CN114958154B - Preparation method of green-light perovskite quantum dot optical film - Google Patents
Preparation method of green-light perovskite quantum dot optical film Download PDFInfo
- Publication number
- CN114958154B CN114958154B CN202210470757.1A CN202210470757A CN114958154B CN 114958154 B CN114958154 B CN 114958154B CN 202210470757 A CN202210470757 A CN 202210470757A CN 114958154 B CN114958154 B CN 114958154B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- acrylate
- perovskite quantum
- prepolymer
- photocuring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a preparation method of a green 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 being polymerized 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 green-light perovskite quantum dot optical film.
Background
In recent years, inorganic metal halide perovskite quantum dots CsPbX 3 (X = I, br, cl) has 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, a great disadvantage of perovskite quantum dots is their poor stability under light, high temperature or ambient moisture and oxygen conditions.
Generally, the perovskite quantum dot is prepared by a thermal injection method, i.e., 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 methyl acetate, wherein the surface ligand is lost after purification to cause the surface of the quantum dot to generate defects, 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 or the monomer is poor. If the synthesized quantum dots are not purified, octadecene cannot be solidified.
The perovskite quantum dots are used as a nanoscale fluorescent material 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 and not layered in the glue solution, and meanwhile, the required components of the glue solution cannot influence the fluorescence performance of the perovskite quantum dots, so that the phase change or decomposition of the perovskite quantum dots cannot be caused. In addition, in order to meet the industrial requirements, the quantum dot light-cured adhesive is required to have a high curing rate, 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 above technical problems, the present invention aims to provide a preparation process of a high-performance perovskite quantum dot film, such that quantum dots in a 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 satisfy the industrial requirements, and the fluorescence performance after film formation is stable. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a 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 active 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 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-source fatty acid, and cesium-source solvent are in the proportions: 4-8. 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 a photocuring prepolymer, an active diluent monomer and a photoinitiator;
s22, mixing the photocuring prepolymer, the active dilution monomer and the photoinitiator to obtain the photocuring glue solution,
wherein the weight ratio of the photocuring prepolymer, the reactive diluent monomer and the photoinitiator is 40-59-40.
In some embodiments of the present invention, the photocurable prepolymer has a functionality of 2 to 6 and a viscosity ranging from 5000 to 500000CPS at normal temperature.
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 unsaturated bond capable of polymerizing the photo-curing quantum dot glue solution 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 glue 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 glue 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 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 ultraviolet 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 prepares the perovskite quantum dots by the photo-polymerizable solvent, and no organic solvent is used in the preparation process, so that the process of removing the solvent by centrifuging, vacuumizing and other modes when the perovskite quantum dot film is synthesized in the prior art is omitted, and the preparation steps of the photo-curing glue solution are simplified.
The preparation method of the invention obtains the perovskite quantum dot optical cement with good compatibility and uniform dispersion of quantum dots by mixing with the prepolymer, photoinitiator, diluent monomer and other photocuring raw materials with special formula, and the cement solution has no particles, no layering, no phase change, no decomposition and no color change after being placed for one month at room temperature. 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 80 percent), narrow half-peak width (less than 22 nm) and good fluorescence stability after being stored for more than one month.
Drawings
Fig. 1 shows a transmission electron micrograph of the perovskite quantum dot prepared in example 1 of the present invention.
Fig. 2 shows a uv-vis absorption spectrum curve of the reaction solution of titanium ore quantum dots 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.
Fig. 15 shows a fluorescence spectrum curve of the perovskite quantum dot film prepared in example 5 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 definition 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 to be 0.0001,0.001,0.01, or 0.1, as appropriate. 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 presented, 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 a chemical compound, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless explicitly stated 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 exclusion of any doubt, all compositions herein using the terms "comprising", "including", or "having" may include any additional additive, adjuvant, or compound, unless explicitly stated otherwise. Rather, the term "consisting essentially of 8230 \8230; \8230composition" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, insofar as they are necessary for performance. The term "consisting of 8230%" \8230comprises "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 all conventional ones unless otherwise specified. The instruments used in the following examples, unless otherwise specified, were all conventional laboratory 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 are charged into a three-necked flask, and the flask is evacuated and heated to 60 ℃ under 100Pa, whereupon the solution is clear and transparent.
2) Preparing a lead source: a three-necked flask was charged with 0.734g of lead bromide 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: nitrogen gas was introduced into the cesium source flask and the lead source flask, and the cesium source was purged with 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. And obtaining the ultraviolet visible light absorption spectrum and the fluorescence spectrum of the perovskite quantum dot reaction liquid, and respectively obtaining the spectrum curves shown in figures 2 and 3. As can be seen from FIG. 2, the band gap of the UV-visible absorption spectrum curve of the perovskite quantum dot reaction solution is 2.48eV, and the half-peak width of the absorption peak is 28nm. 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 518nm, and the half-peak width was 20nm.
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 homogeneously.
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 Energy irradiation ofAnd 10s, obtaining the photocured 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 373nm. 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 520nm and the half-value width was 21nm.
Example 2 preparation 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: 0.734g of lead bromide powder, 1.3mL of oleic acid, 1.5mL of oleylamine, and 3mL of isodecyl acrylate were charged into a three-necked flask, and the flask was evacuated to 100Pa, heated to 80 ℃ and kept warm for 20min.
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 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. 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 20min.
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 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 524nm and the half-value width was 20nm.
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, evacuated to 100Pa and heated to 60 ℃.
2) Preparing a lead source: 0.734g of lead bromide powder, 1.5mL of oleic acid, 1.5mL of oleylamine, 3mL of lauryl methacrylate were charged into a three-necked flask, 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 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.
As a result of observing the morphology of the synthesized perovskite quantum dots by a transmission electron microscope, 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, as shown in fig. 11.
4) Preparing a 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 10s.
The fluorescence pattern of the perovskite quantum dot film #3 was obtained, and as shown in FIG. 12, the fluorescence peak position was found to be 520nm.
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 0.734g of lead bromide 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 uniform in particle size. As shown in FIG. 14, the emission spectrum of the perovskite quantum dot reaction solution shows that the emission peak position is 526nm and the half-peak width is 19nm.
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-coated by a spin coater at the speed of 700r/m, and then a PET film is coated. Using high-pressure mercury lamp at 1000mj/cm 2 The energy of (3) was irradiated for 4s to obtain a perovskite quantum dot film #4.
Example 5 preparation of perovskite Quantum dot film #5
1) Preparation of cesium source: 0.13g of cesium carbonate powder, 0.2mL of octanoic acid, 0.3mL of lauric acid and 1.5mL of isooctyl 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 0.734g of lead bromide powder, 1.5mL of octanoic acid, 1.5mL of octylamine, and 3mL of isooctyl 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.
4) Preparing a photocuring glue solution: 20g of polyester acrylate, 15g of 1-adamantane acrylate, 15g of pentaerythritol triacrylate and 0.7g of 2-methylbenzophenone were mixed well.
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-coated by a spin coater at the speed of 700r/m, and then 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 #5.
The emission spectrum of the perovskite quantum dot film #5 was obtained, and as shown in fig. 15, it was found that the emission peak position was 525nm and the half-value width was 21nm.
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 green 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 active 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,
the 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, and vacuumizing and heating to 60-160 ℃ for 1-2h to obtain a cesium source;
s12, mixing the first reactive diluent monomer serving as a lead source solvent with lead bromide, lead source fatty acid and lead source fatty amine, and vacuumizing and heating to 80-170 ℃ for 2-3h to obtain a lead source;
and 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.
2. The method for preparing the green perovskite quantum dot optical film as claimed in claim 1, wherein the cesium source fatty acid is selected from one or more of caprylic acid, lauric acid, oleic acid and eicosanoic acid.
3. The method for preparing the green perovskite quantum dot optical film as claimed in claim 1, 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.
4. The method of producing a green perovskite quantum dot optical film according to any one of claims 1 to 3, wherein the cesium-source solvent and the lead-source solvent are both reactive diluent monomers capable of photo-initiated polymerization.
5. The method for preparing the green perovskite quantum dot optical film according to claim 1, wherein the step S2 specifically comprises the following steps:
s21, weighing the photocuring prepolymer, a second reactive diluent monomer and a photoinitiator;
s22, mixing the photocuring prepolymer, the second reactive diluent monomer and the photoinitiator to obtain the photocuring glue solution,
wherein the weight ratio of the photocuring prepolymer to the second reactive diluent monomer to the photoinitiator is 40 to 59 to 40.
6. The method for preparing the green perovskite quantum dot optical film as claimed in claim 5, 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 a mixture of the 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.
7. The method according to claim 6, wherein the alkane is linear or cyclic.
8. The method for preparing the green perovskite quantum dot optical film as claimed in claim 5, wherein the second reactive diluent monomer is one or a mixture of monofunctional diluent monomer, difunctional diluent monomer and multifunctional diluent monomer.
9. The method for preparing the green perovskite quantum dot optical film according to claim 8, wherein the monofunctional dilution 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.
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, and polyethylene glycol diacrylate.
11. The method of manufacturing a green perovskite quantum dot optical film according to claim 8, wherein the polyfunctional 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 5, 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 green perovskite quantum dot optical film as claimed in claim 1, wherein after the photo-curing quantum dot liquid 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 liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210470757.1A CN114958154B (en) | 2022-04-28 | 2022-04-28 | Preparation method of green-light perovskite quantum dot optical film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210470757.1A CN114958154B (en) | 2022-04-28 | 2022-04-28 | Preparation method of green-light perovskite quantum dot optical film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114958154A CN114958154A (en) | 2022-08-30 |
| CN114958154B true CN114958154B (en) | 2023-02-03 |
Family
ID=82979264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210470757.1A Active CN114958154B (en) | 2022-04-28 | 2022-04-28 | Preparation method of green-light perovskite quantum dot optical film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114958154B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115418105A (en) * | 2022-08-31 | 2022-12-02 | 江阴金书简新材料科技有限公司 | Quantum dot-MOF composite color filter membrane and preparation method thereof |
| CN116376536B (en) * | 2023-03-20 | 2024-05-28 | 广州大学 | Preparation method of aromatic heterocycle modified narrow-spectrum perovskite nano material |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675550A (en) * | 2016-11-18 | 2017-05-17 | 吉林大学 | Perovskite quantum dot gel and preparation method thereof |
| CN108165259A (en) * | 2017-12-26 | 2018-06-15 | 华东理工大学 | A kind of preparation method of perovskite quantum dot colloidal sol |
| CN109438599A (en) * | 2018-10-29 | 2019-03-08 | 苏州星烁纳米科技有限公司 | The preparation method of perovskite quantum dot composite membrane |
| CN111303864A (en) * | 2020-04-03 | 2020-06-19 | 阳明量子科技(深圳)有限公司 | Method for synthesizing zinc oxide quantum dots with adjustable polarity |
| CN111500280A (en) * | 2019-01-30 | 2020-08-07 | 苏州星烁纳米科技有限公司 | Preparation method of perovskite quantum dot composite film |
| TW202104087A (en) * | 2019-07-25 | 2021-02-01 | 國立虎尾科技大學 | Method for post-processing surface of perovskite quantum dot including using a treatment agent to perform a passivation on the surface of the perovskite quantum dot |
| WO2021020695A2 (en) * | 2019-07-30 | 2021-02-04 | 서울대학교산학협력단 | Hybrid wavelength converter, method for manufacturing same, and light emitting diode comprising same |
| CN113429692A (en) * | 2021-05-28 | 2021-09-24 | 南京航空航天大学 | Transparent perovskite/polymer composite scintillator material and preparation method thereof |
| CN114874765A (en) * | 2022-05-19 | 2022-08-09 | 阳明量子科技(深圳)有限公司 | Preparation method of red-light perovskite quantum dot film |
| CN114957756A (en) * | 2022-05-23 | 2022-08-30 | 阳明量子科技(深圳)有限公司 | Preparation method of manganese-doped red-light perovskite quantum dot optical film with stable performance |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101909541B1 (en) * | 2017-11-14 | 2018-10-18 | (주)이노큐디 | Method for fabricating Quantum Dot Film, Quantum Dot Film prepared thereby, Wavelength Converting Film and Diaplay comprising the Film |
| CN109796976B (en) * | 2019-01-17 | 2020-07-28 | 华中科技大学 | Copper-doped red-light perovskite quantum dot and preparation method thereof |
| US11365347B2 (en) * | 2019-06-06 | 2022-06-21 | Nano And Advanced Materials Institute Limited | Method for preparation of perovskite quantum dot (PQD)/polymer/ceramic ternary complex |
-
2022
- 2022-04-28 CN CN202210470757.1A patent/CN114958154B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675550A (en) * | 2016-11-18 | 2017-05-17 | 吉林大学 | Perovskite quantum dot gel and preparation method thereof |
| CN108165259A (en) * | 2017-12-26 | 2018-06-15 | 华东理工大学 | A kind of preparation method of perovskite quantum dot colloidal sol |
| CN109438599A (en) * | 2018-10-29 | 2019-03-08 | 苏州星烁纳米科技有限公司 | The preparation method of perovskite quantum dot composite membrane |
| CN111500280A (en) * | 2019-01-30 | 2020-08-07 | 苏州星烁纳米科技有限公司 | Preparation method of perovskite quantum dot composite film |
| TW202104087A (en) * | 2019-07-25 | 2021-02-01 | 國立虎尾科技大學 | Method for post-processing surface of perovskite quantum dot including using a treatment agent to perform a passivation on the surface of the perovskite quantum dot |
| WO2021020695A2 (en) * | 2019-07-30 | 2021-02-04 | 서울대학교산학협력단 | Hybrid wavelength converter, method for manufacturing same, and light emitting diode comprising same |
| CN111303864A (en) * | 2020-04-03 | 2020-06-19 | 阳明量子科技(深圳)有限公司 | Method for synthesizing zinc oxide quantum dots with adjustable polarity |
| CN113429692A (en) * | 2021-05-28 | 2021-09-24 | 南京航空航天大学 | Transparent perovskite/polymer composite scintillator material and preparation method thereof |
| CN114874765A (en) * | 2022-05-19 | 2022-08-09 | 阳明量子科技(深圳)有限公司 | Preparation method of red-light perovskite quantum dot film |
| CN114957756A (en) * | 2022-05-23 | 2022-08-30 | 阳明量子科技(深圳)有限公司 | Preparation method of manganese-doped red-light perovskite quantum dot optical film with stable performance |
Non-Patent Citations (4)
| Title |
|---|
| Room Temperature In-Situ Synthesis of Inorganic Lead Halide Perovskite Nanocrystals Sol Using Ultraviolet Polymerized Acrylic Monomers as Solvent and Their Composites with High Stability;Zhu, LD等;《APPLIED SCIENCES-BASEL》;20200612;第10卷(第9期);第1-11页 * |
| 如何提升铅卤钙钛矿量子点的稳定性?;韦等;《中国科学:化学》;20180820(第08期);第9-27页 * |
| 紫外光下高度稳定的无机钙钛矿/有机叠层太阳电池;刘忠范;《物理化学学报》;20181130;第34卷(第11期);第1195-1196页 * |
| 钙钛矿在激光领域的研究进展;王兰等;《中国光学》;20191108(第5期);第993-1014页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114958154A (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114958154B (en) | Preparation method of green-light perovskite quantum dot optical film | |
| CN114874765A (en) | Preparation method of red-light perovskite quantum dot film | |
| JP6448397B2 (en) | Phosphor dispersion composition and fluorescent molded body, wavelength conversion film, wavelength conversion member, backlight unit, and liquid crystal display device obtained by using the same | |
| CN102146272B (en) | Radiation curing sealant for packaging eyeglass nameplate or ornament | |
| TWI577773B (en) | Liquid optical adhesive compositions | |
| CN114957756B (en) | Preparation method of manganese-doped red-light perovskite quantum dot optical film with stable performance | |
| CN109608589A (en) | A kind of 3D printing dual cure resin material and preparation method thereof | |
| CN107001067A (en) | The manufacture method of inorganic microparticle-dispersed liquid, solidification compound and its solidfied material comprising the dispersion liquid | |
| CN109312203A (en) | Assign the quantum spot film adhesive composition and its quantum spot film, back light unit and display device including it of low-moisture permeability | |
| CN102369225A (en) | Curable composition and cured product thereof | |
| CN112239624B (en) | Ophthalmic lens comprising a visible light-cured color-changing coating | |
| TWI784116B (en) | Photocurable composition for imprint | |
| CN102210192A (en) | Organic el element surface sealant, method for producing display, and display | |
| JP2002525424A (en) | Preparation of optical quality organic components, especially organic lenses | |
| CN101367982B (en) | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device | |
| KR102412526B1 (en) | Light/moisture curable adhesive composition and the manufacturing method thereof | |
| CN115305017A (en) | High-refractive-index optical organic glue composition and preparation method and use method thereof | |
| KR101435139B1 (en) | Resin Composition Curable by Active Energy Ray for Pattern of Light Guiding Plate | |
| CN110117428A (en) | A kind of constituent and its preparation and application of flexibility organic packages | |
| KR101997878B1 (en) | Uv-curable and infrared ray transmittance ink composition for inkjetting enhanced high temperature heat resistance | |
| CN109517101A (en) | Acrylate compounds, the Photocurable composition containing it, photo-curable cured film and image display device | |
| JP6836599B2 (en) | Polymer composite containing quantum dots | |
| JP5791036B2 (en) | Organic-inorganic composite, organic-inorganic composite composition, and ink | |
| CN115418017A (en) | Preparation method of red perovskite quantum dot film with stable performance | |
| CN107908048A (en) | A kind of spacer material and preparation method thereof, display device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |