CN113201253A - Ink, thin film, electroluminescent diode, preparation method and display device - Google Patents

Ink, thin film, electroluminescent diode, preparation method and display device Download PDF

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CN113201253A
CN113201253A CN202010314886.2A CN202010314886A CN113201253A CN 113201253 A CN113201253 A CN 113201253A CN 202010314886 A CN202010314886 A CN 202010314886A CN 113201253 A CN113201253 A CN 113201253A
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metal chalcogenide
chalcogenide
ink
nano
solvent
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罗健
庄锦勇
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Guangdong Juhua Printing Display Technology Co Ltd
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Guangdong Juhua Printing Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Luminescent Compositions (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses nano metal chalcogenide ink, a nano metal chalcogenide film, an electroluminescent diode, a preparation method and a display device. The metal chalcogenide nanomaterial includes a metal chalcogenide nanoparticle and a metal chalcogenide nanosheet. The nano metal chalcogenide thin film can be formed after the solvent is removed by the nano metal chalcogenide ink and annealing treatment, and the nano metal chalcogenide thin film can effectively reduce the occurrence of electric leakage phenomenon as an electron transmission layer of the electroluminescent diode device, so that the quantum efficiency and the luminous efficiency of the electroluminescent diode device are obviously improved.

Description

Ink, thin film, electroluminescent diode, preparation method and display device
Technical Field
The invention belongs to the technical field of ink jet printing, and particularly relates to nano metal chalcogenide ink, a nano metal chalcogenide film, an electroluminescent diode, a preparation method and a display device.
Background
Organic Light Emitting Diodes (OLEDs) and quantum dot light emitting diodes (QLEDs) have the advantages of high brightness, fast response, high luminous efficiency, good flexibility and the like, and have very wide application prospects. Generally, such photovoltaic devices comprise at least a cathode, a light-emitting layer and an anode. In order to improve the performance of the optoelectronic device, an Electron Transport Layer (ETL) is also disposed between the cathode and the light emitting layer to reduce the injection efficiency of electrons and improve the performance of the device.
In a conventional electroluminescent diode device, a commonly used material of an electron transport layer is some metal oxides or metal sulfides, which have the advantages of good conductivity and high material stability, and are excellent electron transport layer materials. The method for preparing the metal ion-doped metal oxide or metal sulfide film, such as magnetron sputtering, chemical vapor deposition and the like, has high requirements on equipment and higher preparation cost. The ink-jet printing technology is a non-contact and dot-matrix printing technology developed in recent years, can realize accurate quantification and positioning deposition of materials, and has the advantages of simple process, low cost and easy realization of large-area production.
The compactness of a metal oxide or metal sulfide thin film is an important factor affecting the quality of the thin film. The metal oxide or metal sulfide inks required for ink jet printing are generally formed by dispersing spherical nanoparticles in a solvent. However, after the conventionally used metal oxide or metal sulfide ink is subjected to ink-jet printing and solvent removal to form a film, defects and pores exist on the surface of the formed film, so that the device generates leakage current, and the light-emitting performance of the device is affected.
Disclosure of Invention
Based on this, it is necessary to provide a nano metal chalcogenide ink capable of forming a dense thin film to solve the above problems of defects and voids on the surface of the thin film.
Further provided is a nanometal chalcogenide thin film formed from the nanometal chalcogenide ink.
Further, an electroluminescent diode using the nano metal chalcogenide thin film as an electron transport layer, a method of manufacturing the same, and a display device including the electroluminescent diode are provided.
The invention is realized by adopting the following technical scheme.
A nanometal chalcogenide ink comprising a metal chalcogenide nanomaterial and a solvent, the metal chalcogenide nanomaterial dispersed in the solvent, the metal chalcogenide nanomaterial comprising: metal chalcogenide nanoparticles and metal chalcogenide nanosheets.
In one embodiment, the metal chalcogenide is selected from at least one of a zinc oxide-based compound, a titanium dioxide-based compound, and a zinc sulfide-based compound.
In one embodiment, the metal chalcogenide nanoparticles have a particle size of 3 to 10 nm; and/or
The metal chalcogenide nanosheet is 3-10 nm in thickness and 50-200 nm in width.
In one embodiment, in the metal chalcogenide nanomaterial, the mass ratio of the metal chalcogenide nanoparticles to the metal chalcogenide nanosheets is (5-100): 1.
in one embodiment, the metal chalcogenide is selected from ZnO (zinc oxide), ZnMgO (magnesium-doped zinc oxide), ZnTiO3(Zinc titanate), ZnMgTiO3(magnesium-doped zinc titanate), ZnCdO (cadmium-doped zinc oxide), ZnWO4(zinc tungstate), ZnAlO (aluminum-doped zinc oxide), ZnNiO (nickel-doped zinc oxide), ZnSnO3At least one of (zinc metastannate) and ZnTiSnO (titanium stannic alloy doped with zinc oxide).
In one embodiment, the solvent comprises an alcoholic solvent selected from the group consisting of: at least one of methanol, ethanol, isopropanol, butanol, glycerol, ethylene glycol, polyethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and pentylene glycol.
In one embodiment, the metal chalcogenide nano material is contained in an amount of 1 to 20 wt% and the solvent is contained in an amount of 80 to 99 wt%, based on the total mass of the nano metal chalcogenide ink.
On the other hand, a nano metal chalcogenide thin film formed by removing the solvent from the nano metal chalcogenide ink according to any one of the above embodiments and annealing the nano metal chalcogenide thin film is provided;
the metal chalcogenide nanoparticles form a film matrix, and the metal chalcogenide nanosheets are embedded in the film matrix.
According to an embodiment of the invention, the invention further provides the electroluminescent diode, a preparation method of the electroluminescent diode and a display device.
The electroluminescent diode includes:
a cathode and an anode disposed opposite to each other;
a light emitting layer disposed between the cathode and the anode;
an electron transport layer formed from the nanometal chalcogenide ink according to any of the embodiments above after solvent removal and annealing; or the nano-metal chalcogenide thin film described in the above embodiment.
The preparation method of the electroluminescent diode comprises the following steps:
providing a substrate;
an anode, a light-emitting layer, an electron transport layer and a cathode are sequentially laminated on the substrate, or
Sequentially laminating a cathode, an electron transport layer, a light emitting layer and an anode on the substrate;
wherein, the electron transmission layer is formed by removing the solvent according to the nano metal chalcogenide ink and annealing, or is the nano metal chalcogenide film.
The display device comprises an electroluminescent diode, wherein the electroluminescent diode is the electroluminescent diode or the electroluminescent diode prepared by the method.
In the traditional metal oxide and metal sulfide ink, the used nano metal oxide and metal sulfide materials are generally single spherical particles with certain sizes, and during film formation, as partial gaps between the particles are not tightly connected, the compactness of the particles is influenced, so that leakage current appears when a QLED device is prepared, and the performance of the device is influenced. In the nano metal chalcogenide ink provided by the invention, a granular nano material (metal chalcogenide nanoparticles) of metal chalcogenide and a lamellar nano material (metal chalcogenide nanosheets) are compounded and used. In the film formed by the nano metal chalcogenide ink, the granular nano material is used as a film forming matrix, and the lamellar nano material is embedded in the film formed by the granular nano material to play a role in bridging, so that the formed film is tighter, the leakage current in an electroluminescent diode with the film as an electron transmission layer is reduced, and the luminous efficiency of the device is improved.
Further, by selecting the particle size, size and mass ratio of the granular nano material to the lamellar nano material in the ink, a more compact nano metal chalcogenide film with more sufficient contact between particles can be obtained.
Drawings
Fig. 1 is a schematic view of a quantum dot light emitting diode structure according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
According to one embodiment of the present invention, there is provided a nano-metal chalcogenide ink that can be used for ink-jet printing. The nano metal chalcogenide ink comprises a metal chalcogenide nano material and a solvent, wherein the metal chalcogenide nano material is dispersed in the solvent. The metal chalcogenide nanomaterial includes the metal chalcogenide nanoparticle and the metal chalcogenide nanoplatelet.
The metal chalcogenide compound is at least one selected from the group consisting of a zinc oxide-based compound, a titanium dioxide-based compound, and a zinc sulfide-based compound. Preferably, the metal chalcogenide is a zinc oxide based compound.
Here, the metal chalcogenide compound refers to a compound composed of a metal element and a chalcogen element (e.g., an oxygen element and a sulfur element), and is generally a semiconductor. The metal element may be one metal element or a plurality of metal elements doped with each other, and the energy band width of the semiconductor may be specifically designed according to factors such as the type, doping amount and ratio of different elements.
What is exemplified by the zinc oxide-based compound is a zinc oxide-based compound. The zinc oxide-based compound refers to zinc oxide or zinc oxide material which is derived from zinc oxide and is doped or compounded with other metal elements. For example, the metal chalcogenide is selected from ZnO (zinc oxide), ZnMgO (magnesium-doped zinc oxide), ZnTiO3(Zinc titanate), ZnMgTiO3(magnesium-doped zinc titanate), ZnCdO (cadmium-doped zinc oxide), ZnWO4(zinc tungstate), ZnAlO (aluminum-doped zinc oxide), ZnNiO (nickel-doped zinc oxide), ZnSnO3At least one of (zinc metastannate) and ZnTiSnO (titanium stannic alloy doped with zinc oxide). Zinc oxide is a group ii-vi wide bandgap direct semiconductor. Its forbidden band width is about 3.37eV at room temperature. The zinc oxide is subjected to metal doping and other operations, so that the derived zinc oxide-based compound has different forbidden band widths, has good optical, piezoelectric and gas-sensitive characteristics, and can be widely applied to the fields of solar cells, high-power resistors, gas-sensitive sensors and the like. The nomenclature of the titanium dioxide-based compound and the zinc sulfide-based compound and said zinc oxide-based compound are similar and will not be described herein in detail.
Inkjet printing is a non-contact, dot-matrix printing technique developed in recent years, which has the advantages of high quantitative positioning accuracy and easy realization of large-area work, and thus is widely used in the preparation of metal compound semiconductor thin films. However, in the conventional technology, ink is generally prepared only by nanoparticles, and a film consisting of only nanoparticles cannot be very dense due to contact between particles, and agglomeration also occurs during the process of removing the solvent, so that the formed film generally has more defects and holes. The nanometer metal chalcogenide ink provided by the invention simultaneously adopts the metal chalcogenide nanoparticles and the metal chalcogenide nanosheets, the metal chalcogenide nanoparticles form a matrix of the metal compound film, and the metal chalcogenide nanosheets are embedded in the matrix to play a role in bridging the nanoparticles together to form a film with dense contact among the nanoparticles, so that the problem of leakage current of a photoelectric device existing in the film formed by the traditional ink is solved.
As a specific example, the metal chalcogenide nanoparticles have a particle size of 3 to 10 nm; specifically, the nanoparticles of the metal chalcogenide have an average particle size of 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, or 10 nm; or at least 50% of the particles have a particle size of 3-10 nm.
It should be noted that the particle size of the metal chalcogenide nanoparticles is understood in a broad sense, wherein the size of the particles is called "particle size", also called "particle size" or "diameter", and when a certain physical property or physical behavior of the measured particles is closest to a certain diameter of a homogeneous sphere (or combination), the diameter of the sphere (or combination) is taken as the equivalent particle size (or particle size distribution) of the measured particles. The particle size of the above metal chalcogenide nanoparticles can be obtained, for example, by Transmission Electron Microscopy (TEM) or Scanning Electron Microscopy (SEM) tests.
As a specific example, the metal chalcogenide nanosheet has a thickness of 3 to 10nm and a width of 50 to 200 nm. Nanoplatelets can also be referred to as two-dimensional nanomaterials, the thickness of which is typically very thin. The metal chalcogenide nanosheets are embedded into the film matrix formed by the metal chalcogenide nanoparticles, and can play a role in bridging and supporting, so that current carriers in the film can be conducted, the film can be supported, and the whole film is firmer.
It should be noted that most of the nanosheets are not of a single or regular shape, and there may be many complex shapes such as triangles, quadrilaterals, pentagons, hexagons, heptagons, octagons, and curved polygons corresponding to the above polygons in the same batch of samples. Thus, the conventionally understood "width" does not apply here, and the "width" of the metal chalcogenide nanosheets described above should also be understood in a broad sense, i.e., the distance between any two points that are longest within a nanosheet is referred to as the "width," which may also be referred to as the "radial width" or "length. For example, for an elliptical nanosheet, the width should be its major axis long; for a regular pentagonal shape of the nanosheet, this width should be understood as the distance between any two vertices.
In the metal chalcogenide nanomaterial, the mass ratio of the nanoparticles to the nanosheets is (5-100): 1. preferably, the mass ratio of the nano particles to the nano sheets is (10-50): 1. for example, the mass ratio of nanoparticles to nanoplatelets is 10: 1. 15: 1. 20: 1. 25: 1. 30: 1. 35: 1. 40: 1. 45, and (2) 45: 1. 50: 1.
in the nanometal chalcogenide ink, the solvent is selected from organic solvents. The organic solvent is an alcohol organic solvent, and the alcohol organic solvent is an organic substance in which at least one hydrogen atom is substituted by hydroxyl on a carbon chain or a carbon ring of hydrocarbons, generally has good fluidity, stability and dispersibility, and is suitable for being used as a matrix solvent of ink. The alcoholic organic solvent may be selected from: methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, polyethylene glycol, diethylene glycol, butylene glycol, and pentylene glycol, where polyethylene glycol is understood to be polyethylene glycol that is in a liquid state in the context of use.
In the components of the nano metal chalcogenide ink, based on the total mass of the nano metal chalcogenide ink, the content of the metal chalcogenide nano material is 1-20 wt%, and the content of the solvent is 80-99 wt%. For example, the content of the metal chalcogenide nanomaterial is 10 wt%, and the content of the solvent is 90 wt%; wherein "wt%" means mass percentage. The mass ratio of the two components can be adjusted adaptively according to the specific requirement on the viscosity of the ink.
A stabilizer and/or a viscosity modifier may be added to the nano metal chalcogenide ink to adjust the degree of dispersion of the nano material, the degree of stability of the entire dispersion, or the viscosity of the entire dispersion, according to the specific use of the ink.
The preparation method of the nano metal chalcogenide ink comprises the following steps: preparing materials according to the required component mass, adding the metal chalcogenide nanoparticles and the metal chalcogenide nanosheets into a solvent, and fully and uniformly mixing the materials until the solid material is uniformly dispersed in the solvent and no obvious coagulation occurs.
The solvent may be removed from the nano-metal chalcogenide ink to form a metal chalcogenide thin film, which includes the following steps.
S1, coating the nano metal chalcogenide ink on the surface of the device to be deposited;
and S2, removing the solvent, and then annealing to form the metal chalcogenide nano material into a thin film.
The nano metal chalcogenide ink can be applied to the surface of the device to be deposited by ink-jet printing or spin coating.
As a practical specific example, the nano-metal chalcogenide ink is applied to the surface of the device to be deposited by spin coating at 3000r/min for 40 s. The specific temperature of the annealing treatment was 120 ℃ and the time of the annealing treatment was 30 min.
Further, the nano metal chalcogenide ink can be applied to an organic light emitting diode device or a quantum dot light emitting diode device for forming an Electron Transport Layer (ETL). Taking the example of the quantum dot light emitting diode device, in the quantum dot light emitting diode device, an electron transport layer is generally required to be arranged to improve the device performance. Zinc oxide based compounds are a suitable class of electron transport layer materials.
According to an embodiment of the invention, the electroluminescent diode comprises: a cathode and an anode oppositely arranged, a light-emitting layer and an electron transport layer. The light emitting layer is arranged between the cathode and the anode; the electron transport layer is formed by removing the solvent from the nano-metal chalcogenide ink according to any of the above embodiments and annealing the ink, or the nano-metal chalcogenide thin film according to the above embodiments.
More specifically, the electroluminescent diode may further include: substrate, hole injection layer, hole transport layer. As shown in fig. 1, as a specific example, the quantum dot light emitting diode device includes a glass substrate 110 as a substrate, an ITO thin film 120 as an anode disposed on the glass substrate 110, a hole injection layer 130 disposed on the ITO thin film 120, a hole transport layer 140 disposed on the hole injection layer 130, a quantum dot light emitting layer 150 disposed on the hole transport layer 140, an electron transport layer 160 disposed on the quantum dot light emitting layer 150, and a cathode 170 disposed on the electron transport layer 160. The electron transmission layer is formed by spin-coating the nano metal chalcogenide ink on the quantum dot light-emitting layer and then annealing to remove the solvent.
It is to be understood that the device structure is an inverted structure commonly used in electroluminescent diodes, and it is not inconsistent with the present invention if the above-mentioned stacked structure other than the substrate is inverted layer by layer into an inverted structure.
In the above specific example, the glass substrate 110 and the ITO thin film 120 are typically integrated conductive glass; the cathode material may be selected from conductive metal foils, such as silver and gold, which are difficult to corrode under normal conditions, but is not limited thereto.
According to another embodiment of the invention, a method for manufacturing an electroluminescent diode is also provided. The preparation method of the electroluminescent diode comprises the following steps:
providing a substrate;
an anode, a light-emitting layer, an electron transport layer and a cathode are sequentially laminated on the substrate, or
Sequentially laminating a cathode, an electron transport layer, a light emitting layer and an anode on the substrate;
wherein, the electron transmission layer is formed by removing the solvent according to the nano metal chalcogenide ink and annealing, or is the nano metal chalcogenide film.
According to still another embodiment of the present invention, there is also provided a display device. The display device comprises the electroluminescent diode or the electroluminescent diode prepared according to the method.
Aiming at the problems of defects and pores caused by particle film formation of the traditional metal oxide or metal sulfide ink for ink-jet printing, through intensive research and a large number of experiments, the inventor discovers that the nano metal chalcogenide ink compounded by the granular nano material and the lamellar nano material is adopted, and further correspondingly designs a compact metal chalcogenide film formed by embedding the lamellar nano material in the granular nano material. The lamellar nano material has larger specific surface area, and atoms in a single lamellar layer have strong bonding force, so the lamellar nano material not only can play a role in filling pores and defects, but also can enhance the integral strength of the film to a certain extent, and the film is not easy to break. The electroluminescent diode using the metal chalcogenide film as an electron transmission layer not only reduces the electric leakage phenomenon and improves the luminous efficiency, but also has stronger mechanical strength and is less prone to damage.
In order to facilitate an understanding of the present invention, the present invention is described in further detail below with reference to specific examples, which are provided for the purpose of illustration only and are not intended to limit the invention. The reagents used in the following examples are all commercially available without specific reference.
Example 1
(1) And providing conductive glass as a substrate and an anode, wherein the substrate is a glass substrate, and the anode is a conductive film formed on one side surface of the glass substrate.
(2) Spin-coating [ poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) ] (PEDOT: PSS) on the anode conductive film, wherein the spin-coating revolution is 2000r/min, and the spin-coating time is 40 s; and after the coating is finished, annealing is carried out for 15min at the temperature of 150 ℃ to form a hole injection layer, and the thickness of the hole injection layer is about 40 nm.
(3) Spin-coating a chlorobenzene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB) with a concentration of 10mg/mL on the hole injection layer at a spin-coating speed of 3000r/min for 40 s; and after the coating is finished, annealing is carried out for 30min at the temperature of 150 ℃ to form a hole transport layer, and the thickness of the hole transport layer is about 35 nm.
(4) And (2) performing spin coating on the hole transport layer to form cadmium selenide/zinc sulfide (CdSe/ZnS) red light quantum dots with the concentration of 20mg/mL, wherein the spin coating revolution number is 3000r/min, the spin coating time is 40s, and after the coating is finished, annealing is performed for 10min at the temperature of 120 ℃ to form a quantum dot light-emitting layer, wherein the thickness of the quantum dot light-emitting layer is about 20 nm.
(5) Spin-coating zinc oxide-based ink on the surface of the quantum dot light-emitting layer, wherein the spin-coating revolution is 3000r/min, the spin-coating time is 40s, annealing is carried out for 30min at 120 ℃ after the coating is finished, and an electron transmission layer is formed, wherein the thickness of the electron transmission layer is about 30 nm; the zinc oxide-based ink is formed by mixing 1g of ZnO nanoparticles with the average particle size of 5nm, 0.1g of ZnO nanosheets, 50g of glycerol and 10g of isopropanol, and then stirring for 30min to uniformly disperse the mixture.
(6) Under high vacuum (10)-7Torr) was used as a cathode, silver was deposited on the surface of the electron transport layer to a thickness of 150 nm.
Example 2
(1) And providing conductive glass as a substrate and an anode, wherein the substrate is a glass substrate, and the anode is a conductive film formed on one side surface of the glass substrate.
(2) Spin-coating [ poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) ] (PEDOT: PSS) on the anode conductive film, wherein the spin-coating revolution is 2000r/min, and the spin-coating time is 40 s; and after the coating is finished, annealing is carried out for 15min at the temperature of 150 ℃ to form a hole injection layer, and the thickness of the hole injection layer is about 40 nm.
(3) Spin-coating a chlorobenzene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB) with a concentration of 10mg/mL on the hole injection layer at a spin-coating speed of 3000r/min for 40 s; and after the coating is finished, annealing is carried out for 30min at the temperature of 150 ℃ to form a hole transport layer, and the thickness of the hole transport layer is about 35 nm.
(4) And (2) performing spin coating on the hole transport layer to form cadmium selenide/zinc sulfide (CdSe/ZnS) red light quantum dots with the concentration of 20mg/mL, wherein the spin coating revolution number is 3000r/min, the spin coating time is 40s, and after the coating is finished, annealing is performed for 10min at the temperature of 120 ℃ to form a quantum dot light-emitting layer, wherein the thickness of the quantum dot light-emitting layer is about 20 nm.
(5) Spin-coating zinc oxide-based ink on the surface of the quantum dot light-emitting layer, wherein the spin-coating revolution is 3000r/min, the spin-coating time is 40s, annealing is carried out for 30min at 120 ℃ after the coating is finished, and an electron transmission layer is formed, wherein the thickness of the electron transmission layer is about 30 nm; the zinc oxide-based ink is formed by mixing 1g of ZnMgO nano particles with the average particle size of 5nm, 0.1g of ZnMgO nano sheets with the width of 50nm and the thickness of 5nm, 50g of glycerol and 10g of isopropanol, and then stirring for 30min to uniformly disperse the mixture.
(6) Under high vacuum (10)-7Torr) was used as a cathode, silver was deposited on the surface of the electron transport layer to a thickness of 150 nm.
Example 3
(1) And providing conductive glass as a substrate and an anode, wherein the substrate is a glass substrate, and the anode is a conductive film formed on one side surface of the glass substrate.
(2) Spin-coating [ poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) ] (PEDOT: PSS) on the anode conductive film, wherein the spin-coating revolution is 2000r/min, and the spin-coating time is 40 s; and after the coating is finished, annealing is carried out for 15min at the temperature of 150 ℃ to form a hole injection layer, and the thickness of the hole injection layer is about 40 nm.
(3) Spin-coating a chlorobenzene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB) with a concentration of 10mg/mL on the hole injection layer at a spin-coating speed of 3000r/min for 40 s; and after the coating is finished, annealing is carried out for 30min at the temperature of 150 ℃ to form a hole transport layer, and the thickness of the hole transport layer is about 35 nm.
(4) And (2) performing spin coating on the hole transport layer to form cadmium selenide/zinc sulfide (CdSe/ZnS) red light quantum dots with the concentration of 20mg/mL, wherein the spin coating revolution number is 3000r/min, the spin coating time is 40s, and after the coating is finished, annealing is performed for 10min at the temperature of 120 ℃ to form a quantum dot light-emitting layer, wherein the thickness of the quantum dot light-emitting layer is about 20 nm.
(5) Spin-coating zinc oxide-based ink on the surface of the quantum dot light-emitting layer, wherein the spin-coating revolution is 3000r/min, the spin-coating time is 40s, annealing is carried out for 30min at 120 ℃ after the coating is finished, and an electron transmission layer is formed, wherein the thickness of the electron transmission layer is about 30 nm; the zinc oxide-based ink is formed by mixing 1g of ZnO nanoparticles with the average particle size of 5nm, 0.1g of ZnMgO nanosheets with the width of 50nm and the thickness of 5nm, 50g of glycerol and 10g of isopropanol, and then stirring for 30min to uniformly disperse the mixture.
(6) Under high vacuum (10)-7Torr) was used as a cathode, silver was deposited on the surface of the electron transport layer to a thickness of 150 nm.
Comparative example 1
(1) And providing conductive glass as a substrate and an anode, wherein the substrate is a glass substrate, and the anode is a conductive film formed on one side surface of the glass substrate.
(2) Spin-coating [ poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) ] (PEDOT: PSS) on the anode conductive film, wherein the spin-coating revolution is 2000r/min, and the spin-coating time is 40 s; and after the coating is finished, annealing is carried out for 15min at the temperature of 150 ℃ to form a hole injection layer, and the thickness of the hole injection layer is about 40 nm.
(3) Spin-coating a chlorobenzene solution of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB) with a concentration of 10mg/mL on the hole injection layer at a spin-coating speed of 3000r/min for 40 s; and after the coating is finished, annealing is carried out for 30min at the temperature of 150 ℃ to form a hole transport layer, and the thickness of the hole transport layer is about 35 nm.
(4) And (2) performing spin coating on the hole transport layer to form cadmium selenide/zinc sulfide (CdSe/ZnS) red light quantum dots with the concentration of 20mg/mL, wherein the spin coating revolution number is 3000r/min, the spin coating time is 40s, and after the coating is finished, annealing is performed for 10min at the temperature of 120 ℃ to form a quantum dot light-emitting layer, wherein the thickness of the quantum dot light-emitting layer is about 20 nm.
(5) Spin-coating zinc oxide-based ink on the surface of the quantum dot light-emitting layer, wherein the spin-coating revolution is 3000r/min, the spin-coating time is 40s, annealing is carried out for 30min at 120 ℃ after the coating is finished, and an electron transmission layer is formed, wherein the thickness of the electron transmission layer is about 30 nm; the zinc oxide-based ink is formed by mixing 1g of ZnO nanoparticles with the average particle size of 5nm, 50g of glycerol and 10g of isopropanol and then stirring for 30min to uniformly disperse the mixture.
(6) Under high vacuum (10)-7Torr) was used as a cathode, silver was deposited on the surface of the electron transport layer to a thickness of 150 nm.
In examples 1 to 3, nanoparticles or nanosheets of ZnO and ZnMgO are respectively adopted to be matched as components of the nano-metal chalcogenide ink, and in comparative example 1, ZnO nanoparticles are only adopted as components of the nano-metal chalcogenide ink. The quantum dot light emitting diodes provided in each example and comparative example were tested for their external quantum efficiency and light emitting efficiency, and the results are shown in table 1.
TABLE 1
Example 1 Example 2 Example 3 Comparative example 1
Maximum external quantum efficiency 15％ 19％ 15％ 9％
Luminous efficiency (cd/A) 22 25 23 16
The nano metal chalcogenide ink provided by each embodiment adopts the granular nano material and the lamellar nano material at the same time, and when the electron transmission layer of the quantum dot light-emitting diode device provided by each embodiment is formed, the granular nano material and the lamellar nano material are uniformly coated on the surface of the prepared quantum dot light-emitting layer. In the annealing process, the granular nano material with larger mass forms a metal chalcogenide matrix film of the electron transmission layer, and the lamellar nano material is embedded in the matrix film and makes up holes and defects in the matrix film, so that the leakage current can be effectively reduced, and further, according to the test data in table 1, the maximum external quantum efficiency and the luminous efficiency of each embodiment are effectively improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (11)

1. A nanometal chalcogenide ink comprising:
a solvent;
a metal chalcogenide nanomaterial dispersed in the solvent, the metal chalcogenide nanomaterial comprising: metal chalcogenide nanoparticles and metal chalcogenide nanosheets.
2. The nanometal chalcogenide ink according to claim 1, wherein the metal chalcogenide is selected from the group consisting of: at least one of a zinc oxide-based compound, a titanium dioxide-based compound, and a zinc sulfide-based compound.
3. The nanometal chalcogenide ink according to claim 1, wherein the metal chalcogenide nanoparticles have a particle size of 3 to 10 nm; and/or
The metal chalcogenide nanosheet is 3-10 nm in thickness and 50-200 nm in width.
4. The nanometal chalcogenide ink according to any one of claims 1 to 3, wherein in the metal chalcogenide nanomaterial the mass ratio of the metal chalcogenide nanoparticles to the metal chalcogenide nanoplatelets is (5 to 100): 1.
5. the nanometal chalcogenide ink according to any one of claims 1 to 3, characterized in that the metal chalcogenide is selected from: ZnO, ZnMgO, ZnTiO3、ZnMgTiO3、ZnCdO、ZnWO4、ZnAlO、ZnNiO、ZnSnO3And (b) at least one of.
6. The nanometal chalcogenide ink according to any one of claims 1 to 3, wherein the solvent comprises an alcoholic solvent selected from the group consisting of: at least one of methanol, ethanol, isopropanol, butanol, glycerol, ethylene glycol, polyethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and pentylene glycol.
7. The nanometal chalcogenide ink according to any one of claims 1 to 3, wherein the metal chalcogenide nanomaterial is contained in an amount of 1 to 20 wt% and the solvent is contained in an amount of 80 to 99 wt%, based on the total mass of the nanometal chalcogenide ink.
8. A nano-metal chalcogenide thin film, wherein the nano-metal chalcogenide thin film is formed by removing a solvent from the nano-metal chalcogenide ink according to any one of claims 1 to 7 and annealing the nano-metal chalcogenide thin film;
the metal chalcogenide nanoparticles form a film matrix, and the metal chalcogenide nanosheets are embedded in the film matrix.
9. An electroluminescent diode, comprising:
a cathode and an anode disposed opposite to each other;
a light emitting layer disposed between the cathode and the anode;
an electron transport layer disposed between the light emitting layer and the cathode, the electron transport layer being formed by removing the solvent from the nano-metal chalcogenide ink according to any one of claims 1 to 7 and annealing the nano-metal chalcogenide ink, or being the nano-metal chalcogenide thin film according to claim 8.
10. A preparation method of an electroluminescent diode is characterized by comprising the following steps:
providing a substrate;
an anode, a light-emitting layer, an electron transport layer and a cathode are sequentially laminated on the substrate, or
Sequentially laminating a cathode, an electron transport layer, a light emitting layer and an anode on the substrate;
wherein the electron transport layer is formed by removing the solvent from the nano-metal chalcogenide ink according to any one of claims 1 to 7 and annealing the nano-metal chalcogenide ink, or is the nano-metal chalcogenide thin film according to claim 8.
11. A display device, comprising:
an electroluminescent diode according to claim 9, or prepared by the method according to claim 10.
CN202010314886.2A 2020-04-21 2020-04-21 Ink, thin film, electroluminescent diode, preparation method and display device Pending CN113201253A (en)

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