Organic light-emitting-quantum dot material, preparation method thereof and light conversion adhesive film

Abstract

The invention relates to the technical field of quantum dot materials, and particularly provides an organic light-emitting-quantum dot material, a preparation method thereof and a light conversion adhesive film. The invention aims to solve the problem that the core-shell quantum dot obtained in the prior art cannot improve the luminous efficiency of visible light while realizing high absorption of ultraviolet light. Therefore, the invention provides an organic light-emitting-quantum dot material which comprises quantum dots and an organic light-emitting material connected with sulfydryl ligands on the surfaces of the quantum dots. An organic light-emitting material-quantum dot light-emitting system is formed by connecting an organic light-emitting material to a sulfydryl ligand on the surface of a quantum dot. Wherein the organic light-emitting material is an energy donor, the quantum dots are energy acceptors, ultraviolet light is absorbed through the organic light-emitting material, then the absorbed energy is transferred to the quantum dots through energy resonance, visible light is excited, high absorption of the ultraviolet light is achieved, and the light-emitting efficiency of the visible light can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of quantum dot materials, and particularly provides an organic light-emitting quantum dot material, a preparation method thereof, and a light conversion film. Background Art

[0002] Quantum dots are semiconductor nanocrystals with a size of several nanometers, having obvious quantum size effects and unique optical properties. When stimulated by light or electricity, quantum dots emit light of a certain wavelength, and the emission wavelength is determined by the composition material, size, and shape of the quantum dots. Compared with organic materials, quantum dots can provide excellent color purity and thermal stability. These characteristics make quantum dots have potential application values in fields such as lighting, display, solar energy, and biological labeling, thus attracting extensive attention.

[0003] Quantum dots have advantages such as high fluorescence efficiency, wide absorption spectrum, and adjustable wavelength, and thus have great application potential in the field of photovoltaic light conversion. However, when added to the film as a light conversion agent, the addition amount is small, and the absorption of ultraviolet light by quantum dots is limited; when the addition amount increases, agglomeration is likely to occur in the film, resulting in an increase in the haze of the film.

[0004] Currently, most of the synthesis of highly efficient and stable quantum dots is achieved by coating an organic or inorganic layer on the surface of the light-emitting core. For example, CdSe / ZnS core-shell structure quantum dots. In order to be well applied, it is necessary to improve the stability of quantum dots as much as possible, which requires increasing the thickness of the shell layer. However, due to the mismatch of lattice parameters between the core and the shell, as the shell layer increases, surface defects also increase, and the luminous efficiency gradually decreases. Multiple shell layer coatings, such as CdSe / CdS / ZnS, CdSe / CdSe / ZnS, CdSe / CdS / CdZnS, etc.

[0005] CN107090291A discloses a preparation method of CdSe / CdZnSeS / ZnS core-shell quantum dots with a simple synthesis method, short synthesis time, high quantum efficiency, and high stability, including: (1) mixing a zinc source, a cadmium source, an organic solvent, and an organic ligand and stirring evenly, and then heating to 260 - 320 °C, and introducing a protective gas throughout the reaction process; (2) quickly injecting a uniformly mixed selenium precursor and sulfur precursor under stirring; (3) starting timing after the precursor in step (2) is completely injected, and injecting the sulfur precursor again within 0 - 30 s; (4) reacting at 260 - 300 °C for 1 - 60 min. Although the quantum dots obtained by this method have a high lattice matching between the core and the shell layer, very high light stability and thermal stability, and the quantum yield can also reach more than 80%. However, the core-shell quantum dots obtained by this method are limited by the composition and particle size, and the absorption of ultraviolet light is limited, and it is impossible to ensure the luminous efficiency while achieving high absorption of ultraviolet light.

[0006] Accordingly, there is a need in the art for a new technical solution to solve the above technical problems. Summary of the Invention

[0007] The present invention aims to solve the above technical problems, that is, to solve the problem that the quantum dots obtained in the prior art cannot achieve high absorption of ultraviolet light while improving the luminous efficiency of visible light.

[0008] In a first aspect, the present invention provides an organic light-emitting - quantum dot material, which includes quantum dots and an organic light-emitting material connected to the thiol ligands on the surface of the quantum dots.

[0009] In a preferred technical solution of the above organic light-emitting - quantum dot material, the mass ratio of the quantum dots to the organic light-emitting material is (2 - 10):1, more preferably (3 - 5):1.

[0010] In a preferred technical solution of the above organic light-emitting - quantum dot material, at least a part of the thiol ligands on the surface of the quantum dots are connected to the organic light-emitting material.

[0011] In a preferred technical solution of the above organic light-emitting - quantum dot material, the quantum dots are oil-soluble quantum dots.

[0012] In a preferred technical solution of the above organic light-emitting - quantum dot material, the oil-soluble quantum dots are one or more of CdSe, CdS, CdZnSe, CdZnS, CdZnSeS, CdSe / ZnS, CdSe / CdZnS, CdZnSe / ZnS, CdZnSe / CdZnS, CdSe / ZnSe, ZnSe / ZnS, CdSe / CdZnS / ZnS, CdZnS / ZnS, InP / ZnS, InP / ZnSe / ZnS.

[0013] In a preferred technical solution of the above organic light-emitting - quantum dot material, the organic light-emitting material is one or more of coumarin - type, anthracene - type, pyrene - type, fluorane - type, benzheterocyclic - type compounds;

[0014] In a further preferred technical solution of the above organic light-emitting - quantum dot material, the coumarin - type includes coumarin 6, coumarin 7, dicoumarol; the anthracene - type includes 9,10 - diphenylanthracene, 9,10 - bis(2 - naphthyl)anthracene; the benzheterocyclic - type includes benzimidazole, benzothiazole, benzotriazole, benzoxazole.

[0015] In the most preferred technical solution of the above organic light-emitting quantum dot material, the benzheterocycle is one of 2-(2-aminophenyl)benzimidazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, 2-aminobenzothiazole, 2-amino-6-methylbenzothiazole, or 3-amino-5-mercapto-1,2,4-triazole.

[0016] In a second aspect, the present invention provides a method for preparing the above organic light-emitting quantum dot material, comprising:

[0017] S1. Exchanging a mercapto carboxylic acid with a surface ligand of an oil-soluble quantum dot to obtain a mercapto ligand quantum dot;

[0018] S2. Providing a solution A comprising DCC, NHS, and the mercapto ligand quantum dot;

[0019] S3. Providing a solution B comprising an organic light-emitting material;

[0020] S4. Adding solution B to solution A, stirring, washing, precipitating, and drying to obtain the organic light-emitting quantum dot material.

[0021] In a preferred technical solution of the above preparation method, in step S1, the exchanging of the mercapto carboxylic acid with the surface ligand of the oil-soluble quantum dot comprises:

[0022] S1.1. Providing a mercapto carboxylic acid-methanol solution;

[0023] S1.2. Providing an oil-soluble quantum dot-chloroform solution;

[0024] S1.3. Ligand exchange.

[0025] In a preferred technical solution of the above preparation method, in step S1.3, the ligand exchange is: adding the mercapto carboxylic acid-methanol solution to the oil-soluble quantum dot-chloroform solution, heating to a preset temperature, stirring to allow the quantum dot to undergo sufficient ligand exchange with the mercapto carboxylic acid, after the upper layer liquid becomes clear, cooling to room temperature, adding an excessive amount of chloroform to precipitate the quantum dot, washing, centrifuging, and drying the precipitate to obtain the mercapto ligand quantum dot.

[0026] In a preferred technical solution of the above preparation method, the mercapto carboxylic acid is one of mercaptoacetic acid or mercaptopropionic acid;

[0027] and / or, the pH value of the mercapto carboxylic acid-methanol solution is 9-11;

[0028] and / or, the preset temperature is 50-90 °C.

[0029] In a third aspect, the present invention provides a light-converting adhesive film, which comprises the above-mentioned organic light-emitting quantum dot material or the organic light-emitting quantum dot material prepared by the above-mentioned preparation method.

[0030] The organic light-emitting quantum dot material, its preparation method and the light-converting adhesive film of the present invention have the following technical effects:

[0031] 1. In the present invention, an organic light-emitting material is connected to the mercapto ligand on the surface of the quantum dot to form a light-emitting system of the organic light-emitting material - quantum dot. Among them, the organic light-emitting material is an energy donor, and the quantum dot is an energy acceptor. The organic light-emitting material absorbs ultraviolet light and then transfers the absorbed energy to the quantum dot through energy resonance transfer, exciting visible light, which not only realizes high absorption of ultraviolet light but also improves the luminous efficiency of visible light.

[0032] 2. In the present invention, the organic light-emitting material is connected to the mercapto ligand on the surface of the quantum dot through a condensation reaction to form a light-emitting system of the organic light-emitting material - quantum dot. The distance between the organic light-emitting material and the quantum dot is appropriate, facilitating energy resonance transfer, and the two are connected by an amide bond and are not easily separated.

[0033] 3. In the present invention, the organic light-emitting material has good compatibility with the adhesive film. Connecting the organic light-emitting material on the surface of the quantum dot improves the dispersion of the quantum dot in the adhesive film, and the prepared light-converting adhesive film has a high transmittance. At the same time, the high absorption of ultraviolet light and high luminous efficiency of the adhesive film are applied to the photovoltaic module, which not only reduces the UV attenuation of the module but also improves the initial power of the module. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, in which:

[0035] Figure 1 is a schematic diagram of the energy resonance transfer of the organic light-emitting quantum dot under UV irradiation of the organic light-emitting quantum dot material of the present invention;

[0036] Figure 2 is a process flow chart of the preparation method of the organic light-emitting quantum dot material of the present invention;

[0037] Figure 3 is a process flow chart of the exchange of mercapto carboxylic acid with the surface ligand of oil-soluble quantum dots in the preparation method of the present invention;

[0038] Figure 4 is the ultraviolet-visible absorption spectrum of the organic light-emitting quantum dot material, quantum dot and organic light-emitting material in Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0039] The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. Those skilled in the art should understand that these embodiments are only used to explain the technical principle of the present invention and are not intended to limit the protection scope of the present invention.

[0040] In this application, the term "and / or" describes the association relationship of associated objects and indicates that three relationships may exist. For example, A and / or B may mean: A exists alone, A and B exist simultaneously, or B exists alone. Here, A and B may be singular or plural. The character " / " generally indicates that the associated objects before and after are in an "or" relationship.

[0041] In this application, "at least one" means one or more, and "a plurality" means two or more. "At least one of the following" or its similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0042] It should be understood that in various embodiments of this application, the sequence numbers of the above processes do not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation to the implementation process of the embodiments of this application.

[0043] The terms used in the embodiments of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. The singular forms "a", "the", and "said" used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0044] The weights of the relevant components mentioned in the specification of the embodiments of this application not only can refer to the specific contents of each component, but also can represent the proportional relationship of the weights between the components. Therefore, as long as the contents of the relevant components in the specification of the embodiments of this application are scaled up or down proportionally, they are within the scope disclosed in the specification of the embodiments of this application. Specifically, the mass described in the specification of the embodiments of this application can be mass units well-known in the chemical industry such as μg, mg, g, kg, etc.

[0045] The terms "first" and "second" are only used for descriptive purposes to distinguish objects such as substances from each other, and should not be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features.

[0046] In the following embodiments, the experimental methods are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following embodiments can be obtained from commercial sources unless otherwise specified.

[0047] Based on the problem in the prior art pointed out in the background art that the core-shell quantum dots obtained in the prior art cannot improve the luminous efficiency of visible light while achieving high absorption of ultraviolet light. The present invention provides an organic light-emitting - quantum dot material. By connecting an organic light-emitting material with high ultraviolet absorption performance to the mercapto ligand on the surface of the quantum dot, a light-emitting system of the organic light-emitting material - quantum dot is formed. Using the organic light-emitting material with strong ultraviolet absorption ability as the energy donor and quantum dots with a wide absorption spectrum and adjustable wavelength such as CdSe / ZnS, CdZnS / ZnS, etc. as the energy acceptor, the organic light-emitting material absorbs ultraviolet light, and then transfers the absorbed energy to the quantum dot through energy resonance transfer to excite visible light, thus achieving both high absorption of ultraviolet light and improvement of the luminous efficiency of visible light.

[0048] Specifically, in the first aspect of the present invention, an organic light-emitting - quantum dot material is provided, which includes quantum dots and an organic light-emitting material connected to the mercapto ligand on the surface of the quantum dots.

[0049] The present invention forms a light-emitting system of the organic light-emitting material - quantum dot by connecting an organic light-emitting material to the mercapto ligand on the surface of the quantum dot. Among them, the organic light-emitting material is the energy donor and the quantum dot is the energy acceptor. As Figure 1 shown, under the irradiation of UV light, the organic light-emitting material - quantum dot of the present invention absorbs ultraviolet light through the organic light-emitting material, and then transfers the absorbed energy to the quantum dot through energy resonance transfer to excite visible light, thus achieving both high absorption of ultraviolet light and improvement of the luminous efficiency of visible light.

[0050] In some specific embodiments, the mass ratio of the quantum dots to the organic light-emitting material is (2 - 10):1. For example, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1 or any value within the range of the mass ratio.

[0051] In some preferred embodiments, the mass ratio of the quantum dots to the organic light-emitting material is (3 to 5):1. For example, it can be 3:1, 3.5:1, 4:1, 4.5:1, 5:1 or any value within the mass ratio range.

[0052] In some specific embodiments, at least a part of the mercapto ligands on the surface of the quantum dots are connected to the organic light-emitting material.

[0053] In some specific embodiments, the quantum dots are oil-soluble quantum dots.

[0054] In some preferred embodiments, the oil-soluble quantum dots are one or more of CdSe, CdS, CdZnSe, CdZnS, CdZnSeS, CdSe / ZnS, CdSe / CdZnS, CdZnSe / ZnS, CdZnSe / CdZnS, CdSe / ZnSe, ZnSe / ZnS, CdSe / CdZnS / ZnS, CdZnS / ZnS, InP / ZnS, InP / ZnSe / ZnS.

[0055] In some specific embodiments, the organic light-emitting material is one or more of coumarin-based, anthracene-based, pyrene-based, fluorane-based, benzheterocyclic compounds.

[0056] In some preferred embodiments, the coumarin-based includes coumarin 6, coumarin 7, dicoumarol; the anthracene-based includes 9,10-diphenylanthracene, 9,10-bis(2-naphthyl)anthracene; the benzheterocyclic includes benzimidazole, benzothiazole, benzotriazole, benzoxazole.

[0057] In some specific embodiments, the benzheterocyclic is one of 2-(2-aminophenyl)benzimidazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, 2-aminobenzothiazole, 2-amino-6-methylbenzothiazole or 3-amino-5-mercapto-1,2,4-triazole.

[0058] The present invention in a second aspect provides a method for preparing the organic light-emitting - quantum dot material as Figure 2 shown, including:

[0059] S1. Exchange the surface ligands of the oil-soluble quantum dots with mercapto carboxylic acid to obtain mercapto ligand quantum dots;

[0060] S2. Provide a solution A including DCC, NHS and mercapto ligand quantum dots;

[0061] S3. Provide a solution B including the organic light-emitting material;

[0062] S4. Add solution B to solution A, stir, wash, precipitate, and dry to obtain the organic light-emitting quantum dot material.

[0063] The oil-soluble quantum dot ligands are generally oleic acid and / or oleylamine. In the present invention, thiol carboxylic acid is used to exchange with the surface ligands of oil-soluble quantum dots to obtain thiol ligand quantum dots; then a condensing agent (DCC and NHS) is added to obtain solution A including DCC, NHS, and thiol ligand quantum dots; then solution B including the organic light-emitting material is added to solution A, and the organic light-emitting material is connected to the surface thiol ligands of the quantum dots through an amide bond by a condensation reaction to form an organic light-emitting material-quantum dot light-emitting system. Through energy resonance transfer, the ultraviolet light absorbed by the organic fluorescent material is converted into the excitation light of the quantum dots, improving the ultraviolet light absorption ability and the visible light emission efficiency.

[0064] Specifically, as Figure 3 shown, in step S1, the exchange of thiol carboxylic acid with the surface ligands of oil-soluble quantum dots includes:

[0065] S1.1. Provide a thiol carboxylic acid-methanol solution;

[0066] S1.2. Provide an oil-soluble quantum dot-chloroform solution;

[0067] S1.3. Ligand exchange.

[0068] Further, in step S1.3, the ligand exchange is as follows: Add the thiol carboxylic acid-methanol solution to the oil-soluble quantum dot-chloroform solution, raise the temperature to a preset temperature, stir to allow the quantum dots to fully exchange ligands with the thiol carboxylic acid. After the upper layer liquid becomes clear, cool to room temperature, add an excessive amount of chloroform to precipitate the quantum dots, wash, centrifuge, and dry the precipitate to obtain the thiol ligand quantum dots.

[0069] In some specific embodiments, the thiol carboxylic acid is one of thioglycolic acid or 3-mercaptopropionic acid.

[0070] In some specific embodiments, the pH value of the thiol carboxylic acid-methanol solution is 9-11. For example, it can be 9, 9.5, 10, 10.5, 11 or any value within the pH value range.

[0071] In some specific embodiments, the preset temperature is 50-90 °C. For example, it can be 50 °C, 55 °C, 60 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C or any value within the temperature range.

[0072] In some specific embodiments, in step S4, the stirring time is 24-48 h. For example, it can be 24 h, 30 h, 36 h, 40 h, 48 h or any value within the time range.

[0073] In some specific embodiments, in step S1.3, the stirring time is 12 h.

[0074] In a third aspect, the present invention provides a light conversion film, which comprises the above-mentioned organic light-emitting quantum dot material or the organic light-emitting quantum dot material prepared by the above-mentioned preparation method.

[0075] In some specific embodiments, the light conversion film comprises substrate particles and an organic light-emitting quantum dot material.

[0076] In some specific embodiments, the mass ratio of the organic light-emitting quantum dot material in the light conversion film is 1.5% - 4%.

[0077] In some specific embodiments, the substrate particles comprise the following components: Component wt% Blank Particle 91-99 Crosslinking Agent 0.5-3 Co-crosslinking Agent 0.3-2 Coupling Agent 0.1-2 Light Stabilizer 0.01-1 Antioxidant 0.01-1

[0078] In some specific embodiments, the blank particles are EVA or POE.

[0079] In some specific embodiments, the crosslinking agent is one or more of tert-butyl peroxy-2-ethylhexyl carbonate, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and tert-amyl peroxy(2-ethylhexyl) carbonate;

[0080] In some specific embodiments, the co-crosslinking agent is one or more of triallyl isocyanurate, trimethylolpropane triacrylate, triallyl cyanurate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate;

[0081] In some specific embodiments, the coupling agent is one or more of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane;

[0082] In some specific embodiments, the light stabilizer is one or more of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, polybutanedioic acid (4-hydroxy-2,2,6,6-tetramethyl-1-piperidylethyl) ester, and bis(1,2,2,6,6-pentamethylpiperidyl) sebacate;

[0083] In some specific embodiments, the antioxidant is one or more of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), ethyl 3,3'-thiobis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tris(nonylphenyl)phosphite, and triphenyl phosphite.

[0084] It should be noted that the light conversion adhesive film can be prepared by the methods commonly used in the art, and the present invention does not make specific limitations here. For example, it can be prepared by a method including the following steps:

[0085] 1. Preparation of substrate particles

[0086] After uniformly mixing blank particles, a crosslinking agent, a co-crosslinking agent, a coupling agent, a light stabilizer, and an antioxidant, melting, extrusion, and granulation are carried out to obtain substrate particles;

[0087] 2. Preparation of light conversion adhesive film

[0088] After mixing the organic light-emitting - quantum dot material with the substrate particles, melting extrusion and casting are carried out to form a film, and the light conversion adhesive film is obtained.

[0089] The light conversion adhesive film provided by the present invention has high stability, and at the same time has good absorption capacity for ultraviolet light and high luminous efficiency for visible light.

[0090] The following describes in detail the organic light-emitting - quantum dot material, its preparation method, and the light conversion adhesive film of the present invention through several specific examples.

[0091] Example 1

[0092] This example provides an organic light-emitting - quantum dot material and a light conversion adhesive film.

[0093] [2-(2-Aminophenyl)benzimidazole-CdZnS / ZnS organic light-emitting - quantum dot material]

[0094] The organic light-emitting - quantum dot material provided in this example is 2-(2-aminophenyl)benzimidazole-CdZnS / ZnS, which includes quantum dots CdZnS / ZnS and the organic light-emitting material 2-(2-aminophenyl)benzimidazole connected to the thiol ligands on the surface of the quantum dots. The mass ratio of the quantum dots to the organic light-emitting material is 4:1.

[0095] The above 2-(2-aminophenyl)benzimidazole-CdZnS / ZnS is prepared by the following method:

[0096] S1. Exchange the surface ligands of quantum dots with mercapto carboxylic acid to obtain mercapto ligand quantum dots. The specific steps are as follows:

[0097] S1.1. Provide a mercapto carboxylic acid - methanol solution

[0098] Dissolve 20 mmol of mercapto carboxylic acid (mercaptoacetic acid) in 10 ml of methanol solution, and add 30% NaOH solution to adjust the pH value of the solution to 11 to obtain a mercaptoacetic acid - methanol solution.

[0099] S1.2. Provide an oil - soluble quantum dot - chloroform solution

[0100] Dissolve 1.5 mmol of oil - soluble quantum dots (CdZnS / ZnS) in 10 ml of chloroform to obtain an oil - soluble quantum dot - chloroform solution;

[0101] S1.3. Ligand exchange

[0102] Add the mercaptoacetic acid - methanol solution obtained in step S1.1 to the oil - soluble quantum dot - chloroform solution obtained in step S1.2, heat to the preset temperature (65 °C), stir for 12 h to allow the quantum dots to undergo sufficient ligand exchange with mercaptoacetic acid. After the upper layer liquid becomes clear, add an excess of chloroform to precipitate the quantum dots. Wash and centrifuge the precipitate three times, and then dry to obtain mercapto ligand quantum dots.

[0103] S2. Provide solution A including DCC, NHS and mercapto ligand quantum dots

[0104] Take 67 mmol of N,N'-dicyclohexylcarbodiimide (DCC), 30 mmol of N - hydroxysuccinimide (NHS) and 1 g of mercapto ligand quantum dots, add them to 60 ml of deionized water, and dissolve by ultrasonic treatment to obtain solution A.

[0105] S3. Provide solution B including organic light - emitting material

[0106] Dissolve 0.25 g of organic light - emitting material (2-(2 - aminophenyl)benzimidazole) in 5 g of anhydrous dimethyl sulfoxide to obtain solution B.

[0107] S4. Under dark and stirring conditions, add the solution B obtained in step S3 to solution A, stir for 24 h, wash and precipitate with ethanol and deionized water repeatedly three times, and then dry to obtain 2-(2 - hydroxyphenyl)benzimidazole - CdZnS / ZnS.

[0108] [2-(2 - aminophenyl)benzimidazole - CdZnS / ZnS light - converting film]

[0109] This embodiment further provides a light conversion film, which comprises substrate particles and 2-(2-aminophenyl)benzimidazole-CdZnS / ZnS, and the mass percentage of 2-(2-aminophenyl)benzimidazole-CdZnS / ZnS in the film is 3wt%.

[0110] The preparation method of the above light conversion film comprises the following steps:

[0111] 1. Prepare substrate particles

[0112] Mix the blank particles, crosslinking agent, co-crosslinking agent, coupling agent, light stabilizer and antioxidant evenly, then extrude and granulate to obtain substrate particles. Among them, the components and dosages of the substrate particles are as follows:

[0113] 2. Prepare the light conversion film

[0114] Mix the prepared substrate particles and 2-(2-hydroxyphenyl)benzimidazole-CdZnS / ZnS evenly according to a mass ratio of 97:3, and then obtain the light conversion film through melt extrusion and casting.

[0115] Example 2

[0116] This embodiment provides an organic light-emitting - quantum dot material and a light conversion film.

[0117] [2-(4-aminophenyl)-5-aminobenzimidazole-CdSe / CdZnS / ZnS organic light-emitting - quantum dot material]

[0118] The organic light-emitting - quantum dot material provided in this embodiment is 2-(4-aminophenyl)-5-aminobenzimidazole-CdSe / CdZnS / ZnS, which comprises quantum dots CdSe / CdZnS / ZnS and an organic light-emitting material 2-(4-aminophenyl)-5-aminobenzimidazole connected to the mercapto ligands on the surface of the quantum dots, and the mass ratio of the quantum dots to the organic light-emitting material is 3:1.

[0119] The preparation method is the same as that in Example 1, and the differences from Example 1 are as follows:

[0120] In step S1.1, adjust the pH value of the solution to 10;

[0121] In step S1.2, the oil-soluble quantum dots used are CdSe / CdZnS / ZnS;

[0122] In step S1.3, the preset temperature is 50°C;

[0123] In step S2, the dosage of the mercapto ligand quantum dots is 0.75 g;

[0124] In step S3, the organic light-emitting material used is 2-(4-aminophenyl)-5-aminobenzimidazole;

[0125] In step S4, the stirring time is 48 h.

[0126] [2-(4-aminophenyl)-5-aminobenzimidazole-CdSe / CdZnS / ZnS light conversion film]

[0127] This example further provides a light conversion film, which includes substrate particles and 2-(4-aminophenyl)-5-aminobenzimidazole-CdSe / CdZnS / ZnS. The mass ratio of 2-(4-aminophenyl)-5-aminobenzimidazole-CdSe / CdZnS / ZnS in the film is 4 wt%.

[0128] Among them, the components and dosages of the substrate particles are as follows:

[0129] The preparation method is the same as that of Example 1. The difference from Example 1 is:

[0130] In step 2, the mass ratio of the substrate particles to 2-(4-aminophenyl)-5-aminobenzimidazole-CdSe / CdZnS / ZnS is 96:4.

[0131] Example 3

[0132] This example provides an organic light-emitting - quantum dot material and a light conversion film.

[0133] [5-amino-2-mercaptobenzimidazole-CdZnSe organic light-emitting - quantum dot material]

[0134] The organic light-emitting - quantum dot material provided in this example is 5-amino-2-mercaptobenzimidazole-CdZnSe, which includes quantum dot CdZnSe and organic light-emitting material 5-amino-2-mercaptobenzimidazole connected to the mercapto ligand on the surface of the quantum dot. The mass ratio of the quantum dot to the organic light-emitting material is 5:1.

[0135] The preparation method is the same as that of Example 1. The difference from Example 1 is:

[0136] In step S1.1, adjust the pH value of the solution to 11;

[0137] In step S1.2, the oil-soluble quantum dot used is CdZnSe;

[0138] In step S1.3, the preset temperature is 90 °C;

[0139] In step S2, the dosage of the mercapto-ligand quantum dots is 1.25 g;

[0140] In step S3, the used organic light-emitting material is 5-amino-2-mercaptobenzimidazole;

[0141] In step S4, the stirring time is 36 h.

[0142] [5-amino-2-mercaptobenzimidazole-CdZnSe light conversion film]

[0143] This example further provides a light conversion film, which includes substrate particles and 5-amino-2-mercaptobenzimidazole-CdZnSe, and the mass proportion of the 5-amino-2-mercaptobenzimidazole-CdZnSe in the film is 1.5 wt%.

[0144] Among them, the components and dosages of the substrate particles are as follows:

[0145] The preparation method is the same as that of Example 1, and the difference from Example 1 is:

[0146] In step 2, the mass ratio of the substrate particles to 5-amino-2-mercaptobenzimidazole-CdZnSe is 98.5:1.5.

[0147] Example 4

[0148] This example provides an organic light-emitting quantum dot material and a light conversion film.

[0149] [2-aminobenzothiazole-CdZnSe / CdZnS organic light-emitting quantum dot material]

[0150] The organic light-emitting quantum dot material provided in this example is 2-aminobenzothiazole-CdZnSe / CdZnS, which includes quantum dots CdZnSe / CdZnS and an organic light-emitting material 2-aminobenzothiazole connected to the mercapto ligands on the surface of the quantum dots, and the mass ratio of the quantum dots to the organic light-emitting material is 2:1.

[0151] The preparation method is the same as that of Example 1, and the difference from Example 1 is:

[0152] In step S1.1, the used mercapto carboxylic acid is mercaptopropionic acid, and the pH value of the solution is adjusted to 10.5;

[0153] In step S1.2, the used oil-soluble quantum dots are CdZnSe / CdZnS;

[0154] In step S1.3, the preset temperature is 70 °C;

[0155] In step S2, the dosage of the mercapto-ligand quantum dots is 0.5 g;

[0156] In step S3, the used organic light-emitting material is 2-aminobenzothiazole;

[0157] In step S4, the stirring time is 40 h.

[0158] [2-Aminobenzothiazole-CdZnSe / CdZnS light conversion film]

[0159] This example further provides a light conversion film, which includes substrate particles and 2-aminobenzothiazole-CdZnSe / CdZnS, and the mass ratio of the 2-aminobenzothiazole-CdZnSe / CdZnS in the film is 2 wt%.

[0160] Among them, the components and dosages of the substrate particles are as follows:

[0161] The preparation method is the same as that of Example 1, and the difference from Example 1 is:

[0162] In step 2, the mass ratio of the substrate particles to 2-aminobenzothiazole-CdZnSe / CdZnS is 98:2.

[0163] Example 5

[0164] This example provides an organic light-emitting quantum dot material and a light conversion film.

[0165] [2-Amino-6-methylbenzothiazole-InP / ZnS organic light-emitting quantum dot material]

[0166] The organic light-emitting quantum dot material provided in this example is 2-amino-6-methylbenzothiazole-InP / ZnS, which includes quantum dots InP / ZnS and an organic light-emitting material 2-amino-6-methylbenzothiazole connected to the surface mercapto ligand of the quantum dots, and the mass ratio of the quantum dots to the organic light-emitting material is 10:1.

[0167] The preparation method is the same as that of Example 1, and the difference from Example 1 is:

[0168] In step S1.1, the used mercapto carboxylic acid is mercaptopropionic acid, and the pH value of the solution is adjusted to 9.5;

[0169] In step S1.2, the used oil-soluble quantum dots are InP / ZnS;

[0170] In step S1.3, the preset temperature is 80 °C;

[0171] In step S2, the dosage of the mercapto-ligand quantum dots is 2.5 g;

[0172] In step S3, the organic light-emitting material used is 2-amino-6-methylbenzothiazole;

[0173] In step S4, the stirring time is 35 h.

[0174] [2-amino-6-methylbenzothiazole-InP / ZnS light conversion film]

[0175] This embodiment further provides a light conversion film, which includes substrate particles and 2-amino-6-methylbenzothiazole-InP / ZnS, and the mass ratio of the 2-amino-6-methylbenzothiazole-InP / ZnS in the film is 3.5 wt%.

[0176] Among them, the components and dosages of the substrate particles are as follows:

[0177] The preparation method is the same as that of Example 1. The difference from Example 1 is:

[0178] In step 2, the mass ratio of the substrate particles to 2-amino-6-methylbenzothiazole-InP / ZnS is 96.5:3.5.

[0179] Example 6

[0180] This embodiment provides an organic light-emitting quantum dot material and a light conversion film.

[0181] [3-amino-5-mercapto-1,2,4-triazole-InP / ZnSe / ZnS organic light-emitting quantum dot material]

[0182] The organic light-emitting quantum dot material provided by this embodiment is 3-amino-5-mercapto-1,2,4-triazole-InP / ZnSe / ZnS, which includes quantum dots InP / ZnSe / ZnS and an organic light-emitting material 3-amino-5-mercapto-1,2,4-triazole connected to the mercapto ligands on the surface of the quantum dots, and the mass ratio of the quantum dots to the organic light-emitting material is 6:1.

[0183] The preparation method is the same as that of Example 1. The difference from Example 1 is:

[0184] In step S1.1, the mercapto carboxylic acid used is mercaptopropionic acid, and the pH value of the solution is adjusted to 10.2;

[0185] In step S1.2, the oil-soluble quantum dots used are InP / ZnSe / ZnS;

[0186] In step S1.3, the preset temperature is 85 °C;

[0187] In step S2, the dosage of the mercapto ligand quantum dots is 1.5 g.

[0188] In step S3, the organic light-emitting material used is 3-amino-5-mercapto-1,2,4-triazole;

[0189] In step S4, the stirring time is 28 h.

[0190] [2-Amino-6-methylbenzothiazole-InP / ZnSe / ZnS light conversion film]

[0191] This example further provides a light conversion film, which includes substrate particles and 3-amino-5-mercapto-1,2,4-triazole-InP / ZnSe / ZnS. The mass ratio of the 3-amino-5-mercapto-1,2,4-triazole-InP / ZnSe / ZnS in the film is 2.5 wt%.

[0192] Among them, the components and dosages of the substrate particles are as follows:

[0193] The preparation method is the same as that of Example 1. The difference from Example 1 is:

[0194] In step 2, the mass ratio of the substrate particles to 3-amino-5-mercapto-1,2,4-triazole-InP / ZnSe / ZnS is 97.5:2.5.

[0195] Comparative Example 1

[0196] This comparative example provides a CdZnS / ZnS quantum dot light conversion film. The preparation method includes the following steps:

[0197] (1) Mix the blank particles, crosslinking agent, co-crosslinking agent, coupling agent, light stabilizer and antioxidant evenly according to the dosage in Example 1, then extrude and granulate to obtain the substrate particles;

[0198] (2) Mix the substrate particles and CdZnS / ZnS quantum dots evenly, and then obtain the CdZnS / ZnS quantum dot light conversion film through melt extrusion and casting. Among them, the addition amount of the CdZnS / ZnS quantum dots in the film is 3 wt%.

[0199] Comparative Example 2

[0200] This comparative example provides a 2-(2-aminophenyl)benzimidazole light conversion film. The preparation method includes the following steps:

[0201] (1) Mix the blank particles, crosslinking agent, co-crosslinking agent, coupling agent, light stabilizer and antioxidant evenly according to the amounts used in Example 1, then extrude and granulate to obtain base material particles;

[0202] (2) Mix the base material particles evenly with 2-(2-aminophenyl)benzimidazole, and then melt-extrude and cast into a film to obtain the organic light conversion film. Among them, the addition amount of the organic light conversion agent in the film is 3 wt%.

[0203] Test Example 1

[0204] This test example tested the ultraviolet-visible light absorption and fluorescence quantum efficiency.

[0205] Test method: Perform ultraviolet-visible light transmittance tests and fluorescence quantum efficiency tests on the organic light-emitting quantum dot 2-(2-aminophenyl)benzimidazole-CdZnS / ZnS, quantum dot CdZnS / ZnS and organic light-emitting material 2-(2-aminophenyl)benzimidazole in Example 1 respectively, and the tests are carried out according to national standards GB / T 37664.1-2019 and GB / T 44454-2024. The results are as Figure 4 shown in Table 1.

[0206] Table 1 Internal Quantum Efficiency (%) External Quantum Efficiency (%) Absorption (%) Quantum Dot 124.02 117.81 94.99 Organic Light-emitting Material 123.31 116.23 94.25 Organic Light-emitting - Quantum Dot 132.26 124.68 94.27

[0207] From Figure 4 it can be seen that: After the mercapto ligand on the surface of the quantum dot connects the organic light-emitting material to form the organic light-emitting quantum dot material, compared with the quantum dot material, the ultraviolet absorption of the organic light-emitting quantum dot at 300-400 nm is significantly enhanced, and compared with the organic light-emitting material, the organic light-emitting quantum dot retains the high absorption of the quantum dot at 200-300 nm.

[0208] From Table 1, it can be seen that after the mercapto ligand on the surface of the quantum dot connects the organic light-emitting material to form the organic light-emitting quantum dot material, compared with the quantum dot material and the organic light-emitting material, the internal (external) quantum efficiency of the organic light-emitting quantum dot is improved.

[0209] Test Example 2

[0210] This test example tested the performance of the photovoltaic module.

[0211] Test method: Stack the photovoltaic glass, light conversion film, solar cell, encapsulation film and lower-layer photovoltaic glass in sequence from bottom to top on the photovoltaic glass, then put it into a vacuum laminator, evacuate for 10 min, heat up to 120 °C, and laminate at a pressure of 25 MPa to obtain the photovoltaic module.

[0212] Example 1, Comparative Example 1 and Comparative Example 2 were respectively used as light conversion adhesive films to laminate photovoltaic modules. The initial power of the modules was tested and the attenuation rate was calculated for comparison. The power test standard for photovoltaic modules was carried out in accordance with IEC61215-2:2021, and the UV aging test standard was carried out in accordance with IEC61215-2:2021. The test results are shown in Table 2.

[0213] Table 2 Initial Power of Component (W) Power after UV60KWH (W) Decay Rate (%) Comparative Example 1 338.42 324.58 4.09 Comparative Example 2 338.21 327.69 3.11 Example 1 339.56 330.90 2.55

[0214] The test results of applying the light conversion adhesive film to the photovoltaic module show that Example 1 has the highest initial power, which is higher than that of Comparative Example 1 and Comparative Example 2 respectively. After irradiation with UV of 60 kwh, the attenuation rate of the module in Example 1 is the lowest. This is because Example 1, as a light conversion adhesive film, enhances the absorption of UV, so that while protecting the battery cells, more ultraviolet light that has a gain effect on the power generation can be converted into visible light, improving the initial power of the module.

[0215] So far, the technical solution of the present invention has been described in combination with the preferred embodiments shown in the drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will fall within the protection scope of the present invention.

Claims

1. An organic light-emitting quantum dot material, characterized in that, It includes quantum dots and an organic light-emitting material connected to the mercapto ligands on the surface of the quantum dots.

2. The organic light-emitting quantum dot material according to claim 1, wherein The mass ratio of the quantum dots to the organic light-emitting material is (2 to 10):1, more preferably (3 to 5):

1.

3. The organic light-emitting quantum dot material according to claim 2, wherein At least a part of the mercapto ligands on the surface of the quantum dots are connected to the organic light-emitting material.

4. The organic light-emitting quantum dot material according to any one of claims 1-3, characterized in that The quantum dots are oil-soluble quantum dots; Preferably, the oil-soluble quantum dots are one or more of CdSe, CdS, CdZnSe, CdZnS, CdZnSeS, CdSe / ZnS, CdSe / CdZnS, CdZnSe / ZnS, CdZnSe / CdZnS, CdSe / ZnSe, ZnSe / ZnS, CdSe / CdZnS / ZnS, CdZnS / ZnS, InP / ZnS, InP / ZnSe / ZnS.

5. The organic light-emitting quantum dot material according to any one of claims 1-3, characterized in that The organic light-emitting material is one or more of coumarin-based, anthracene-based, pyrene-based, fluorane-based, benzheterocyclic compounds; Preferably, the coumarin-based includes coumarin 6, coumarin 7, dicoumarol; the anthracene-based includes 9,10-diphenylanthracene, 9,10-di(2-naphthyl)anthracene; the benzheterocyclic includes benzimidazole, benzothiazole, benzotriazole, benzoxazole; More preferably, the benzheterocyclic is one of 2-(2-aminophenyl)benzimidazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 5-amino-2-mercaptobenzimidazole, 2-aminobenzothiazole, 2-amino-6-methylbenzothiazole or 3-amino-5-mercapto-1,2,4-triazole.

6. A method for preparing the organic light-emitting quantum dot material according to any one of claims 1-5, characterized in that, The preparation method includes: S1. Exchange the ligands on the surface of the oil-soluble quantum dots with mercapto carboxylic acid to obtain mercapto ligand quantum dots; S2. Provide solution A including DCC, NHS and mercapto ligand quantum dots; S3. Provide solution B including the organic light-emitting material; S4. Add solution B to solution A, stir, wash, precipitate and dry to obtain the organic light-emitting quantum dot material.

7. The preparation method according to claim 6, wherein In step S1, the exchange of the ligands on the surface of the oil-soluble quantum dots with mercapto carboxylic acid includes: S1.

1. Provide a mercapto carboxylic acid-methanol solution; S1.

2. Provide an oil-soluble quantum dot-chloroform solution; S1.

3. Ligand exchange.

8. The preparation method according to claim 7, characterized in that, In step S1.3, the ligand exchange is: Add the mercapto carboxylic acid-methanol solution to the oil-soluble quantum dot-chloroform solution, heat to the preset temperature and stir to make the quantum dots and mercapto carboxylic acid undergo sufficient ligand exchange. After the upper layer liquid becomes clear, cool to room temperature, add an excessive amount of chloroform to precipitate the quantum dots, wash, centrifuge and dry the precipitate to obtain the mercapto ligand quantum dots.

9. According to the preparation method described in claim 8, it is characterized in that The mercapto carboxylic acid is one of mercaptoacetic acid or mercaptopropionic acid; And / or, the pH value of the mercapto carboxylic acid-methanol solution is 9-11; And / or, the preset temperature is 50-90 °C.

10. A light conversion film, characterized in that, The light conversion film includes the organic light-emitting quantum dot material described in any one of claims 1-5 or the organic light-emitting quantum dot material prepared by the preparation method described in any one of claims 6-9.

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