CN114874764A - Preparation method of perovskite thin film with enhanced luminescence property - Google Patents
Preparation method of perovskite thin film with enhanced luminescence property Download PDFInfo
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Abstract
The invention provides a preparation method of a perovskite thin film with enhanced luminescence property, which comprises nanosphere pretreatment, nanosphere array preparation, substrate preparation, plasma etching treatment, TiO 2 Sol preparation, core-shell structure super-surface construction, perovskite precursor liquid preparation, perovskite composite film forming and the like. The invention develops and constructs the preparation process of the super surface of the core-shell structure, each unit takes the nanosphere as the core on the substrate, the metal oxide coating covers on the outer shell of each nanosphere, and through adjusting the size, the coating thickness and the crystal lattice size of the nanosphere and due to the synergistic effect of the periodic structure and the low loss, the adjacent resonance effectively enhances the amplitude of the resonance peak, obviously improves the brightness and has pure structureContrast and contrast. When the resonance peak is tuned to the intrinsic emission peak of the perovskite nanocrystal, the intrinsic photoluminescence intensity reaches the greatest increase. The stability of the perovskite nanocrystalline after the polymer encapsulation is also obviously improved. Showing great potential in high-end lighting and display areas.
Description
Technical Field
One or more embodiments of the present disclosure relate to the field of optoelectronic material preparation, and more particularly, to a method for preparing a perovskite thin film with enhanced luminescence properties.
Background
Liquid Crystal Displays (LCDs) have become an important milestone in the history of human display technology (nat. mater.14(2015) 454-458). Although LCDs have certain differences in contrast, black expression, color gamut, thinness, flexibility, etc., compared to high-end Organic Light Emitting Diode (OLED) displays, they are still one of the mainstream display technologies (Light sci. appl.7(2018) 17168) in terms of their high stability, long lifetime, eye protection, low cost, no burn-in and no flash). Even if the overall quality of an LCD screen is not inferior to that of an OLED screen, its wide color gamut and color saturation still face great challenges (adv. mate.22 (2010) 3076-3080). Therefore, there is a need to develop a high performance White Light Emitting Diode (WLED) backlight for LCDs. Currently, commercial LCDs typically use InGaN blue chips to excite yellow YAG: ce 3+ Phosphor or green Eu 2 + : beta-SiAlON and Red Mn 4+ ：K 2 SiF 6 Phosphor to achieve white backlighting (prog. mater. sci.84(2016) 59-117; chem. mater.30(2018) 494-505; nat. Commun.5(2014) 4312). The color gamut and saturation of backlights manufactured by this method are slightly lower and cannot meet the application requirements of high-end displays (Light sci. appl.6(2017) 16271).
Alternatively, perovskite nanocrystals (CsPbX) 3 PNCs, X ═ I, Br, Cl) are attracting more attention in the display field because they have optical properties superior to those of organic fluorescent materials and conventional NCs in terms of manufacturing flow, color purity, cost, tunable Photoluminescence (PL) spectral range. Unfortunately, perovskite halide materials degrade under external stimuli (e.g., moisture, light, and heat) due to their inherent ionic crystal characteristics and low formation Energy, and the corresponding thin films have low luminous efficiencies, which have hindered the development of perovskite-based devices (ACS Energy Lett.6(2021) 519-528; adv. Funct. Mater.31(2021) 2008211). To date, many strategies have been employed to address the limitations of luminescence yield (adv. mater.29(2017) 1604268; Nano lett.20(2020)7906- & 7911), which are implemented essentially based on Electron Beam Lithography (EBL) and Focused Ion Beam (FIB) techniques. Nearly 90% of reports use this strategyThe sample is manufactured slightly, so that the method has the advantages of good accuracy, high reliability, repeatability and the like, but the defects of limited processing area, high cost, high complexity, long time consumption and the like still exist (adv. opt. mater.9(2021) 2001474). In addition, light, oxygen and moisture can cause decomposition or regeneration of PNCs, resulting in fluorescence quenching and spectral shift (chem. soc. rev.48(2019) 310-. Perovskite related opto-electronic devices therefore also require advantageous encapsulation to eliminate their aggregation and regrowth.
Perovskite Nanocrystals (PNCs) are expected to replace traditional phosphor color conversion layers in backlight displays due to their excellent optical properties, which can enhance the color gamut and saturation of the display. However, poor stability and low luminous efficiency have hindered the development of perovskite-based devices.
Disclosure of Invention
The technical problem is as follows: in view of the above, the present invention aims to provide a method for preparing a perovskite thin film with enhanced light emitting performance, and the method combines the scalability of large-area manufacturing, and the cost-effective weak disordered super surface is an effective method, which can make up the gap between high-efficiency laboratory demonstration and commercial displays, and promote the industrial production thereof.
The technical scheme is as follows: the invention aims to provide a preparation method of a perovskite thin film with enhanced luminescence property, which comprises the following steps:
step 1: preprocessing nanospheres;
sampling nanosphere colloid by ethanol according to the volume ratio of 1: 1-1: 1.5, mixing the nanosphere colloid and the ethanol in a glass bottle, and performing ultrasonic treatment for 30-60 min to mix the nanospheres and the ethanol to prepare a water-based nanosphere colloid solution;
step 2: preparing a nanosphere array based on a Langmuir-Blodgett film technology;
sucking the water-based nanosphere colloidal solution in the step 1, and injecting the water-based nanosphere colloidal solution into a clean water tank so that the nanospheres cover the water surface and form a single-layer nanosphere array;
and step 3: preparing a substrate;
taking a quartz plate, removing stains by using a cleaning agent, sequentially placing the quartz plate in deionized water, acetone and ethanol for ultrasonic cleaning for 20-30 min, drying the cleaned quartz plate by using nitrogen, and placing the quartz plate in an ultraviolet ozone cleaning machine for 15-30 min to prepare a substrate for attaching the single-layer nanosphere array in the step 2;
and 4, step 4: placing the substrate prepared in the step (3) in the water tank, reducing the liquid level of the water tank to enable the single-layer nanosphere array to transfer to the surface of the substrate after the liquid level is reduced, taking out the substrate and naturally drying the substrate, wherein the single-layer nanosphere array is hexagonal close-packed on the surface of the substrate;
and 5: carrying out plasma etching treatment;
placing the substrate attached with the single-layer nanosphere array prepared in the step 4 in an inductively coupled plasma etching machine, and introducing reaction gas into the inductively coupled plasma etching machine to etch the surface of the substrate to obtain a plasma-etched substrate;
step 6: putting ice water into a container, putting the container into a magnetic stirrer to stir the ice water, and taking TiCl with the concentration of 0.8-1.2 mol/L 4 Slowly dripping ice water to obtain hydrolysate, dripping ammonia water into the container to make the pH value of the hydrolysate be 7, obtaining white turbid solution, and filtering the white turbid solution to remove NH 4+ And Cl - ；
And 7: taking the white turbid solution prepared in the step 6, adding distilled water, and dispersing to obtain Ti (OH) 4 Taking an alkaline burette, and dropwise adding H into the turbid solution 2 O 2 Until a clear orange solution appears;
and 8: passing the orange solution through an anion-cation exchange resin column to wash away NH 4+ And Cl - ；
And step 9: placing the solution obtained in the step 8 in an oil bath at the temperature of 40-60 ℃, and heating to the temperature of 100-120 ℃ for 2-4 hours to prepare TiO 2 Sol, then stopping heating the TiO 2 Sol gelCooling to normal temperature, taking out and storing;
step 10: constructing a core-shell structure super surface;
taking the plasma etched substrate prepared in the step 5 and the sol prepared in the step 9, placing the plasma etched substrate in the sol to be soaked for 20-30 min, washing the substrate with a small amount of ethanol and then drying the substrate, repeating the steps for 2-4 times, heating the substrate to 75-90 ℃ and keeping the temperature for 2-6 h to obtain nanospheres serving as inner cores, and coating TiO on each spherical shell 2 The core-shell structure of (2) is super-surface;
step 11: taking metal halide and cesium halide to stir in an N, N-dimethylformamide solvent at 800 rpm-1200 rpm for 30 min-60 min to form transparent perovskite precursor liquid;
step 12: adding PVDF powder into the perovskite precursor liquid prepared in the step 11, and violently stirring at room temperature for 36-48 hours to obtain a completely dissolved mixture; the PVDF powder is polyvinylidene fluoride powder;
step 13: and (3) taking the substrate with the core-shell structure super surface prepared in the step (10) and the mixture prepared in the step (12), casting the mixture onto the core-shell structure super surface, putting the mixture into a vacuum drying box, extracting air to enable the interior of the vacuum drying box to reach a negative pressure state so as to enable the N, N-dimethylformamide solvent to volatilize, forming a colorless film on the core-shell structure super surface by the mixture, taking the substrate out of the vacuum drying box, putting the substrate into the atmosphere, gradually changing the color of the colorless film, and stripping the film from the substrate to obtain the perovskite composite film with independent photoluminescence spectra at the wavelength of 400-500nm, the wavelength of 500-600nm and the wavelength of 600-700 nm.
Wherein the content of the first and second substances,
when the photoluminescence spectrum of the perovskite composite film is at the wavelength of 400-500nm, the nanospheres in the water-based nanosphere colloidal solution are polystyrene spheres with the diameter of 300-380 nm and the concentration of 2.5-5 wt%.
When the photoluminescence spectrum of the perovskite composite film is at the wavelength of 400-500nm, the specific operation method in the step 5 comprises the following steps: selecting an inductive coupling plasma etching machine with the power of 100W-150W, and introducing oxygen and argon with the gas flow of 20sccm to 50sccm for 16 to 77 seconds; coating TiO on each spherical shell 2 The super surface of the core-shell structure generates a resonance peak with the resonance wavelength of 400-500nm to match with the perovskite precursor liquid with the photoluminescence spectrum of 400-500nm of the thin film.
The preparation method of the perovskite precursor liquid with the film photoluminescence spectrum of 400-500nm comprises the following steps: mixing PbCl 2 、CsCl、PbBr 2 And CsBr powder is weighed according to the molar ratio of 1:1:0: 0-0: 0:1:1, and the powder is pre-dissolved in DMF solvent after being mixed to form perovskite precursor liquid with the concentration of 0.01 mmol/ml-0.015 mmol/ml and the film photoluminescence spectrum of 400-500 nm.
When the photoluminescence spectrum of the perovskite composite film is at the wavelength of 500-600nm, the nanospheres are polystyrene spheres with the diameter of 380-460 nm and the concentration of 2.5-5 wt%.
When the photoluminescence spectrum of the perovskite composite film is at the wavelength of 500-600nm, the specific operation method of the step 5 comprises the following steps: selecting an inductive coupling plasma etching machine with the power of 100W-150W, and introducing oxygen and argon, wherein the flow rate is 20 sccm-50 sccm, and the time is 23 s-105 s; coating TiO on each spherical shell 2 The super surface of the core-shell structure generates a resonance peak with the resonance wavelength of 500-600nm to match with the perovskite precursor liquid with the photoluminescence spectrum of 500-600nm of the thin film.
The preparation method of the perovskite precursor liquid with the film photoluminescence spectrum of 500-600nm comprises the following steps: reacting PbBr 2 、CsBr、PbI 2 And weighing the CsI powder according to a molar ratio of 1:1:0: 0-1.8: 1.8:1.2:1.2, mixing the powder, and pre-dissolving the powder in a DMF solvent to form the perovskite precursor solution with the concentration of 0.01 mmol/ml-0.015 mmol/ml and the film photoluminescence spectrum of 500-600 nm.
When the photoluminescence spectrum of the perovskite composite film is at the wavelength of 600-700nm, the nanospheres are polystyrene spheres with the diameter of 460-540 nm and the concentration of 2.5-5 wt%.
When the photoluminescence spectrum of the perovskite composite film is at the wavelength of 600-700nm, the specific operation method of the step 5 comprises the following steps: selecting an inductive coupling plasma etcher with the power of 100W-150W, and introducing oxygen and argon at the flow rate of 20 sccm-50 sccm34s to 152 s; coating TiO on each spherical shell 2 The super surface of the core-shell structure generates a resonance peak with the resonance wavelength of 600-700nm to match with the perovskite precursor liquid with the photoluminescence spectrum of 600-700nm of the thin film.
The preparation method of the perovskite precursor liquid with the film photoluminescence spectrum of 600-700nm comprises the following steps: reacting PbBr 2 、CsBr、PbI 2 And weighing the CsI powder according to a molar ratio of 1.8:1.8:1.2: 1.2-0: 0:1:1, mixing the powder, and pre-dissolving the powder in a DMF solvent to form the perovskite precursor solution with the concentration of 0.01 mmol/ml-0.015 mmol/ml and the film photoluminescence spectrum of 600-700 nm.
Has the advantages that: as can be seen from the above description, one or more embodiments of the present disclosure provide a method for preparing a perovskite thin film with enhanced luminescence property, which has several advantages:
1. in order to perfectly compound PNCs into a polymer matrix to form a composite film, the method adopts an in-situ synthesis strategy of controlling crystallization by solvent volatilization, namely, perovskite precursor solution and high polymer powder are uniformly mixed, the solvent is removed in vacuum after coating, and the composite film is grown by recrystallization. The existence of the high polymer can inhibit the growth size of PNCs and ensure the excellent luminescence property of the perovskite composite film;
2. this approach further limits the crystal size and increases the light transmittance of the film. There is a strong chemical interaction between PNCs and the high polymer, and due to the large interfacial interactions, PNCs can grow in situ in high quality and coherent interfaces. The method has higher controllability than compounding pre-synthesized PNCs into a polymer matrix, because additional interface modification is needed to improve the dispersibility and compatibility between the PNCs and the matrix, which provides basic characteristics for embedding the full-medium super-surface into a film and showing excellent optical performance;
3. the prepared super surface has the structure that each unit takes nanospheres as cores on a substrate, and a metal oxide coating covers the shell of each nanosphere. By adjusting the size of the nanospheres, the thickness of the coating and the size of the crystal lattice, and due to the synergistic effect of the periodic structure and low loss, the amplitude of a resonance peak is effectively enhanced by adjacent resonance, and theoretically, the value of the resonance peak of the optimized unit structure characteristic can reach nearly 100%; this also means that the prepared super-surface has a series of advantages in producing structural color, significantly improving brightness, purity and contrast.
4. The arrangement mode, the period size, the crystal lattice size, the disorder degree and different crystal phases of the super surface all influence electromagnetic resonance, so that the photoluminescence enhancement degree is regulated and controlled; the arrangement mode comprises bead array, tetragonal array and hexagonal array, so the substrate is not limited to a quartz plate, but also can be a flexible substrate, and the arrangement mode of a composite structure is changed through stretching/bending to influence electromagnetic resonance so as to regulate and control the photoluminescence enhancement degree; the size of the hexagonal close-packed nanospheres determines the final period size of the super surface because the metal oxide coating has less influence on the position of the nanospheres; the disorder degree can be adjusted by the speed of sucking the nanosphere colloidal solution into the clean water tank by the syringe, and the increase of the disorder degree can greatly weaken the amplitude of a resonance peak and is accompanied with a certain degree of blue shift; TiO 2 2 The crystalline phases of (a) include amorphous, anatase, brookite, rutile, different crystalline phases will influence the refractive index and thus the electromagnetic resonance;
5. the combination of Electron Beam Lithography (EBL) and Reactive Ion Etching (RIE) technology is adopted, so that the method has the advantages of good accuracy, high reliability, repeatability and the like;
6. the core-shell structure super-surface preparation process is developed, and the super-surface preparation process is combined with the in-situ prepared perovskite nanocrystalline, so that the perovskite composite film with large area, low cost and high luminescence can be obtained. Using CsPbBr 3 Composite film (Green) and CsPbBrI 2 The composite film (red) is used as a color conversion layer, and a blue light guide plate is added to manufacture backlight, so that a wide color gamut display can be designed. Its color gamut area is 107% of the traditional National Television Systems Committee (NTSC) standard and 157% of the current commercial backlight display. Compared with a commercial liquid crystal screen, the full-medium super-surface enhanced CsPbX is adopted 3 Liquid crystal screens assembled from composite films exhibit more color detail and higher saturation, which means that CsPbX 3 Before the composite film is widely applied to future photoelectric devicesAnd (5) landscape. In addition, the cost-effective weak disordered super surface is an effective method in combination with the scalability of large-area manufacturing, and can make up the gap between high-efficiency laboratory demonstrations and commercial displays and promote the industrial production thereof.
Drawings
In order to more clearly illustrate one or more embodiments or prior art solutions of the present specification, the drawings that are needed in the description of the embodiments or prior art will be briefly described below, and it is obvious that the drawings in the following description are only one or more embodiments of the present specification, and that other drawings may be obtained by those skilled in the art without inventive effort from these drawings.
FIG. 1 is TiO 2 A scanning electron microscopy image of a/PS-based super-surface;
FIG. 2 is an energy diagram of a PNCs-super surface coupling system;
FIG. 3 is a photoluminescence spectrum of a PNCs/PVDF film and a composite film;
FIG. 4 shows the absorption spectra of the PNCs/PVDF thin film and the composite thin film.
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to specific embodiments.
Example 1
Step 1: preprocessing nanospheres;
sampling nanospheres and ethanol according to the volume ratio of 1:1, mixing the nanospheres and the ethanol in a glass bottle, and carrying out ultrasonic treatment for 30-60 min to mix the nanospheres and the ethanol to prepare a water-based nanosphere colloidal solution;
among them, nanospheres are polystyrene spheres (PS spheres), available from alfa aesar (china) chemical limited, with a diameter of 340nm and a concentration of 2.5 wt%, ethanol is added as a dispersant to a water-based PS sphere colloid solution to reduce surface tension, thereby spreading PS spheres on the water surface more effectively, the driving force for PS sphere diffusion is related to Marangoni effect (Marangoni effect), which is mass transfer along the interface between two fluids due to surface tension gradient;
and 2, step: preparing a nanosphere array based on an LB (Langmuir-Blodgett) membrane technology;
sucking the water-based nanosphere colloidal solution in the step 1 by using a 1ml syringe, and injecting the water-based nanosphere colloidal solution into a clean water tank so that the nanospheres cover the water surface and form a single-layer nanosphere array; the LB film technology is Langmuir-Blodgett film;
when injected, the ethanol-containing PS sphere colloidal solution contacts the water surface to form a strong Marangoni force, which pushes the colloidal spheres to rapidly disperse outwards from the region with low surface tension until they cover the whole surface of the water bath; the nozzle must be positioned strictly to just contact the water surface, the interface dynamic and equilibrium conditions are also dependent on the injection speed, and must be carefully controlled below 2ml/h to prevent excessive injection from causing PS spheres to precipitate;
and step 3: preparing a substrate;
taking a quartz plate, removing stains by using a cleaning agent, sequentially placing the quartz plate in deionized water, acetone and ethanol for ultrasonic cleaning for 20min, drying the cleaned quartz plate by using nitrogen, and then placing the quartz plate in an ultraviolet ozone cleaning machine for 20min to prepare a substrate for attaching the single-layer nanosphere array in the step 2;
the substrate is not limited to a quartz plate, but can also be a silicon wafer or a flexible substrate;
and 4, step 4: placing the substrate prepared in the step (3) in a water tank, reducing the liquid level of the water tank to enable the single-layer nanosphere array to transfer to the surface of the substrate after the liquid level is reduced, taking out the substrate and naturally drying the substrate, wherein the single-layer nanosphere array is hexagonal close-packed on the surface of the substrate;
when the solvent is self-evaporated or baked at low temperature (lower than 60 ℃), the nanospheres are attracted together by capillary force, and the nanospheres are stacked in a hexagonal close-packed mode and tightly attached to the substrate to serve as a template; compared with a vertical deposition method and spin coating of a spin coater for preparing a single-layer nanosphere array, nanospheres are stacked in a stable single-layer hexagonal close-packed mode, the sample quality is obviously improved, the price is low, the stability and the reliability are high, and the requirements on experimental equipment and environment are low;
and 5: carrying out plasma etching treatment;
placing the substrate attached with the single-layer nanosphere array prepared in the step 4 in an inductively coupled plasma etching machine, and introducing reaction gas into the inductively coupled plasma etching machine to etch the surface of the substrate to obtain a plasma-etched substrate;
wherein, the reaction gas is a combined gas of oxygen and argon, and the power is 120W; the gas flow rate is 50 sccm; time 22 s);
step 6: placing 250ml of ice water into a beaker, placing the beaker into a magnetic stirrer to stir the ice water, and taking 1.0mol/L TiCl 4 3ml of solution, slowly dropping into ice water to obtain hydrolysate, dropping ammonia water into the beaker to make the pH value of the hydrolysate be 7 and obtain white turbid solution, and filtering the white turbid solution to remove NH 4+ And Cl - ；
The magnetic stirrer is specifically operated in such a way that a beaker filled with ice water is placed at the stirring position of the table top of the instrument, a stirrer is placed in the beaker, a power supply is started, and the stirring speed is set to be 800-1200 rpm; cleaning and wiping the electrode by using a pH value detector for the pH value of the hydrolysate, putting the electrode into the solution to be measured, stopping placing after properly shaking, and reading after the numerical value is stable;
and 7: taking the white turbid solution prepared in the step 6, adding 75ml of distilled water, and dispersing to obtain Ti (OH) 4 Taking an alkaline burette, and dropwise adding H into the turbid solution 2 O 2 Until a clear orange solution appears;
and 8: passing the orange solution through an anion-cation exchange resin column to wash away NH 4+ And Cl - (ii) a Wherein the cation exchange resin is preceded;
and step 9: the solution obtained in step 8 was placed in an oil bath at 50 ℃ for three hours, heated to 110 ℃ and maintainedFor 3 hours to prepare TiO 2 Sol, then stopping heating the TiO 2 Dissolving the sol, cooling to normal temperature, taking out and storing;
when the oil bath pan is heated and used, the heating switch is turned on, the temperature is adjusted to the required temperature by pressing the function key, and the temperature is confirmed;
step 10: constructing a core-shell structure super surface;
taking the plasma etched substrate prepared in the step 5 and the sol prepared in the step 9, placing the plasma etched substrate in the sol, soaking for 20-30 min, washing with a small amount of ethanol, drying, repeating the steps for three times, heating the substrate to 90 ℃, keeping for 2 hours, and obtaining the nano sphere serving as the inner core, wherein each spherical shell is coated with TiO 2 Of TiO 2 2 A PS-based core-shell structured super-surface;
step 11: taking PbCl 2 (0.2mmol)、PbBr 2 (0.2mmol), CsCl (0.185mmol) and CsBr (0.185mmol) in 30ml DMF solvent at 800-1200 rpm for 30-60 min to form transparent CsPbCl with concentration of 0.012mmol/ml 1.5 Br 1.5 A perovskite precursor liquid; DMF is N, N-dimethylformamide;
step 12: adding 4.2g of PVDF powder into the perovskite precursor liquid prepared in the step 11, and violently stirring at room temperature for 36-48 hours to obtain a completely dissolved mixture; the PVDF powder is polyvinylidene fluoride powder;
step 13: taking the substrate with the core-shell structure and the super surface and the mixture prepared in the step 10 and the mixture prepared in the step 12, casting the mixture on the super surface of the core-shell structure, putting the mixture into a vacuum drying box, extracting air to enable the interior of the vacuum drying box to reach a negative pressure state so as to enable the DMF solvent to be volatilized, forming a colorless film on the super surface of the core-shell structure by the mixture, taking the substrate out of the vacuum drying box, placing the substrate in the atmosphere, gradually changing the color of the colorless film, stripping the film from the substrate, and obtaining CsPbCl with an independent photoluminescence spectrum at the wavelength of 400-plus-material 500nm 1.5 Br 1.5 A perovskite composite film;
wherein, the polyvinylidene fluoride powder can be replaced by polymethyl methacrylate (PMMA), the crystallization of the polyvinylidene fluoride powder is slightly different from that of PVDF, and the polyvinylidene fluoride powder needs to be crystallized at the temperature of 80-120 ℃ for 3-12 min; n, N-Dimethylformamide (DMF) may be replaced by dimethyl sulfoxide (DMSO).
TiO 2 The super surface of the/PS-based core-shell structure has obvious Mie resonance characteristics, and the photoluminescence enhancement degree can be regulated and controlled by changing the resonance of all-dielectric nanospheres in the perovskite film. The maximum 2.73-fold increase in intrinsic photoluminescence intensity was achieved when the resonance peak was tuned to the intrinsic emission peak of the perovskite nanocrystals. Under the irradiation of 380nm ultraviolet light, the film presents high-brightness blue (photoluminescence spectrum is at 445nm wavelength), and can be stably stored in a high-humidity environment. In addition, the perovskite composite film prepared by the method has the advantages of high luminous efficiency, narrow full width at half maximum, low cost and large-scale preparation.
Example 2
Step 1: preprocessing nanospheres;
sampling nanospheres and ethanol according to the volume ratio of 1:1, mixing the nanospheres and the ethanol in a glass bottle, and carrying out ultrasonic treatment for 30-60 min to mix the nanospheres and the ethanol to prepare a water-based nanosphere colloidal solution;
wherein the nanospheres are polystyrene spheres (PS spheres) obtained from Alfa-Angsa chemical Co., Ltd., diameter of 400nm, and concentration of 2.5 wt%;
step 2: preparing a nanosphere array based on an LB membrane technology;
sucking the water-based nanosphere colloidal solution in the step 1 by using a 1ml syringe, and injecting the water-based nanosphere colloidal solution into a clean water tank so that the nanospheres cover the water surface and form a single-layer nanosphere array; the LB film technology is Langmuir-Blodgett film;
and step 3: preparing a substrate;
taking a quartz plate, removing stains by using a cleaning agent, sequentially placing the quartz plate in deionized water, acetone and ethanol for ultrasonic cleaning for 20min, drying the cleaned quartz plate by using nitrogen, and then placing the quartz plate in an ultraviolet ozone cleaning machine for 20min to prepare a substrate for attaching the single-layer nanosphere array in the step 2;
and 4, step 4: placing the substrate prepared in the step (3) in a water tank, reducing the liquid level of the water tank to enable the single-layer nanosphere array to transfer to the surface of the substrate after the liquid level is reduced, taking out the substrate and naturally drying the substrate, wherein the single-layer nanosphere array is hexagonal close-packed on the surface of the substrate;
and 5: carrying out plasma etching treatment;
placing the substrate attached with the single-layer nanosphere array prepared in the step 4 in an inductively coupled plasma etching machine, and introducing reaction gas into the inductively coupled plasma etching machine to etch the surface of the substrate to obtain a plasma-etched substrate;
wherein, the reaction gas is a combined gas of oxygen and argon, and the power is 120W; the gas flow rate is 50 sccm; time 31 s);
step 6: placing 250ml of ice water in a beaker, placing the beaker in a magnetic stirrer to stir the ice water, and taking 1.0mol/L TiCl 4 3ml of solution, slowly dropping into ice water to obtain hydrolysate, dropping ammonia water into the beaker to make the pH value of the hydrolysate be 7 and obtain white turbid solution, and filtering the white turbid solution to remove NH 4+ And Cl - ；
And 7: taking the white turbid solution prepared in the step 6, adding 75ml of distilled water, and dispersing to obtain Ti (OH) 4 Taking an alkaline burette, and dropwise adding H into the turbid solution 2 O 2 Until a clear orange solution appears;
and 8: passing the orange solution through an anion-cation exchange resin column to wash away NH 4+ And Cl - ；
And step 9: the solution obtained in step 8 was placed in an oil bath at 50 ℃ for three hours, heated to 110 ℃ and maintained for 3 hours to prepare TiO 2 Sol, then stopping heating the TiO 2 Dissolving the sol, cooling to normal temperature, taking out and storing;
step 10: constructing a core-shell structure super surface;
taking stepsPlacing the plasma etched substrate prepared in the step 5 and the sol prepared in the step 9 into the sol to be soaked for 20-30 min, washing the substrate with a small amount of ethanol and then drying the substrate, repeating the steps for three times, heating the substrate to 90 ℃ and keeping the temperature for 2 hours to obtain the nano-spheres serving as the inner cores, and coating TiO on each spherical shell 2 Of TiO 2 2 A PS-based core-shell structured super-surface;
step 11: taking PbBr 2 (0.4mmol) and CsBr (0.37mmol) in 30ml DMF solvent at 800-1200 rpm for 30-60 min to form transparent CsPbBr with concentration of 0.012mmol/ml 3 A perovskite precursor liquid; DMF is N, N-dimethylformamide;
step 12: adding 4.2g of PVDF powder into the perovskite precursor liquid prepared in the step 11, and violently stirring at room temperature for 36-48 hours to obtain a completely dissolved mixture; the PVDF powder is polyvinylidene fluoride powder;
step 13: taking the substrate with the core-shell structure and the super surface and the mixture prepared in the step 10 and the mixture prepared in the step 12, casting the mixture on the super surface of the core-shell structure, putting the mixture into a vacuum drying box, extracting air to enable the interior of the vacuum drying box to reach a negative pressure state so as to enable the DMF solvent to be volatilized, forming a colorless film on the super surface of the core-shell structure by the mixture, taking the substrate out of the vacuum drying box, placing the substrate in the atmosphere, gradually changing the color of the colorless film, stripping the film from the substrate, and obtaining CsPbBr with the independent photoluminescence spectrum at the wavelength of 500-plus-material 600nm 3 A perovskite composite film;
TiO 2 the super surface of the/PS-based core-shell structure has obvious Mie resonance characteristics, and the photoluminescence enhancement degree can be regulated and controlled by changing the resonance of all-dielectric nanospheres in the perovskite film. The maximum 3.19-fold increase in intrinsic photoluminescence intensity was achieved when the resonance peak was tuned to the intrinsic emission peak of the perovskite nanocrystals. Under the irradiation of 380nm ultraviolet light, the film presents high-brightness green (photoluminescence spectrum is at 520nm wavelength), and can be stably stored in a high-humidity environment. In addition, the perovskite composite film prepared by the method has the advantages of high luminous efficiency, narrow full width at half maximum, low cost and large-scale preparation.
Example 3
Step 1: preprocessing nanospheres;
sampling nanospheres and ethanol according to the volume ratio of 1:1, mixing the nanospheres and the ethanol in a glass bottle, and carrying out ultrasonic treatment for 30-60 min to mix the nanospheres and the ethanol to prepare a water-based nanosphere colloidal solution;
wherein the nanospheres are polystyrene spheres (PS spheres) obtained from Alfa-Angsa chemical Co., Ltd., diameter of 500nm, and concentration of 2.5 wt%;
step 2: preparing a nanosphere array based on an LB membrane technology;
sucking the water-based nanosphere colloidal solution in the step 1 by using a 1ml syringe, and injecting the water-based nanosphere colloidal solution into a clean water tank so that the nanospheres cover the water surface and form a single-layer nanosphere array; the LB film technology is Langmuir-Blodgett film;
and step 3: preparing a substrate;
taking a quartz plate, removing stains by using a cleaning agent, sequentially placing the quartz plate in deionized water, acetone and ethanol for ultrasonic cleaning for 20min, drying the cleaned quartz plate by using nitrogen, and then placing the quartz plate in an ultraviolet ozone cleaning machine for 20min to prepare a substrate for attaching the single-layer nanosphere array in the step 2;
and 4, step 4: placing the substrate prepared in the step (3) in a water tank, reducing the liquid level of the water tank to enable the single-layer nanosphere array to transfer to the surface of the substrate after the liquid level is reduced, taking out the substrate and naturally drying the substrate, wherein the single-layer nanosphere array is hexagonal close-packed on the surface of the substrate;
and 5: carrying out plasma etching treatment;
placing the substrate attached with the single-layer nanosphere array prepared in the step 4 in an inductively coupled plasma etching machine, and introducing reaction gas into the inductively coupled plasma etching machine to etch the surface of the substrate to obtain a plasma-etched substrate;
wherein, the reaction gas is a combined gas of oxygen and argon, and the power is 120W; the gas flow rate is 50 sccm; time 42 s);
step 6: placing 250ml of ice water into a beaker, placing the beaker into a magnetic stirrer to stir the ice water, and taking 1.0mol/L TiCl 4 3ml of solution, slowly dropping into ice water to obtain hydrolysate, dropping ammonia water into the beaker to make the pH value of the hydrolysate be 7 and obtain white turbid solution, and filtering the white turbid solution to remove NH 4+ And Cl - ；
And 7: taking the white turbid solution prepared in the step 6, adding 75ml of distilled water, and dispersing to obtain Ti (OH) 4 Taking an alkaline burette, and dropwise adding H into the turbid solution 2 O 2 Until a clear orange solution appears;
and 8: passing the orange solution through an anion-cation exchange resin column to wash away NH 4+ And Cl - ；
And step 9: the solution obtained in step 8 was placed in an oil bath at 50 ℃ for three hours, heated to 110 ℃ and maintained for 3 hours to prepare TiO 2 Sol, then stopping heating the TiO 2 Dissolving the sol, cooling to normal temperature, taking out and storing;
step 10: constructing a core-shell structure super surface;
taking the plasma etched substrate prepared in the step 5 and the sol prepared in the step 9, placing the plasma etched substrate in the sol, soaking for 20-30 min, washing with a small amount of ethanol, and drying, repeating the steps for three times, heating the substrate to 90 ℃, keeping for 2 hours, and obtaining the nano-spheres serving as the cores, wherein each sphere shell is coated with TiO 2 Of TiO 2 2 A PS-based core-shell structured super-surface;
step 11: taking PbBr 2 (0.13mmol)、PbI 2 (0.27mmol), CsBr (0.13mmol) and CsI (0.25mmol) in 30ml DMF solvent at 800-1200 rpm for 30-60 min to form transparent CsPbBrI with concentration of 0.013mmol/ml 2 A perovskite precursor liquid; DMF is N, N-dimethylformamide;
step 12: adding 4.2g of PVDF powder into the perovskite precursor liquid prepared in the step 11, and violently stirring at room temperature for 36-48 hours to obtain a completely dissolved mixture; the PVDF powder is polyvinylidene fluoride powder;
step 13: taking the substrate with the core-shell structure and the super surface and the mixture prepared in the step 10 and the mixture prepared in the step 12, casting the mixture on the super surface of the core-shell structure, putting the mixture into a vacuum drying box, extracting air to enable the interior of the vacuum drying box to reach a negative pressure state so as to enable the DMF solvent to volatilize, forming a colorless film on the super surface of the core-shell structure by the mixture, taking the substrate out of the vacuum drying box, placing the substrate in the atmosphere, gradually changing the color of the colorless film, stripping the film from the substrate, and obtaining CsPbBrI with the independent photoluminescence spectrum at the wavelength of 600-700nm 2 A perovskite composite film;
TiO 2 the super surface of the/PS-based core-shell structure has obvious Mie resonance characteristics, and the photoluminescence enhancement degree can be regulated and controlled by changing the resonance of all-dielectric nanospheres in the perovskite film. The maximum 2.84-fold increase in intrinsic photoluminescence intensity was achieved when the resonance peak was tuned to the intrinsic emission peak of the perovskite nanocrystals. Under the irradiation of 380nm ultraviolet light, the film presents high-brightness red (photoluminescence spectrum is at 643nm wavelength), and can be stably stored in a high-humidity environment. In addition, the perovskite composite film prepared by the method has the advantages of high luminous efficiency, narrow full width at half maximum, low cost and large-scale preparation.
Observing the microstructure of the super surface of the core-shell structure on a scanning electron microscope (SEM, SU 8020); the Photoluminescence (PL) spectra and the absorption spectra of the films were measured using a confocal micro fluorescence spectroscopy system (LabRAM HR Evolution) and a UV/Vis/NIR spectrophotometer (LAMBDA 950), respectively. CsPbCl can be observed 1.5 Br 1.5 、CsPbBr 3 And CsPbBrI 2 The PL spectrum and absorption of the composite film are very similar in appearance to the corresponding PNCs/PVDF films, but the PL intensity of the composite film is significantly enhanced. When the super-surface resonances are tuned to the intrinsic emission peaks of the PNCs, their intrinsic PL intensities are 2.73, 3.19 and 2.84 times that of the PNCs/PVDF thin films, respectively.
In general, in order to perfectly compound PNCs into a polymer matrix to form a composite film, the method adopts an in-situ synthesis strategy of solvent volatilization control crystallization, namely, perovskite precursor solution and high polymer powder are uniformly mixed, the solvent is removed in vacuum after coating, and the composite film is formed by recrystallization growth. The existence of the high polymer can inhibit the growth size of PNCs and ensure the excellent luminescence property of the perovskite composite thin film.
This approach further limits the crystal size and increases the light transmittance of the film. There is a strong chemical interaction between PNCs and the high polymer, and due to the large interfacial interactions, PNCs can grow in situ in high quality and coherent interfaces. The method is more controllable than compounding pre-synthesized PNCs into a polymer matrix, as additional interfacial modification is required to improve the dispersibility and compatibility between the PNCs and the matrix, which provides basic characteristics for embedding the full-media super-surface into a film and exhibiting excellent optical properties.
In the method, the prepared super surface has the structure that each unit takes nanospheres as the core on the substrate, and the metal oxide coating covers the shell of each nanosphere. By adjusting the size of the nanospheres, the thickness of the coating and the size of the crystal lattice, and due to the synergistic effect of the periodic structure and low loss, the amplitude of a resonant mode is effectively enhanced by adjacent resonance, and theoretically, the value of the characteristic resonant peak of the optimized unit structure can reach nearly 100%; this also means that the prepared super-surface has a series of advantages in producing structural color, significantly improving brightness, purity and contrast.
The arrangement mode, the period size, the crystal lattice size, the disorder degree and different crystal phases of the super surface all influence electromagnetic resonance, so that the photoluminescence enhancement degree is regulated and controlled; the arrangement mode comprises bead array, tetragonal array and hexagonal array, so the substrate is not limited to a quartz plate, but also can be a flexible substrate, and the arrangement mode of a composite structure is changed through stretching/bending to influence electromagnetic resonance so as to regulate and control the photoluminescence enhancement degree; the hexagonal close-packed nanosphere size determines the final periodic size of the super-surface because the metal oxide coating has less effect on the position of the nanospheres; the degree of disorder can be notedThe speed of injecting the nanosphere colloidal solution into the clean water tank is regulated by the injector, the amplitude of a resonance peak is greatly weakened by the increase of disorder degree, and a certain degree of blue shift is accompanied; TiO 2 2 The crystalline phases of (a) include amorphous, anatase, brookite, rutile, different crystalline phases will influence the refractive index and thus the electromagnetic resonance;
the combination of Electron Beam Lithography (EBL) and Reactive Ion Etching (RIE) technology is adopted, so that the method has the advantages of good accuracy, high reliability, repeatability and the like;
the core-shell structure super-surface preparation process is developed, and the super-surface preparation process is combined with the in-situ prepared perovskite nanocrystalline, so that the perovskite composite film with large area, low cost and high luminescence can be obtained. Using CsPbBr 3 Composite film (Green) and CsPbBrI 2 The composite film (red) is used as a color conversion layer, and a blue light guide plate is added to manufacture backlight, so that a wide color gamut display can be designed. Its color gamut area is 107% of the traditional National Television Systems Committee (NTSC) standard and 157% of the current commercial backlight display. Compared with a commercial liquid crystal screen, the full-medium super-surface enhanced CsPbX is adopted 3 Liquid crystal screens assembled from composite films exhibit more color detail and higher saturation, which means that CsPbX 3 The composite film has wide application prospect in future photoelectric devices. In addition, the cost-effective weak disordered super surface is an effective method in combination with the scalability of large-area manufacturing, and can make up the gap between high-efficiency laboratory demonstrations and commercial displays and promote the industrial production thereof.
It is intended that the one or more embodiments of the present specification embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (10)
1. A preparation method of a perovskite thin film with enhanced luminescence property is characterized by comprising the following steps:
step 1: preprocessing nanospheres;
sampling nanosphere colloid by ethanol according to the volume ratio of 1: 1-1: 1.5, mixing the nanosphere colloid and the ethanol in a glass bottle, and performing ultrasonic treatment for 30-60 min to mix the nanospheres and the ethanol to prepare a water-based nanosphere colloid solution;
step 2: preparing a nanosphere array based on a Langmuir-Blodgett film technology;
sucking the water-based nanosphere colloidal solution in the step 1, and injecting the water-based nanosphere colloidal solution into a clean water tank so that the nanospheres cover the water surface and form a single-layer nanosphere array;
and step 3: preparing a substrate;
taking a quartz plate, removing stains by using a cleaning agent, sequentially placing the quartz plate in deionized water, acetone and ethanol for ultrasonic cleaning for 20-30 min, drying the cleaned quartz plate by using nitrogen, and placing the quartz plate in an ultraviolet ozone cleaning machine for 15-30 min to prepare a substrate for attaching the single-layer nanosphere array in the step 2;
and 4, step 4: placing the substrate prepared in the step (3) in the water tank, reducing the liquid level of the water tank to enable the single-layer nanosphere array to transfer to the surface of the substrate after the liquid level is reduced, taking out the substrate and naturally drying the substrate, wherein the single-layer nanosphere array is hexagonal close-packed on the surface of the substrate;
and 5: carrying out plasma etching treatment;
placing the substrate attached with the single-layer nanosphere array prepared in the step 4 in an inductively coupled plasma etching machine, and introducing reaction gas into the inductively coupled plasma etching machine to etch the surface of the substrate to obtain a plasma-etched substrate;
step 6: putting ice water into a container, putting the container into a magnetic stirrer to stir the ice water, and taking TiCl with the concentration of 0.8-1.2 mol/L 4 Slowly dripping ice water to obtain hydrolysate, dripping ammonia water into the container to make the pH value of the hydrolysate be 7, obtaining white turbid solution, and filtering the white turbid solution to remove NH 4+ And Cl - ；
And 7: taking the white turbid solution prepared in the step 6, adding distilled water, and dispersing to obtain Ti (OH) 4 Taking an alkaline burette, and dropwise adding H into the turbid solution 2 O 2 Until a clear orange solution appears;
and step 8: passing the orange solution through an anion-cation exchange resin column to wash away NH 4+ And Cl - ；
And step 9: placing the solution obtained in the step 8 in an oil bath at 40-60 ℃, heating to 100-120 ℃ and maintaining for 2-4 hours to prepare TiO 2 Sol, then stopping heating the TiO 2 Dissolving the sol, cooling to normal temperature, taking out and storing;
step 10: constructing a core-shell structure super surface;
taking the plasma etched substrate prepared in the step 5 and the sol prepared in the step 9, placing the plasma etched substrate in the sol, soaking for 20-30 min, washing with a small amount of ethanol, drying, repeating the steps for 2-4 times, heating the substrate to 75-90 ℃, keeping for 2-6 h, obtaining the nanospheres serving as the inner cores, and coating TiO on each spherical shell 2 The core-shell structure of (1) is a super surface;
step 11: taking metal halide and cesium halide to stir in an N, N-dimethylformamide solvent at 800 rpm-1200 rpm for 30 min-60 min to form transparent perovskite precursor liquid;
step 12: adding PVDF powder into the perovskite precursor liquid prepared in the step 11, and violently stirring at room temperature for 36-48 hours to obtain a completely dissolved mixture; the PVDF powder is polyvinylidene fluoride powder;
step 13: and (3) taking the substrate with the core-shell structure super surface prepared in the step (10) and the mixture prepared in the step (12), casting the mixture onto the core-shell structure super surface, putting the mixture into a vacuum drying box, extracting air to enable the interior of the vacuum drying box to reach a negative pressure state so as to enable the N, N-dimethylformamide solvent to volatilize, forming a colorless film on the core-shell structure super surface by the mixture, taking the substrate out of the vacuum drying box, putting the substrate into the atmosphere, gradually changing the color of the colorless film, and stripping the film from the substrate to obtain the perovskite composite film with independent photoluminescence spectra at the wavelength of 400-500nm, the wavelength of 500-600nm and the wavelength of 600-700 nm.
2. The method for preparing a perovskite thin film with enhanced light-emitting property as claimed in claim 1, wherein the nano-spheres in the water-based nano-sphere colloidal solution are polystyrene spheres with a diameter of 300nm to 380nm and a concentration of 2.5 wt% to 5 wt% when the photoluminescence spectrum of the perovskite composite thin film is at a wavelength of 400-500 nm.
3. The method for preparing a perovskite thin film with enhanced light-emitting property as claimed in claim 1, wherein the specific operation method of step 5 is as follows: selecting an inductive coupling plasma etching machine with the power of 100W-150W, and introducing oxygen and argon, wherein the flow rate is 20 sccm-50 sccm, and the time is 16 s-77 s; coating TiO on each spherical shell 2 The super surface of the core-shell structure generates a resonance peak with the resonance wavelength of 400-500nm to match with the perovskite precursor liquid with the photoluminescence spectrum of 400-500nm of the thin film.
4. The method for preparing the perovskite thin film with the enhanced luminescence property as claimed in claim 3, wherein the perovskite precursor liquid with the photoluminescence spectrum of the thin film of 400-500nm is prepared by the following specific method: mixing PbCl 2 、CsCl、PbBr 2 And CsBr powder is weighed according to the molar ratio of 1:1:0: 0-0: 0:1:1, and the powder is pre-dissolved in DMF solvent after being mixed to form perovskite precursor liquid with the concentration of 0.01 mmol/ml-0.015 mmol/ml and the film photoluminescence spectrum of 400-500 nm.
5. The method for preparing a perovskite thin film with enhanced light-emitting property as claimed in claim 1, wherein the nanospheres are polystyrene spheres with a diameter of 380 nm-460 nm and a concentration of 2.5 wt% -5 wt% when the photoluminescence spectrum of the perovskite composite thin film is at a wavelength of 500-600 nm.
6. The method for preparing a perovskite thin film with enhanced light-emitting property as claimed in claim 1, wherein when the photoluminescence spectrum of the perovskite composite thin film is at a wavelength of 500-600nm, the specific operation method of the step 5 comprises: selecting an inductive coupling plasma etching machine with the power of 100W-150W, and introducing oxygen and argon, wherein the flow rate is 20 sccm-50 sccm, and the time is 23 s-105 s; coating TiO on each spherical shell 2 The super surface of the core-shell structure generates a resonance peak with the resonance wavelength of 500-600nm to match with the perovskite precursor liquid with the photoluminescence spectrum of 500-600nm of the thin film.
7. The method for preparing the perovskite thin film with the enhanced luminescence property as claimed in claim 6, wherein the perovskite precursor liquid with the photoluminescence spectrum of 500-600nm is prepared by the specific method comprising the following steps: reacting PbBr 2 、CsBr、PbI 2 And weighing the CsI powder according to a molar ratio of 1:1:0: 0-1.8: 1.8:1.2:1.2, mixing the powder, and pre-dissolving the powder in a DMF solvent to form the perovskite precursor solution with the concentration of 0.01 mmol/ml-0.015 mmol/ml and the film photoluminescence spectrum of 500-600 nm.
8. The method for preparing a perovskite thin film with enhanced light-emitting property as claimed in claim 1, wherein the nano-spheres are polystyrene spheres with a diameter of 460-540 nm and a concentration of 2.5-5 wt% when the photoluminescence spectrum of the perovskite composite thin film is at a wavelength of 600-700 nm.
9. The method for preparing a perovskite thin film with enhanced light-emitting property as claimed in claim 1, wherein when the photoluminescence spectrum of the perovskite composite thin film is at the wavelength of 600-700nm, the specific operation method of the step 5 comprises: selecting an inductive coupling plasma etching machine with the power of 100W-150W, and introducing oxygen and argon, wherein the flow rate is 20 sccm-50 sccm, and the time is 34 s-152 s; coating TiO on each spherical shell 2 The super surface of the core-shell structure generates a resonance peak with the resonance wavelength of 600-700nm to matchThe perovskite precursor liquid with the film photoluminescence spectrum of 600-700nm is prepared.
10. The method for preparing the perovskite thin film with the enhanced luminescence property as claimed in claim 9, wherein the perovskite precursor liquid with the photoluminescence spectrum of 600-700nm is prepared by the specific method comprising the following steps: reacting PbBr 2 、CsBr、PbI 2 And weighing the CsI powder according to a molar ratio of 1.8:1.8:1.2: 1.2-0: 0:1:1, mixing the powder, and pre-dissolving the powder in a DMF solvent to form the perovskite precursor solution with the concentration of 0.01 mmol/ml-0.015 mmol/ml and the film photoluminescence spectrum of 600-700 nm.
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