposing precursor solutions of cesium trifluoroacetate, lead bromide, rubidium chloride, 18-crown ether-6 and triphenylphosphine oxide.
It has achieved efficient preparation of three-dimensional perovskite blue light films in air environments, improving its performance and luminous efficiency, and has huge application potential.
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Figure CN120076679A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of semiconductor light-emitting thin film preparation, and specifically relates to a method for preparing a three-dimensional perovskite blue light thin film in an air environment. Background Art
[0002] Metal halide perovskite (MHP) has characteristics such as solution processability, high color purity, and easy bandgap adjustment, and is an ideal light-emitting layer material in light-emitting diodes. At present, most perovskite light-emitting materials with high luminous efficiency are prepared in an inert system (isolated from air), which is not conducive to large-scale production and preparation. In addition, the luminous efficiency of blue light perovskite materials, as one of the three primary colors of light, is lower than that of red and green perovskite light-emitting materials.
[0003] Perovskite light-emitting materials mainly include zero-dimensional, two-dimensional or quasi-two-dimensional, and three-dimensional perovskite light-emitting materials. Three-dimensional perovskite blue light-emitting materials have characteristics such as high mobility and small Auger recombination effect, and have significant advantages in high-brightness blue light perovskite light-emitting devices. Summary of the Invention
[0004] To solve the above problems, the present invention provides a method for preparing a three-dimensional perovskite blue light thin film in an air environment, which does not require air isolation for preparation and shows great application potential in the large-scale preparation of blue light perovskite thin films and the application of high-brightness light-emitting devices.
[0005] The present invention is realized through the following technical solutions: The present invention provides a method for preparing a three-dimensional perovskite blue light thin film in an air environment, including the following steps: S1: Prepare a polyvinylpyrrolidone-modified substrate; S2: Configure a precursor solution for the three-dimensional perovskite blue light thin film; S3: Heat the precursor solution prepared in S2 and then form a film on the polyvinylpyrrolidone-modified substrate to prepare a three-dimensional perovskite blue light thin film.
[0006] Further, the specific method in S1 is: dissolve polyvinylpyrrolidone in a dimethylformamide solution, and then prepare a polyvinylpyrrolidone thin film on the substrate by spin coating.
[0007] Further, the substrate is a glass substrate.
[0008] Further, before preparing the polyvinylpyrrolidone thin film on the substrate, the substrate is pre-treated, and the specific steps of the pre-treatment are: ultrasonically clean the substrate successively with a glass cleaning solution and ultrapure water, dry it with nitrogen, and then treat it with ultraviolet ozone and set it aside.
[0009] Further, the precursor solution in S2 includes cesium trifluoroacetate, lead bromide, rubidium chloride, and 18-crown-6. The preparation method of the precursor solution is as follows: Dissolve cesium trifluoroacetate, lead bromide, rubidium chloride, and 18-crown-6 in dimethyl sulfoxide, heat and stir to dissolve, and store for later use after filtration.
[0010] Further, the precursor solution further includes triphenylphosphine oxide.
[0011] Further, the precursor solution further includes triphenylphosphine oxide and cesium bromide.
[0012] Further, the specific steps in S3 are as follows: Spin-coat the heated precursor solution onto a polyvinylpyrrolidone-modified substrate to form a film. During the spin-coating process, add an antisolvent for treatment, and anneal to form a three-dimensional perovskite blue-light thin film.
[0013] Further, the antisolvent is isooctane solvent.
[0014] The beneficial effects of the present invention are as follows: (1) The substrate used in the present invention is a polyvinylpyrrolidone-modified substrate, which is beneficial to the crystallization of the subsequent light-emitting layer; (2) The present invention uses cesium trifluoroacetate, lead bromide, rubidium chloride, 18-crown-6, triphenylphosphine oxide, and cesium bromide to prepare a dimethyl sulfoxide precursor solution. By using the defect passivation effects of cesium trifluoroacetate, triphenylphosphine oxide, and 18-crown-6, defects in the subsequently prepared thin film can be eliminated or reduced, and its performance can be significantly improved; moreover, the bromine content in the light-emitting layer can be changed by varying the ratio of cesium trifluoroacetate and cesium bromide, thereby achieving blue-light emission of different wavelengths; (3) The present invention spin-coats the heated precursor solution onto a polyvinylpyrrolidone-modified substrate to form a film, and adds isooctane solvent for treatment during the spin-coating process, which can inhibit the influence of water vapor in the air on the crystallization of the light-emitting layer; In summary, the present invention prepares a series of perovskite blue-light thin films in an air environment through a polyvinylpyrrolidone-modified substrate and a precursor solution composed of dimethyl sulfoxide containing different ratios of cesium trifluoroacetate, lead bromide, rubidium chloride, triphenylphosphine oxide, 18-crown-6, and cesium bromide, combined with the spin-coating of the heated precursor solution and the solvent treatment process during the spin-coating solution process. This method provides a new reference for the large-scale application of perovskite light-emitting layers, especially perovskite blue-light-emitting layers, in light-emitting thin films and devices. Description of the Drawings
[0015] Figure 1 Photoluminescence spectrum of the three-dimensional perovskite blue-light thin film prepared in an air environment under 365 nm excitation light for Example 1; Figure 2Photoluminescence spectrum of the three-dimensional perovskite blue light thin film prepared in an air environment under 365 nm excitation light for Example 2; Figure 3 Photoluminescence spectrum of the three-dimensional perovskite blue light thin film prepared in an air environment under 365 nm excitation light for Example 3; Figure 4 Photoluminescence spectrum of the three-dimensional perovskite blue light thin film prepared in an air environment under 365 nm excitation light for Example 4; Figure 5 Photoluminescence spectrum of the three-dimensional perovskite blue light thin film prepared in an air environment under 365 nm excitation light for Example 5. Detailed implementation manners
[0016] The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present invention is not limited thereby. Embodiment
[0017] In this embodiment, a method for preparing a three-dimensional perovskite blue light thin film in an air environment includes the following steps: S1: Prepare a polyvinylpyrrolidone-modified substrate; The substrate is a glass substrate. First, the glass substrate is pretreated: First, wipe the glass substrate with a dust-free cloth dipped in dishwashing liquid, and then ultrasonically clean it with a glass cleaning solution (a mixed solution of dishwashing liquid and deionized water at a ratio of 1:30), water, and alcohol for 15 minutes. After that, dry the glass substrate and treat its surface with oxygen plasma gas for 600 seconds. Then, spin-coat a 4 mg / ml polyvinylpyrrolidone / dimethylformamide solution on the glass substrate at 5000 rpm for 30 seconds, and anneal it at 120 °C for 5 minutes.
[0018] S2: Prepare a precursor solution for the three-dimensional perovskite blue light thin film; Dissolve 0.1 mmol of cesium trifluoroacetate, 0.1 mmol of lead bromide, 0.1 mmol of rubidium chloride, and 5 mg of 18-crown-6 in 1 ml of dimethyl sulfoxide, heat and stir at 60 °C for 4 hours to obtain a three-dimensional mixed halogen perovskite precursor solution with a molar concentration of 0.1 mol / ml. After filtration, store it in a nitrogen environment for use.
[0019] S3: Prepare the three-dimensional perovskite blue light thin film Heat the perovskite precursor solution and isooctane antisolvent at 90 °C for more than 5 minutes in advance; Place it in a spin coater. In an air environment, spin-coat the heated perovskite precursor solution on the polyvinylpyrrolidone layer at 4000 rpm for 90 seconds. At 35 seconds remaining, add 150 μl of the heated isooctane antisolvent, and anneal at 80 °C for 1 minute to obtain a perovskite light-emitting layer.
[0020] S4: Test the emission spectrum and efficiency of the three-dimensional perovskite blue light thin film Perform photoluminescence spectroscopy characterization on the three-dimensional blue light PeLEDs of Example 1 to obtain the photoluminescence spectrum diagram of the three-dimensional blue light PeLEDs, as Figure 1 shown. The peak position of its emission is at 478 nm, the full width at half maximum (FWHM) is 16.9 nm, which is sky blue light. The narrower FWHM means higher color purity, and the PLQY is 26.69%. Example
[0021] In this example, a method for preparing a three-dimensional perovskite blue light thin film in an air environment includes the following steps: S1: Prepare a polyvinylpyrrolidone-modified substrate The substrate is a glass substrate. First, pre-treat the glass substrate: First, wipe the glass substrate with a dust-free cloth dipped in dishwashing liquid, then ultrasonically clean it with a glass cleaning solution (a mixed solution of dishwashing liquid and deionized water at a ratio of 1:30), water, and alcohol for 15 minutes. After that, dry the glass substrate and treat its surface with oxygen plasma gas for 600 seconds. Then, spin-coat a 4 mg / mL polyvinylpyrrolidone / dimethylformamide solution on the glass substrate at 5000 rpm for 30 seconds and anneal it at 120 °C for 5 minutes.
[0022] S2: Prepare the precursor solution of the three-dimensional perovskite blue light thin film Dissolve 0.1 mmol of cesium trifluoroacetate, 0.1 mmol of lead bromide, 0.1 mmol of rubidium chloride, 11 mg of 18-crown-6, and 30 mg of triphenylphosphine oxide in 1 mL of dimethyl sulfoxide, heat and stir at 60 °C for 4 hours to obtain a 0.1 mol / mL three-dimensional mixed halogen perovskite precursor solution. After filtration, store it in a nitrogen environment for use; S3: Prepare the three-dimensional perovskite blue light thin film Heat the perovskite precursor solution and isooctane antisolvent at 90 °C for more than 5 minutes in advance.
[0023] Place it in a spin coater. In an air environment, spin-coat the heated perovskite precursor solution on the polyvinylpyrrolidone layer at 4000 rpm for 90 seconds. At 35 seconds remaining, drop 150 μL of the heated isooctane antisolvent, and anneal it at 80 °C for 1 minute to obtain the perovskite light-emitting layer.
[0024] S4: Test the emission spectrum and efficiency of the three-dimensional perovskite blue light thin film Perform photoluminescence spectroscopy characterization on the three-dimensional blue light PeLEDs of Example 2 to obtain the photoluminescence spectrum diagram of the three-dimensional blue light PeLEDs, as Figure 2As shown, the peak position of its luminescence is at 480.3 nm, the full width at half maximum (FWHM) is 18.2 nm, it is sky blue light, and the narrower FWHM means higher color purity, and the PLQY is 54.23%. Example
[0025] In this example, a method for preparing a three-dimensional perovskite blue light thin film in an air environment includes the following steps: S1: Prepare a polyvinylpyrrolidone-modified substrate The substrate is a glass substrate. First, the glass substrate is pretreated: First, wipe the glass substrate with a dust-free cloth dipped in dishwashing liquid, then ultrasonically clean it with a glass cleaning solution (a mixed solution of dishwashing liquid and deionized water at a ratio of 1:30), water, and alcohol for 15 minutes. After that, dry the glass substrate and treat its surface with oxygen plasma gas for 600 seconds. Then, spin-coat a 4 mg / ml polyvinylpyrrolidone / dimethylformamide solution on the glass substrate at 5000 rpm for 30 seconds, and anneal it at 120 °C for 5 minutes.
[0026] S2: Prepare a precursor solution for the three-dimensional perovskite blue light thin film Dissolve 0.07 mmol of cesium trifluoroacetate, 0.1 mmol of lead bromide, 0.1 mmol of rubidium chloride, 0.03 mmol of cesium bromide, 11 mg / ml of 18-crown-6, and 30 mg of triphenylphosphine oxide in 1 ml of dimethyl sulfoxide, heat and stir at 60 °C for 4 hours to obtain a 0.1 mmol / ml three-dimensional mixed halogen perovskite precursor solution. After filtration, store it in a nitrogen environment for use; S3: Prepare a three-dimensional perovskite blue light thin film Heat the perovskite precursor solution and isooctane antisolvent at 90 °C for more than 5 minutes in advance.
[0027] Place it in a spin coater. In an air environment, spin-coat the heated perovskite precursor solution on the polyvinylpyrrolidone layer at 4000 rpm for 90 seconds. At 35 seconds remaining, add 150 μl of the heated isooctane antisolvent, and anneal at 80 °C for 1 minute to obtain a perovskite light-emitting layer.
[0028] S4: Test the luminescence spectrum and efficiency of the three-dimensional perovskite blue light thin film Perform photoluminescence spectroscopy characterization on the three-dimensional blue light PeLEDs in Example 3 to obtain the photoluminescence spectrum diagram of the three-dimensional blue light PeLEDs, as Figure 3 shown, the peak position of its luminescence is at 481.8 nm, the full width at half maximum (FWHM) is 15.8 nm, it is sky blue light, and the narrower FWHM means higher color purity, and the PLQY is 20.36%. Example
[0029] In this embodiment, a method for preparing a three-dimensional perovskite blue light thin film in an air environment includes the following steps: S1: Prepare a polyvinylpyrrolidone-modified substrate The substrate is a glass substrate. First, the glass substrate is pretreated: First, wipe the glass substrate with a dust-free cloth dipped in dish soap, and then ultrasonically clean it with a glass cleaning solution (a mixed solution of dish soap and deionized water at a ratio of 1:30), water, and alcohol for 15 minutes. After that, dry the glass substrate and treat its surface with oxygen plasma gas for 600 seconds. Then, spin-coat a 4 mg / mL polyvinylpyrrolidone / dimethylformamide solution on the glass substrate at 5000 rpm for 30 seconds, and anneal it at 120 °C for 5 minutes.
[0030] S2: Prepare a precursor solution for the three-dimensional perovskite blue light thin film Dissolve 0.05 mmol of cesium trifluoroacetate, 0.1 mmol of lead bromide, 0.1 mmol of rubidium chloride, 0.05 mmol of cesium bromide, 11 mg of 18-crown-6, and 30 mg of triphenylphosphine oxide in 1 mL of dimethyl sulfoxide, heat and stir at 60 °C for 4 hours to obtain a three-dimensional mixed halogen perovskite precursor solution with a molar concentration of 0.1 mmol / mL. After filtration, store it in a nitrogen environment for use. S3: Prepare a three-dimensional perovskite blue light thin film Heat the perovskite precursor solution and isooctane antisolvent at 90 °C for more than 5 minutes in advance.
[0031] Place it in a spin coater. In an air environment, spin-coat the heated perovskite precursor solution on the polyvinylpyrrolidone layer at 4000 rpm for 90 seconds. At 35 seconds remaining, drop 150 μL of the heated isooctane antisolvent, and anneal at 80 °C for 1 minute to obtain a perovskite light-emitting layer.
[0032] S4: Test the emission spectrum and efficiency of the three-dimensional perovskite blue light thin film Perform photoluminescence spectroscopy characterization on the three-dimensional blue light PeLEDs in Example 4 to obtain the photoluminescence spectrum diagram of the three-dimensional blue light PeLEDs, as Figure 4 shown. The peak position of its emission is at 482.6 nm, the full width at half maximum (FWHM) is 15.6 nm, which is sky blue. The narrower FWHM means higher color purity, and the PLQY is 28.49% Example
[0033] In this embodiment, a method for preparing a three-dimensional perovskite blue light thin film in an air environment includes the following steps: S1: Prepare a polyvinylpyrrolidone-modified substrate The substrate is a glass substrate, and the glass substrate is pre-treated first: First, wipe the glass substrate with a dust-free cloth dipped in dish soap, and then ultrasonically clean it with a glass cleaning solution (a mixed solution of dish soap and deionized water at a ratio of 1:30), water, and alcohol for 15 minutes in sequence. After that, dry the glass substrate and treat its surface with oxygen plasma gas for 600 seconds. Then, spin-coat a 4 mg / mL polyvinylpyrrolidone / dimethylformamide solution on the glass substrate at 5000 rpm for 30 seconds, and anneal it at 120 °C for 5 minutes.
[0034] S2: Prepare the precursor solution for the three-dimensional perovskite blue light thin film Dissolve 0.03 mmol of cesium trifluoroacetate, 0.1 mmol of lead bromide, 0.1 mmol of rubidium chloride, 0.07 mmol of cesium bromide, 11 mg of 18-crown-6, and 30 mg of triphenylphosphine oxide in 1 mL of dimethyl sulfoxide, heat and stir at 60 °C for 4 hours to obtain a three-dimensional mixed halogen perovskite precursor solution with a molar concentration of 0.1 mmol / mL. After filtration, store it in a nitrogen environment for later use; S3: Prepare the three-dimensional perovskite blue light thin film Heat the perovskite precursor solution and the isooctane antisolvent at 90 °C more than 5 minutes in advance.
[0035] Place it in a spin coater. Under an air environment, spin-coat the heated perovskite precursor solution on the polyvinylpyrrolidone layer at 4000 rpm for 90 seconds. At 35 seconds remaining, drop 150 μL of the heated isooctane antisolvent, and anneal at 80 °C for 1 minute to obtain the perovskite light-emitting layer.
[0036] S4: Test the emission spectrum and efficiency of the three-dimensional perovskite blue light thin film Perform photoluminescence spectroscopy characterization on the three-dimensional blue light PeLEDs in Example 5 to obtain the photoluminescence spectrum diagram of the three-dimensional blue light PeLEDs, as Figure 5 shown. The peak position of its emission is at 483.4 nm, the full width at half maximum (FWHM) is 15.8 nm, which is sky blue light. The narrower FWHM means higher color purity, and the PLQY is 41.33%.
[0037] In the present invention, by regulating the ratios of cesium trifluoroacetate, lead bromide, rubidium chloride, triphenylphosphine oxide, 18-crown-6, and cesium bromide in the perovskite precursor, a series of perovskite blue light thin films are prepared. The emission peak positions, full widths at half maximum, and emission efficiencies (PLQY) are shown in the following table: 。
[0038] It should be noted that although the present invention has been described by the above embodiments, the present invention may have many other embodiments. Without departing from the spirit and scope of the present invention, those skilled in the art can obviously make various corresponding changes and modifications to the present invention, but these changes and modifications should fall within the scope protected by the appended claims of the present invention and their equivalents.
Claims
1. A method for preparing a three-dimensional perovskite blue light film in an air environment, characterized in that: The following steps are involved: S1: Preparation of polyvinyl pyrrolidone-modified substrate; S2: Preparing the precursor solution of three-dimensional perovskite blue light film; S3: The precursor solution prepared in S2 is heated and then formed into a film on a substrate modified with polyvinyl pyrrolidone to prepare a three-dimensional perovskite blue light film.
2. The method for preparing a three-dimensional perovskite blue light film in an air environment according to claim 1, characterized in that: The specific method in S1 is: after dissolving polyvinyl pyrrolidone in dimethylformamide solution, a polyvinyl pyrrolidone film is prepared on a substrate by spin coating.
3. The method for preparing a three-dimensional perovskite blue light film in an air environment according to claim 1 or 2, characterized in that: The substrate is a glass substrate.
4. The method for preparing a three-dimensional perovskite blue light film in an air environment according to claim 2, characterized in that: Before preparing the polyvinyl pyrrolidone film on the substrate, the substrate is pretreated first. The specific steps of the pretreatment are: wipe the substrate, clean it with glass cleaning liquid and ultrapure water ultrasonically in sequence, blow dry it with nitrogen, and treat it with ultraviolet ozone for use.
5. The method for preparing a three-dimensional perovskite blue light film in an air environment according to claim 1, characterized in that: The precursor solution in S2 includes cesium trifluoroacetate, lead bromide, rubidium chloride, and 18-crown ether-6. The preparation method of the precursor solution is: dissolve cesium trifluoroacetate, lead bromide, rubidium chloride, and 18-crown ether-6 in dimethyl sulfoxide, heat and stir to dissolve, filter, and store for later use.
6. The method for preparing a three-dimensional perovskite blue light film in an air environment according to claim 5, characterized in that: The precursor solution also includes triphenylphosphine oxide.
7. The method for preparing a three-dimensional perovskite blue light film in an air environment according to claim 5, characterized in that: The precursor solution also includes triphenylphosphine oxide and cesium bromide.
8. The method for preparing a three-dimensional perovskite blue light film in an air environment according to claim 1, characterized in that: The specific steps in S3 are: forming a film of the heated precursor solution on a polyvinyl pyrrolidone-modified substrate by spin coating, adding an anti-solvent for treatment during the spin coating process, and forming a three-dimensional perovskite blue light film after annealing.
9. The method for preparing a three-dimensional perovskite blue light film in an air environment according to claim 8, characterized in that: The anti-solvent is isoheptane solvent.