CN113809272A - Zinc oxide nano material, preparation method, electron transmission film and light emitting diode - Google Patents
Zinc oxide nano material, preparation method, electron transmission film and light emitting diode Download PDFInfo
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- CN113809272A CN113809272A CN202010546788.1A CN202010546788A CN113809272A CN 113809272 A CN113809272 A CN 113809272A CN 202010546788 A CN202010546788 A CN 202010546788A CN 113809272 A CN113809272 A CN 113809272A
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- lithium hydroxide
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 318
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 159
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims description 19
- 230000005540 biological transmission Effects 0.000 title description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 150
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims abstract description 34
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002096 quantum dot Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
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- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
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- 239000004246 zinc acetate Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- YWKKLBATUCJUHI-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(C)=CC=1)C1=CC=CC=C1 YWKKLBATUCJUHI-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- 229910017115 AlSb Inorganic materials 0.000 description 1
- QHIFFLZFTBAPIX-UHFFFAOYSA-N C(C)O.[O-2].[Zn+2] Chemical compound C(C)O.[O-2].[Zn+2] QHIFFLZFTBAPIX-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
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- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 1
- 229910004262 HgTe Inorganic materials 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
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- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
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- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical group C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
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- 150000004679 hydroxides Chemical class 0.000 description 1
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- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
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- 238000002604 ultrasonography Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
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- Optics & Photonics (AREA)
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Abstract
本发明属于发光二极管技术领域，尤其涉及一种氧化锌纳米材料的制备方法，包括步骤：获取氢氧化锂溶液和无水醋酸锌；在无水无氧的环境下，将所述无水醋酸锌与所述氢氧化锂溶液混合溶解后，进行热反应，分离得到氧化锌纳米材料。本发明提供的氧化锌纳米材料的制备方法，以氢氧化锂和无水醋酸锌为原料，在无水无氧的环境下通过热反应制得氧化锌纳米材料，通过对反应原料及反应条件参数的合理调控，从而使制得的氧化锌纳米材料的粒径为5～7纳米的，粒径小，分散稳定性好，能隙宽，达到3.7eV。
The invention belongs to the technical field of light-emitting diodes, and in particular relates to a method for preparing zinc oxide nanomaterials, comprising the steps of: obtaining a lithium hydroxide solution and anhydrous zinc acetate; After mixing and dissolving with the lithium hydroxide solution, thermal reaction is performed to separate and obtain zinc oxide nanomaterials. The method for preparing zinc oxide nanomaterials provided by the invention takes lithium hydroxide and anhydrous zinc acetate as raw materials, and prepares zinc oxide nanomaterials by thermal reaction in an anhydrous and oxygen-free environment. The particle size of the prepared zinc oxide nanomaterial is 5-7 nanometers, the particle size is small, the dispersion stability is good, and the energy gap is wide, reaching 3.7 eV.
Description
Technical Field
The invention belongs to the technical field of light emitting diodes, and particularly relates to a zinc oxide nano material and a preparation method thereof, an electron transmission film and a quantum dot light emitting diode.
Background
The quantum dots have the advantages of adjustable luminescence wavelength, narrow peak width, high luminescence efficiency, long service life, high thermal stability, excellent solution processability and the like due to the obvious quantum dot confinement effect, and have wide application prospects in the fields of novel display and illumination, solar cells, biomarkers and the like. The quantum dot light emitting diode (QLED) prepared by taking inorganic quantum dots with more stable performance as a light emitting layer has the advantages of wide color gamut range, full color, high color purity, low preparation cost and the like, and becomes a next-generation novel display with great potential. Through development and progress for many years, particularly, performance preparation of the QLED with the alloy structure as a representative in all aspects is greatly improved, and especially, the efficiency and the service life of the red and green quantum dots can meet the commercial application requirements.
At present, the zinc oxide nano material is a semiconductor oxide with wider direct band gap, has good chemical stability and lower growth temperature, and is widely favored by researchers. The zinc oxide is used as a commonly used electron transport layer material in a semiconductor photovoltaic device or a luminescent device, can obviously improve the recombination efficiency of carriers in a luminescent layer of the device, and has wide application range in the field of semiconductor devices. However, in the current zinc oxide nano material adopted by the electron transport layer, the energy gap of a sample is about 3.5eV under the condition of no metal doping, and a certain difference still exists between the energy gap and the energy gap corresponding to the intrinsic luminescence of the zinc oxide crystal defect, but the high metal doping condition can affect the dispersibility and concentration of the solution and cause phase change.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc oxide nano material, and aims to solve the technical problem that the prepared zinc oxide nano material is poor in dispersion stability in the existing preparation method of the zinc oxide nano material to a certain extent.
The invention also aims to provide a zinc oxide nano material.
It is still another object of the present invention to provide an electron transport film.
It is another object of the present invention to provide a quantum dot light emitting diode.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a zinc oxide nano material comprises the following steps:
obtaining a lithium hydroxide solution and anhydrous zinc acetate;
and under the anhydrous and oxygen-free environment, mixing and dissolving the anhydrous zinc acetate and the lithium hydroxide solution, carrying out thermal reaction, and separating to obtain the zinc oxide nano material.
Correspondingly, the zinc oxide nano material is prepared by adopting the method.
Correspondingly, the electron transmission film comprises the zinc oxide nano material prepared by the method or the zinc oxide nano material.
Correspondingly, the quantum dot light-emitting diode comprises an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, and an electron transmission layer arranged between the cathode and the quantum dot light-emitting layer; the material of the electron transmission layer comprises the zinc oxide nano material prepared by the method, or comprises the zinc oxide nano material, or comprises the electron transmission film.
The preparation method of the zinc oxide nano material provided by the invention takes lithium hydroxide and anhydrous zinc acetate as raw materials and prepares the zinc oxide nano material through thermal reaction in an anhydrous and oxygen-free environment. On one hand, the invention considers the adverse effect of water and oxygen on the stability of zinc oxide, adopts anhydrous zinc acetate as a zinc source to synthesize the zinc oxide in an anhydrous and oxygen-free environment, removes water in a reaction system from two aspects of raw material selection and process environment, and avoids the agglomeration phenomenon among zinc oxide molecules caused by the combination of hydrogen atoms of crystal water or water molecules in the system and strong electronegative oxygen atoms in the zinc oxide to form hydrogen bonds, thereby ensuring the dispersion stability of the zinc oxide nano material and the film forming effect of the zinc oxide nano material on a device. On the other hand, lithium hydroxide with weak alkalinity is taken as an alkali solution precursor, and the reaction strength can be effectively regulated and controlled, so that the generated particle size of the zinc oxide nano-particles is regulated and controlled, the particle size of the zinc oxide nano-particles is reduced, the band gap of the zinc oxide is improved, and the dispersion stability of the zinc oxide nano-material is improved.
The zinc oxide nano material provided by the invention is prepared by adopting the method, has a small particle size of 5-7 nm, is good in dispersion stability in a solution and wide in energy gap which can reach 3.7eV, is closer to the energy gap corresponding to intrinsic luminescence, and can effectively improve the stability of a photoelectric device after being applied to the photoelectric device.
The electron transmission film provided by the invention contains the zinc oxide nano material with small particle size, wide energy gap and good dispersion stability, so that the electron transmission film has good film forming uniformity and good stability, and is beneficial to improving the photoelectric stability of devices.
The quantum dot light-emitting diode provided by the invention contains the zinc oxide nano material with the particle size, wide energy gap and good dispersion stability or the electronic transmission film with good film forming uniformity, good stability and the like, so that the quantum dot light-emitting diode has stable photoelectric properties such as luminous brightness, efficiency and the like.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a zinc oxide nanomaterial provided by an embodiment of the present invention.
Fig. 2 is a quantum dot light emitting diode with a positive configuration according to an embodiment of the present invention.
Fig. 3 is an inverse quantum dot light emitting diode according to an embodiment of the present invention.
FIG. 4 is a UV-Vis test spectrum of zinc oxide solutions of example 1 and comparative examples 1-3 of the present invention.
Fig. 5 is an external view of a comparative example 1 zinc oxide solution (left) and a comparative example 4 zinc oxide solution (right) according to the present invention.
FIG. 6 is an appearance diagram of comparative example 1 zinc oxide solution (left) and comparative example 4 zinc oxide solution (right) of the present invention under 365nm UV fluorescence.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a zinc oxide nanomaterial, including the following steps:
s10, obtaining a lithium hydroxide solution and anhydrous zinc acetate;
s20, mixing and dissolving the anhydrous zinc acetate and the lithium hydroxide solution in an anhydrous and oxygen-free environment, carrying out thermal reaction, and separating to obtain the zinc oxide nano material.
According to the preparation method of the zinc oxide nano material provided by the embodiment of the invention, lithium hydroxide and anhydrous zinc acetate are used as raw materials, and the zinc oxide nano material is prepared through a thermal reaction in an anhydrous and oxygen-free environment. On one hand, the embodiment of the invention considers the adverse effect of water and oxygen on the stability of zinc oxide, adopts anhydrous zinc acetate as a zinc source to synthesize the zinc oxide in an anhydrous and oxygen-free environment, removes water in a reaction system from two aspects of raw material selection and process environment, and avoids the agglomeration phenomenon among zinc oxide molecules caused by the formation of hydrogen bonds by the combination of hydrogen atoms of crystal water or water molecules in the system and strong electronegative oxygen atoms in the zinc oxide, thereby ensuring the dispersion stability of the zinc oxide nano material and the film forming effect of the zinc oxide nano material on a device. On the other hand, lithium hydroxide with weak alkalinity is taken as an alkali solution precursor, and the reaction strength can be effectively regulated and controlled, so that the generated particle size of the zinc oxide nano-particles is regulated and controlled, the particle size of the zinc oxide nano-particles is reduced, the band gap of the zinc oxide is improved, and the dispersion stability of the zinc oxide nano-material is improved.
Specifically, in the above step S10, a lithium hydroxide solution and anhydrous zinc acetate are obtained. According to the embodiment of the invention, lithium hydroxide and anhydrous zinc acetate are used as raw materials, and if the alkaline precursor adopts other hydroxides such as sodium hydroxide or the zinc precursor adopts other substances such as zinc acetate dihydrate, the particle size of the prepared zinc oxide nano particles is increased, the band gap is reduced, and the dispersion stability of the zinc oxide nano material is not ensured. According to the invention, through selection of the preparation raw materials and control of reaction condition parameters, the particle size and energy gap of the zinc oxide nano material can be effectively regulated and controlled, and the zinc oxide nano material with small particle size, wide energy gap and good dispersion stability is prepared.
In some embodiments, the step of obtaining a lithium hydroxide solution comprises: after mixing lithium hydroxide with an alcohol solvent, dissolving the lithium hydroxide in the alcohol solvent by means of ultrasound, stirring and the like to obtain a lithium hydroxide solution. In some embodiments, after mixing lithium hydroxide with an alcohol solvent, sonication is performed for 2.5 to 3 hours, and magneton stirring is performed for 20 to 30 minutes to obtain a lithium hydroxide solution.
In some embodiments, the solvent in the lithium hydroxide solution is selected from: at least one of ethanol, butanol and pentanol. In the embodiment of the invention, alcohol solvents such as ethanol, butanol and pentanol are used as the solvent components of the lithium hydroxide and the reaction system, so that the lithium hydroxide raw material and the generated zinc oxide nanoparticles have relatively good solubility.
Specifically, in step S20, the anhydrous zinc acetate and the lithium hydroxide solution are mixed and dissolved in an anhydrous and oxygen-free environment, and then are subjected to a thermal reaction and separated to obtain the zinc oxide nanomaterial. In some embodiments, the step of performing a thermal reaction after mixing and dissolving the anhydrous zinc acetate and the lithium hydroxide solution comprises: and adding the anhydrous zinc acetate into the lithium hydroxide solution at the temperature of 70-120 ℃ in an anhydrous protective gas atmosphere to form a mixed system, and then carrying out thermal reaction for 10-20 minutes. On one hand, in the embodiment of the invention, in order to avoid the interference of water and oxygen on the stability of zinc oxide, the anhydrous zinc acetate and the lithium hydroxide solution are mixed and dissolved in a protective gas atmosphere of dry nitrogen, argon and the like, and then are subjected to thermal reaction. On the other hand, the anhydrous zinc acetate is added into the lithium hydroxide solution at the temperature of 70-120 ℃, so that the solubility of the anhydrous zinc acetate in the lithium hydroxide solution is favorably improved, the hydroxide ions in the lithium hydroxide solution at the temperature of 70-120 ℃ have high reaction activity, and the dissolved zinc acetate and the hydroxide ions are favorably reacted to generate the zinc oxide nano-particles. If anhydrous zinc acetate is added under the condition of lower than 70 ℃, the solubility of the zinc acetate is extremely poor under the temperature condition, and the reaction activity of hydroxide ions in a reaction system is low due to the excessively low temperature, so that insoluble byproducts such as zinc hydroxide and the like are easily generated. If the reaction temperature is too high, the activity of hydroxyl ions in the reaction system is too high, the reaction is too violent, and the particle size and the energy gap of the zinc oxide nano material are not easy to regulate and control. In addition, the particle size of the generated zinc oxide nano particles and the energy gap of the zinc oxide nano material are further regulated and controlled by regulating and controlling the thermal reaction time to be 10-20 minutes. If the reaction time is too low, the reaction is insufficient, the yield of the zinc oxide nano material is low, the solution concentration is low, and the application requirement of a device on the concentration of the zinc oxide nano material cannot be met; if the reaction time is too long, the particle size and energy gap of the zinc oxide nano-particles are not easy to regulate and control. In some specific embodiments, the anhydrous zinc acetate is added into the lithium hydroxide solution at 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ under a dry protective gas atmosphere, and is subjected to a thermal reaction for 10 minutes, 15 minutes or 20 minutes, and then the zinc oxide nanomaterial is obtained by separation.
In some embodiments, the molar ratio of lithium hydroxide to the anhydrous zinc acetate in the mixed system is (1-1.2): 1. the molar ratio of lithium hydroxide to anhydrous zinc acetate in the reaction system of the embodiment of the invention is (1-1.2): 1, if the lithium hydroxide content is too low, the zinc oxide yield decreases; if the content of the lithium hydroxide is too high, the concentration of hydroxide ions in a reaction system is enhanced, the alkalinity is too strong, the reaction rate is too fast, and the particle size of the zinc oxide cannot be effectively controlled, so that the particle size of the generated zinc oxide nanoparticles is too large, and the energy gap is reduced. In some embodiments, the concentration of the lithium hydroxide solution is 0.08-0.12 mmol/mL, and the lithium hydroxide solution has a suitable hydroxide ion concentration in the reaction system.
In some specific embodiments, the anhydrous zinc acetate is added into the lithium hydroxide solution with a concentration of 0.08 to 0.12mmol/mL at a temperature of 70 to 120 ℃ under a dry protective gas atmosphere such as nitrogen, argon and the like, and the molar ratio of lithium hydroxide in the lithium hydroxide solution to the anhydrous zinc acetate is (1 to 1.2): and 1, carrying out thermal reaction for 10-20 minutes, and separating to obtain the zinc oxide nano material.
In some embodiments, the step of separating comprises: and cooling the reaction system subjected to the thermal reaction to below 10 ℃, and then respectively adopting a precipitator and a dispersant to purify and separate the reaction system for multiple times to obtain the zinc oxide nano material. In the embodiment of the invention, the reaction system after the thermal reaction is cooled to below 10 ℃, and the zinc oxide nano material generated in the system is purified and separated by adopting the precipitator and the dispersant respectively, so that the purified zinc oxide nano material is obtained. The low-temperature environment is favorable for the sedimentation effect of the precipitator on the zinc oxide nano material in the system, so that the sedimentation of the zinc oxide nano particles is more sufficient, and simultaneously, the reaction between the raw materials is reduced, and the reaction for generating the zinc oxide nano particles is passivated.
In some embodiments, the precipitating agent is selected from: at least one of n-heptane, n-octane, n-hexane, and acetone. In some embodiments, the dispersant is selected from: at least one of ethanol, butanol, pentanol, toluene, chlorobenzene, and chloroform. According to the method, the zinc oxide nanoparticles generated in the reaction system in the embodiment are poor in solubility in the precipitator and good in solubility in the dispersant, and are sequentially purified for multiple times through the dispersant and the precipitator to obtain the purified zinc oxide nanomaterial.
In some embodiments, the temperature of the reaction system after the thermal reaction can be reduced to below 10 ℃ within 2 minutes (the temperature reduction rate is about 30-40 ℃/min), and the reaction system is rapidly reduced to a low-temperature environment below 10 ℃, so that the sedimentation of the zinc oxide nano material is facilitated. In some specific embodiments, the reaction system after the thermal reaction is quickly placed into ice water for ice bath, the temperature is reduced to below 10 ℃, then the reaction solution is transferred into a centrifuge tube, at least one precipitator in n-heptane, n-octane, n-hexane and acetone is added, the mixed solution is shaken up and then subjected to ice bath for 30 minutes, and then the supernatant is centrifugally separated; dispersing the precipitate with at least one dispersant selected from ethanol, butanol, pentanol, toluene, chlorobenzene and chloroform, mixing, and centrifuging to separate supernatant. And repeatedly purifying for 2-3 times to obtain the purified zinc oxide nano material. Wherein the rotation speed of the centrifugation is 4000-6000 rpm, and the duration is preferably 4-5 minutes.
According to the embodiment of the invention, the purified and separated zinc oxide nano material can be directly stored in the dispersing agent at a concentration of 15-20mg/ml, so that the dispersing stability of zinc oxide nano particles is improved, the zinc oxide nano material with the concentration can be directly applied to deposition preparation of an electronic transmission layer of a device, and the application is flexible and convenient.
In some embodiments, the zinc oxide nanomaterial has a particle size of 5 to 7 nanometers. According to the embodiment of the invention, through reasonably regulating and controlling reaction raw materials and reaction condition parameters, the prepared zinc oxide nano material has the advantages of 5-7 nm of particle size, small particle size, good dispersion stability and wide energy gap, and the energy gap reaches 3.7 eV.
Correspondingly, the embodiment of the invention also provides a zinc oxide nano material prepared by adopting the method.
The zinc oxide nano material provided by the embodiment of the invention has the advantages that the zinc oxide nano material is prepared by adopting the method, has small particle size of 5-7 nanometers, has good dispersion stability in a solution and wide energy gap which can reach 3.7eV, is closer to the energy gap corresponding to intrinsic luminescence, and can effectively improve the stability of a photoelectric device after being applied to the photoelectric device.
Correspondingly, the embodiment of the invention also provides an electron transmission film which comprises the zinc oxide nano material.
The electronic transmission film provided by the embodiment of the invention contains the zinc oxide nano material with small particle size, wide energy gap and good dispersion stability, so that the electronic transmission film has good film forming uniformity and good stability, and is beneficial to improving the photoelectric stability of devices.
Correspondingly, the embodiment of the invention also provides a quantum dot light-emitting diode, which comprises an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, and an electron transmission layer arranged between the cathode and the quantum dot light-emitting layer; the material of the electron transmission layer comprises the zinc oxide nano material or the electron transmission film.
The quantum dot light-emitting diode provided by the embodiment of the invention comprises the zinc oxide nano material with the particle size, the wide energy gap and the good dispersion stability, or comprises the electronic transmission film with the good film forming uniformity, the good stability and the like, so that the photoelectric properties such as the luminous brightness, the efficiency and the like of the quantum dot light-emitting diode are stable.
In some embodiments, the quantum dot light emitting diode of embodiments of the present invention includes a positive structure and an inversion structure.
In one embodiment, a positive structure quantum dot light emitting diode includes a stacked structure of an anode and a cathode disposed opposite each other, a quantum dot light emitting layer disposed between the anode and the cathode, and the anode is disposed on a substrate. Further, a hole function layer such as a hole injection layer, a hole transport layer, an electron blocking layer and the like can be arranged between the anode and the quantum dot light-emitting layer; an electron-transport layer, an electron-injection layer, a hole-blocking layer and other electron-functional layers can be arranged between the cathode and the quantum dot light-emitting layer. In some embodiments of positive-type devices, as shown in fig. 2, the quantum dot light emitting diode includes a substrate, an anode disposed on the surface of the substrate, a hole transport layer disposed on the surface of the anode, a quantum dot light emitting layer disposed on the surface of the hole transport layer, an electron transport layer disposed on the surface of the quantum dot light emitting layer, and a cathode disposed on the surface of the electron transport layer.
In one embodiment, an inversion-structured quantum dot light emitting diode includes a stacked structure of an anode and a cathode disposed opposite each other, a quantum dot light emitting layer disposed between the anode and the cathode, and the cathode is disposed on a substrate. Further, a hole function layer such as a hole injection layer, a hole transport layer, an electron blocking layer and the like can be arranged between the anode and the quantum dot light-emitting layer; an electron-transport layer, an electron-injection layer, a hole-blocking layer and other electron-functional layers can be arranged between the cathode and the quantum dot light-emitting layer. In some embodiments of the device with the inverted structure, as shown in fig. 3, the qd-led comprises a substrate, a cathode disposed on the surface of the substrate, an electron transport layer disposed on the surface of the cathode, a qd-light emitting layer disposed on the surface of the electron transport layer, a hole transport layer disposed on the surface of the qd-light emitting layer, and an anode disposed on the surface of the hole transport layer.
In further embodiments, the substrate layer comprises a rigid, flexible substrate, or the like;
the anode includes: ITO, FTO or ZTO, etc.;
the hole injection layer includes PEODT: PSS (poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid)), WoO3、MoO3、NiO、V2O5HATCN (2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene), CuS, etc.;
the hole transport layer can be a micromolecular organic matter or a macromolecule conducting polymer, and comprises the following components: TFB (Poly [ (9, 9-di-N-octylfluorenyl-2, 7-diyl) -alt- (4,4' - (N- (4-N-butyl) phenyl) -diphenylamine)]) PVK (polyvinylcarbazole), TCTA (4,4 '-tris (carbazol-9-yl) triphenylamine), TAPC (4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline)])、Poly-TBP、Poly-TPD、NPB(N,N'-diphenyl-N, N '- (1-naphthyl) -1,1' -biphenyl-4, 4 '-diamine), CBP (4,4' -bis (9-carbazole) biphenyl), peot: PSS, MoO3、WoO3、NiO、CuO、V2O5CuS, etc.;
quantum dot light emitting layers include, but are not limited to: at least one of the semiconductor compounds of II-IV group, II-VI group, II-V group, III-VI group, IV-VI group, I-III-VI group, II-IV-VI group and II-IV-V group of the periodic table of the elements, or at least two of the semiconductor compounds. In some embodiments, the quantum dot light emitting layer material is selected from: at least one semiconductor nanocrystal compound of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe and CdZnSe, or at least two semiconductor nanocrystal compounds with mixed type, gradient mixed type, core-shell structure type or combined type structures. In other embodiments, the quantum dot light emitting layer material is selected from: at least one semiconductor nanocrystal compound of InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe and ZnCdSe, or a semiconductor nanocrystal compound with a mixed type, a gradient mixed type, a core-shell structure type or a combined type of at least two components. In other embodiments, the quantum dot light emitting layer material is selected from: at least one of a perovskite nanoparticle material (in particular a luminescent perovskite nanoparticle material), a metal nanoparticle material, a metal oxide nanoparticle material. The quantum dot materials have the characteristics of quantum dots and have good photoelectric properties. The thickness of the quantum dot light emitting layer is 10-100 nm;
the electron transmission layer comprises the zinc oxide nano material or the electron transmission film;
the cathode includes: al, Ag, Au, Cu, Mo, or an alloy thereof.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the progress of the zinc oxide nanomaterial and the method for preparing the same apparent, the above technical solutions are illustrated by the following examples.
Example 1
A zinc oxide solution (ZnO (r)), comprising the preparation steps of:
1. in an argon glove box, firstly, 7mmol of lithium hydroxide solid is dissolved in 60mL of ethanol solution, the solution is put into a round-bottom flask and is subjected to ultrasonic treatment for 3 hours, after the ultrasonic treatment is finished, the round-bottom flask is heated to 80 ℃, a bottle stopper is covered, and stirring is carried out by a magneton to obtain a lithium hydroxide precursor solution.
2. And (3) putting the weighed 7.7mmol of anhydrous zinc acetate solid into the lithium hydroxide precursor solution, keeping the temperature at 80 ℃, and carrying out stirring reaction for 20 minutes by using magnetons.
3. After the reaction, the round-bottomed flask containing the mixed solution was quickly placed in ice water for ice-bath, and after the temperature of the round-bottomed flask was reduced to 10 ℃, the round-bottomed flask was divided into eight centrifugal tubes (7.5 mL/tube) and 40mL of n-heptane was added. The mixed solution was shaken up and then subjected to ice-bath for 30 minutes, followed by centrifugation at 6000rpm for 5 minutes, after which the supernatant was decanted and dispersed with 2.5 mL/tube of an ethanol dispersant, and the solution dispersed in two tubes was combined into one tube, and 40mL of n-hexane was added to each tube, and then subjected to ice-bath for 30 minutes again and then to centrifugation at 6000rpm for 5 minutes. After centrifugation, the supernatant was decanted and dispersed with 2 mL/tube of ethanol, and finally the four tubes of dispersed solution were combined into one tube to obtain 8mL of zinc oxide ethanol solution.
Comparative example 1
A zinc oxide solution (ZnO ②) was prepared as a 30mg/mL ethanol solution using commercial ZnO powder purchased from Sigma.
Comparative example 2
A zinc oxide solution (ZnO 3) which is different from example 1 in that lithium hydroxide solid was replaced with sodium hydroxide solid, and the other components were the same.
Comparative example 3
A zinc oxide solution (ZnO) which differs from example 1 in that anhydrous zinc acetate solids were replaced with zinc acetate dihydrate solids, all other things being equal.
Comparative example 4
A zinc oxide solution (ZnO (c)) which is different from example 1 in that anhydrous zinc acetate solid is replaced with anhydrous zinc chloride, and the rest is the same.
Comparative example 5
A zinc oxide solution (ZnO) which differs from example 1 in that the anhydrous zinc acetate solid was replaced with anhydrous zinc nitrate, all other things being equal.
Comparative example 6
A zinc oxide solution (ZnO) which is different from example 1 in that anhydrous zinc acetate solid is replaced with anhydrous zinc stearate, and the rest is the same.
Comparative example 7
A zinc oxide solution (ZnO) which is different from example 1 in that the "round bottom flask containing the mixed solution was rapidly put in ice water to perform ice bath" operation was omitted, and the other operations were the same.
Example 2
The quantum dot light-emitting diode is characterized in that the zinc oxide solution prepared in the embodiment 1 is stored in a refrigerator, and the device is prepared once every 7 days by adopting the same process as follows, so that the device prepared by the zinc oxide solution stored for different time is obtained, and the method comprises the following steps:
1. spin-coating a layer of PEDOT (PSS: s-MoO) on an ITO substrate3Injecting the hole into the layer and annealing in the air;
2. in a nitrogen atmosphere, a 25nm PVK hole transport layer is spin-coated on the hole injection layer and annealed at 140 ℃;
3. a 35nm CdSe @ ZnS quantum dot light-emitting layer is spin-coated on the hole transport layer;
4. the zinc oxide solution prepared in example 1 was spin-coated on the quantum dot light emitting layer on day 1, day 8, day 15 and day 22, respectively, to form a ZnO electron transport layer with a thickness of 50 nm;
5. a 100nm Ag electrode is vapor-plated on the electron transport layer;
6. and packaging to obtain the QLED device with the positive structure.
Comparative examples 8 to 10
The quantum dot light-emitting diode is different from the quantum dot light-emitting diode in example 2 in that the electron transport layers are formed by depositing the zinc oxide solutions prepared in comparison 1-3 respectively, and the rest are the same.
Furthermore, in order to verify the progress of the preparation method of the zinc oxide nanomaterial in the embodiment of the invention, the embodiment of the invention performs a performance test.
Test example 1
The zinc oxide solutions prepared in the example 1 and the comparative examples 1 to 7 are observed and tested for concentration, wherein the zinc oxide solutions in the example 1 and the comparative examples 1 to 3 are both clear dispersion solutions, and the concentration of the zinc oxide solutions is 30 mg/mL; the zinc oxide solutions (ZnO (c) to (c) of comparative examples 4 to 7 were too turbid to be filtered, and the test amount was determined. As shown in fig. 4, the zinc oxide solution of comparative example 1 (left) was clear, while the zinc oxide solution of comparative example 4 (right) was significantly too turbid to be filtered for subsequent treatment. As shown in fig. 6, under 365nm ultraviolet irradiation, light can enter the zinc oxide solution (left) in the comparative example 1, and the zinc oxide solution (right) in the comparative example 4 is too turbid, so that the light cannot enter the solution, and subsequent treatment and application cannot be carried out.
Test example 2
The particle size and spectral performance of the zinc oxide nanoparticles in the zinc oxide solutions of example 1 and comparative examples 1-3 were tested by DLS particle size test and UV-VIS (ultraviolet-visible) test, respectively.
The UV-VIS test of the example 1 and the comparison examples 1-3 is shown in the attached figure 4, and the DLS particle size test structure is shown in the table 1:
TABLE 1
| Sample (I) | Energy gap/eV | Particle size 1/nm | Particle size 2/nm | Particle size 3/nm | Average particle diameter/nm |
| ZnO① | 3.7 | 6.33 | 6.32 | 6.31 | 6.32 |
| ZnO② | 3.53 | 14.65 | 15.39 | 15.60 | 15.21 |
| ZnO③ | 3.57 | 9.31 | 10.11 | 10.86 | 10.09 |
| ZnO④ | 3.52 | 13.05 | 13.41 | 13.80 | 13.42 |
From the above test results, the zinc oxide solution prepared in example 1 of the present invention has a wider band gap, the energy gap is 3.7eV, which is higher than the energy gaps of comparative examples 1 to 3, and is closer to the energy gap corresponding to the intrinsic luminescence of the zinc oxide crystal. And the grain size is obviously smaller than that of the grain sizes prepared in comparative examples 1-4, the average grain size is only 6.32 nanometers, and the zinc oxide nano-particles with small grain sizes have better dispersion stability and better film-forming property.
Test example 3
The brightness and External Quantum Efficiency (EQE) of the quantum dot light emitting diodes prepared in example 2 and comparative examples 8 to 10 every 7 days were respectively tested, and the test results are shown in table 2 below:
TABLE 2
From the above test results, it can be seen that the quantum dot light emitting diode prepared by the zinc oxide solution of example 1 every 7 days in example 2 of the present invention has good stability of brightness and external quantum efficiency, and even if a device is prepared by using the zinc oxide solution left for 22 days, the brightness and external quantum efficiency can maintain high stability, which indicates that the zinc oxide solution prepared in the example of the present invention has good dispersion stability, thereby improving the stability of the photoelectric properties of the device. However, the luminance and external quantum efficiency of the quantum dot light-emitting devices prepared using the zinc oxide solutions of comparative examples 6 to 8 were significantly reduced as the solution standing time was prolonged, indicating that the zinc oxide solutions of comparative examples 6 to 8 had poor dispersion stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
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