CN113717715A - Material of electron transport layer, preparation method of material and quantum dot light-emitting diode - Google Patents
Material of electron transport layer, preparation method of material and quantum dot light-emitting diode Download PDFInfo
- Publication number
- CN113717715A CN113717715A CN202111014910.1A CN202111014910A CN113717715A CN 113717715 A CN113717715 A CN 113717715A CN 202111014910 A CN202111014910 A CN 202111014910A CN 113717715 A CN113717715 A CN 113717715A
- Authority
- CN
- China
- Prior art keywords
- electron transport
- nanoparticles
- ligand
- transport layer
- electron transporting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000002096 quantum dot Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 72
- 239000013110 organic ligand Substances 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 239000003446 ligand Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 230000005525 hole transport Effects 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- -1 nitrogen ions Chemical class 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 5
- 229910003363 ZnMgO Inorganic materials 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical class [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical class C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present disclosure provides a material for an electron transport layer, the material including a plurality of electron transport particles, wherein the electron transport particles include electron transport nanoparticles and organic ligands formed on the surfaces of the electron transport nanoparticles, wherein the organic ligands include coordinating groups, the organic ligands are formed on the surfaces of the electron transport nanoparticles through the coordinating bonds of the coordinating groups, and the organic ligands have P-type semiconductor characteristics. The present disclosure also provides a quantum dot light emitting diode and a method of preparing a material for an electron transport layer.
Description
Technical Field
The disclosure relates to the field of quantum dot light emitting diodes, and in particular to a material for an electron transport layer, a preparation method of the material, and a quantum dot light emitting diode comprising the material.
Background
Quantum Dot Light Emitting Diodes (QLEDs) have been widely used because of their narrow emission spectra, wide color gamut, good stability, long lifetime, low manufacturing cost, and other characteristics. However, the quantum dot light emitting diode still has the disadvantages of fluorescence quenching and low luminous efficiency.
Disclosure of Invention
An object of the present disclosure is to provide a material for an electron transport layer, a method of preparing the same, and a quantum dot light emitting diode including the same.
As a first aspect of the present disclosure, there is provided a material for an electron transport layer, the material comprising a plurality of electron transport particles, wherein the electron transport particles comprise electron transport nanoparticles and organic ligands formed on the surfaces of the electron transport nanoparticles, wherein the organic ligands comprise coordinating groups, and the organic ligands are formed on the surfaces of the electron transport nanoparticles through coordination bonds of the coordinating groups, and the organic ligands have P-type semiconductor characteristics.
Optionally, the number of carbon atoms in the organic ligand is not less than 4.
Optionally, the organic ligand has a conjugated group therein.
Optionally, the organic ligand further comprises a polar group to render the organic ligand alcohol soluble.
Optionally, the coordinating group is selected from any one of amino, thiol, carboxyl, and nitrogen ions.
Optionally, the organic ligand is formed from any one of the following materials:
r is selected from-H and-CH3、-CH2CH3、-CH2CH2CH3、-CH2OCH3、-CH2CH2SH、-CH2CH2COOCH3Any one of them.
Optionally, the electron transporting nanoparticles comprise ZnO nanoparticles and/or ZnMgO nanoparticles.
As a second aspect of the present disclosure, there is provided a quantum dot light emitting diode comprising a cathode, an electron transport layer, a quantum dot light emitting layer, a hole transport layer and an anode, which are sequentially arranged, wherein the electron transport layer is made of the material provided in the first aspect of the present disclosure.
Optionally, the quantum dot light emitting diode further comprises a hole injection layer disposed between the anode and the hole transport layer.
As a third aspect of the present disclosure, there is provided a method of preparing a material for an electron transport layer, wherein the method comprises:
mixing a plurality of electron transporting nanoparticles with a ligand supplying compound solution to obtain a plurality of electron transporting particles, wherein the ligand supplying compound in the ligand supplying compound solution has a coordinating group capable of binding to the surface of the electron transporting nanoparticles through a coordination bond, the ligand supplying compound has a P-type semiconductor characteristic such that the electron transporting particles include electron transporting nanoparticles and organic ligands formed on the surface of the electron transporting nanoparticles, and the coordinating group of the ligand supplying compound binds to the electron transporting nanoparticles to form the organic ligands.
Optionally, in the step of mixing a plurality of electron transporting nanoparticles with a ligand supplying compound solution, an ethanol solution including a plurality of the electron transporting nanoparticles is mixed with the ligand supplying compound solution.
Optionally, the number of carbon atoms in the ligand supplying compound is not less than 4 and the ligand supplying compound has a conjugated group.
Optionally, the ligand supply compound is selected from any one of the following compounds:
r is selected from-H and-CH3、-CH2CH3、-CH2CH2CH3、-CH2OCH3、-CH2CH2SH、-CH2CH2COOCH3Any one of them.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of a structure of electron transporting particles in one embodiment of the materials provided by the present disclosure;
FIG. 2 is a schematic structural diagram of one embodiment of a quantum dot light emitting diode provided by the present disclosure;
fig. 3 is a flow diagram of one embodiment of a method of making a material provided by the present disclosure.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The inventor of the present disclosure found that one reason for the fluorescence quenching and low luminous efficiency of the quantum dot light emitting diode is related to the characteristics of the electron transport layer.
In the related art, an electron transport layer of a quantum dot light emitting diode generally has ZnO or ZnO-doped nanoparticles having high mobility and a high degree of energy level matching with quantum dots. As an alternative embodiment, ZnO may be doped with any one of Al, Ga, and Mg. For example, doping ZnO with Mg can yield ZnMgO. The material of the hole transport layer is typically PEDOT: PSS, TFB, PVK and other organic materials. The mobility of the hole transport material is low, and the matching degree of the energy level of the hole transport material and the quantum dot is not high than that of the electron transport layer. The above reasons may cause the quantum dot light emitting diode to emit light with more electrons than holes in the light emitting layer, and the excess electrons may cause the quantum dots to be charged and cause low luminous efficiency due to fluorescence quenching and non-radiative recombination.
Based on the above findings, the inventors of the present disclosure believe that appropriately slowing down the electron transport in the electron transport layer may make the number of electrons and the number of holes in the light emitting layer of the quantum dot light emitting diode tend to match, and thus may avoid the quantum dot from being charged, and avoid fluorescence quenching and non-radiative recombination, and improve the light emitting efficiency.
The ZnO nanoparticles or ZnMgO nanoparticles for electron transport have high surface defects, and in order to improve the electron transport ability thereof, organic ligands are generally disposed on the surfaces of the nanoparticles for electron transport to passivate the surface defects. Although the provision of an organic ligand on the surface of the nanoparticle is generally considered as a means for improving the electron transport ability, the inventors of the present disclosure found that both the surface defects of the nanoparticle can be passivated and the electron transport in the electron transport layer can be slowed down by providing an organic ligand having a hole transport ability on the surface of the nanoparticle.
In view of this, as one aspect of the present disclosure, there is provided a material for an electron transport layer, the material comprising a plurality of electron transport particles, wherein, as shown in fig. 1, the electron transport particles comprise electron transport nanoparticles 110 and organic ligands 120 formed on the surfaces 110 of the electron transport nanoparticles, wherein the organic ligands 120 comprise coordination groups, and the organic ligands are formed on the surfaces of the electron transport nanoparticles 110 through coordination bonds of the coordination groups, and the organic ligands 120 have P-type semiconductor characteristics.
The electron transport nanoparticles 110 in the electron transport particles have an electron transport function, and the organic ligands 120 have a hole transport function, so that when the material is used to prepare an electron transport layer of a quantum dot light emitting diode, the electron transport speed in the electron transport layer can be reduced, the number of electrons in a light emitting layer of the quantum dot light emitting diode tends to match the number of holes, further, the quantum dot charging can be avoided, fluorescence quenching and non-radiative recombination are avoided, and the light emitting efficiency is improved.
Furthermore, by disposing the organic ligand 120 on the surface of the electron transporting nanoparticles 110, the surface defects of the electron transporting nanoparticles 110 can be passivated, and the electron transporting ability of the finally formed electron transporting particles can be ensured.
In the present disclosure, the number of carbon atoms in the organic ligand 120 is not particularly limited, and generally, an organic molecule having P-type semiconductor characteristics has a long chain structure, that is, the number of carbon atoms in the organic ligand is not less than 4.
The organic conjugated polymer has excellent P-type semiconductor properties, and thus, as an alternative embodiment, the organic ligand 120 has a conjugated group therein.
When the quantum dot light-emitting diode is prepared, the electron transport particles are required to be dissolved to form a solution, and then the electron transport layer of the quantum dot light-emitting diode is obtained through coating and curing. To facilitate the preparation of the solution, optionally, the organic ligand further comprises a polar group. Whether a compound molecule is a polar molecule or not can be judged by judging whether positive and negative charge centers of the molecules overlap or not, the molecules whose positive and negative charge centers overlap are non-polar molecules, the molecules whose positive and negative charge centers do not overlap are polar molecules, an organic compound including a polar group is soluble in a polar solvent (e.g., ethanol), and a contact angle of the organic compound including a polar group with water is generally less than 90 °. In other words, the organic ligand including a polar group has alcohol solubility.
When the transmission layer is prepared, the electron transmission particles can be dissolved in ethanol to prepare a solution, the solution of the electron transmission particles is coated on the quantum dot light-emitting layer in a spin coating mode, and then the electron transmission layer can be obtained after solidification.
In the present disclosure, specific types of the coordinating groups are not particularly limited, and for example, the coordinating groups are selected from any one of amino groups, mercapto groups, carboxyl groups, and nitrogen ions.
For example, in the embodiment shown in fig. 1, the coordinating group of the organic ligand 120 is an amino group.
Further, the organic ligand is formed of any one of the following materials:
r is selected from-H, -CH3 and-CH2CH3、-CH2CH2CH3、-CH2OCH3、-CH2CH2SH、-CH2CH2COOCH3Any one of them.
In the present disclosure, the specific type of the nanoparticles is also not particularly limited as long as it can play a role of electron transport, and optionally, the electron transport nanoparticles 110 include ZnO nanoparticles and/or ZnMgO nanoparticles.
As a second aspect of the present disclosure, there is provided a quantum dot light emitting diode, as shown in fig. 2, comprising a cathode 210, an electron transport layer 220, a quantum dot light emitting layer 230, a hole transport layer 240, and an anode 250, which are sequentially disposed, wherein the electron transport layer 220 is made of the material provided in the first aspect of the present disclosure.
As described above, the electron transport nanoparticles in the electron transport particles in the electron transport layer 220 have an electron transport function, and the organic ligands have a hole transport function, so that when the material is used to form the electron transport layer of the quantum dot light emitting diode, the electron transport speed in the electron transport layer can be slowed down, the number of electrons in the light emitting layer of the quantum dot light emitting diode and the number of holes can be matched, the quantum dot charging can be avoided, the fluorescence quenching and non-radiative recombination can be avoided, and the light emitting efficiency can be improved.
In addition, the organic ligand is arranged on the surface of the electron transport nanoparticles, so that the surface defects of the nanoparticles can be passivated, and the electron transport capability of the electron transport particles can be ensured.
In the present disclosure, the materials of the layers other than the electron transport layer 220 in the qd-led are not particularly limited. As an alternative embodiment, the cathode 210 may be made of silver, the quantum dots in the quantum dot light emitting layer 230 may be CdSe/ZnS quantum dots, the hole transport layer 240 may be made of PVK material, and the anode 250 may be made of ITO, which is a transparent electrode material.
As described above, one of the reasons that fluorescence quenching and low luminous efficiency occur when the quantum dot light emitting diode in the related art emits light is that the electron transport speed is relatively high and the hole transport speed is relatively low, resulting in that the quantum dot carries electrons. In order to make the number of electrons in the quantum dot light emitting layer comparable to the hole data, the quantum dot light emitting diode may further include a hole injection layer 260 disposed between the anode 250 and the hole transport layer 240.
As an alternative embodiment, the hole injection layer 260 may be made of a NiO material.
As a second aspect of the present disclosure, there is provided a method of preparing a material for an electron transport layer, wherein, as shown in fig. 3, the method comprises:
in step S310, a plurality of electron transporting nanoparticles are mixed with a ligand supplying compound solution to obtain a plurality of electron transporting particles, wherein a ligand supplying compound in the ligand supplying compound solution has a coordinating group capable of binding with a surface of the electron transporting nanoparticles through a coordination bond, and the ligand supplying compound has P-type semiconductor characteristics, so that the electron transporting particles include the electron transporting nanoparticles and organic ligands formed on the surface of the electron transporting nanoparticles, and the coordinating group of the ligand supplying compound binds with the electron transporting nanoparticles to form the organic ligands.
The coordinating group of the ligand supplying compound may be bonded at the surface defect of the electron transporting nanoparticle through a coordination bond by step S310 to obtain the electron transporting particle as described above.
In order to facilitate obtaining the electron transport particles, optionally, the preparation method may further include:
in step S320, an anti-solvent is added to the mixture obtained after the end of step S310 to obtain a precipitate, which is the material for the electron transport layer.
The material provided by the first aspect of the present disclosure can be obtained by the preparation method provided by the present disclosure. The advantageous effects of the electron transport layer made of electron transport particles have been described in detail above and will not be described in detail here.
In the present disclosure, no particular limitation is imposed on how the nanoparticles are obtained. For example, when the nanoparticles are ZnO nanoparticles, the electron transporting nanoparticles may be prepared by a solution method. Specifically, the solution method for preparing the electron transport nanoparticles comprises the following steps:
dissolving zinc acetate dihydrate in DMSO to obtain a first solution;
dissolving tetramethylammonium hydroxide in ethanol to obtain a second solution;
dripping the second solution into the first solution to obtain a mixed solution;
to the mixed solution, 1 time of ethyl acetate (used as an antisolvent) was added to obtain a precipitate, which was ZnO nanoparticles.
In order to enable the nanoparticles to react uniformly with the ligand supply compound, the nanoparticles may optionally be dispersed uniformly in the solution. In other words, in the step S310 of mixing the nanoparticles with the ligand supplying compound solution to obtain the first mixed solution, the ethanol solution of the nanoparticles may be mixed with the ligand supplying compound solution.
As mentioned hereinbefore, the number of carbon atoms in the organic ligand on the nanoparticle is preferably not less than 4, and accordingly the number of carbon atoms in the ligand donating compound is not less than 4.
As described hereinbefore, the organic ligand on the nanoparticle comprises a conjugated group and accordingly the ligand supplying compound has a conjugated group.
Optionally, the ligand supply compound is selected from any one of the following compounds:
r is selected from-H and-CH3、-CH2CH3、-CH2CH2CH3、-CH2OCH3、-CH2CH2SH、-CH2CH2COOCH3Any one of them. .
Examples
A material for an electron transport layer was prepared by the following method:
firstly, synthesizing ZnO nano particles, comprising the following steps:
weighing 0.66g of zinc acetate dihydrate, and dissolving in 30ml of DMSO;
weighing 1g of tetramethylammonium hydroxide, dissolving in 10ml of ethanol, dripping into a zinc acetate solution at a speed of 2ml/min, and stirring for reacting for 24 hours;
precipitation begins after about 1 time of ethyl acetate is added, and precipitation does not increase after about 1.5 times of ethyl acetate is added;
rotating at 4200, centrifuging at 20 ℃ for 5 minutes;
and pouring out the clear liquid to obtain the ZnO nano particles.
After obtaining the ZnO nano-particles, the following steps are carried out:
adding a small amount of ethanol (about 10ml) into the ZnO nanoparticles remained after the supernatant liquid is poured out, and dissolving the ZnO nanoparticles by ultrasonic waves;
dissolving 2.5g tetraphenylporphyrin derivative in ethanol, adding into the solution, and stirring for half an hour;
adding ethyl acetate of about 1-1.5 times, precipitating, centrifuging to remove clear liquid, dissolving in ethanol to obtain 30mg/ml solution, and making into solution for preparing electron transport layer.
Preparation example
The quantum dot light emitting diode is prepared by the following method:
spin-coating 25mg/ml nickel acetate solution on cleaned ITO conductive glass, and annealing at 275 ℃ for 40 minutes to form a 45 nm-thick hole injection layer;
spin-coating 8mg/ml of PVK chlorobenzene solution, and annealing at 135 ℃ for 30 minutes to form a hole transport layer with the thickness of 30 nm;
spin-coating CdSe/ZnS quantum dot solution of 10mg/ml, and annealing at 120 deg.C for 10 min to form a light-emitting layer with thickness of 30 nm;
spin-coating the solution of the material for preparing the electron transport layer prepared in the example, and annealing at 120 ℃ for 20 minutes to form an electron transport layer having a thickness of 45 nm;
transferring the device to a vacuum evaporator to evaporate 100nm of Ag as a cathode;
and packaging the device.
Example embodiments have been disclosed herein, and although specific terms are employed, they are used and should be interpreted in a generic and descriptive sense only and not for purposes of limitation. In some instances, features, characteristics and/or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics and/or elements described in connection with other embodiments, unless expressly stated otherwise, as would be apparent to one skilled in the art. Accordingly, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the disclosure as set forth in the appended claims.
It is to be understood that the above embodiments are merely exemplary embodiments that are employed to illustrate the principles of the present disclosure, and that the present disclosure is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the disclosure, and these are to be considered as the scope of the disclosure.
Claims (13)
1. A material for an electron transport layer, the material comprising a plurality of electron transport particles, wherein the electron transport particles comprise electron transport nanoparticles and organic ligands formed on the surfaces of the electron transport nanoparticles, wherein the organic ligands comprise coordinating groups, the organic ligands are formed on the surfaces of the electron transport nanoparticles through coordination bonds of the coordinating groups, and the organic ligands have P-type semiconductor properties.
2. A material according to claim 1, wherein the number of carbon atoms in the organic ligand is not less than 4.
3. The material of claim 2, wherein the organic ligand has a conjugated group therein.
4. A material according to any one of claims 1 to 3, wherein the organic ligand further comprises polar groups to render the organic ligand alcohol soluble.
5. The material of claim 4, wherein the coordinating group is selected from any one of amino, thiol, carboxyl, and nitrogen ions.
6. The material of claim 5, wherein the organic ligand is formed from any one of the following materials:
wherein R is selected from-H, -CH3 and-CH2CH3、-CH2CH2CH3、-CH2OCH3、-CH2CH2SH、-CH2CH2COOCH3Any one of them.
7. A material as claimed in any one of claims 1 to 3 wherein the electron transporting nanoparticles comprise ZnO nanoparticles and/or ZnO-doped nanoparticles.
8. A quantum dot light emitting diode comprising a cathode, an electron transport layer, a quantum dot light emitting layer, a hole transport layer and an anode, which are sequentially disposed, wherein the electron transport layer is made of the material of any one of claims 1 to 7.
9. The quantum dot light-emitting diode of claim 8, further comprising a hole injection layer disposed between the anode and the hole transport layer.
10. A method for preparing a material for an electron transport layer, the method comprising:
mixing a plurality of electron transporting nanoparticles with a ligand supplying compound solution to obtain a plurality of electron transporting particles, wherein the ligand supplying compound in the ligand supplying compound solution has a coordinating group capable of binding to the surface of the electron transporting nanoparticles through a coordination bond, the ligand supplying compound has a P-type semiconductor characteristic such that the electron transporting particles include electron transporting nanoparticles and organic ligands formed on the surface of the electron transporting nanoparticles, and the coordinating group of the ligand supplying compound binds to the electron transporting nanoparticles to form the organic ligands.
11. The method for preparing a porous material according to claim 10, wherein in the step of mixing a plurality of electron transporting nanoparticles with a ligand supplying compound solution, an ethanol solution including a plurality of the electron transporting nanoparticles is mixed with the ligand supplying compound solution.
12. The production method according to claim 10 or 11, wherein the number of carbon atoms in the ligand supplying compound is not less than 4, and the ligand supplying compound has a conjugated group.
13. The method of claim 12, wherein the ligand supplying compound is selected from any one of the following compounds:
wherein,
r is selected from-H and-CH3、-CH2CH3、-CH2CH2CH3、-CH2OCH3、-CH2CH2SH、-CH2CH2COOCH3Any one of them.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111014910.1A CN113717715B (en) | 2021-08-31 | 2021-08-31 | Material of electron transport layer, preparation method of material and quantum dot light emitting diode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111014910.1A CN113717715B (en) | 2021-08-31 | 2021-08-31 | Material of electron transport layer, preparation method of material and quantum dot light emitting diode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113717715A true CN113717715A (en) | 2021-11-30 |
| CN113717715B CN113717715B (en) | 2023-12-12 |
Family
ID=78680090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111014910.1A Active CN113717715B (en) | 2021-08-31 | 2021-08-31 | Material of electron transport layer, preparation method of material and quantum dot light emitting diode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113717715B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190112491A1 (en) * | 2017-10-12 | 2019-04-18 | Boe Technology Group Co., Ltd. | Zinc oxide ink and method for manufacturing the same, electron transport layer and display device |
| CN111224000A (en) * | 2018-11-26 | 2020-06-02 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| JP2020132844A (en) * | 2019-02-12 | 2020-08-31 | 東洋インキＳｃホールディングス株式会社 | Quantum dot, quantum dot-containing composition, inkjet ink and printed matter |
| CN112331787A (en) * | 2019-12-27 | 2021-02-05 | 广东聚华印刷显示技术有限公司 | Application of metal tetraphenylporphyrin complex in electron transport material, quantum dot light-emitting device and preparation method thereof, and light-emitting device |
| CN112397659A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN112542555A (en) * | 2019-09-20 | 2021-03-23 | Tcl集团股份有限公司 | Compound and preparation method thereof and quantum dot light-emitting diode |
| US20210126218A1 (en) * | 2019-10-24 | 2021-04-29 | Samsung Electronics Co., Ltd. | Electroluminescent device, and display device comprising thereof |
| CN113023767A (en) * | 2019-12-25 | 2021-06-25 | Tcl集团股份有限公司 | Modified zinc oxide nano-particles, modification method thereof and quantum dot light-emitting diode |
| WO2021136325A1 (en) * | 2019-12-30 | 2021-07-08 | Tcl科技集团股份有限公司 | Zinc oxide nanoparticle and modification method therefor, and quantum dot light emitting diode and preparation method therefor |
| CN113121382A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Metal compound material and preparation method thereof, quantum dot light-emitting diode and light-emitting device |
-
2021
- 2021-08-31 CN CN202111014910.1A patent/CN113717715B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190112491A1 (en) * | 2017-10-12 | 2019-04-18 | Boe Technology Group Co., Ltd. | Zinc oxide ink and method for manufacturing the same, electron transport layer and display device |
| CN111224000A (en) * | 2018-11-26 | 2020-06-02 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| JP2020132844A (en) * | 2019-02-12 | 2020-08-31 | 東洋インキＳｃホールディングス株式会社 | Quantum dot, quantum dot-containing composition, inkjet ink and printed matter |
| CN112397659A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN112542555A (en) * | 2019-09-20 | 2021-03-23 | Tcl集团股份有限公司 | Compound and preparation method thereof and quantum dot light-emitting diode |
| US20210126218A1 (en) * | 2019-10-24 | 2021-04-29 | Samsung Electronics Co., Ltd. | Electroluminescent device, and display device comprising thereof |
| CN113023767A (en) * | 2019-12-25 | 2021-06-25 | Tcl集团股份有限公司 | Modified zinc oxide nano-particles, modification method thereof and quantum dot light-emitting diode |
| CN112331787A (en) * | 2019-12-27 | 2021-02-05 | 广东聚华印刷显示技术有限公司 | Application of metal tetraphenylporphyrin complex in electron transport material, quantum dot light-emitting device and preparation method thereof, and light-emitting device |
| WO2021136325A1 (en) * | 2019-12-30 | 2021-07-08 | Tcl科技集团股份有限公司 | Zinc oxide nanoparticle and modification method therefor, and quantum dot light emitting diode and preparation method therefor |
| CN113121382A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Metal compound material and preparation method thereof, quantum dot light-emitting diode and light-emitting device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113717715B (en) | 2023-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10818859B2 (en) | Electroluminescent device, and display device comprising thereof | |
| US9293654B2 (en) | Light-emitting device | |
| US9331298B2 (en) | Nanocluster based light emitting device | |
| KR20190079111A (en) | Electroluminescent device, and display device comprising thereof | |
| US11233211B2 (en) | Electroluminescent device, manufacturing method thereof, and display device comprising the same | |
| US10818858B2 (en) | Electroluminescent device and display device comprising the same | |
| US20020151094A1 (en) | Thin film Inorganic Light Emitting Diode | |
| JP2013511157A (en) | Lattice-mismatched core / shell quantum dots | |
| JP2002246177A (en) | Thin film inorganic light emitting diode | |
| US10923668B2 (en) | Electroluminescent device, and display device comprising thereof | |
| US11377591B2 (en) | Liquid composition, photoelectric conversion element production method, and photoelectric conversion element | |
| CN113809272A (en) | Zinc oxide nano material, preparation method, electron transmission film and light emitting diode | |
| CN111900258B (en) | Light-emitting device, quantum dot light-emitting diode and preparation method thereof | |
| CN113299866A (en) | Film layer and preparation method thereof, and light-emitting device and preparation method thereof | |
| CN113717715B (en) | Material of electron transport layer, preparation method of material and quantum dot light emitting diode | |
| Chou et al. | Thiophenol‐Modified CdS Nanoparticles Enhance the Luminescence of Benzoxyl Dendron‐Substituted Polyfluorene Copolymers | |
| CN112531123B (en) | Preparation method of electron transport film layer and preparation method of quantum dot light-emitting diode | |
| CN113122258A (en) | Quantum dot, preparation method thereof and quantum dot light-emitting diode | |
| CN113054120B (en) | Electron blocking film, quantum dot light emitting diode and preparation method thereof | |
| Zhang et al. | To improve the performance of green light-emitting devices by enhancing hole injection efficiency | |
| CN113421986A (en) | QD light emitting layer, quantum dot light emitting device and preparation method thereof | |
| CN113773614A (en) | Composite material, preparation method thereof and light-emitting diode | |
| US20220320453A1 (en) | Hole transport material, quantum dot light-emitting device and manufacturing method thereof, and display apparatus | |
| CN112397620B (en) | Nano composite particle and preparation method and application thereof | |
| US20240147839A1 (en) | Light-emitting element and production method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |