CN113122069A - Composition, preparation method thereof and light-emitting diode - Google Patents

Composition, preparation method thereof and light-emitting diode Download PDF

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CN113122069A
CN113122069A CN201911421156.6A CN201911421156A CN113122069A CN 113122069 A CN113122069 A CN 113122069A CN 201911421156 A CN201911421156 A CN 201911421156A CN 113122069 A CN113122069 A CN 113122069A
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composition
quantum dots
ink
solvent
light
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何斯纳
吴龙佳
吴劲衡
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TCL Corp
TCL Research America Inc
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    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots

Abstract

The invention belongs to the technical field of display, and particularly relates to a composition, a preparation method thereof and a light-emitting diode. The present invention provides a composition comprising: 10% -30% of quantum dots, 1% -3% of anionic surfactant, 1% -3% of cationic surfactant, 0% -3% of solubilizer, 0% -5% of additive and 56% -87% of solvent; the solubilizer is selected from polar organic solvents, and the solvent is selected from non-polar organic solvents. The quantum dot film has good compatibility, uniformity and stability, low surface tension, good wettability and good film-forming property, is beneficial to forming a uniform and compact quantum dot film, can be used as ink, and is applied to preparing a light-emitting layer of a light-emitting diode by an ink-jet printing method.

Description

Composition, preparation method thereof and light-emitting diode
Technical Field
The invention belongs to the technical field of display, and particularly relates to a composition, a preparation method thereof and a light-emitting diode.
Background
With the continuous progress of technology, Quantum Dot light emitting diodes (QDs) have been gradually emerging as unique advantages of extremely thin appearance, wider color gamut, high purity, high brightness, low starting voltage, and better stability, and may become a new generation of display products to replace Organic Light Emitting Diodes (OLEDs). The semiconductor quantum dots have quantum size effect, and people can realize the required light emission with specific wavelength by regulating the size of the quantum dots, for example, the size of CdSe QDs can be regulated to make the light emission wavelength tuning range from blue light to red light. The device structure of the QLED generally includes an anode layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode, where electrons and holes are injected from the cathode and the anode, respectively, and then recombined in the light emitting layer to form excitons for light emission.
The traditional method for preparing the QLED mainly adopts modes of sputtering, chemical deposition and the like to deposit and form a quantum dot film layer on a glass substrate, and the preparation method has higher cost and more complex process. The ink-jet printing technology does not need to adopt a mask plate, so that the requirement on a substrate for depositing the material is low, the material can be accurately deposited at a target position according to the required dosage, the production cost is low, the process is simple and convenient, large-scale mass production is easy, and the cost is reduced, so that the ink-jet printing technology becomes a popular technology in the field of the current QLED preparation.
When the luminescent layer is printed by adopting an ink-jet printing method, the quantum dot material is directly dispersed in a solvent to prepare ink, and then the ink is printed on the carrier transport layer. In order to prevent mutual solubility between the ink and the carrier transport layer during printing, the polarity of the ink is usually opposite to that of the carrier transport layer, so that the printed ink forms a mutually repulsive interface on the surface of the carrier transport layer with the polarity, the film formation of the ink is influenced, the formed light emitting layer has the problems of rough surface, poor uniformity and the like, and the light emitting performance of the QLED device is greatly influenced.
Disclosure of Invention
The invention mainly aims to solve the problem of poor film forming performance of quantum dot ink.
The technical scheme adopted by the invention is as follows:
the composition comprises the following components in parts by weight, based on 100% of the total weight of the composition:
Figure BDA0002352425240000021
the composition provided by the invention is formed by compounding the quantum dots, the anionic surfactant, the cationic surfactant, the solubilizer and the solvent in specific parts by weight, and the components have synergistic effect, so that the composition has good compatibility, uniformity, stability and low surface tension, is good in wettability, has good film-forming property, is beneficial to forming a uniform and compact quantum dot film, can be used as ink, and can be applied to preparing a light-emitting layer of a light-emitting diode by an ink-jet printing method.
In the composition, the cationic surfactant forms cations through ionization, and the cations can combine with non-metal atoms on the surfaces of the quantum dots to form cationic double-layer micelle particles, so that the quantum dots can be stably dispersed in a solvent; the anionic surfactant forms anions through ionization, and similarly, anion double-layer micelle particles are also formed, so that the dispersion stability of the quantum dots in a system is further improved; in addition, due to the electric mutual attraction between the anions and the cations, the anions and the cations in the system have strong interaction, the surface activity of the ink is greatly improved, the critical micelle concentration (CMC value) of the ink is reduced, the surface tension of the solution is reduced, the formation of ink drops can be promoted, the contact angle of the ink on a substrate is reduced, the film formation of the ink on the substrate is promoted, and a uniform and compact film layer is obtained.
Accordingly, a method of preparing a composition comprising the steps of:
dissolving quantum dots in a solvent to form a first mixed solution;
and adding an anionic surfactant and a cationic surfactant into the first mixed solution, and mixing to obtain the composition.
The preparation method of the composition provided by the invention is obtained by mixing the quantum dots, the anionic surfactant and the cationic surfactant in the solvent, and has the advantages of simple method and simple operation.
Correspondingly, the light-emitting diode comprises a functional layer prepared from the composition or the composition prepared by the preparation method.
The light-emitting diode provided by the invention contains the functional layer prepared from the composition, the functional layer is uniform and compact, the influence of overlarge leakage current and large lighting voltage caused by nonuniform film layers is reduced, the light-emitting efficiency of a device is further increased, and the light-emitting diode has good light-emitting performance.
Drawings
FIG. 1 is a schematic diagram of a light emitting diode according to an embodiment of the present invention;
fig. 2 is a flow chart of a method for preparing a composition according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The composition comprises the following components in parts by weight, based on 100% of the total weight of the composition:
Figure BDA0002352425240000031
Figure BDA0002352425240000041
the composition provided by the embodiment of the invention is formed by compounding the quantum dots, the anionic surfactant, the cationic surfactant, the solubilizer and the solvent in specific parts by weight, and the components have synergistic effect, so that the composition has good compatibility, uniformity, stability and low surface tension, is good in wettability, has good film-forming property, is beneficial to forming a uniform and compact quantum dot film, can be used as ink, and can be applied to preparing a light-emitting layer of a light-emitting diode by an ink-jet printing method.
As an embodiment, the composition is composed of the following components in parts by weight, based on 100% of the total weight of the composition:
Figure BDA0002352425240000042
the solubilizer is selected from polar organic solvents, and the solvent is selected from non-polar organic solvents.
In one embodiment, the boiling points of the anionic surfactant, cationic surfactant, solubilizer, and additive and the boiling point of the solvent all differ by less than or equal to 50 degrees Celsius. Therefore, the method can ensure that the anion surfactant, the cation surfactant, the solubilizer and the additive keep similar volatilization rates with the solvent during film forming so as to improve the uniformity of the film layer.
Specifically, the quantum dots are used as functional materials of the ink, are inorganic nano materials with quantum size effect, can be selected as inorganic semiconductor nanoparticles, perovskite nanoparticles, metal nanoparticles and the like, and are used for preparing a light emitting layer of a QLED device. In the embodiment of the invention, the quantum dots are 10-30% of the total weight of the composition as 100%, and at the content, the quantum dots can be completely compatible with other components, so that the quantum dots have good dispersibility in a system.
In one embodiment, the quantum dot includes at least one of group IV quantum dots, group II-VI quantum dots, group II-V quantum dots, group III-VI quantum dots, group IV-VI quantum dots, group I-III-VI quantum dots, group II-IV-VI quantum dots, and group II-IV-V quantum dots, and has quantum dot characteristics and high luminous efficiency.
The quantum dots include, but are not limited to, binary phase, ternary phase, quaternary phase quantum dots, and the like, and may be selected from blue quantum dots, green quantum dots, red quantum dots, or yellow quantum dots, and may be specifically based on the needs of an actual QLED device. In some embodiments, the quantum dots are selected as binary phase quantum dots, preferably at least one of CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, and HgS. In some embodimentsThe quantum dots are selected to be ternary phase quantum dots, preferably ZnXCd1-XS、CuXIn1-XS、ZnXCd1-XSe、ZnXSe1-XS、ZnXCd1-XTe and PbSeXS1-XAt least one of (1). In some embodiments, the quantum dots are selected to be quaternary phase quantum dots, preferably ZnXCd1-XS/ZnSe、CuXIn1-XS/ZnS、ZnXCd1-XTe/ZnS、PbSeXS1-X/ZnS、ZnXCd1-XAt least one of Se/ZnS and CuInSeS.
In some embodiments, the concentration of the quantum dots in the ink is 1-100mg/mL, preferably 10-30 mg/mL. The concentration of the quantum dots in the ink is adjusted and controlled within the range, so that the printing performance and the film-forming performance of the ink can reach the optimal state.
In some embodiments, the particle size of the quantum dots is 5-15 nm, and the dispersibility of the quantum dots in the ink and the stability of the ink system are improved through size control.
In particular, anionic surfactants are a class of surfactants that can form anions in polar solvents and are negatively charged. Dissolving an anionic surfactant in a solvent added with a polar solvent, wherein the anionic surfactant can be ionized under the action of the polar organic solvent to form negative ions, and the negative ions can be combined with metal atoms on the surfaces of the quantum dots to form anionic double-layer micelle particles, so that the quantum dots can be promoted to be stably dispersed in the solvent. In the embodiment of the invention, the anionic surfactant accounts for 1% -3% of the total weight of the composition, and at the content, the quantum dots can be uniformly and stably dispersed in the system by being used together with the cationic surfactant, so that the dispersibility is good. If the content of the anionic surfactant is lower than 1%, the dispersion degree of the quantum dots in the system cannot be effectively improved; if the content is more than 3%, problems such as turbidity and material precipitation are likely to occur.
In one embodiment, the boiling point of the anionic surfactant is less than or equal to 50 degrees celsius different from the boiling point of the solvent. By adjusting the boiling point of the anionic surfactant to be kept in the range, the anionic surfactant can keep a similar volatilization rate with the solvent during film forming, and the uniformity of the film layer is favorably improved. In some embodiments, the anionic surfactant has a boiling point of 50 to 250 degrees celsius.
The anionic surfactant can be selected from anionic Gemini surfactants and anionic polymer surfactants. As an embodiment, the anionic surfactant includes: at least one of carboxylate, sulfonate, sulfate ester salt and phosphate ester salt. Wherein, the carboxylate is an organic salt containing carboxyl, including but not limited to fatty acid salt, polycarboxylate, N-acylamino carboxylate, polyether carboxylate, etc. Sulfonates are organic salts containing sulfonic acid groups including, but not limited to, alkyl sulfonates, alkylbenzene sulfonates, petroleum sulfonates, lignosulfonates, succinate sulfonates, fatty alcohol ether succinic acid monoester sulfonates, higher fatty acid a-sulfonates, alkenyl sulfonates, and the like. The sulfate salt is an organic salt containing sulfate groups, including but not limited to fatty alcohol sulfate salts, fatty alcohol ether sulfates, sulfates of sulfuric acid and fatty acid salts, and the like. The phosphate ester salt is an organic salt containing phosphate groups, and includes but is not limited to alkyl phosphate ester salts, fatty alcohol polyoxyethylene ether phosphate ester salts, alkylphenol polyoxyethylene ether ester salts and the like.
In some embodiments, the anionic surfactant is selected from at least one of sodium N-oleoyl-N-methyltaurate, alpha-sulfo fatty acid methyl ester, sodium dodecylbenzenesulfonate.
In some embodiments, the anionic surfactant has a CMC value of 10-2-10-4mol/L。
Specifically, the cationic surfactant can be ionized in a polar organic solvent to form cations, and in the composition, the cations formed by the ionization of the cationic surfactant can be combined with non-metal atoms on the surface of the quantum dot to form cationic double-layer micelle particles, so that the quantum dot can be stably dispersed in the solvent, and the dispersion stability of the quantum dot in a system is further improved through the synergistic effect of the cationic surfactant and the anionic surfactant. Meanwhile, due to the electric mutual attraction between the anions and the cations, the anions and the cations in the system have strong interaction, the surface activity of the ink is greatly improved, the critical micelle concentration (CMC value) of the ink is reduced, the surface tension of the solution is reduced, the formation of ink drops can be promoted, the contact angle of the ink on a substrate is reduced, the film formation of the ink on the substrate is promoted, and a uniform and compact film layer is obtained.
In the present examples, the cationic surfactant is present in an amount of 1% to 3% based on 100% by weight of the total composition. At this content, the quantum dots are promoted to be uniformly and stably dispersed in the system by the synergistic use with the anionic surfactant, and the dispersibility is good. If the content of the cationic surfactant is lower than 1%, the effect of improving the dispersion degree of the quantum dots in the system cannot be realized; if the content is more than 3%, problems such as turbidity and material precipitation are likely to occur.
In one embodiment, the boiling point of the cationic surfactant is less than or equal to 50 degrees celsius different from the boiling point of the solvent. By adjusting the boiling point of the cationic surfactant to be kept in the range, the cationic surfactant can keep a similar volatilization rate with the solvent during film formation, and the uniformity of the film layer is favorably improved. In some embodiments, the boiling point of the cationic surfactant is 50-250 degrees celsius.
The cationic surfactant can be selected from cationic Gemini surfactants and cationic high molecular surfactants. As an embodiment, the cationic surfactant includes: amine salt type surfactants and/or quaternary ammonium salt type surfactants. The amine salt type surfactant is an organic substance containing amine groups, and includes but is not limited to primary amine salts, secondary amine salts, tertiary amine salts and the like. The quaternary ammonium salt surfactant contains ammonium ions, and is preferably alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzyl quaternary ammonium salt, imidazole quaternary ammonium salt, pyridine quaternary ammonium salt, or the like.
In some embodiments, the cationic surfactant is selected from at least one of octadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, and didodecyl dimethyl ammonium chloride.
In some embodiments, the cationic surfactant has a CMC value of 10-2-10-4mol/L。
Specifically, the solvent is used to disperse the quantum dots and to dissolve anionic surfactants, cationic surfactants, and additives. In the embodiment of the invention, the solvent is 56-86.9% of the total weight of the composition as 100%, and at this content, the complete compatibility between the quantum dots and other components can be ensured, and the good dispersibility of the quantum dots in a system can be ensured, so that the ink formed by the method has excellent uniformity and stability, and the formation of a uniform and dense quantum dot thin film is promoted.
In the embodiment of the present invention, the solvent is a non-polar organic solvent, including but not limited to saturated or unsaturated chain alkanes, cycloalkanes, halogenated alkanes, aromatic hydrocarbons, and the like. The nonpolar organic solvent and the oil phase quantum dots have good compatibility, and the dispersity of the oil phase quantum dots in a system is favorably improved.
In one embodiment, the solvent is selected from hydrocarbon with 6-18 carbon atoms, which has high compatibility with the oil phase quantum dots, low boiling point, and easy removal during film formation. In the present specification, "hydrocarbon" is produced as an organic substance consisting of carbon atoms and hydrogen atoms, including but not limited to alkanes, cycloalkanes, alkenes, alkynes, and the like. In some embodiments, the solvent is selected from at least one of n-hexane, n-octane, cyclooctane, tetradecane, 1-tetradecene, octadecene, and chloroform.
As an embodiment, the boiling point of the solvent is 150 ℃ and 330 ℃. By controlling the boiling point of the solvent within the range, the solvent can be promoted to be completely removed from an ink system in the post-treatment process of film formation, the dense arrangement of quantum dots is promoted, and the performance of a film layer is improved. When the boiling point of the solvent is lower than 150 ℃, the problem of uneven film layers such as coffee rings and the like can occur in the ink film forming process; when the boiling point of the solvent is higher than 330 ℃, the solvent cannot be completely volatilized in the subsequent film forming process, and the light emitting performance of the device can be reduced.
As an embodiment, the solvent has a surface tension of 20-40mN/m and a viscosity of 1-10 centipoise (units can be expressed as: cP) at 20-35 ℃. The surface tension and viscosity of the solvent are directly related to the surface tension and viscosity of the ink, and the surface tension and viscosity affect the formation of ink droplets and the film-forming quality. When the surface tension is more than 40mN/m or less than 20mN/m, and the viscosity is more than 10cp or less than 1cp, the ink is less likely to form small droplets, and a long break-off length, or a tail-like droplet break-off, may occur, directly affecting the film-forming quality. Therefore, by adjusting the viscosity and surface tension of the ink to the above ranges, the basic conditions of the ink-jet printing are satisfied, stable ink discharge of the ink in the printing process is ensured, and uniform film formation of the ink is ensured.
Specifically, the solubilizer is a polar organic solvent, and since the anionic surfactant is difficult to ionize or even does not ionize in the non-polar organic solvent, the composition can be added with a proper amount of polar organic solvent as the solubilizer, so that the anionic surfactant can be promoted to ionize to form anions, and the dispersion degree of the quantum dots in the solvent is improved. In the embodiment of the invention, the solubilizer accounts for 1-3% based on the total weight of the composition, so that the quantum dots have good dispersibility in the system, the ink formed by the ink has excellent uniformity and stability, and the formation of a uniform and compact quantum dot film is promoted. The content of the solubilizer is less than 1% or more than 3%, and the solubilizer cannot play a role in adjusting the dispersity of the quantum dots in the system.
In one embodiment, the difference between the boiling point of the solubilizer and the boiling point of the solvent is less than or equal to 50 ℃, so that the solubilizer can keep a similar volatilization rate during film formation, thereby improving the uniformity of the film layer.
The solubilizer is preferably an alcohol and/or an alcohol derivative. In the present specification, "derivatives of alcohols" refer to derivatives formed by reacting alcohols and other compounds, such as alcohols, ethers, esters, etc., and the hydrocarbon molecular weight of alcohols and derivatives thereof may be a saturated molecular chain or an unsaturated molecular chain.
As an embodiment, the solubilizer is selected from alcohol with 4-18 carbon atoms and/or derivatives of the alcohol, and the solubilizer has good compatibility with solvent, quantum dots and surfactant, low boiling point and easy removal in film formation. In some embodiments, the solubilizing agent is selected from at least one of glycerol, n-butanol, n-pentanol, dipropyl ether, ethylene glycol methyl ether, 1, 4-butanediol divinyl ether, dipropyl ether, n-hexyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol methyl ether acetate. In some embodiments, the solubilizing agent has a boiling point of 50-250 degrees Celsius.
Specifically, the additive is used for further adjusting the dispersibility, viscosity, wettability and other properties of the quantum dots in the composition so as to improve the comprehensive performance of the ink.
In one embodiment, the difference between the boiling point of the additive and the boiling point of the solvent is less than or equal to 50 degrees centigrade to ensure that the additive and the solvent can keep similar volatilization rates during film formation, so as to improve the uniformity of the film layer.
In one embodiment, the composition comprises from 0.1% to 5% by weight of said additive, said additive comprising at least one of a viscosity modifier and/or a humectant.
The viscosity regulator is used for regulating the viscosity of the ink, making the fluidity more suitable for ink-jet printing and improving the wettability between the ink and a substrate. The viscosity modifier may be selected from organic compounds such as esters, phenols, amines, and the like, and in some embodiments, the viscosity modifier is selected from at least one of ethylene glycol monostearate, triethanolamine monooleate, phenolic resin, and polyacrylamide. In some embodiments, the viscosity modifier has a boiling point of 50-250 degrees celsius.
The defoaming agent is used for further adjusting the surface tension of the ink, eliminating bubbles in the ink and avoiding the generation of a large amount of bubbles due to too low surface tension, thereby being beneficial to forming a film layer with high surface flatness. In some embodiments, the defoamer is selected from at least one of polysiloxane, polyether, silicone emulsion, higher alcohol, tributyl phosphate, higher alcohol fatty acid ester complex, polyoxypropylene, and polyether modified silicone. In some embodiments, the defoamer has a boiling point of 50-250 degrees celsius.
In conclusion, the anionic surfactant and the cationic surfactant are compounded in the ink, so that the dispersibility of the quantum dots in the ink is improved, the quantum dots are prevented from being agglomerated, the stable ink output of the ink in the printing process is ensured, and the ink is suitable for ink-jet printing; meanwhile, the surface activity of the ink is improved, the surface tension of the ink is reduced, the formation of ink drops is facilitated, the contact angle of the ink on a substrate is reduced, the wettability of the ink is improved, the film formation of the ink on the substrate is promoted, and therefore a uniform and compact film layer is obtained.
During preparation, the quantum dots, the anionic surfactant and the cationic surfactant are mixed in the solvent until the materials are uniformly mixed. In some embodiments, the quantum dots are added to the solvent and stirred until the quantum dots are uniformly dispersed in the solvent; and then, adding the rest materials, and continuously stirring until all the materials are completely and uniformly mixed.
Based on the technical scheme, the embodiment of the invention also provides a preparation method of the composition and a light-emitting diode.
Accordingly, a method of preparing a composition, as shown in fig. 2, comprises the steps of:
dissolving quantum dots in a solvent to form a first mixed solution;
and adding an anionic surfactant and a cationic surfactant into the first mixed solution, and mixing to obtain the composition.
The preparation method of the composition provided by the embodiment of the invention is obtained by mixing the quantum dots, the anionic surfactant and the cationic surfactant in the solvent, and is simple and convenient in method and simple in operation.
In the preparation method of the composition provided in the embodiment of the present invention, the selection and the usage amount of the quantum dot, the anionic surfactant, the cationic surfactant, and the solvent are the same as those of the quantum dot, the anionic surfactant, the cationic surfactant, and the solvent described above, and the properties and the effects of the quantum dot, the anionic surfactant, the cationic surfactant, and the solvent should be the same as those described above, and the details of the embodiment of the present invention are omitted here.
Further, in order to adjust the overall performance of the composition, a solubilizer and additives may be added in the step of adding the anionic surfactant and the cationic surfactant to the first mixed solution. Wherein, the kind and the amount of the solubilizer and the additive can refer to the solubilizer and the additive mentioned above.
Correspondingly, the light-emitting diode comprises a functional layer prepared from the composition.
The light-emitting diode provided by the embodiment of the invention contains the functional layer prepared from the composition, the functional layer is uniform and compact, the influence of overlarge leakage current and large lighting voltage caused by nonuniform film layers is reduced, the light-emitting efficiency of a device is further increased, and the light-emitting diode has good light-emitting performance.
In one embodiment, the functional layer is a light-emitting layer.
The basic structure of the light emitting diode comprises an anode, a light emitting layer, a cathode and the like, and the specific structure can be referred to the conventional technology in the field. In some embodiments, the light emitting diode is a positive type structure, and the anode is connected with the substrate as a bottom electrode. In some embodiments, the light emitting diode is an inverted structure, and the cathode is connected to the substrate as a bottom electrode.
Further, the light emitting diode includes a carrier function layer in addition to the function film layers such as the cathode, the anode, and the light emitting layer. In some embodiments, the light emitting diode is an upright light emitting diode, and the anode is used as a bottom electrode, a hole blocking layer, a hole injection layer, a hole transport layer, and other hole functional layers formed on the anode, a light emitting layer, and a cathode. In some embodiments, the light emitting diode is an inverted light emitting diode, and has a cathode as a bottom electrode, an electron functional layer formed on the cathode, such as an electron blocking layer, an electron injection layer, an electron transport layer, and the like, a light emitting layer, and an anode.
As an embodiment, as shown in fig. 1, the light emitting diode prepared by the preparation method provided by the embodiment of the present invention is an upright light emitting diode, and includes a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a cathode 6; wherein, the luminous layer 4 is prepared by the composition provided by the embodiment of the invention. The materials of the substrate 1, the anode 2, the hole transport layer 3, the electron transport layer 5 and the cathode 6 in the light emitting diode can refer to the conventional technology in the field, and in some embodiments, the material of the substrate 1 is a glass sheet, the material of the anode 2 is an ITO matrix, the material of the hole transport layer 3 is TFB, the material of the electron transport layer 5 is ZnO, and the material of the cathode 6 is Al.
In order that the details of the above-described practice and operation of the invention will be clearly understood by those skilled in the art, and the improved performance of the composition, method of making the same, and light emitting diode of the present invention will be apparent, the practice of the invention will now be illustrated by way of example.
Example 1
This example prepares an ink and light emitting diode:
(1) preparation of ink
Weighing the ink raw materials according to the formula, wherein the ink comprises the following components in percentage by weight of 100 percent of the total weight of the ink: 10% of green light CdSe quantum dots; 86% of n-hexane; octadecyl trimethyl ammonium chloride 1%; 1% of sodium N-oleoyl-N-methyltaurate; 1% of 1, 4-butanediol divinyl ether; ethylene glycol monostearate 0.5%; 0.5 percent of higher alcohol.
Adding the green CdSe quantum dots into n-hexane, and stirring at room temperature for 2h to obtain a first solution; then, the rest raw materials are added into the first solution, stirring is continued until all the materials are completely dissolved, and filtering is carried out to obtain the ink.
(2) Preparation of light emitting diodes
Providing a substrate comprising: an anode, a TFB hole transport layer formed on the anode;
printing the ink prepared in the step (1) on the TFB hole transport layer by adopting an ink-jet printing method, and drying to form a light-emitting layer;
and depositing a ZnO electron transport layer and an Al cathode on the luminescent layer to obtain the light-emitting diode.
Example 2
This example prepares an ink and light emitting diode:
(1) preparation of ink
Weighing the ink raw materials according to the formula, wherein the ink comprises the following components in percentage by weight of 100 percent of the total weight of the ink: 20% of red light CdSe quantum dots; 71% of cyclooctane; 3% of didodecyl dimethyl ammonium chloride; 2% of alpha-sulfo fatty acid methyl ester; 2% of ethylene glycol butyl ether; 1% of phenolic resin; 1 percent of emulsified silicone oil.
Adding the red light CdSe quantum dots into cyclooctane, and stirring until the red light CdSe quantum dots are uniformly dispersed to obtain a first solution; then, the rest raw materials are added into the first solution, stirring is continued until all the materials are completely dissolved, and filtering is carried out to obtain the ink.
(2) Preparation of light emitting diodes
Providing a substrate comprising: an anode, a TFB hole transport layer formed on the anode;
printing the ink prepared in the step (1) on the TFB hole transport layer by adopting an ink-jet printing method, and drying to form a light-emitting layer;
and depositing a ZnO electron transport layer and an Al cathode on the luminescent layer to obtain the light-emitting diode.
Example 3
This example prepares an ink and light emitting diode:
(1) preparation of ink
Weighing the ink raw materials according to the formula, wherein the ink comprises the following components in percentage by weight of 100 percent of the total weight of the ink: 30% of CdS quantum dots; 57% of tetradecane; dodecyl dimethyl benzyl ammonium chloride 3%; sodium dodecyl benzene sulfonate 3%; 3% of dipropyl ether; 2% of polyacrylamide; and 2% of polysiloxane.
Adding CdS quantum dots into tetradecane, and stirring until the CdS quantum dots are uniformly dispersed to obtain a first solution; then, the rest raw materials are added into the first solution, stirring is continued until all the materials are completely dissolved, and filtering is carried out to obtain the ink.
(2) Preparation of light emitting diodes
Providing a substrate comprising: an anode, a TFB hole transport layer formed on the anode;
printing the ink prepared in the step (1) on the TFB hole transport layer by adopting an ink-jet printing method, and drying to form a light-emitting layer;
and depositing a ZnO electron transport layer and an Al cathode on the luminescent layer to obtain the light-emitting diode.
Example 4
This example prepares an ink and a light emitting diode:
(1) preparation of ink
Weighing the ink raw materials according to the formula, wherein the ink comprises the following components in percentage by weight of 100 percent of the total weight of the ink: 10% of green light CdSe quantum dots; 87% of n-octane; 1% of didodecyl dimethyl ammonium chloride; 1% of sodium N-oleoyl-N-methyltaurate; 1% of 1, 4-butanediol divinyl ether.
Adding the green light CdSe quantum dots into n-octane, and stirring at room temperature for 2h to obtain a first solution; then, the rest raw materials are added into the first solution, stirring is continued until all the materials are completely dissolved, and filtering is carried out to obtain the ink.
(2) Preparation of light emitting diodes
Providing a substrate comprising: an anode, a TFB hole transport layer formed on the anode;
printing the ink prepared in the step (1) on the TFB hole transport layer by adopting an ink-jet printing method, and drying to form a light-emitting layer;
depositing a ZnO electron transport layer on the luminescent layer;
and preparing an Al cathode on the electron transport layer to obtain the light-emitting diode.
Comparative example 1
This comparative example prepared a light emitting diode which differed from example 1 in that: the ink prepared in the step (1) is not added with an anionic surfactant and a cationic surfactant; the rest of the steps are substantially the same as those in embodiment 1, and are not repeated herein.
The first solution and the ink prepared in the step (1) of examples 1 to 4 were used as test samples, and the surface tension of each sample was measured, respectively, and the results are shown in table 1.
The light emitting diodes prepared in examples 1 to 4 and comparative example 1 were used as test samples to respectively test the quantum yield, and the test results are shown in table 1.
As shown in the results, in each example, after the cationic surfactant and the cationic surfactant were added to the first solution, the surface tension of the solution was reduced, and the CMC value of the ink thus formed was smaller than that of the added cationic surfactant and cationic surfactant; meanwhile, the quantum yield of the light emitting diode provided by the embodiments 1 to 4 is greater than that of the comparative example 1, which shows that the cationic surfactant and the cationic surfactant are compounded in the ink, so that the surface activity of the ink can be effectively improved, the surface tension is reduced, good film forming performance is obtained, and the method is suitable for preparing a carrier transmission layer of a QLED device by adopting an ink-jet printing method.
TABLE 1
Figure BDA0002352425240000141
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (11)

1. The composition is characterized by comprising the following components in parts by weight, based on 100 percent of the total weight of the composition:
Figure FDA0002352425230000011
2. the composition according to claim 1, wherein the composition comprises the following components in parts by weight, based on 100% by weight of the total composition:
Figure FDA0002352425230000012
the solubilizer is selected from polar organic solvents, and the solvent is selected from non-polar organic solvents.
3. A composition according to claim 1 or 2, characterized in that the anionic surfactant comprises: at least one of carboxylate, sulfonate, sulfate ester salt and phosphate ester salt; and/or
The cationic surfactant includes: at least one of an amine salt type surfactant and/or a quaternary ammonium salt type surfactant.
4. The composition of claim 1 or 2, wherein the anionic surfactant is selected from at least one of sodium N-oleoyl-N-methyltaurate, alpha-sulfo fatty acid methyl ester, sodium dodecylbenzenesulfonate; and/or
The cationic surfactant is at least one selected from octadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and didodecyl dimethyl ammonium chloride.
5. The composition according to claim 1 or 2, wherein the solubilizer is selected from alcohols having a carbon number of 4 to 18 and/or derivatives of said alcohols; and/or
The solvent is selected from hydrocarbon with 6-18 carbon atoms; and/or
The boiling point of the solvent is 150 ℃ and 330 ℃; and/or
The surface tension of the solvent at 20-35 ℃ is 20-40mN/m, and the viscosity is 1-10 centipoises.
6. The composition according to claim 1 or 2, wherein the solubilizer is selected from at least one of glycerol, n-butanol, n-pentanol, dipropyl ether, ethylene glycol methyl ether, 1, 4-butanediol divinyl ether, ethylene glycol methyl ether acetate; and/or
The solvent is at least one selected from n-hexane, n-octane, cyclooctane, tetradecane, 1-tetradecene, octadecene and chloroform.
7. The composition of claim 1 or 2, wherein the quantum dots comprise at least one of group IV quantum dots, group II-VI quantum dots, group II-V quantum dots, group III-VI quantum dots, group IV-VI quantum dots, group I-III-VI quantum dots, group II-IV-V quantum dots; and/or
The concentration of the quantum dots in the composition is 1-100 mg/mL; and/or
The additives include viscosity modifiers and/or defoamers.
8. The composition according to claim 1 or 2, characterized in that the boiling points of the cationic surfactant, the solubilizer and the additive differ from the boiling point of the solvent by less than or equal to 50 degrees celsius.
9. The composition of claim 7, wherein the viscosity modifier is selected from at least one of ethylene glycol monostearate, triethanolamine monooleate, phenolic resin, and polyacrylamide; and/or
The defoaming agent is selected from at least one of polysiloxane, polyether, emulsified silicone oil, higher alcohol, tributyl phosphate, a higher alcohol fatty acid ester compound, polyoxypropylene and polyether modified organic silicon.
10. A method of preparing a composition comprising the steps of:
dissolving quantum dots in a solvent to form a first mixed solution;
and adding an anionic surfactant and a cationic surfactant into the first mixed solution, and mixing to obtain the composition.
11. A light-emitting diode comprising a functional layer prepared from the composition according to any one of claims 1 to 9 or the composition prepared by the preparation method according to claim 10.
CN201911421156.6A 2019-12-31 2019-12-31 Composition, preparation method thereof and light-emitting diode Pending CN113122069A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060062902A1 (en) * 2004-09-18 2006-03-23 Nanosolar, Inc. Coated nanoparticles and quantum dots for solution-based fabrication of photovoltaic cells
CN105131712A (en) * 2015-07-28 2015-12-09 Tcl集团股份有限公司 Quantum dot printing ink and preparation method thereof, and quantum dot light emitting diode
CN106009930A (en) * 2016-04-25 2016-10-12 苏州星烁纳米科技有限公司 Quantum dot ink

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060062902A1 (en) * 2004-09-18 2006-03-23 Nanosolar, Inc. Coated nanoparticles and quantum dots for solution-based fabrication of photovoltaic cells
CN105131712A (en) * 2015-07-28 2015-12-09 Tcl集团股份有限公司 Quantum dot printing ink and preparation method thereof, and quantum dot light emitting diode
CN106009930A (en) * 2016-04-25 2016-10-12 苏州星烁纳米科技有限公司 Quantum dot ink

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Application publication date: 20210716