CN109181414B - Quantum dot ink and light emitting diode - Google Patents
Quantum dot ink and light emitting diode Download PDFInfo
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- CN109181414B CN109181414B CN201810766805.5A CN201810766805A CN109181414B CN 109181414 B CN109181414 B CN 109181414B CN 201810766805 A CN201810766805 A CN 201810766805A CN 109181414 B CN109181414 B CN 109181414B
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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
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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
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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
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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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
- C09D11/50—Sympathetic, colour changing or similar inks
Abstract
The invention discloses quantum dot ink and a light-emitting diode, wherein the quantum dot ink comprises a first solvent, a second solvent, quantum dots and a carrier transmission material, and the solubility of the quantum dots and the solubility of the carrier transmission material in the first solvent are different from that of the carrier transmission material in the second solvent. When the quantum dot ink is printed, in the process of removing the solvent, the precipitation degree and time of the quantum dots and the carriers are different according to the different solubilities of the quantum dots and the carrier materials in the first solvent and the second solvent, so that a two-layer structure can be formed. Therefore, the operation is simplified, and the process cost of the ink-jet printing is reduced. The quantum dot layer and the carrier layer of the light-emitting diode are printed by the quantum dot ink.
Description
Cross Reference to Related Applications
The present application claims priority from chinese patent application "201710572600.9 entitled" quantum dot ink "filed on 14/07/2017, the entire contents of which are incorporated herein by reference.
Technical Field
The present application relates to quantum dots, and more particularly, to quantum dot inks and quantum dot light emitting diodes.
Background
Quantum dot Light Emitting diodes (QLEDs) are a new generation of display technology developed based on organic Light Emitting display technology. Except that the organic electroluminescent layer is replaced with a quantum dot electroluminescent layer. QLEDs have a higher color gamut, longer lifetime, and lower cost than organic light emitting displays.
The most likely way to industrialize QLED technology is by inkjet printing technology. The core of ink jet printing technology is quantum dot ink and ink jet printing processes. An important aspect for restricting the QLED inkjet printing technology is that the luminescent layer and the carrier transport layer involved in the QLED preparation process need to be configured with ink separately, and different inks need to be configured for printing in sequence, so that the technical difficulty is increased, and the process cost is increased.
Disclosure of Invention
In view of the above technical problem, the present application provides an ink that can reduce the number of printing steps.
The invention provides quantum dot ink which is characterized by comprising a first solvent, a second solvent, quantum dots and a carrier transmission material, wherein the solubility of the quantum dots and the solubility of the carrier transmission material in the first solvent are different from that of the carrier transmission material in the second solvent.
In one embodiment, the first solvent and the second solvent are different in polarity.
In one embodiment, the quantum dot ink further comprises a surfactant; preferably, the surfactant is selected from at least one of alkyl ether, alkyl alcohol, alkyl ester, alkyl acid salt and alkyl amine with molecular weight less than 500; more preferably, the surfactant is at least one selected from the group consisting of octyl ether, decyl ether, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, caprylic acid, capric acid, oleic acid, stearic acid, lauric acid, lauryl amine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, sodium dodecylsulfonate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate and polyethylene glycol.
In one embodiment, the mass fraction percentage range of each component in the quantum dot ink is as follows: 15-60% of first solvent, 15-60% of second solvent, 10-40% of surfactant, 1-20% of quantum dot and 2-20% of carrier transmission material
In one embodiment, the first solvent and the second solvent are liquid at 25 ℃ and have boiling points less than 200 ℃ at atmospheric pressure.
In one embodiment, the first solvent comprises at least one of alkane, cycloalkane, halogenated alkane, alkene, benzene or alkylbenzene compounds with the carbon number ranging from 5 to 18; preferably, the first solvent is selected from at least one of heptane, octane, decane, undecane, dodecane, tetradecane, hexadecane and octadecane, chlorobenzene, xylene, toluene, ethylbenzene, diethylbenzene, saturated or unsaturated mineral spirits.
In one embodiment, the second solvent comprises an ester, ether or ether ester compound with 10-30 carbon atoms; preferably, the second solvent is at least one selected from the group consisting of propylene glycol methyl ether, hydroxyethyl ethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol propyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol-2-ethylhexyl ether, propylene glycol monophenyl ether, diethylene glycol monophenyl ether, hydroxyisopropyl ethylene glycol monophenyl ether, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol phenyl ether acetate, methyl isobutyl ketone, methyl isoamyl ketone, and diisobutyl ketone.
In one embodiment, the carrier transport material comprises a nano-oxide; preferably, the nano-oxide comprises at least one of nickel oxide, tungsten oxide, molybdenum oxide, zinc oxide, magnesium zinc oxide, aluminum oxide, zinc tin oxide and titanium dioxide.
In one embodiment, the viscosity of the quantum dot ink is 10-15 cP, and the surface tension is 30-45 dynes/cm.
The invention also provides a quantum dot light-emitting diode which comprises a quantum dot layer and a current carrier layer, wherein the quantum dot layer and the current carrier layer are made of any one of the quantum dot ink.
The invention has the following beneficial effects: when the quantum dot ink is printed, in the process of removing the solvent, the degree and time of precipitation of the quantum dots and the carriers are different according to the difference of the solubility of the quantum dots and the carrier materials in the first solvent and the second solvent, so that a two-layer structure can be formed. Therefore, the operation is simplified, and the process cost of the ink-jet printing is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be described in detail below with reference to the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention. Unless otherwise stated, the percentages in the present invention are mass percentages.
It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the present invention.
It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, steps, operations, elements, components, and/or groups thereof.
Unless otherwise defined, all terms (including technical and scientific terms) used herein that pertain to the disclosures herein have the same meaning as commonly understood by one of ordinary skill in the art. It will be further understood that terms, such as those defined commonly in dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention discloses quantum dot ink which comprises a first solvent, a second solvent, a surfactant, quantum dots and a carrier transmission material. Wherein the solubility of the quantum dot in the first solvent is greater than the solubility in the second solvent, and the solubility of the carrier transport material in the second solvent is greater than the solubility in the first solvent. After the quantum dot ink is dried to form a film, a quantum dot layer and a carrier transmission material layer with carrier transmission capacity can be obtained at the same time, wherein the carrier refers to any one of holes or electrons.
Through the proportion adjustment of the components, the viscosity and the surface tension of the quantum dot ink can be adjusted to be suitable for the requirements of ink-jet printing, and the viscosity and the surface tension of the quantum dot ink are 10-15 cP and 30-45 dynes/cm. In a preferred embodiment, the mass fraction percentage range of each component in the quantum dot ink is as follows: 15-60% of a first solvent, 15-60% of a second solvent, 10-40% of a surfactant, 1-20% of quantum dots and 2-20% of a nano oxide. In a preferred embodiment, the mass ratio of the quantum dots to the nano-oxide is in a range of (0.2: 1) to (5: 1), and more preferably in a range of 1:4 to 1: 2.
In a preferred embodiment, the first solvent and the second solvent have different polarities so as to make them immiscible, and the surfactant makes the first solvent and the second solvent, which are not miscible, so as to construct a stable and uniformly dispersed quantum dot ink. Preferably, the first solvent and the second solvent are of substantially different polarity or of opposite polarity.
After the quantum dot ink is subjected to ink-jet printing, a pattern is formed on a substrate, the pattern is separated along with the volatilization of a solvent, and the quantum dot ink is dried and then is divided into a quantum dot layer and a current carrier transmission material layer.
In order to achieve delamination of the quantum dots and the nano-oxide, in a preferred embodiment, the quantum dots have a solubility in the first solvent that is greater than a solubility in the second solvent, and the carrier transporting material has a solubility in the second solvent that is greater than a solubility in the first solvent. Because the boiling points of the first solvent and the second solvent are different, one component can be preferentially volatilized by adjusting the temperature in the invention, and when any one of the first solvent or the second solvent is preferentially volatilized, the quantum dots or the oxides with high solubility in the component can be preferentially separated out to form a corresponding film layer.
In another preferred embodiment, the quantum dot ink allows the surfactant, which is miscible with the first solvent and the second solvent, to preferentially volatilize when the film is dried, the first solvent and the second solvent phase-separate with the volatilization of the surfactant, and the quantum dot layer and the carrier transport material layer are finally obtained with the volatilization of the first solvent and the second solvent.
In order to increase other functional characteristics of the quantum dot ink, such as stability of the quantum dot ink, wettability to a substrate, and the like, in a preferred embodiment, the quantum dot ink further includes other additives including, but not limited to, a charge transport agent, a surface tension modifier, a film forming agent, a diffusion agent.
The particle size range of the quantum dots and the carrier transmission material is 2-20 nm. The surface of the quantum dot is modified with a ligand with the polarity similar to that of the first solvent. The quantum dots and the carrier transport material can be dissolved in the first solvent or the second solvent to form a uniform colloidal dispersion.
The quantum dots useful in the present invention include nanocrystals having any three-dimensional size within 100nm, and in a preferred embodiment, the quantum dots include at least one of groups II-VI, III-V, IV-VI, VIII-VI, I-III-VI, II-IV-VI, and II-IV-V of the periodic Table of elements, and can be prepared by reference to the prior art. Specifically, the quantum dots comprise binary-structure and multi-structure nanocrystals of IIB-VIA group, IIIA-VA group, IVA-VIA group, VIB-VIA group, VIIIB-VIA group, IB-IIIA-VIA group, IIB-IVA-VIA group and IIA-IVB-VA group of the periodic table of elements. For example, binary-structured nanocrystals include Cd-S, Cd-Se, Cd-Te, Zn-Se, Zn-Te, In-P, In-As, and the like;the multi-element structure nanocrystal comprises Cd-Zn-Se, Cd-Zn-S, Zn-Se-S, Cd-Zn-Se-S, In-Zn-P, In-Ga-P, In-Ga-As, Cu-In-S, Ca-Ti-O, Ba-Ti-O and the like. The present invention has no limitation on the ratio of each element in the multi-element structure nanocrystal, such as: the Cd-Zn-Se nanocrystal can be summarized as a chemical formula CdxZn1-xSe (x is more than 0 and less than 1), Cd-Zn-Se-S nanocrystals can be summarized as chemical formula CdyZn1-ySezS1-z(y is more than 0 and less than 1, and z is more than 0 and less than 1), the lattice structure, the luminescent property and the like of the nanocrystalline can be effectively adjusted by adjusting the ratio of each element in the multi-element alloy. In order to optimize the luminescence property of the nanocrystal core, the invention also comprises doping the binary or multi-structure nanocrystal, and the doping element preferably comprises at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, silver, gold, chlorine, bromine and iodine. In order to obtain high quality quantum dots, in a preferred embodiment, the quantum dots of the present invention have a core-shell structure, the core and the shell respectively comprise one or more semiconductor materials, the shell may comprise a single-layer or multi-layer structure. In a preferred embodiment, the shell has a thickness of about 1 to 20 layers. In a more preferred embodiment, the shell has a thickness of about 5 to 10 layers. In certain embodiments, two or more shells are grown on the surface of the quantum dot core, and the semiconductor material used for the shells has a larger band gap than the core. In a preferred embodiment, the semiconductor material used for the shell has an atomic crystal structure that is the same as or close to the core, and such a choice is advantageous in reducing the stress between the core and the shell, making the quantum dot more stable.
In a preferred embodiment, the carrier transport material is a nano-oxide, and the carrier transport material includes a P-type semiconductor material having a hole transporting ability or an N-type semiconductor material having an electron transporting ability. P-type semiconductor materials include, but are not limited to, nickel oxide, tungsten oxide, molybdenum oxide, chromium oxide, vanadium oxide, copper oxide, rubidium oxide, nickel sulfide, tungsten sulfide, molybdenum sulfide, copper sulfide. N-type semiconductor materials include, but are not limited to, zinc oxide, magnesium zinc oxide, zinc tin oxide, titanium dioxide.
In order to facilitate film formation and phase separation of the quantum dot ink, in a preferred embodiment, the first solvent and the second solvent are both liquid at 25 ℃ and have boiling points less than 200 ℃ at normal pressure, and the boiling points of the first solvent and the second solvent differ by no more than 30 ℃. In a preferred embodiment, the first solvent comprises alkane, cycloalkane, halogenated alkane, alkene, benzene or alkylbenzene compounds with the carbon number ranging from 5 to 18, and the second solvent comprises alcohol, ester, ether or ether ester compounds with the carbon number ranging from 10 to 30. In a preferred embodiment, the first solvent is selected from at least one of heptane, octane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and octadecane, chlorobenzene, ethylbenzene, diethylbenzene, saturated or unsaturated mineral spirits, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, n-hexane, 1, 4-dioxane, 1, 2-dichloroethane, tetrahydronaphthalene, decalin. In a preferred embodiment, the first solvent comprises at least two of the alkane, cycloalkane, haloalkane, alkene, benzene or alkylbenzene compounds with carbon atoms in the range of 5 to 18 to obtain a wider boiling point.
The second solvent is selected from the group consisting of ethanol, propanol, butanol, hexanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol phenyl ether, hydroxyethyl ethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol propyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol-2-ethylhexyl ether, propylene glycol monophenyl ether, diethylene glycol monophenyl ether, hydroxyisopropylethylene glycol monophenyl ether, ethyl acetate, isopropyl acetate, n-butyl acetate, amyl acetate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol phenyl ether acetate, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, polyethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and mixtures thereof, At least one of dipropylene glycol monomethyl ether and propylene glycol n-propyl ether.
To achieve miscibility of the first solvent and the second solvent, the surfactant of the present invention comprises a first portion having a polarity similar to the first solvent and a second portion having a polarity similar to the second solvent. The surfactant is liquid at 25 ℃ and has a boiling point of less than 300 ℃ at normal pressure. The first part is preferably one of an alkyl group, a cycloalkyl group and a substituted or unsubstituted phenyl group having 5 to 15 carbon atoms, and the second part is preferably one of an ether group, an alcohol group, an ester group and an amino group. In a preferred embodiment, the surfactant is selected from one of alkyl ethers, alkyl alcohols, alkyl esters, alkyl acids, alkyl acid salts, alkyl amines having a molecular weight of less than 500. In one embodiment, the surfactant is selected from at least one of octyl ether, decyl ether, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, abietyl alcohol, caprylic acid, capric acid, oleic acid, stearic acid, lauric acid, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleyl amine, sodium dodecylsulfonate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and polyethylene glycol. In a preferred embodiment, the quantum dot ink has two surfactants.
The invention also provides a preparation method of the quantum dot ink, which comprises the following steps: mixing a first organic solvent, a second organic solvent, a surfactant, quantum dots and a nano oxide to obtain the quantum dot ink; the stable and uniformly dispersed quantum dot ink is formed by adjusting the proportion of the components. After the quantum dot ink is printed, the quantum dots and the nano oxide are separated to form a quantum dot layer and a nano oxide layer. The mixing mode is stirring, oscillation or ultrasonic dispersion.
The invention also provides a quantum dot light-emitting diode which comprises an anode, a hole injection layer, a hole transmission layer, a quantum dot light-emitting layer, an electron transmission layer and a cathode, wherein the quantum dot light-emitting layer is prepared by ink-jet printing of quantum dot ink. Electroluminescent devices emit light by recombination of electrons and holes in the light-emitting layer quantum dots.
The anode preferably comprises a conductive metal or metal oxide, or a conductive polymer. The anode comprises at least one of glass/indium tin oxide, fluorine-doped tin oxide, indium zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, cadmium-doped zinc oxide, copper indium oxide, tin oxide, zirconium oxide, graphene, carbon nanotubes, nickel, gold, platinum, palladium, magnesium, iron, cobalt and aluminum. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam, and the like.
The hole injection layer preferably comprises at least one of poly (ethylenedioxythiophene) -poly (styrenesulfonate) (PEDOT: PSS), poly (perfluoroethylene-perfluoroethersulfonic acid) (PFFSA) -doped Polythienothiophene (PTT).
The hole transport layer preferably comprises nickel oxide, tungsten oxide, molybdenum oxide, chromium oxide, poly [ N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine ], poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (4,4'- (N- (4-sec-butylphenyl) diphenylamine) ], 4',4 ″ -tris (N-oxazolyl) -triphenylamine, poly (9-vinylcarbazole), poly (9, 9-di-N-octylfluorenyl-2, 7-diyl), 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoldimethylp-benzoquinone, poly [ (9, 9-di-N-octylfluorenyl-2, 7-diyl) -alt- (benzo [2,1,3] thiadiazole-4, 8-diyl) ], 4 '-bis (9-carbazole) biphenyl, 4',4 "-tris (carbazol-9-yl) triphenylamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, N '-bis- (1-naphthyl) -N, N' -diphenyl-1, 1 '-biphenyl-4, 4' -diamine, 4-butylphenyl-diphenylamine and N, N '-bis (3-methylphenyl) -N, N' -bis (phenyl) -9, 9-spirobifluorene.
The electron transport layer preferably comprises an inorganic oxide or a doped inorganic oxide, in particular, an inorganic oxide selected from ZnO, TiO2And SnO, wherein the dopant In the doped inorganic oxide is selected from one or more of Li, Mg, Al, Cd, In, Cu, Cs, Ga, Gd and 8-hydroxyquinoline aluminum, and the doping proportion of the dopant is 0.001-50 wt%.
The cathode preferably comprises one or more of the group consisting of Al, LiF/Al, Ca, Ba, Ca/Al, Ag, LiF/Ag, Ca/Ag. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam, and the like. In one embodiment, the quantum dot light emitting diode is prepared as follows: spin coating PEDOT on ITO anode layer: PSS material, then forming a hole injection layer with a certain thickness through high-temperature annealing; then forming a TFB material on the hole injection layer, and annealing at high temperature to form a hole transport layer with a certain thickness; printing a layer of the quantum dot ink on the hole transport layer by using an ink-jet printer, and drying in vacuum to form a luminescent layer; spin-coating ZnO ethanol solution on the luminescent layer, and forming an electron transport layer with a certain thickness through high-temperature annealing; and finally, evaporating an Al cathode electrode layer, and packaging to form the electroluminescent device.
The present invention is described in further detail below with reference to specific examples, which are not to be construed as limiting the scope of the invention as claimed.
Example 1
Preparing hydrophobic quantum dots, dodecane and tetradecane into a quantum dot solution according to a certain proportion; preparing zinc oxide nano material and propylene glycol phenyl ether into zinc oxide solution according to a certain proportion. And respectively mixing 60 microliters of quantum dot solution, 50 microliters of zinc oxide solution and 50 microliters of undecanol to form clear quantum dot ink without turbidity. The composition of the quantum dot ink was about 20% dodecane, 15% tetradecane, 30% propylene glycol phenyl ether, 28% undecanol, 2% hydrophobic quantum dots, and 5% zinc oxide nanomaterial.
Example 2
Quantum dot ink was prepared according to the method of example 1, except that 600. mu.l of the quantum dot solution, 500. mu.l of the zinc oxide solution, and 500. mu.l of undecanol were mixed, respectively, to form clear quantum dot ink without turbidity.
Example 3
Quantum dot ink was prepared according to the method of example 1, except that hydrophobic quantum dots, tetradecane and hexadecane were prepared into a quantum dot solution according to a certain ratio. The composition of the quantum dot ink is 20% of tetradecane, 15% of hexadecane, 30% of propylene glycol phenyl ether, 28% of undecanol, 2% of hydrophobic quantum dots and 5% of zinc oxide nano material.
Example 4
Quantum dot ink was prepared according to the method of example 1, except that hydrophobic quantum dots, toluene, and ethylbenzene were prepared into a quantum dot solution according to a certain ratio. The composition of the quantum dot ink is 20% of toluene, 15% of ethylbenzene, 35% of propylene glycol phenyl ether, 23% of undecanol, 2% of hydrophobic quantum dots and 5% of zinc oxide nano material.
Example 5
Quantum dot ink was prepared according to the method of example 1, except that hydrophobic quantum dots and solvent oil were prepared into a quantum dot solution according to a certain ratio. The composition of the quantum dot ink is 30% of solvent oil, 35% of propylene glycol phenyl ether, 28% of undecanol, 2% of hydrophobic quantum dots and 5% of zinc oxide nano material.
Example 6
A quantum dot ink was prepared according to the method of example 1, except that rosin alcohol was used instead of undecanol. The composition of the quantum dot ink is 20% of dodecane, 15% of tetradecane, 30% of propylene glycol phenyl ether, 25% of rosin alcohol, 3% of hydrophobic quantum dots and 7% of zinc oxide nano material.
Example 7
The quantum dot ink for the ink-jet printing QLED device comprises 20% of dodecane, 10% of tetradecane, 30% of propylene glycol methyl ether, 20% of sodium lauryl sulfate, 8% of hydrophobic quantum dots and 12% of zinc oxide nano material.
Although the invention has been described and illustrated in greater detail by the inventors, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent alterations thereto, will become apparent to those skilled in the art without departing from the spirit of the invention, and that no limitation to the invention is intended by the terms of the present invention as set forth herein is intended to be exhaustive or to be construed as limiting the invention.
Claims (8)
1. A quantum dot ink, comprising a first solvent, a second solvent, hydrophobic quantum dots, a carrier transport material, and a surfactant, wherein the mass fraction percentage of the surfactant in the quantum dot ink is in the range of 10-40%, the hydrophobic quantum dots and the carrier transport material have different solubilities in the first solvent and the second solvent, respectively, the first solvent and the second solvent have opposite polarities, and the surfactant comprises a first portion having a polarity similar to that of the first solvent and a second portion having a polarity similar to that of the second solvent, so as to achieve miscibility of the first solvent and the second solvent; the carrier transmission material comprises nano oxide, and the nano oxide comprises at least one of nickel oxide, tungsten oxide, molybdenum oxide, zinc oxide, magnesium zinc oxide, aluminum oxide, zinc tin oxide and titanium dioxide;
the first solvent comprises at least one of alkane, cycloalkane, halogenated alkane, alkene, benzene or alkylbenzene compounds with the carbon atom number ranging from 5 to 18;
the second solvent is at least one selected from propylene glycol methyl ether, hydroxyethyl ethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol propyl ether, diethylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol-2-ethylhexyl ether, diethylene glycol monophenyl ether, hydroxyl isopropyl ethylene glycol monophenyl ether, ethyl acetate, isopropyl acetate, n-butyl acetate, amyl acetate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol phenyl ether acetate, methyl isobutyl ketone, methyl isoamyl ketone and diisobutyl ketone.
2. The quantum dot ink of claim 1, wherein the surfactant is selected from at least one of alkyl ethers, alkyl alcohols, alkyl esters, alkyl acids, alkyl acid salts, and alkyl amines having a molecular weight of less than 500.
3. The quantum dot ink according to claim 2, wherein the surfactant is at least one selected from the group consisting of octyl ether, decyl ether, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, caprylic acid, capric acid, oleic acid, stearic acid, lauric acid, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, sodium dodecylsulfonate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and polyethylene glycol.
4. The quantum dot ink as claimed in claim 2, wherein the mass fraction percentage range of each component in the quantum dot ink is as follows: 15-60% of a first solvent, 15-60% of a second solvent, 1-20% of hydrophobic quantum dots and 2-20% of a carrier transmission material.
5. The quantum dot ink of any one of claims 1 to 4, wherein the first solvent and the second solvent are liquid at 25 ℃ and have boiling points less than 200 ℃ at atmospheric pressure.
6. The quantum dot ink of any one of claims 1 to 4, wherein the first solvent is selected from at least one of heptane, octane, decane, undecane, dodecane, tetradecane, hexadecane, octadecane, chlorobenzene, xylene, toluene, ethylbenzene, and diethylbenzene.
7. The quantum dot ink as claimed in claim 1, wherein the viscosity of the quantum dot ink is 10-15 cP, and the surface tension is 30-45 dynes/cm.
8. A quantum dot light emitting diode comprising a quantum dot layer and a carrier layer, the quantum dot layer and the carrier layer being made of the quantum dot ink of any one of claims 1 to 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017105726009 | 2017-07-14 | ||
| CN201710572600 | 2017-07-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109181414A CN109181414A (en) | 2019-01-11 |
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| CN111484770A (en) * | 2019-05-21 | 2020-08-04 | 广东聚华印刷显示技术有限公司 | Ink, preparation method thereof and preparation method of display device |
| CN110144142A (en) * | 2019-05-27 | 2019-08-20 | 广东普加福光电科技有限公司 | A kind of nano-oxide ink, preparation method and electroluminescent device |
| CN112442300B (en) * | 2019-09-04 | 2022-06-07 | Tcl科技集团股份有限公司 | Preparation method of quantum dot ink and quantum dot light-emitting diode |
| CN111876021A (en) * | 2019-09-16 | 2020-11-03 | 广东聚华印刷显示技术有限公司 | Ink composition, preparation method thereof and quantum dot light-emitting device |
| CN113045934A (en) * | 2019-12-28 | 2021-06-29 | Tcl集团股份有限公司 | Printing ink, application thereof and preparation method of quantum dot film |
| CN113122070A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Composition, preparation method thereof and light-emitting diode |
| KR20210109079A (en) | 2020-02-26 | 2021-09-06 | 삼성디스플레이 주식회사 | Ink composition, light emitting device using the same and fabrication method thereof |
| CN114106623B (en) * | 2020-12-15 | 2023-04-07 | 广东聚华印刷显示技术有限公司 | Quantum dot ink, quantum dot thin film, electroluminescent diode and display device |
| CN115996994B (en) * | 2021-08-20 | 2024-04-12 | 京东方科技集团股份有限公司 | Quantum dot ink, quantum dot film, preparation method of quantum dot ink and quantum dot film, and display substrate |
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| CN105153807A (en) * | 2015-07-21 | 2015-12-16 | 京东方科技集团股份有限公司 | Quantum dot ink |
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