CN107400414B - Quantum dot ink and electroluminescent device - Google Patents
Quantum dot ink and electroluminescent device Download PDFInfo
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- CN107400414B CN107400414B CN201710531413.6A CN201710531413A CN107400414B CN 107400414 B CN107400414 B CN 107400414B CN 201710531413 A CN201710531413 A CN 201710531413A CN 107400414 B CN107400414 B CN 107400414B
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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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- 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 inventionThe quantum dot ink is characterized by comprising the following components in percentage by weight: 0.01-50.00% of quantum dots, 30.00-99.98% of solvent and 0.01-40.00% of cosolvent; the co-solvent comprising interconnected groups R1And a group R2Said group R1Containing at least one oxygen-containing functional group, said group R2Comprises at least one coordination functional group W capable of being combined with the quantum dots, and the total number of carbon atoms of the cosolvent is 2-25. The invention can effectively solve the problems of low solubility and poor dispersibility of the quantum dots in the existing quantum dot printing ink.
Description
Technical Field
The invention relates to the field of luminescent devices, in particular to quantum dot ink and an electroluminescent device.
Background
With the continuous progress of technology, display devices are gradually developed to be thinner, have higher color gamut and be more stable. As a self-luminous display device, a quantum dot light emitting diode (QLED) just meets the requirements of users on the next generation display device, and the QLED has the advantages of high color gamut, good stability and the like.
The application of the inkjet printing technology to the QLED display manufacturing technology is considered to be an effective way to solve the high cost and realize a large area, and this technology can combine the solution-based functional material and the advanced inkjet printing apparatus, and can improve the utilization rate and production efficiency of the quantum dot material, reduce the manufacturing cost, and improve the productivity. Unlike the preparation process of the light-emitting layer such as spin coating and printing, the ink jet printing apparatus has high requirements on the ink, such as proper boiling point, viscosity, surface tension, and uniform and stable dispersion, which cause great difficulty in ink formulation.
In the prior art, the solubility and the dispersibility of quantum dots in quantum dot ink are poor, and particularly, the high-concentration quantum dot ink has the defects that the quantum dots are easy to agglomerate, a sprayer is easy to block during ink-jet printing, and the film forming property is poor.
Disclosure of Invention
The invention provides quantum dot ink, which aims to overcome the defect that the solubility and the dispersibility of quantum dots in the conventional quantum dot ink are poor.
According to one aspect of the invention, the quantum dot ink comprises the following components in percentage by weight: 0.01-50.00% of quantum dots, 30.00-99.98% of solvent and 0.01-40.00% of cosolvent; the co-solvent comprising interconnected groups R1And a group R2Said group R1Containing at least one oxygen-containing functional group, said group R2Comprises at least one energy and stationThe number of the total carbon atoms of the cosolvent of the coordination functional group W combined by the quantum dots is 2-25.
Preferably, the quantum dot ink comprises 20.01-50.00% of quantum dots by weight percentage.
Preferably, the viscosity of the quantum dot ink is 6-14cP and the surface tension is 25-45mN/m at 25 ℃.
Preferably, the coordinating functional group W includes at least one of a mercapto group, an amine group, a carboxyl group, and a phosphate group.
Preferably, the group R2Comprising one of said coordinating functional groups W, said group R2At least one selected from the following structural formulas:
W-(CH2)n1-
wherein n1 is selected from 0-5, and the coordination functional group W comprises sulfhydryl, amino, carboxyl or phosphate.
Preferably, the group R2Comprising at least two of said coordinating functional groups W, said groups R2At least one selected from the following structural formulas:
wherein n2-n6 are independently selected from 0-5, and the coordination functional group W comprises sulfydryl, amino, carboxyl or phosphate.
Preferably, the oxygen-containing functional group includes at least one of-O-, -OH, -CO-, -CHO, -COOH and-COO-
Preferably, the group R1Is a linear structure, the group R1At least one selected from the following structural formulas:
wherein n7-n13 are each independently selected from 0-10, Y1-Y4Independently selected from hydroxyl, aldehyde group, alkoxy, carboxyl, alkanoyloxy, alkoxycarbonyl, alkoxyhydroxyAn alkanoyloxy hydroxyl group, an alkoxycarboxyl group or an alkanoyloxy carboxyl group.
Preferably, the group R2Having a branched structure, said group R2At least one selected from the following structural formulas:
wherein n14-n16 are each independently selected from 0-10, Y5、Y6Independently selected from hydroxyl, aldehyde group, alkoxy, carboxyl, alkanoyloxy, alkoxycarbonyl, alkoxyhydroxyl, alkanoyloxy hydroxyl, alkoxycarboxyl or alkanoyloxy carboxyl.
The boiling point of the solvent is 60-300 ℃, and the solvent comprises at least one of saturated or unsaturated ether, saturated or unsaturated ketone, saturated or unsaturated ester, saturated or unsaturated alcohol ether, saturated or unsaturated alcohol ester, saturated or unsaturated alcohol ether ester, saturated or unsaturated alkane and saturated or unsaturated aromatic hydrocarbon.
Preferably, the solvent comprises at least one small molecule alcohol.
Preferably, the small molecule alcohol includes ethanol, propanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, isopentanol, sec-pentanol, sec-isopentanol, hexanol, heptanol, octanol, nonanol, decaol, undecanol, dodecanol, tridecanol, n-ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, 1, 5-pentylene glycol, 2-methyl-2, 4-pentylene glycol, 2-dimethyl-1, 3-propylene glycol, 2-butene-1, 4-diol, 2-methyl-2, 4-pentylene glycol, 2, 3-dimethyl-2, 3-butylene glycol, 2-ethyl-1, at least one of 3-hexanediol, glycerol, 1,2, 4-butanetriol, 1,2, 6-hexanetriol and pentaerythritol.
Preferably, the quantum dots comprise at least one of the group II-VI, group III-V, group IV-VI, group VI-VI, group VIII-VI, group I-III-VI, group II-IV-VI and group II-IV-V single or composite structure quantum dots in the periodic table.
Preferably, the quantum dot ink further comprises at least one organic functional material, and the organic functional material comprises a hole injection material, a hole transport material, a hole blocking material, an electron transport material, an electron injection material, an electron blocking material, a charge transfer material or a phosphorescence transfer material.
Preferably, after the quantum dot ink is dried, the quantum dots can be phase separated from the organic functional material.
Preferably, the solubility of the organic functional material in the quantum dot ink is less than 5.00% by weight.
Preferably, the quantum dot ink further comprises at least one functional assistant, and the functional assistant comprises an interfacial wetting agent, a defoaming agent or a humectant.
According to another aspect of the present invention, there is provided an electroluminescent device comprising at least one functional layer comprising an electron transport layer, a light emitting layer or a hole transport layer, the functional layer being prepared from the above quantum dot ink by inkjet printing.
The invention has the following beneficial effects: the invention adds a group R with an oxygen-containing functional group into quantum dot ink1And a group R having a quantum dot coordinating functional group2The cosolvent can effectively improve the dispersibility and the solubility of the quantum dots in the ink; the quantum dot printing ink disclosed by the invention can be suitable for ink-jet printing, and is smooth in printing process and excellent in film-forming property; the method has important significance for preparing the quantum dot printing ink with high concentration and high stability.
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.
As analyzed in the background art, the existing quantum dot ink has the defects of poor dispersibility and solubility of quantum dots, particularly, the quantum dots in the high-concentration quantum dot ink are easy to agglomerate and are not suitable for ink-jet printing.
The invention provides quantum dot printing ink which comprises the following components in percentage by weight: 0.01-50.00% of quantum dots, 30.00-99.98% of solvent and 0.01-40.00% of cosolvent; the co-solvent comprising interconnected groups R1And a group R2Said group R1Containing at least one oxygen-containing functional group, said group R2Comprises at least one coordination functional group W capable of being combined with the quantum dots, and the total number of carbon atoms of the cosolvent is 2-25.
The cosolvent has a structural formula of R1-R2The cosolvent comprises two functional group parts, wherein, the group R2Comprises at least one coordination functional group used for being combined with the quantum dots, and the coordination functional group is at least partially used for being coordinated with the quantum dots; radical R1The medium oxygen-containing functional group has better compatibility with polar and nonpolar solvents, and the group R is adjusted1The hydrophilicity and lipophilicity of the quantum dot can meet the solubility of the quantum dot in solvents with different polarities. In the invention, the cosolvent is used as a connecting substance between the quantum dot and the solvent, the dispersibility of the quantum dot can be obviously improved, the weight ratio of the quantum dot in the quantum dot ink provided by the invention can be as high as 50.00%, and the dissolving amount of the quantum dot in the ink in the prior art is far greater.
In order to facilitate the removal of the co-solvent during the drying of the ink, the total number of carbon atoms of the co-solvent in the present invention is preferably 2 to 25, more preferably 4 to 10. In addition, the chain length of the cosolvent is short, so that the distance between the nano particles is small, and the photoelectric property of the quantum dot ink after drying and film forming can be improved.
The quantum dot ink comprises 0.01-50.00% of quantum dots by weight, and specifically can comprise 0.01%, 10.00%, 20.00%, 30.00%, 40.00%, and 50.00%. In a preferred embodiment, the quantum dots are included in the quantum dot ink in a range of 20.01% to 50.00%, and the use of the quantum dot ink with high concentration can effectively reduce the use of solvents, save printing time, avoid multiple times of printing, and the like.
In order to meet the requirements of different printing modes such as ink-jet printing, spin coating, spray printing, screen printing and the like, the viscosity and the surface tension of the quantum dot ink can be adjusted within a larger numerical range by adjusting the content of each component in the quantum dot ink. In a preferred embodiment, the viscosity of the quantum dot ink is in the range of 1-40cP and the surface tension is in the range of 20-60mN/m at 25 ℃; more preferably, the viscosity of the quantum dot ink is 6-14cP, and the surface tension is 25-45 mN/m.
In a preferred embodiment, the coordinating functionality W includes at least one of a thiol group, an amine group, a carboxyl group, and a phosphate group.
The group R is different from the coordination capacity of the quantum dots in strength2The number of the coordinating functional groups in the compound can be one or more. When the number of coordinating functional groups is greater than 1, one R2The kind of the mesogenic functional group is not limited to one. Radical R2Comprises at least one of a straight-chain or branched alkane group, an olefin group and an aromatic group substituted by a coordination functional group W. In a preferred embodiment, the group R2The total number of carbon atoms in (1) is 0 to 15.
In a preferred embodiment, the group R2Comprising a coordinating functional group W, a group R2At least one selected from the following structural formulas:
W-(CH2)n1-
wherein n1 is selected from 0-5, and the coordination functional group W comprises sulfhydryl, amino, carboxyl or phosphate.
To increase the ability of the co-solvent to coordinate to the quantum dot, in a preferred embodiment, the group R2Comprising at least two coordinating functional groups W, R2At least one selected from the following structural formulas:
wherein n2-n6 are independently selected from 0-5, and the coordination functional group W comprises sulfydryl, amino, carboxyl or phosphate.
In the invention, the radical R1Containing at least one oxygen-containing functional group, in a preferred embodiment, the group R1Contains at least one of-O-, -OH, -CO-, -CHO, -COOH and-COO-.
In a preferred embodiment, the group R1Is a linear structure, the radical R1At least one selected from the following structural formulas:
wherein n7-n13 are each independently selected from 0-10, Y1-Y4Independently selected from hydroxyl, aldehyde group, alkoxy, carboxyl, alkanoyloxy, alkoxycarbonyl, alkoxyhydroxyl, alkanoyloxy hydroxyl, alkoxycarboxyl or alkanoyloxy carboxyl.
In another preferred embodiment, the group R2The ink has a branched chain structure, and the branched chain structure can further inhibit the interaction between quantum dots in the ink, so that the coagulation phenomenon of nano particles in a solvent can be effectively inhibited, and the stability of the quantum dot ink is greatly improved. In particular, the radical R2At least one selected from the following structural formulas:
wherein n14-n16 are each independently selected from 0-10, Y5、Y6Independently selected from hydroxyl, aldehyde group, alkoxy, carboxyl, alkanoyloxy, alkoxycarbonyl, alkoxyhydroxyl, alkanoyloxy hydroxyl, alkoxycarboxyl or alkanoyloxy carboxyl.
The solvent in the present invention is selected from compounds which are easily volatilized and removed during the drying process of the ink, and the boiling point of the solvent is preferably 60 to 300 ℃. In a preferred embodiment, the solvent comprises at least one of saturated or unsaturated ether, saturated or unsaturated ketone, saturated or unsaturated ester, saturated or unsaturated alcohol ether, saturated or unsaturated alcohol ester, saturated or unsaturated alcohol ether ester, saturated or unsaturated alkane, and saturated or unsaturated aromatic hydrocarbon.
In a preferred embodiment, the solvent further comprises at least one small molecule alcohol. The micromolecular alcohol is used as a viscosity regulator of the solvent, so that the quantum dot ink can be suitable for different printing modes, and meanwhile, the micromolecular alcohol can effectively regulate the surface tension and polarity of the solvent. In a preferred embodiment, the small molecule alcohol comprises 0.01% to 40.00% of the quantum dot ink by weight percent.
The small molecule alcohol comprises a monohydric or polyhydric alcohol, and in a preferred embodiment the monohydric alcohol comprises an alcohol having less than 15 total carbon atoms, specifically methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, isopentanol, sec-pentanol, sec-isopentanol, 3-pentanol, tert-pentanol, cyclopentanol, 2-methyl-1-butanol, 2-methylpentanol, 4-methyl-2-pentanol, n-hexanol, 2-ethylbutanol, 2-methylpentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-ethyl-3-pentanol, n-heptanol, 2-heptanol, 3-heptanol, 2-ethylhexanol, 2-methylcyclohexanol, N-octanol, 2-octanol, 3,5, 5-trimethylhexanol, nonanol, 2, 6-dimethyl-4-heptanol, n-decanol, 5-ethyl-2-nonanol, undecanol, 5-ethyl-2-nonanol, dodecanol, trimethylnonanol, cyclohexanol, cis-2-methylcyclohexanol, cis-3-methylcyclohexanol, cis-4-methylcycloethanol, 2-butoxyethanol, benzyl alcohol, alpha-phenylethyl alcohol, beta-phenylethyl alcohol, tridecanol. In a preferred embodiment, the total number of carbon atoms in the polyol is less than 10, specifically, comprises at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2-dimethyl-1, 3-propanediol, 2-butene-1, 4-diol, 2-methyl-2, 4-pentanediol, 2, 3-dimethyl-2, 3-butanediol, 2-ethyl-1, 3-hexanediol, glycerol, 1,2, 4-butanetriol, 1,2, 6-hexanetriol and pentaerythritol.
The quantum dots preferably comprise at least one of the group II-VI, group III-V, group IV-VI, group VI-VI, group VIII-VI, group I-III-VI, group II-IV-VI and group II-IV-V single or composite structure quantum dots in the periodic table.
Specifically, the quantum dots preferably comprise at least one of single or composite structure quantum dots of groups IIB-VIA, IIIA-VA, IVA-VIA, VIB-VIA, VIIIB-VIA, IB-IIIA-VIA, IIB-IVA and IIA-IVB-VA of the periodic table. The composite structure quantum dots preferably comprise core-shell structure quantum dots, doped structure quantum dots or multi-component alloy quantum dots. In a preferred embodiment, the quantum dots comprise at least one of Cd-Se, Cd-S, Cd-Zn-Se, Cd-Zn-S, Cd-Zn-Se-S, ZnO, CdO, ZnS, ZnSe, In-P, In-Zn-P, In-Ga-P, In-As, In-Ga-As, W-O, Ni-O, Cu-O, Fe-O, Fe-S, Ta-O, Ti-O, Zr-O, Hf-O, Y-O, Cu-In-S, Ca-Ti-O, Ba-Ti-O.
In a preferred embodiment, the particle size of the quantum dots is 1-20 nm. According to different properties of quantum dot materials, the quantum dot can be used as a material comprising a light emitting layer, an electronic function layer or a hole function layer, wherein the electronic function layer material is a transition layer material used for transmitting and injecting cathode electrons into the quantum dot in an electroluminescent device, and the hole function layer material is a transition layer material used for transmitting and injecting anode holes into the quantum dot in the electroluminescent device. In a preferred embodiment, the quantum dots are luminescent layer materials, and specifically comprise Cd-Se/Zn-S, Cd-S/Zn-S, Cd-Zn-Se/Zn-S, Cd-Zn-S/Zn-S, Cd-Zn-Se-S/Zn-S, In-P/Zn-S, In-Zn-P/Zn-S, In-Ga-P/Zn-S, In-As/Zn-S, In-Ga-As/Zn-S, Cu-In-S/Zn-S, Ca-Ti-O/Zn-S or Ba-Ti-O/Zn-S. In a preferred embodiment, the quantum dots are electronic function layer materials, and particularly comprise Zn-O, Zn-Mg-O, W-O, Ni-O, Cu-O, Fe-O, Fe-S, Ta-O, Ti-O, Zr-O, Hf-O or Y-O. In a preferred embodiment, the quantum dots are hole functional layer materials, and particularly comprise Zn-O, Zn-Mg-O, W-O, Ni-O, Cu-O, Fe-O, Fe-S, Ta-O, Ti-O, Zr-O, Hf-O or Y-O.
In a preferred embodiment, the quantum dot ink further comprises at least one organic functional material, and the organic functional material can provide additional functional contributions to the electroluminescent device, such as optimizing the light emitting performance of the device, improving the charge injection efficiency, and the like. The organic functional material preferably includes a hole injecting material, a hole transporting material, a hole blocking material, an electron transporting material, an electron injecting material, an electron blocking material, a charge transporting material, or a phosphorescent transporting material.
For the printing process of the quantum dot ink, in a preferred embodiment, the quantum dot ink can be phase-separated from the organic functional material after drying. In a preferred embodiment, the solubility of the organic functional material in the solvent is less than 5.00%, more preferably less than 2.00% by weight. Because the solubility of the organic functional material in the quantum dot ink is far less than that of the quantum dot in the ink, the organic functional material can be separated out from the solvent and deposited along with the volatilization of the solvent and the cosolvent in the drying process of the quantum dot ink, so that the layering with the quantum dot is realized.
In a preferred embodiment, the quantum dot ink further comprises at least one functional auxiliary agent, and the functional auxiliary agent can optimize the performance of the ink itself, such as increasing the shelf life of the ink, increasing the stability of the ink in use, increasing the wettability of the ink to a substrate during printing, and the like. The functional adjuvant preferably includes an interfacial wetting agent, a defoaming agent, or a humectant.
The invention also discloses an electroluminescent device which comprises at least one functional layer, wherein the functional layer comprises an electron transport layer, a luminescent layer or a hole transport layer, and the functional layer is prepared by the quantum dot ink after ink-jet printing. The solvent of the quantum dot ink disclosed by the invention is proper in polarity, boiling point, viscosity and the like and good in dispersibility to quantum dots, so that the ink is smooth in ink-jet printing process, the printed solvent is volatile, and the prepared functional layer is uniform in film forming.
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.
In the embodiment of the invention, the viscosity of the quantum dot ink is measured by using a LAMY CP2000-100T/200T instrument; the surface tension of the quantum dot ink is measured by using a JYW-200C full-automatic surface interfacial tension instrument.
Example 1
In the quantum dot ink provided in this embodiment, the quantum dots are CdSe/ZnS quantum dots with a particle size of about 7nm, and the solvent is composed of n-octane and 2-methyl-2, 4-pentanediol.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, 15.00% of CdSe/ZnS quantum dots, 40.00% of n-octane, and 45.00% of 2-methyl-2, 4-pentanediol.
Example 2
The quantum dot ink of this example is the same as example 1, except that the quantum dot ink of this example further includes a cosolvent, which is mercaptopropionic acid.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, 30.00% of CdSe/ZnS quantum dots, 40.00% of n-octane, 28.00% of 2-methyl-2, 4-pentanediol, and 2.00% of mercaptopropionic acid.
Example 3
The quantum dot ink of this example is similar to example 1, except that the quantum dot ink of this example further includes a cosolvent, which is mercaptohexanol.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, 45.00% of CdSe/ZnS quantum dots, 40.00% of n-octane, 10.00% of 2-methyl-2, 4-pentanediol, and 5.00% of mercaptohexanol.
Example 4
In the quantum dot ink provided in this embodiment, the quantum dots are ZnMgO quantum dots with a particle size of about 7nm, and the solvent is composed of isopropanol and ethylene glycol.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, ZnMgO quantum dots 10.00%, isopropyl alcohol 50.00%, and ethylene glycol 40.00%.
Example 5
The quantum dot ink of this embodiment is the same as embodiment 4, except that the quantum dot ink of this embodiment further includes a co-solvent, which is 3-mercapto-1-propylamine.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, 20.00% of ZnMgO quantum dots, 50.00% of isopropyl alcohol, 35.00% of ethylene glycol, and 5.00% of 3-mercapto-1-propylamine.
Example 6
The quantum dot ink of this example is the same as example 4, except that the quantum dot ink of this example further includes a cosolvent, which is 2-aminobutanol.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, ZnMgO quantum dots 30.00%, isopropyl alcohol 50.00%, ethylene glycol 25.00%, and 2-aminobutanol 5.00%.
Example 7
In the quantum dot ink provided in this example, the quantum dots are NiO quantum dots with a particle size of about 7nm, and the solvent is composed of chloroform and triacetin.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, 12.00% of NiO quantum dots, 50.00% of chloroform, and 40.00% of triacetin.
Example 8
The quantum dot ink of this example is the same as example 7, except that a co-solvent, which is 2-amino ethyl acetate, is further included.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, 20.00% of NiO quantum dots, 50.00% of chloroform, 38.00% of triacetin, and 3.00% of 2-amino ethyl acetate.
Example 9
The quantum dot ink of this example is the same as example 7, except that the quantum dot ink of this example further includes a cosolvent, which is ethylenediamine tetraacetic acid.
The specific composition of the quantum dot ink in this example is as follows, and includes, by weight, 25.00% of NiO quantum dots, 50.00% of chloroform, 20.00% of triacetin, and 6.00% of ethylenediaminetetraacetic acid.
Example 10
This example provides an electroluminescent device with a light emitting layer prepared by ink jet printing the CdSe/ZnS quantum dot ink of example 3.
The specific preparation method of the electroluminescent device in this embodiment is as follows: spin coating PEDOT on ITO anode layer: PSS material, then annealing for 30min at 120 ℃ to form a hole injection layer; then forming a TFB material on the hole injection layer, and annealing at 150 ℃ for 30min to form a hole transport layer; inkjet printing the CdSe/ZnS quantum dot solution of example 3 on a hole transport layer as a support to form a quantum dot light emitting layer; spin-coating the luminescent layer to prepare a zinc oxide nanoparticle electron transport layer; and finally, evaporating an Al cathode electrode layer, and packaging to form the electroluminescent device.
In the embodiment, the high-concentration CdSe/ZnS quantum dot ink is smooth in ink-jet printing, and after drying, a light-emitting layer is flat and uniform in film formation.
Example 11
This example provides an electroluminescent device with an electron transport layer prepared by ink jet printing the ZnMgO quantum dot ink of example 9.
The specific preparation method of the electroluminescent device in this embodiment is as follows: spin coating PEDOT on ITO anode layer: PSS material, then annealing for 30min at 120 ℃ to form a hole injection layer; then forming a TFB material on the hole injection layer, and annealing at 150 ℃ for 30min to form a hole transport layer; forming a quantum dot light-emitting layer by spin-coating a CdSe/ZnS quantum dot solution; the ZnMgO quantum dot ink in example 6 was ink-jet printed on the quantum dot light-emitting layer as a carrier to prepare an electron transporting layer; and finally, evaporating an Al cathode electrode layer, and packaging to form the electroluminescent device.
In the embodiment, the high-concentration ZnMgO quantum dot ink is smooth in ink-jet printing process, and after drying, an electron transmission layer is formed into a flat and uniform film.
Example 13
This example provides an electroluminescent device with a hole transport layer prepared by ink-jet printing the NiO quantum dot ink of example 9.
The specific preparation method of the electroluminescent device in this embodiment is as follows: spin coating PEDOT on ITO anode layer: PSS material, then annealing for 30min at 120 ℃ to form a hole injection layer; the NiO quantum dot ink in example 9 was ink-jet printed on the hole injection layer as a carrier, and dried to form a hole transport layer; forming a quantum dot light-emitting layer by spin-coating a CdSe/ZnS quantum dot solution; spin-coating the luminescent layer to prepare a zinc oxide nanoparticle electron transport layer; and finally, evaporating an Al cathode electrode layer, and packaging to form the electroluminescent device.
In the embodiment, the high-concentration NiO quantum dot ink is smooth in ink-jet printing process, and after the ink is dried, a hole transport layer is formed into a flat and uniform film.
And (3) testing results:
the results of the tests on the viscosity, surface tension and stability of the quantum dot inks of examples 1 to 9 are shown in the following table.
The stability of the quantum dot ink is judged by observing the dispersion state of the quantum dot ink after the quantum dot ink is placed for 180 days at normal temperature.
As can be seen from the test results, compared with the quantum dot ink without the cosolvent, the solubility, the dispersibility and the stability of the quantum dots in the quantum dot ink with the cosolvent are obviously improved, and the high-concentration quantum dot ink can still keep clear and transparent after being placed for 180 days.
The quantum dot ink provided by the invention has the advantages of high solubility, good dispersibility and high stability for quantum dots; the quantum dot printing ink is particularly suitable for the field of ink-jet printing, and during ink-jet printing, the printing is smooth, a spray head is not blocked, and the film forming performance after printing is excellent.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (15)
1. The quantum dot ink is characterized by comprising the following components in percentage by weight: 20.01-45.00% of quantum dots, 30.00-99.98% of solvent and 2.00-6.00% of cosolvent; the co-solvent comprising interconnected groups R1And a group R2Said group R1Having a branched structure and comprising at least two oxygen-containing functional groups, said group R2Comprises at least two coordination functional groups W capable of binding with the quantum dots, wherein at least part of the coordination functional groups W are used for coordinating with the quantum dots, and the total number of carbon atoms of the cosolvent is 2-25.
2. The quantum dot ink of claim 1, wherein the quantum dot ink has a viscosity of 6-14cP and a surface tension of 25-45mN/m at 25 ℃.
3. The quantum dot ink of claim 1, wherein the coordinating functional group W comprises at least one of a thiol group, an amine group, a carboxyl group, and a phosphate group.
4. The quantum dot ink of claim 3, wherein the group R2At least one selected from the following structural formulas:
wherein n2-n6 are independently selected from 0-5, and the coordination functional group W comprises sulfydryl, amino, carboxyl or phosphate.
5. The quantum dot ink of claim 1, wherein the oxygen-containing functional group comprises at least one of-O-, -OH, -CO-, -CHO, -COOH, and-COO-.
6. The quantum dot ink of claim 5, wherein the group R1Having a branched structure, said group R1At least one selected from the following structural formulas:
wherein n14-n16 are each independently selected from 0-10, Y5、Y6Independently selected from hydroxyl, aldehyde group, alkoxy, carboxyl, alkanoyloxy, alkoxycarbonyl, alkoxyhydroxyl, alkanoyloxy hydroxyl, alkoxycarboxyl or alkanoyloxy carboxyl.
7. The quantum dot ink according to claim 1, wherein the solvent has a boiling point of 60-300 ℃, and the solvent comprises at least one of saturated or unsaturated ether, saturated or unsaturated ketone, saturated or unsaturated ester, saturated or unsaturated alcohol ether, saturated or unsaturated alcohol ester, saturated or unsaturated alcohol ether ester, saturated or unsaturated alkane, and saturated or unsaturated aromatic hydrocarbon.
8. The quantum dot ink of claim 1, wherein the solvent comprises at least one small molecule alcohol.
9. The quantum dot ink according to claim 8, wherein the small molecule alcohol comprises ethanol, propanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, isopentanol, sec-pentanol, sec-isopentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, n-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2-dimethyl-1, 3-propanediol, 2-butene-1, 4-diol, 2-methyl-2, 4-pentanediol, 2, 3-dimethyl-2, at least one of 3-butanediol, 2-ethyl-1, 3-hexanediol, glycerol, 1,2, 4-butanetriol, 1,2, 6-hexanetriol, and pentaerythritol.
10. The quantum dot ink of claim 1, wherein the quantum dot comprises at least one of group II-VI, group III-V, group IV-VI, group VI-VI, group viii-VI, group I-III-VI, group II-IV-V single or composite structure quantum dots of the periodic table.
11. The quantum dot ink of claim 1, further comprising at least one organic functional material comprising a hole injection material, a hole transport material, a hole blocking material, an electron transport material, an electron injection material, an electron blocking material, an insulating material, a charge transport material, or a phosphorescent transport material.
12. The quantum dot ink of claim 11, wherein the quantum dot ink is capable of phase separating from the organic functional material after drying.
13. The quantum dot ink of claim 12, wherein the organic functional material has a solubility of less than 5.00% in the quantum dot ink, in weight percent.
14. The quantum dot ink as claimed in claim 1, further comprising at least one functional adjuvant, wherein the functional adjuvant comprises an interfacial wetting agent, a defoaming agent or a humectant.
15. An electroluminescent device comprising at least one functional layer comprising an electron transport layer, a light emitting layer or a hole transport layer, characterized in that the functional layer is prepared from a quantum dot ink according to any of claims 1 to 14 by ink jet printing.
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| CN107177239B (en) * | 2017-02-17 | 2019-03-08 | 纳晶科技股份有限公司 | The preparation method of the functional layer of ink set, photoelectric device and photoelectric device |
| CN109181414B (en) * | 2017-07-14 | 2022-04-15 | 苏州星烁纳米科技有限公司 | Quantum dot ink and light emitting diode |
| CN109962168B (en) * | 2017-12-26 | 2021-03-23 | Tcl科技集团股份有限公司 | Thin film and QLED device |
| CN109535836B (en) * | 2018-10-16 | 2021-12-31 | 苏州星烁纳米科技有限公司 | Quantum dot ink and quantum dot color film |
| CN111518543A (en) * | 2019-02-01 | 2020-08-11 | 苏州星烁纳米科技有限公司 | Quantum dot dispersion system, color film and display device |
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