CN110144139B - Zinc oxide-based nanoparticle ink and photoelectric device - Google Patents
Zinc oxide-based nanoparticle ink and photoelectric device Download PDFInfo
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Abstract
The invention discloses a zinc oxide-based nanoparticle ink and a photoelectric device. The zinc oxide-based nanoparticle ink comprises zinc oxide nanoparticles and a solvent, wherein the solvent comprises at least one first solvent and at least one second solvent, the first solvent is alcohols, ethers or alcohol ethers not comprising benzene rings, the carbon number of the first solvent is not more than 7, the second solvent is alcohols, ethers or alcohol ethers comprising benzene rings, and the carbon number of the second solvent is not less than 7. The zinc oxide-based nanoparticle ink has good dispersion stability, is beneficial to avoiding the formation of ink drop coffee prints and improving the uniformity of film thickness; the zinc oxide-based nanoparticle ink solves the problem that the ink dissolves bottom layer materials when the ink is applied to a photoelectric device, and is beneficial to improving the stability, photoelectric performance and service life of the photoelectric device.
Description
Technical Field
The invention relates to the field of ink for ink-jet printing, in particular to zinc oxide-based nanoparticle ink and a photoelectric device.
Background
Nanometer zinc oxide is a novel multifunctional inorganic material, and recently, the nanometer zinc oxide is found to show a plurality of special functions in the fields of optics, electrics, magnetism and the like. More importantly, the nano zinc oxide can be dispersed in organic solvents, providing the possibility of using solution-based post-processing techniques, such as spraying, doctor blading, ink-jet printing, etc.
The zinc oxide-based nanoparticles have the characteristics of large specific surface area, large specific surface area energy and the like, and are easy to agglomerate; on the other hand, the nano zinc oxide has stronger surface polarity and is difficult to uniformly disperse in an organic medium. The material is usually dispersed in short carbon chain monohydric alcohol with stronger polarity such as methanol, ethanol and the like, and the zinc oxide based nano solution has low viscosity and high volatilization speed, and is not suitable for the requirements of ink-jet printing.
In the patent with publication number CN106349815A, a zinc oxide-based nanoparticle ink and a preparation method thereof are disclosed, wherein a solvent is an alcohol ether solvent, and the alcohol ether solvent has the functions of dispersing ZnO particles, adjusting viscosity and surface tension, and slowing down the volatilization rate of the solvent, and the inventor considers that the functions can only meet the most basic requirements of inkjet printing, and the patent does not relate to whether the ink formula can form coffee prints, whether the film thickness is uniform, and whether the bottom layer materials in the device can be damaged.
In the patent publication No. CN106380934A, a zinc oxide-based nanoparticle ink and a method for preparing the same are disclosed, wherein the solvent includes a low-boiling-point alcohol solvent and a high-boiling-point alcohol solvent, the low-boiling-point alcohol solvent has a boiling point range of 60 to 120 ℃, and the inventors believe that the boiling point is low, the solvent evaporates quickly, and the nozzle is easily clogged during inkjet printing, so that the ink is not suitable for inkjet printing. In addition, the high boiling point solvent in the patent is easy to dissolve the quantum dots, and the application of the solvent in the QLED device can destroy the quantum dot layer below the quantum dot layer.
Therefore, the prior art has yet to be improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a zinc oxide-based nanoparticle ink which is suitable for various processes such as ink-jet printing, coating and the like.
According to one aspect of the present invention, there is provided a zinc oxide-based nanoparticle ink, comprising zinc oxide nanoparticles and a solvent, wherein the solvent comprises at least one first solvent and at least one second solvent, the first solvent is an alcohol, an ether or an alcohol ether not including a benzene ring, the carbon number of the first solvent is not more than 7, the second solvent is an alcohol, an ether or an alcohol ether including a benzene ring, and the carbon number of the second solvent is not less than 7.
Further, the number of carbons in the first solvent is 4 to 7.
Further, the molecular formula of the second solvent is CnH2n-6OmWherein n is more than or equal to 7 and less than or equal to 12, and m is more than or equal to 1 and less than or equal to 3.
Further, the first solvent is selected from one or more of the following: n-butanol, n-pentanol, n-hexanol, n-heptanol, propyl butyl ether and isomers thereof, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol n-butyl ether, propylene glycol isobutyl ether, propylene glycol tert-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol isopropyl ether, dipropylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol isopropyl ether, triethylene glycol methyl ether.
Further, the second solvent is selected from one or more of: 3-phenylpropanol, 2-phenylpropanol, 1-phenylpropanol, 4-phenylbutanol, 3-phenylbutanol, 2-phenylbutanol, 1-methyl-2-phenylpropanol, 1-phenyl-2-methylpropanol, 5-phenylpentanol, 4-phenylpentanol, 3-phenylpentanol, 2-phenylpentanol, 1-methyl-2-phenylbutanol, 1-methyl-3-phenylbutanol, 1-phenyl-2-methylbutanol, 2-methyl-3-phenylbutanol, 1-phenyl-3-methylbutanol, 2-phenyl-3-methylbutanol, 1-dimethyl-2-phenylpropanol, 1-phenyl-2-phenylbutanol, and mixtures thereof, 1-phenyl-2, 2-dimethylpropanol, 1-methyl-2, 2-dimethylbenzyl alcohol, 1-isopropylmethylbenzyl alcohol, 6-phenyl-1-hexanol, 5-phenyl-1-hexanol, 4-phenyl-1-hexanol, 3-phenyl-1-hexanol, 1-methylphenyl-1-pentanol, 1-methyl-2-phenyl-1-pentanol, 1-methyl-3-phenyl-1-pentanol, 1-methyl-4-phenyl-1-pentanol, 1-methyl-5-phenyl-1-pentanol, 2, 2-methylphenyl-1-pentanol, 1-phenyl-2-methyl-1-pentanol, 2-methyl-3-phenyl-pentanol, 2-methyl-4-phenyl-pentanol, 2-methyl-5-phenyl-pentanol, 3-methylphenyl-1-pentanol, 1-phenyl-3-methyl-1-pentanol, 2-phenyl-3-methyl-1-pentanol, 3-methyl-4-phenyl-1-pentanol, 3-methyl-5-phenyl-1-pentanol, 1-phenyl-4-methyl-1-pentanol, 2-methyl-3-pentanol, 2-methyl-1-pentanol, 2-methyl-3-methyl-1-pentanol, 2-methyl-pentanol, 2-methyl-2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-2, 3, 2, or 2,3, 2,3, 2,3, 2,3, 2,3, 2,3, 2,3, 2, 3-phenyl-4-methyl-1-pentanol, 4-methylphenyl-1-pentanol, 4-methyl-5-phenyl-1-pentanol, 1, 2-dimethyl-1-phenyl-1-butanol, 1, 2-dimethyl-2-phenyl-1-butanol, 1, 2-dimethyl-3-phenyl-1-butanol, 1, 2-dimethyl-4-phenyl-1-butanol, 1, 3-dimethyl-1-phenyl-1-butanol, 1, 3-dimethyl-2-phenyl-1-butanol, 1, 3-dimethyl-3-phenyl-1-butanol, and mixtures thereof, 1, 3-dimethyl-4-phenyl-1-butanol, 2, 3-dimethyl-1-phenyl-1-butanol, 2, 3-dimethyl-2-phenyl-1-butanol, 2, 3-dimethyl-3-phenyl-1-butanol, 2, 3-dimethyl-4-phenyl-1-butanol, 1-dimethyl-2-phenyl-1-butanol, 1-dimethyl-3-phenyl-1-butanol, 1-dimethyl-4-phenyl-1-butanol, 1-phenyl-2, 2-dimethyl-1-butanol, 2-dimethyl-3-phenyl-1-butanol, 2, 3-dimethyl-1-phenyl-1-butanol, 2, 3-dimethyl-1-butanol, 2-dimethyl-phenyl-1-butanol, 2-dimethyl-1-butanol, 2, 3-dimethyl-phenyl-butanol, 2-dimethyl-1-butanol, 2-dimethyl-phenyl-butanol, 2-dimethyl-butanol, 2, and 2-dimethyl-phenyl-butanol, 2, 2-dimethyl-4-phenyl-1-butanol, 1-phenyl-3, 3-dimethyl-1-butanol, 2-phenyl-3, 3-dimethyl-1-butanol, 3-dimethyl-4-phenyl-1-butanol, 1, 1-methylphenyl-2-tert-butyl-1-propanol, 1, 1-dimethyl-2, 2-methylphenyl-1-propanol, 2-phenoxyethanol, 1- (2-methoxyphenyl) ethanol, 2-methoxy-2-phenylethyl alcohol, 3-methoxyphenylethyl alcohol, p- (dimethoxymethyl) phenylethyl alcohol, di (ethylene glycol) anisole, di (propylene glycol) benzyl alcohol, n-ethyl alcohol, n- (2-methyl) benzyl alcohol, n- (2-ethyl alcohol, p- (2-methyl) benzyl alcohol, p- (p-ethyl alcohol, p-methyl alcohol, p-ethyl alcohol, di (ethylene glycol) phenetole.
Further, in the solvent, the volume percentage of the first solvent is 50% or more, and the volume percentage of the second solvent is 50% or less.
Furthermore, the content of the zinc oxide nanoparticles in the ink is 1-200 mg/mL, and the particle size of the zinc oxide nanoparticles is 1-100 nm.
Furthermore, the zinc oxide nanoparticles are ZnO nanoparticles, or doped nanoparticles formed by doping ZnO and metal ions or oxides.
Further, the ligand on the surface of the zinc oxide nano-particle is alcamines or siloxane.
Further, the ink also comprises one or more of a surfactant, a dispersant and a silane coupling agent.
Further, the ink also comprises an alcohol-soluble polymer, wherein the alcohol-soluble polymer is selected from one or more of polyvinylpyrrolidone, polyethyleneimine, polyethoxyethyleneimine, polyvinyl alcohol, polyvinyl acetal, polyacrylate, polyethylene glycol and polycaprolactone.
According to another aspect of the invention, a photoelectric device is provided, which comprises a cathode, an electron transport layer, a light emitting layer, a hole transport layer and an anode, wherein the electron transport layer is prepared by drying the zinc oxide-based nanoparticle ink prepared by the solution method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the zinc oxide-based nanoparticle ink has good dispersion stability, is beneficial to avoiding the formation of ink drop coffee prints and improving the uniformity of film thickness;
(2) the zinc oxide-based nanoparticle ink solves the problem that when the ink is applied to a photoelectric device, the ink dissolves bottom materials, and is beneficial to improving the stability, photoelectric performance and service life of the photoelectric device;
(3) when the zinc oxide-based nanoparticle ink is applied to a substrate with a pixel structure, the uniformity of the film thickness is good.
Drawings
FIG. 1 is a film layer formed after evaporation of the solvent from the ink drop of example 1, with no visible coffee ring print on the edges;
FIG. 2 is a graph obtained by scanning the film layer of FIG. 1 using a step-profiler;
FIG. 3 is a schematic view of a quantum dot light-emitting device of example 2 when emitting light;
FIG. 4 is a film layer formed by the ink droplets of comparative example 1 after evaporation of the solvent, with a more pronounced coffee ring-print at the edges;
fig. 5 is a schematic view of the quantum dot light emitting device of comparative example 2 when emitting light.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It should be understood that the data so used may be interchanged under appropriate circumstances such that embodiments of the application described herein may be used. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides zinc oxide-based nanoparticle ink which comprises zinc oxide nanoparticles and a solvent, wherein the solvent comprises at least one first solvent and at least one second solvent, the first solvent is alcohols, ethers or alcohol ethers not comprising benzene rings, the carbon number of the first solvent is not more than 7, the second solvent is alcohols, ethers or alcohol ethers comprising benzene rings, and the carbon number of the second solvent is not less than 7.
The first solvent adopts alcohols, ethers or alcohol ethers with the carbon number not more than 7, so that the zinc oxide nano-particles can be well dispersed, the requirements on the viscosity and the surface tension of the ink can be met, and the solvent with the carbon number less than 7 has small damage on the bottom layer material of a device structure applying the ink. The second solvent also adopts alcohols, ethers or alcohol ethers, has good compatibility with the first solvent, comprises benzene rings and has high boiling point, so that the ink formula is not easy to block a nozzle or a cutter head, and in addition, the second solvent can adjust the overall viscosity of the ink and increase the ink discharging stability.
In some embodiments, the first solvent has a carbon number of 4 to 7. The carbon number of the first solvent is more than or equal to 4, so that the first solvent has a high boiling point which can reach 110-200 ℃, and the requirement of ink-jet printing can be met.
At one endIn some embodiments, the second solvent has the formula CnH2n-6OmWherein n is more than or equal to 7 and less than or equal to 12, and m is more than or equal to 1 and less than or equal to 3.
In some embodiments, the first solvent is selected from one or more of: n-butanol, n-pentanol, n-hexanol, n-heptanol, propyl butyl ether and isomers thereof, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol n-butyl ether, propylene glycol isobutyl ether, propylene glycol tert-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol isopropyl ether, dipropylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol isopropyl ether, triethylene glycol methyl ether.
In some embodiments, the second solvent is selected from one or more of: 3-phenylpropanol, 2-phenylpropanol, 1-phenylpropanol, 4-phenylbutanol, 3-phenylbutanol, 2-phenylbutanol, 1-methyl-2-phenylpropanol, 1-phenyl-2-methylpropanol, 5-phenylpentanol, 4-phenylpentanol, 3-phenylpentanol, 2-phenylpentanol, 1-methyl-2-phenylbutanol, 1-methyl-3-phenylbutanol, 1-phenyl-2-methylbutanol, 2-methyl-3-phenylbutanol, 1-phenyl-3-methylbutanol, 2-phenyl-3-methylbutanol, 1-dimethyl-2-phenylpropanol, 1-phenyl-2-phenylbutanol, and mixtures thereof, 1-phenyl-2, 2-dimethylpropanol, 1-methyl-2, 2-dimethylbenzyl alcohol, 1-isopropylmethylbenzyl alcohol, 6-phenyl-1-hexanol, 5-phenyl-1-hexanol, 4-phenyl-1-hexanol, 3-phenyl-1-hexanol, 1-methylphenyl-1-pentanol, 1-methyl-2-phenyl-1-pentanol, 1-methyl-3-phenyl-1-pentanol, 1-methyl-4-phenyl-1-pentanol, 1-methyl-5-phenyl-1-pentanol, 2, 2-methylphenyl-1-pentanol, 1-phenyl-2-methyl-1-pentanol, 2-methyl-3-phenyl-pentanol, 2-methyl-4-phenyl-pentanol, 2-methyl-5-phenyl-pentanol, 3-methylphenyl-1-pentanol, 1-phenyl-3-methyl-1-pentanol, 2-phenyl-3-methyl-1-pentanol, 3-methyl-4-phenyl-1-pentanol, 3-methyl-5-phenyl-1-pentanol, 1-phenyl-4-methyl-1-pentanol, 2-methyl-3-pentanol, 2-methyl-1-pentanol, 2-methyl-3-methyl-1-pentanol, 2-methyl-pentanol, 2-methyl-2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-2, 3, 2, or 2,3, 2,3, 2,3, 2,3, 2,3, 2,3, 2,3, 2, 3-phenyl-4-methyl-1-pentanol, 4-methylphenyl-1-pentanol, 4-methyl-5-phenyl-1-pentanol, 1, 2-dimethyl-1-phenyl-1-butanol, 1, 2-dimethyl-2-phenyl-1-butanol, 1, 2-dimethyl-3-phenyl-1-butanol, 1, 2-dimethyl-4-phenyl-1-butanol, 1, 3-dimethyl-1-phenyl-1-butanol, 1, 3-dimethyl-2-phenyl-1-butanol, 1, 3-dimethyl-3-phenyl-1-butanol, and mixtures thereof, 1, 3-dimethyl-4-phenyl-1-butanol, 2, 3-dimethyl-1-phenyl-1-butanol, 2, 3-dimethyl-2-phenyl-1-butanol, 2, 3-dimethyl-3-phenyl-1-butanol, 2, 3-dimethyl-4-phenyl-1-butanol, 1-dimethyl-2-phenyl-1-butanol, 1-dimethyl-3-phenyl-1-butanol, 1-dimethyl-4-phenyl-1-butanol, 1-phenyl-2, 2-dimethyl-1-butanol, 2-dimethyl-3-phenyl-1-butanol, 2, 3-dimethyl-1-phenyl-1-butanol, 2, 3-dimethyl-1-butanol, 2-dimethyl-phenyl-1-butanol, 2-dimethyl-1-butanol, 2, 3-dimethyl-phenyl-butanol, 2-dimethyl-1-butanol, 2-dimethyl-phenyl-butanol, 2-dimethyl-butanol, 2, and 2-dimethyl-phenyl-butanol, 2, 2-dimethyl-4-phenyl-1-butanol, 1-phenyl-3, 3-dimethyl-1-butanol, 2-phenyl-3, 3-dimethyl-1-butanol, 3-dimethyl-4-phenyl-1-butanol, 1, 1-methylphenyl-2-tert-butyl-1-propanol, 1, 1-dimethyl-2, 2-methylphenyl-1-propanol, 2-phenoxyethanol, 1- (2-methoxyphenyl) ethanol, 2-methoxy-2-phenylethyl alcohol, 3-methoxyphenylethyl alcohol, p- (dimethoxymethyl) phenylethyl alcohol, di (ethylene glycol) anisole, di (propylene glycol) benzyl alcohol, n-ethyl alcohol, n- (2-methyl) benzyl alcohol, n- (2-ethyl alcohol, p- (2-methyl) benzyl alcohol, p- (p-ethyl alcohol, p-methyl alcohol, p-ethyl alcohol, di (ethylene glycol) phenetole.
In some embodiments, the volume percent of the first solvent in the total solvent is greater than or equal to 50% and the volume percent of the second solvent in the total solvent is greater than or equal to 50%.
The content of the zinc oxide nanoparticles in the ink is 1-200 mg/mL, and the particle size of the zinc oxide nanoparticles is 1-100 nm. The zinc oxide nano-particles can be undoped ZnO nano-particles, doped nano-particles formed by doping ZnO and metal ions, or doped nano-particles formed by doping ZnO and oxides. In some embodiments, the ligands on the surface of the zinc oxide nanoparticles are alkanolamines or siloxanes.
The ink of the present invention may further comprise one or more of the following adjuvants: surfactant, dispersant and silane coupling agent.
In some embodiments, the ink of the present invention further comprises an alcohol-soluble polymer selected from one or more of the following: polyvinylpyrrolidone, polyethyleneimine, polyethoxyethyleneimine, polyvinyl alcohol, polyvinyl acetal, polyacrylate, polyethylene glycol, and polycaprolactone. The alcohol-soluble polymer in the ink can improve the compactness of the film layer and make the film layer more uniform.
The invention also provides a photoelectric device which comprises a cathode, an electron transport layer, a luminescent layer, a hole transport layer and an anode, wherein the electron transport layer is prepared by drying the zinc oxide-based nanoparticle ink after a solution method. The solution method may be spin coating, ink jet printing, spray coating, slit coating, or the like. The drying mode can be heating drying in inert gas after low-pressure drying, or directly heating drying in inert gas.
[ example 1 ]
A zinc oxide-based nanoparticle ink is provided, which comprises undoped ZnO nanoparticles (with a butanol amine ligand and an average size of 5nm) and a solvent, wherein the concentration of the ZnO nanoparticles in the ink is 120mg/mL, and the solvent comprises n-hexanol and phenoxyethanol in a volume ratio of 1: 1.
The ink drops of example 1 form the film shown in fig. 1 after the solvent evaporates, the edges of the film have no obvious coffee ring prints, and the thickness of the middle of the film is basically consistent with that of the edges as can be seen from the scanning curve of the step-meter in fig. 2, and the phenomenon that the edges are thick and the middle is thin caused by the coffee prints does not occur.
[ example 2 ]
Preparing a quantum dot light-emitting device: setting a layer of PEDOT (PSS) on the pixel substrate with the pixel isolation layer, and annealing for 30 minutes at 150 ℃ in air; then, a hole transport layer TFB is arranged, and annealing is carried out for 30 minutes in a glove box at the temperature of 150 ℃; then, a quantum dot layer is arranged on the TFB, and annealing is carried out for 20 minutes at 100 ℃; ink-jet printing the ink prepared in example 1 on the quantum dot light-emitting layer, and annealing the glove box for 20 minutes at 100 ℃ after drying at low pressure; and putting the prepared sample wafer into a vacuum cavity, evaporating the silver of the top electrode, and then packaging the device.
Fig. 3 shows the light emission of the QLED device of example 2, and it can be seen from fig. 3 that each pixel unit of the QLED emits light uniformly, which shows that the uniformity of the electron transport layer prepared by ink-jet printing is better.
Comparative example 1
A zinc oxide-based nanoparticle ink is provided, which comprises undoped ZnO nanoparticles (with a butanol amine ligand and an average size of 5nm) and a solvent, wherein the concentration of the ZnO nanoparticles in the ink is 80mg/mL, and the solvent is n-hexanol.
The ink drop of comparative example 1 formed a film layer as shown in fig. 4 after evaporation of the solvent, with a more pronounced coffee ring-print at the edges.
Comparative example 2
Provided is a zinc oxide-based nanoparticle ink including undoped ZnO nanoparticles (average size 5nm) having a butanolamine ligand, wherein the concentration of the ZnO nanoparticles in the ink is 60mg/mL, and a solvent including n-octanol and 1-phenylbutanol in a volume of 1: 1.
Referring to the method of example 2 and using the ink of this comparative example to prepare a quantum dot light emitting device, the prepared quantum dot light emitting device was shown in fig. 5 as a schematic view when it emitted light, and it was found from the figure that the light emission was not uniform within each pixel, which may be related to quantum dots in which n-octanol was able to dissolve the quantum dot layer.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A zinc oxide-based nanoparticle ink comprises zinc oxide nanoparticles and a solvent, and is characterized in that the solvent comprises at least one first solvent and at least one second solvent, the first solvent is an alcohol not comprising a benzene ring, the carbon number of the first solvent is 4-7, the second solvent is an alcohol or alcohol ether comprising a benzene ring, and the carbon number of the second solvent is not less than 7;
in the solvent, the volume percentage of the first solvent is 50% or more, and the volume percentage of the second solvent is 50% or less.
2. The zinc oxide-based nanoparticle ink of claim 1, wherein the second solvent has a molecular formula of CnH2n-6OmWherein n is more than or equal to 7 and less than or equal to 12, and m is more than or equal to 1≤3。
3. The zinc oxide-based nanoparticle ink of claim 1, wherein the first solvent is selected from one or more of the following: n-butanol, n-pentanol, n-hexanol, n-heptanol.
4. The zinc oxide-based nanoparticle ink of claim 1, wherein the second solvent is selected from one or more of the following: 3-phenylpropanol, 2-phenylpropanol, 1-phenylpropanol, 4-phenylbutanol, 3-phenylbutanol, 2-phenylbutanol, 1-methyl-2-phenylpropanol, 1-phenyl-2-methylpropanol, 5-phenylpentanol, 4-phenylpentanol, 3-phenylpentanol, 2-phenylpentanol, 1-methyl-2-phenylbutanol, 1-methyl-3-phenylbutanol, 1-phenyl-2-methylbutanol, 2-methyl-3-phenylbutanol, 1-phenyl-3-methylbutanol, 2-phenyl-3-methylbutanol, 1-dimethyl-2-phenylpropanol, 1-phenyl-2-phenylbutanol, 1-phenyl-3-methylbutanol, 2-phenyl-3-methylbutanol, 1-dimethyl-2-phenylpropanol, 1-phenylbutanol, 2-phenylbutanol, and mixtures thereof, 1-phenyl-2, 2-dimethylpropanol, 1-methyl-2, 2-dimethylbenzyl alcohol, 1-isopropylmethylbenzyl alcohol, 6-phenyl-1-hexanol, 5-phenyl-1-hexanol, 4-phenyl-1-hexanol, 3-phenyl-1-hexanol, 1-methylphenyl-1-pentanol, 1-methyl-2-phenyl-1-pentanol, 1-methyl-3-phenyl-1-pentanol, 1-methyl-4-phenyl-1-pentanol, 1-methyl-5-phenyl-1-pentanol, 2, 2-methylphenyl-1-pentanol, 1-phenyl-2-methyl-1-pentanol, 2-methyl-3-phenyl-pentanol, 2-methyl-4-phenyl-pentanol, 2-methyl-5-phenyl-pentanol, 3-methylphenyl-1-pentanol, 1-phenyl-3-methyl-1-pentanol, 2-phenyl-3-methyl-1-pentanol, 3-methyl-4-phenyl-1-pentanol, 3-methyl-5-phenyl-1-pentanol, 1-phenyl-4-methyl-1-pentanol, 2-methyl-3-pentanol, 2-methyl-1-pentanol, 2-methyl-3-methyl-1-pentanol, 2-methyl-pentanol, 2-methyl-2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-2, 3, 2, or 2,3, 2,3, 2,3, 2,3, 2,3, 2,3, 2,3, 2, 3-phenyl-4-methyl-1-pentanol, 4-methylphenyl-1-pentanol, 4-methyl-5-phenyl-1-pentanol, 1, 2-dimethyl-1-phenyl-1-butanol, 1, 2-dimethyl-2-phenyl-1-butanol, 1, 2-dimethyl-3-phenyl-1-butanol, 1, 2-dimethyl-4-phenyl-1-butanol, 1, 3-dimethyl-1-phenyl-1-butanol, 1, 3-dimethyl-2-phenyl-1-butanol, 1, 3-dimethyl-3-phenyl-1-butanol, and mixtures thereof, 1, 3-dimethyl-4-phenyl-1-butanol, 2, 3-dimethyl-1-phenyl-1-butanol, 2, 3-dimethyl-2-phenyl-1-butanol, 2, 3-dimethyl-3-phenyl-1-butanol, 2, 3-dimethyl-4-phenyl-1-butanol, 1-dimethyl-2-phenyl-1-butanol, 1-dimethyl-3-phenyl-1-butanol, 1-dimethyl-4-phenyl-1-butanol, 1-phenyl-2, 2-dimethyl-1-butanol, 2-dimethyl-3-phenyl-1-butanol, 2, 3-dimethyl-1-phenyl-1-butanol, 2, 3-dimethyl-1-butanol, 2-dimethyl-phenyl-1-butanol, 2-dimethyl-1-butanol, 2, 3-dimethyl-phenyl-butanol, 2-dimethyl-1-butanol, 2-dimethyl-phenyl-butanol, 2-dimethyl-1-butanol, 2, and 2, 2-dimethyl-phenyl-butanol, 2, 2-dimethyl-4-phenyl-1-butanol, 1-phenyl-3, 3-dimethyl-1-butanol, 2-phenyl-3, 3-dimethyl-1-butanol, 3-dimethyl-4-phenyl-1-butanol, 1, 1-methylphenyl-2-tert-butyl-1-propanol, 1, 1-dimethyl-2, 2-methylphenyl-1-propanol, 2-phenoxyethanol, 1- (2-methoxyphenyl) ethanol, 2-methoxy-2-phenylethyl alcohol, 3-methoxyphenylethyl alcohol, p- (dimethoxymethyl) phenylethyl alcohol, di (ethylene glycol) anisole, di (propylene glycol) benzyl alcohol, n-ethyl alcohol, n- (2-methyl) benzyl alcohol, n- (2-ethyl alcohol, p- (2-methyl) benzyl alcohol, p- (p-ethyl alcohol, p-methyl alcohol, p-ethyl alcohol, di (ethylene glycol) phenetole.
5. The zinc oxide-based nanoparticle ink according to claim 1, wherein the content of the zinc oxide nanoparticles in the ink is 1-200 mg/mL, and the particle size of the zinc oxide nanoparticles is 1-100 nm.
6. The zinc oxide-based nanoparticle ink according to claim 1, wherein the zinc oxide nanoparticles are ZnO nanoparticles, or doped nanoparticles formed by doping ZnO with metal ions or oxides.
7. The zinc oxide-based nanoparticle ink according to claim 1, wherein the ligand on the surface of the zinc oxide nanoparticles is an alkanolamine or a siloxane.
8. The zinc oxide-based nanoparticle ink according to claim 1, wherein the ink further comprises one or more of a surfactant, a dispersant and a silane coupling agent.
9. The zinc oxide-based nanoparticle ink according to claim 1, further comprising an alcohol-soluble polymer, wherein the alcohol-soluble polymer is one or more selected from polyvinylpyrrolidone, polyethyleneimine, polyethoxyethyleneimine, polyvinyl alcohol, polyvinyl acetal, polyacrylate, polyethylene glycol and polycaprolactone.
10. An optoelectronic device comprising a cathode, an electron transport layer, a light emitting layer, a hole transport layer, and an anode, wherein the electron transport layer is prepared by drying the zinc oxide-based nanoparticle ink of any one of claims 1 to 9 after being prepared by a solution method.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102573313A (en) * | 2012-02-13 | 2012-07-11 | 苏州晶讯科技股份有限公司 | Method for utilizing base metal catalytic ink to manufacture printed circuit |
| CN106349815A (en) * | 2016-10-12 | 2017-01-25 | Tcl集团股份有限公司 | Zinc oxide-based nanoparticle ink and preparation method thereof |
| CN106380934A (en) * | 2016-08-30 | 2017-02-08 | Tcl集团股份有限公司 | Zinc-oxide-based nanometer particle ink and preparation method thereof |
| WO2018095381A1 (en) * | 2016-11-23 | 2018-05-31 | 广州华睿光电材料有限公司 | Printing ink composition, preparation method therefor, and uses thereof |
| CN108795154A (en) * | 2017-04-28 | 2018-11-13 | Tcl集团股份有限公司 | Zinc oxide base nano particle ink |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100860446B1 (en) * | 2006-04-12 | 2008-09-25 | 주식회사 엘지화학 | Dispersion adjuvant for metal nanoparticles and metal nanoink comprising the same |
| JP2019006862A (en) * | 2017-06-22 | 2019-01-17 | キヤノン株式会社 | Aqueous ink, ink cartridge and image recording method |
-
2019
- 2019-04-15 CN CN201910299627.4A patent/CN110144139B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102573313A (en) * | 2012-02-13 | 2012-07-11 | 苏州晶讯科技股份有限公司 | Method for utilizing base metal catalytic ink to manufacture printed circuit |
| CN106380934A (en) * | 2016-08-30 | 2017-02-08 | Tcl集团股份有限公司 | Zinc-oxide-based nanometer particle ink and preparation method thereof |
| CN106349815A (en) * | 2016-10-12 | 2017-01-25 | Tcl集团股份有限公司 | Zinc oxide-based nanoparticle ink and preparation method thereof |
| WO2018095381A1 (en) * | 2016-11-23 | 2018-05-31 | 广州华睿光电材料有限公司 | Printing ink composition, preparation method therefor, and uses thereof |
| CN108795154A (en) * | 2017-04-28 | 2018-11-13 | Tcl集团股份有限公司 | Zinc oxide base nano particle ink |
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