CN114874765A - Preparation method of red-light perovskite quantum dot film - Google Patents
Preparation method of red-light perovskite quantum dot film Download PDFInfo
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Abstract
The invention discloses a preparation method of a red-light perovskite quantum dot film, and belongs to the field of fluorescent materials. The preparation method comprises the following steps: preparing perovskite quantum dot reaction liquid by using a monomer capable of polymerizing by ultraviolet light as a solvent; mixing and stirring a specially-made photocuring prepolymer, an active diluent monomer and a photoinitiator to prepare a photocuring glue solution; mixing and stirring the special perovskite quantum dot reaction liquid and the special photocuring glue liquid to obtain a photocuring quantum dot glue liquid; and coating the photocuring quantum dot adhesive liquid on a base material, and curing by illumination to obtain the perovskite quantum dot film. The quantum dot reaction solution prepared by the invention saves raw materials and simplifies the preparation steps; the prepared quantum dot photocuring glue solution has high curing rate, the viscosity is suitable for industrial coating, the quantum dots are uniformly dispersed after standing for a long time at normal temperature, and the fluorescence stability is good; the prepared quantum dot photocureable film has high quantum yield, narrow half-peak width and good fluorescence stability.
Description
Technical Field
The invention relates to the field of fluorescent materials, in particular to a preparation method of a red-light perovskite quantum dot optical film.
Background
In recent years, the technology of the present invention has been developedTo that, inorganic metal halide perovskite quantum dots CsPbX 3 (X = I, Br, Cl) is considered to have wide application prospect in the field of LED illumination and display due to unique optical properties such as ultra-narrow emission spectrum and ultra-high fluorescence quantum yield. However, the red perovskite quantum dot is easy to decompose or change phase in the subsequent application process after the material is synthesized due to the unstable phase structure of the red perovskite quantum dot, so that the red perovskite quantum dot cannot be prepared into a film for application.
Generally, the method for preparing red perovskite quantum dots is a thermal injection method, namely, octadecene with a high boiling point is used as a solvent, oleic acid oleylamine is used as a ligand, and a cesium source is injected at a high temperature of about 160 ℃ to obtain a quantum dot reaction solution. And purifying the reaction liquid by using methyl acetate, wherein the surface ligand is lost after purification to cause the surface of the quantum dot to generate defects, part of phase structure is converted from gamma phase to delta phase, the quantum yield is reduced, and the purified quantum dot is mixed with a polymer or a monomer, so that the dissolution of the polymer and the polymer is poor, and even most of the polymer can directly cause the decomposition of the red perovskite quantum dot. If the synthesized quantum dots are not purified, octadecene cannot be solidified.
The perovskite quantum dots are used as nanoscale fluorescent materials and need to be fixed in a transparent substrate. At present, the most common method is to disperse the quantum dots in the photo-curing glue to form a film by photo-curing. Therefore, the perovskite quantum dots are required to be uniformly dispersed in the glue solution and not to be layered, and meanwhile, the fluorescent performance of the perovskite quantum dots cannot be influenced by all components of the glue solution, so that the phase change or decomposition of the perovskite quantum dots cannot be caused. In addition, in order to meet the industrial requirement, the quantum dot light-cured adhesive is required to have high curing speed, and the viscosity of the adhesive reaches the industrial production standard. These are all difficulties that have been solved or overcome in the art.
Disclosure of Invention
In order to solve at least one of the technical problems, the invention aims to provide a preparation process of a high-performance red-light perovskite quantum dot film, so that quantum dots in glue solution are uniformly dispersed and have no influence on the fluorescence performance of the quantum dots, the viscosity and the curing rate of the glue solution meet the industrial requirement, and the fluorescence performance is stable after film forming. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a red perovskite quantum dot film comprises the following steps:
s1, preparing a perovskite quantum dot reaction solution by using a photopolymerizable first reactive diluent monomer as a solvent;
s2, mixing and stirring the photocuring prepolymer, a photopolymerizable second reactive diluent monomer and a photoinitiator to prepare a photocuring glue solution;
s3, mixing and stirring the perovskite quantum dot reaction liquid obtained in the step S1 and the photocuring glue liquid obtained in the step S2 to obtain a photocuring quantum dot glue liquid;
s4, coating the photocuring quantum dot adhesive liquid on a base material, curing by illumination to obtain a perovskite quantum dot film,
the first reactive diluent monomer is one or a mixture of more of hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, cyclotrimethylolpropane carboxyformaldehyde acrylate, tetrahydrofuran acrylate, phenoxyethyl acrylate, isodecyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate and acryloyl morpholine.
Further, step S1 specifically includes the following steps:
s11, mixing the first active diluted monomer serving as a cesium source solvent with cesium carbonate and cesium source fatty acid, vacuumizing and heating to 60-160 ℃ for 1-2 hours to obtain a cesium source;
s12, mixing the first reactive diluent monomer serving as a lead source solvent with lead bromide, lead iodide, lead source fatty acid and lead source fatty amine, vacuumizing and heating to 80-170 ℃ for 2-3 hours to obtain a lead source;
s13, injecting a cesium source with the temperature of 70-160 ℃ into a lead source with the temperature of 80-170 ℃, stirring for 3-15S, and immediately cooling in cold water to obtain the perovskite quantum dot reaction liquid.
In some embodiments of the present invention, the cesium-source fatty acids are selected from one or more of the group consisting of caprylic acid, lauric acid, oleic acid, behenic acid.
In some embodiments of the invention, the cesium carbonate, cesium-derived fatty acid, and cesium-derived solvent are in the proportions: 4-8: 15-30: 60-80. In some embodiments of the present invention, the fatty acid of lead source is selected from one or more of the group consisting of caprylic acid, lauric acid, oleic acid and behenic acid.
In some embodiments of the present invention, the lead source fatty amine is selected from one or more of the group consisting of octylamine, laurylamine, oleylamine and eicosylamine.
In some embodiments of the invention, the lead-source solvent has the same selection range as the cesium-source solvent.
Further, step S2 specifically includes the following steps:
s21, weighing the photo-curing prepolymer, the reactive diluent monomer and the photoinitiator;
s22, mixing the photo-curing prepolymer, the active diluent monomer and the photoinitiator to obtain the photo-curing glue solution,
wherein the weight ratio of the photocuring prepolymer to the reactive diluent monomer to the photoinitiator is 40-59: 59-40: 0.1-3.
In some embodiments of the present invention, the photocurable prepolymer has a functionality of 2 to 6 and a viscosity at room temperature in the range of 5000-.
In some preferred embodiments of the present invention, the photo-curing prepolymer is one or more of unsaturated polyester prepolymer, epoxy acrylate prepolymer, polyurethane acrylate prepolymer, polyester acrylate prepolymer, polyether acrylate prepolymer, pure acrylic resin prepolymer, epoxy resin prepolymer, and silicone oligomer, and their mixture with alkane (including linear chain and cyclic chain).
In some embodiments of the present invention, the second reactive diluent monomer is a monomer with an unsaturated bond capable of polymerizing the photocurable quantum dot paste by irradiation of ultraviolet light, violet light or blue light.
Further, the second reactive diluent monomer is one or a mixture of several of a monofunctional acrylate diluent monomer, a bifunctional diluent monomer and a polyfunctional diluent monomer.
Optionally, the monofunctional diluting monomer is one or more selected from the group consisting of hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, cyclotrimethylolpropane carboxyformaldehyde acrylate, tetrahydrofuran acrylate, phenoxyethyl acrylate, isodecyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and acryloylmorpholine.
Optionally, the difunctional diluent monomer is one or more selected from the group consisting of tripropylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, ethoxylated bisphenol a dimethacrylate, polyethylene glycol diacrylate and 1-adamantane acrylate.
Optionally, the multifunctional diluent monomer is one or more selected from the group consisting of (ethoxylated) trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.
In some embodiments of the invention, the photoinitiator is a photoinitiator that initiates free radical type polymerization.
In some preferred embodiments of the present invention, the photoinitiator is one or a mixture of 1-hydroxycyclohexyl phenyl ketone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-dioxymethyl-2-phenyl acetophenone, (2, 4, 6-trimethylbenzoyl chloride) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2-methylbenzophenone, and 4-isopropylthioxanthone.
Further, in step S3, after the photo-curing quantum dot solution is coated on the substrate, the method further includes covering the substrate, which is the same as or different from the coated substrate, on the upper surface of the photo-curing quantum dot solution, thereby obtaining the perovskite quantum dot film with the sandwich structure, which is a cured film and an optical film, wherein the upper layer and the lower layer are the substrates serving as the protective supports, and the middle layer is a photo-curing quantum dot glue layer formed after the photo-curing quantum dot glue solution is cured.
In the embodiment of the present invention, in step S3, the coating manner includes, but is not limited to, spin coating, knife coating, roll coating, spray coating, printing, dipping, or casting.
In some embodiments of the present invention, in step S3, the illumination refers to illumination with uv light, violet light or blue light for a period of time.
In an embodiment of the invention, the substrate is a polymeric film, such as PMMA, PET, PE, PP, etc.
In some embodiments of the present invention, a barrier film may be further coated on a surface of the substrate in contact with the photocurable glue layer, and further, the material of the barrier film is a silicon-containing material, and the like.
The invention has the advantages of
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the invention directly uses the photo-polymerization solvent to prepare the red light perovskite quantum dot, and the preparation process does not use non-monomer organic solvent, thereby omitting the process of removing the solvent by centrifugation, vacuum pumping and other modes when the perovskite quantum dot film is synthesized in the prior art and simplifying the preparation steps of the photo-curing glue solution.
The preparation method of the invention obtains the perovskite quantum dot optical adhesive with good compatibility and uniform dispersion of quantum dots by mixing the perovskite quantum dot optical adhesive with a special formula of prepolymer, photoinitiator, diluent monomer and other photocuring raw materials, and the perovskite quantum dot optical adhesive has no layering, no phase change, no decomposition and no color change. The adhesive has moderate viscosity, is suitable for preparing a photocuring film, and needs small photocuring energy (less than 1000 mj/cm) 2 ) The photocuring rate is high (less than 10 s), and the method is suitable for industrial production. The light-cured film has high fluorescence quantum yield (more than 90 percent) and narrow half-peak width (less than 40 nm).
Drawings
Fig. 1 shows a transmission electron microscope photograph of red perovskite quantum dots prepared in example 1 of the present invention.
Fig. 2 shows an ultraviolet-visible light absorption spectrum curve of the perovskite quantum dot reaction liquid prepared in example 1 of the present invention.
FIG. 3 shows the fluorescence spectrum curve of the reaction solution of titanium ore quantum dots prepared in example 1 of the present invention.
Fig. 4 shows a photo-curing quantum dot glue solution prepared by mixing in example 1 of the present invention.
Fig. 5 shows a photograph of the perovskite quantum dot film prepared in example 1 of the present invention.
Fig. 6 shows a schematic structural diagram of the perovskite quantum dot film prepared in example 1 of the present invention.
Fig. 7 shows an excitation spectrum of the perovskite quantum dot film prepared in example 1 of the present invention.
Fig. 8 shows a fluorescence spectrum curve of the perovskite quantum dot film prepared in example 1 of the present invention.
Fig. 9 shows a transmission electron micrograph of the perovskite quantum dot prepared in example 2 of the present invention.
Fig. 10 shows a fluorescence spectrum curve of the perovskite quantum dot film prepared in example 2 of the present invention.
Fig. 11 shows a transmission electron micrograph of the perovskite quantum dot prepared in example 3 of the present invention.
Fig. 12 shows a fluorescence spectrum curve of the perovskite quantum dot film prepared in example 3 of the present invention.
Fig. 13 shows a transmission electron micrograph of the perovskite quantum dot prepared in example 4 of the present invention.
Fig. 14 shows the fluorescence spectrum curve of the perovskite quantum dot film prepared in example 4 of the present invention.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101, 102, etc., and all subranges, e.g., 100 to 166, 155 to 170, 198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, insofar as such terms are necessary for operational performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments.
Examples
The following examples are used herein to demonstrate preferred embodiments of the invention. It will be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function in the invention, and thus can be considered to constitute preferred modes for its practice. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit or scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the disclosures and references cited herein and the materials to which they refer are incorporated by reference.
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.
The experimental procedures in the following examples are conventional unless otherwise specified. The instruments used in the following examples are, unless otherwise specified, laboratory-standard instruments; the test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
Example 1 preparation method of perovskite Quantum dot film # 1
1) Preparation of cesium source: 0.13g of cesium carbonate powder, 0.5mL of oleic acid and 1.5mL of isobornyl methacrylate were charged into a three-necked flask, and heated to 60 ℃ under a vacuum of only 100Pa, whereupon the solution was clear and transparent.
2) Preparing a lead source: a three-necked flask was charged with 0.59g of lead bromide powder, 0.2642g of lead iodide powder, 1.5mL of oleic acid, 1.5mL of oleylamine, and 3mL of isobornyl acrylate, and the flask was evacuated to 75Pa and heated to 80 ℃.
3) Preparing a photocuring quantum dot glue solution: a cesium source flask and a lead source flask were purged with nitrogen gas by a syringe. Quickly injecting into lead source, stirring for 10s, quickly cooling with warm water to room temperature. As a result of observing the morphology of the synthesized perovskite quantum dot by a transmission electron microscope, as shown in fig. 1, it is understood from fig. 1 that the quantum dot is in a square shape and has a uniform particle diameter. Ultraviolet visible light absorption spectrum and fluorescence spectrum of the perovskite quantum dot reaction liquid are obtained, and spectrum curves shown in fig. 2 and fig. 3 are obtained respectively. As can be seen from fig. 2, the band gap of the ultraviolet-visible light absorption spectrum curve of the perovskite quantum dot reaction solution is 1.90 eV. As can be seen from FIG. 3, the peak position of the emission peak of the fluorescence spectrum curve of the perovskite quantum dot reaction solution was 630nm, and the half-peak width was 35 nm.
4) Preparing a photocuring glue solution: 35g of epoxy acrylate, 35g of isobornyl methacrylate and 2.1g of (2, 4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide were mixed uniformly.
5) Preparing a photocuring quantum dot glue solution: 5g of perovskite quantum dot reaction liquid and 40g of photocuring glue liquid are mixed and stirred for 20min to obtain photocuring quantum dot glue liquid. As shown in FIG. 4, it can be seen from the observation of FIG. 4 that the photo-setting liquid is uniform and fine.
6) Preparing a photocuring quantum dot film: 2g of the photocuring quantum dot glue solution is poured on a PET film, and the PET film is coated by blade coating at the speed of 100cm/min by an automatic coating machine and then covered. Using high-pressure mercury lamp at 2000mj/cm 2 The energy of (2) was irradiated for 10 seconds to obtain a photocurable film.
A perovskite quantum dot film # 1 was obtained as shown in fig. 5.
The schematic structural diagram of the perovskite quantum dot film # 1 prepared by the method is shown in fig. 6
The excitation spectrum of the perovskite quantum dot film # 1 was obtained, and as shown in fig. 7, the excitation peak position was found to be 424 nm. The emission spectrum of the perovskite quantum dot film # 1 was obtained, and as shown in fig. 8, it was found that the emission peak position was 650nm and the half-value width was 30 nm.
Example 2 preparation method of perovskite Quantum dot film #2
1) Preparation of cesium source: 0.13g of cesium carbonate powder, 0.5mL of oleic acid and 1.5mL of isodecyl acrylate were charged into a three-necked flask, evacuated to 100Pa and heated to 80 ℃.
2) Preparing a lead source: 0.59g of lead bromide powder, 0.2642g of lead iodide powder, 1.3mL of oleic acid, 1.5mL of oleylamine and 3mL of isodecyl acrylate were put into a three-necked flask, and the flask was evacuated to 100Pa, heated to 80 ℃ and kept warm for 20 min.
3) Preparing a titanium ore quantum dot reaction solution: nitrogen gas was introduced into the lead source flask and the cesium source flask, and the cesium source was purged with a syringe and quickly injected into the lead source solution. After stirring for 10s, the flask was cooled to room temperature with ice water. The transmission electron micrograph of the reaction solution is shown in FIG. 9, and the quantum dots are square and uniform in particle size.
4) Preparation of photocuring glue solution: 20g of epoxy acrylate, 20g of aromatic urethane acrylate, 15g of isobornyl acrylate, 15g of trihydroxymethylpropane triacrylate and 2.8g of 2, 2-dioxymethyl-2-phenylacetophenone were mixed uniformly.
5) Preparing a photocuring quantum dot glue solution: 5g of perovskite quantum dot reaction liquid and 40g of photocuring glue liquid are mixed and stirred for 20 min.
6) Preparing a perovskite quantum dot film: 2g of the photocuring quantum dot glue solution is poured on a PET film, and the PET film is coated by blade coating at the speed of 100cm/min by an automatic coating machine. Using high-pressure mercury lamp at 2000mj/cm 2 The energy of (3) was irradiated for 10 seconds to obtain a perovskite quantum dot film # 2.
The emission spectrum of the perovskite quantum dot film #2 was obtained, and as shown in fig. 10, it was found that the emission peak position was 630nm and the half-value width was 40 nm.
Example 3 preparation method of perovskite Quantum dot film # 3
1) Preparation of cesium source: 0.13g of cesium carbonate powder, 0.5mL of oleic acid and 1.5mL of isobornyl methacrylate were charged into a three-necked flask, and heated to 60 ℃ under vacuum to 100 Pa.
2) Preparing a lead source: a three-necked flask was charged with 0.59g of lead bromide powder, 0.2642g of lead iodide powder, 1.5mL of oleic acid, 1.5mL of oleylamine, and 3mL of lauryl methacrylate, and the flask was evacuated to 100Pa and heated to 80 ℃.
3) Preparing a perovskite quantum dot reaction solution: nitrogen gas was introduced into the lead source flask and the cesium source flask, and the cesium source was evacuated with a syringe and quickly injected into the lead source solution. After stirring for 10s, the flask was cooled to room temperature with ice water.
As a result of observing the morphology of the synthesized perovskite quantum dots by a transmission electron microscope, as shown in FIG. 11, it is clear from FIG. 11 that the perovskite quantum dots in the reaction solution are in a square block shape, have a particle diameter of approximately 10 to 15nm, and have a uniform particle diameter.
4) Preparation of photocuring glue solution: 20g of epoxy acrylate, 20g of aromatic urethane acrylate, 50g of isobornyl methacrylate, 10g of 1, 6-hexanediol dimethacrylate and 1.4g of (2, 4, 6-trimethylbenzoyl chloride) diphenylphosphine oxide were mixed uniformly.
5) Preparing a photocuring quantum dot glue solution: 1g of perovskite quantum dot reaction liquid and 40g of photocuring glue liquid are mixed and stirred for 20min to obtain photocuring quantum dot glue liquid.
6) Preparing a perovskite quantum dot film: 2g of the photocuring quantum dot glue solution is poured on a PET film, and the PET film is coated by blade coating at the speed of 100cm/min by an automatic coating machine and then covered. Using high-pressure mercury lamp at 2000mj/cm 2 Is irradiated for 10 s.
The fluorescence pattern of the perovskite quantum dot film # 3 was obtained, and as shown in FIG. 12, the fluorescence peak position was 632 nm.
Example 4 preparation method of perovskite Quantum dot film #4
1) Preparation of cesium source: 0.13g of cesium carbonate powder, 0.5mL of oleic acid and 1.5mL of n-octyl methacrylate were charged into a three-necked flask, evacuated to 100Pa and heated to 80 ℃.
2) Preparing a lead source: a three-necked flask was charged with 0.59g of lead bromide powder, 0.2642g of lead iodide powder, 1.5mL of oleic acid, 1.5mL of octylamine, and 3mL of n-octyl methacrylate, and the flask was evacuated to 100Pa and heated to 80 ℃.
3) Preparing a titanium ore quantum dot reaction solution: nitrogen gas was introduced into the lead source flask and the cesium source flask, and the cesium source was purged with a syringe and quickly injected into the lead source solution. After stirring for 10s, the flask was cooled to room temperature with ice water. The transmission electron micrograph of the reaction solution is shown in FIG. 13, and the quantum dots are square and have uniform particle size. As shown in FIG. 14, the emission spectrum of the perovskite quantum dot reaction solution shows that the emission peak position is 650nm and the half-peak width is 40 nm.
4) Preparing a photocuring glue solution: 20g of urethane acrylate, 15g of lauryl acrylate, 15g of pentaerythritol triacrylate and 0.7g of 2-methylbenzophenone were mixed uniformly.
5) Preparing a photocuring quantum dot glue solution: 2g of perovskite quantum dot reaction liquid and 15g of photocuring glue liquid are mixed and stirred for 1 hour.
6) Preparing a perovskite quantum dot film: 2g of the photocuring quantum dot glue solution is poured on a PMMA film, spin coating is carried out by a spin coater at the speed of 700r/m, and a PET film is coated. Using high-pressure mercury lamp at 1000mj/cm 2 The energy of (3) was irradiated for 4 seconds to obtain a perovskite quantum dot film # 4.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (13)
1. A preparation method of a red perovskite quantum dot optical film is characterized by comprising the following steps:
s1, preparing a perovskite quantum dot reaction solution by using a photopolymerizable first reactive diluent monomer as a solvent;
s2, mixing and stirring the photocuring prepolymer, a photopolymerizable second reactive diluent monomer and a photoinitiator to prepare a photocuring glue solution;
s3, mixing and stirring the perovskite quantum dot reaction liquid obtained in the step S1 and the photocuring glue liquid obtained in the step S2 to obtain a photocuring quantum dot glue liquid;
s4, coating the photocuring quantum dot adhesive liquid on a base material, curing by illumination to obtain a perovskite quantum dot film,
wherein the photopolymerizable first reactive diluent monomer is one or a mixture of several selected from the group consisting of hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, cyclotrimethylolpropane carboxyformaldehyde acrylate, tetrahydrofuran acrylate, phenoxyethyl acrylate, isodecyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and acryloylmorpholine.
2. The method for preparing the red perovskite quantum dot optical film according to claim 1, wherein the step S1 specifically comprises the following steps:
s11, mixing the first active diluted monomer serving as a cesium source solvent with cesium carbonate and cesium source fatty acid, vacuumizing and heating to 60-160 ℃ for 1-2 hours to obtain a cesium source;
s12, mixing the first reactive diluent monomer serving as a lead source solvent with lead bromide, lead iodide, lead source fatty acid and lead source fatty amine, vacuumizing and heating to 80-170 ℃ for 2-3 hours to obtain a lead source;
s13, injecting a cesium source with the temperature of 70-160 ℃ into a lead source with the temperature of 80-170 ℃, stirring for 3-15S, and immediately cooling in cold water to obtain the perovskite quantum dot reaction liquid.
3. The method for preparing the red perovskite quantum dot optical film according to claim 2, wherein the cesium fatty acid is selected from one or more of caprylic acid, lauric acid, oleic acid and eicosanoic acid.
4. The method for preparing the red perovskite quantum dot optical film according to claim 2, wherein the lead source fatty acid is one or more selected from the group consisting of caprylic acid, lauric acid, oleic acid and eicosanoic acid; the lead source fatty amine is selected from one or more of octylamine, laurylamine, oleylamine and eicosylamine.
5. The method of making a red perovskite quantum dot optical film according to any one of claims 2 to 4, wherein the cesium source solvent and the lead source solvent are reactive diluent monomers capable of photoinitiated polymerization.
6. The method for preparing the red perovskite quantum dot optical film according to claim 1, wherein the step S2 specifically comprises the following steps:
s21, weighing the photo-curing prepolymer, a second reactive diluent monomer and a photoinitiator;
s22, mixing the photo-curing prepolymer, the second reactive diluent monomer and the photoinitiator to obtain the photo-curing glue solution,
wherein the weight ratio of the photocuring prepolymer, the second reactive diluent monomer and the photoinitiator is 40-59: 59-40: 0.1-3.
7. The method for preparing the red perovskite quantum dot optical film as claimed in claim 6, wherein the photo-curing prepolymer is one or more of unsaturated polyester prepolymer, epoxy acrylate prepolymer, polyurethane acrylate prepolymer, polyester acrylate prepolymer, polyether acrylate prepolymer, pure acrylic resin prepolymer, epoxy resin prepolymer and organic silicon oligomer, and the mixture of the unsaturated polyester prepolymer, epoxy acrylate prepolymer, polyester acrylate prepolymer, polyether acrylate prepolymer, pure acrylic resin prepolymer, epoxy resin prepolymer and organic silicon oligomer, and the mixture of the epoxy resin prepolymer, the polyester acrylate prepolymer and the organic silicon oligomer with alkane (including linear chain and cyclic).
8. The method for preparing the perovskite quantum dot film as claimed in claim 6, wherein the second reactive diluent monomer is one or a mixture of several of a monofunctional diluent monomer, a difunctional diluent monomer and a multifunctional diluent monomer.
9. The method of claim 8, wherein the monofunctional diluent monomer is one or more selected from the group consisting of hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, cyclotrimethylolpropane carboxyformaldehyde acrylate, tetrahydrofuran acrylate, phenoxyethyl acrylate, isodecyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and acryloylmorpholine.
10. The method of claim 8, wherein the difunctional diluent monomer is one or more selected from the group consisting of tripropylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, ethoxylated bisphenol A dimethacrylate, polyethylene glycol diacrylate and 1-adamantane acrylate.
11. The method of producing a perovskite quantum dot film as claimed in claim 8, wherein the multifunctional dilution monomer is one or a mixture of several selected from the group consisting of (ethoxylated) trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.
12. The method of claim 6, wherein the photoinitiator is one or a mixture of 1-hydroxycyclohexyl phenyl ketone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-dioxymethyl-2-phenyl acetophenone, (2, 4, 6-trimethylbenzoyl chloride) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2-methylbenzophenone, and 4-isopropylthioxanthone.
13. The method for preparing a perovskite quantum dot film as claimed in claim 1, wherein after the photo-curing quantum dot solution is coated on the substrate, the method further comprises covering the same or different substrate as the coated substrate on the upper surface of the photo-curing quantum dot solution.
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