WO2023083098A1 - Light-emitting diode and preparation method therefor - Google Patents
Light-emitting diode and preparation method therefor Download PDFInfo
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- WO2023083098A1 WO2023083098A1 PCT/CN2022/129662 CN2022129662W WO2023083098A1 WO 2023083098 A1 WO2023083098 A1 WO 2023083098A1 CN 2022129662 W CN2022129662 W CN 2022129662W WO 2023083098 A1 WO2023083098 A1 WO 2023083098A1
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- Prior art keywords
- layer
- hole transport
- light
- doped
- emitting diode
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
-
- 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
- H10K50/15—Hole transporting layers
-
- 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
- H10K50/80—Constructional details
- H10K50/87—Arrangements for heating or cooling
-
- 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
Definitions
- the present application relates to the field of display technology, in particular to a light emitting diode and a preparation method thereof.
- Light Emitting Diode is a solid-state semiconductor point light source device that can convert electrical energy into light energy.
- light-emitting diodes mainly include inorganic light-emitting diodes (Inorganic Light Emitting Diode, iLED), polymer light-emitting diodes (Polymer Light Emitting Diode, PLED), organic light-emitting diodes (Organic Light Emitting Diode, OLED) and quantum Quantum Dots Light Emitting Doides (QLEDs).
- the structure of light-emitting diodes usually adopts a multi-layer structure including transparent anode/hole transport layer (HTL)/emissive layer (EML)/electron transport layer (ETL)/metal cathode; therefore, under device operating conditions, the light-emitting area
- HTL transparent anode/hole transport layer
- EML emissive layer
- ETL electron transport layer
- metal cathode metal cathode
- the heat generated when the light-emitting region emits light will affect the hole transport layer, resulting in damage to the hole transport layer and affecting the performance of the light-emitting diode.
- the application provides a light emitting diode and a preparation method thereof.
- the present application provides a light-emitting diode, comprising a hole transport layer and a light-emitting layer stacked.
- the material of the hole transport layer includes a hole transport material and a thermally conductive material; the thermally conductive material is a hollow nanomaterial.
- the hole transport material and the heat conducting material form a mixed material body.
- At least part of the thermally conductive material forms an independent material body on a side of the hole transport layer close to the light emitting layer.
- the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the hole transport film layer is formed of the hole transport material; the thermally conductive modification The layer is formed by the heat-conducting material; the heat-conducting modification layer is arranged between the hole transport film layer and the light-emitting layer.
- the thermal conductivity of the hollow nanomaterial is above 2 W/m ⁇ 1 ⁇ K ⁇ 1 .
- the hole mobility of the hollow nanomaterial is above 1 ⁇ 10 -5 cm 2 ⁇ V -1 ⁇ s -1 .
- the hollow nanomaterials are hollow metal oxide nanoparticles.
- the hollow metal oxide nanoparticles are selected from one or more of NiO y , MoO y , WO y , and CuO y , wherein 1 ⁇ y ⁇ 3.
- the particle size of the hollow nanomaterial is 10-50 nm.
- the thickness of the thermally conductive modification layer is 20-60 nm.
- the light-emitting diode further includes an electron transport layer; the electron transport layer is disposed on a side of the light-emitting layer away from the hole transport layer; the electron transport The carrier mobility of the layer is higher than the carrier mobility of the hole transport layer.
- the hole transport material is selected from organic hole transport materials or inorganic hole transport materials; wherein, the organic hole transport material is selected from poly(9,9 -dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), polyvinylcarbazole, poly(N,N'bis(4-butylphenyl)-N,N'-bis( phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine), 4,4',4'-tris(carbazole -9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1 '-Biphenyl-4,4'-diamine, N,N
- the present application also provides a method for preparing a light-emitting diode, including: providing a semi-finished device; forming a stacked hole transport layer and a light-emitting layer on the semi-finished device; wherein, the material of the hole transport layer includes A hole transport material and a thermally conductive material, the thermally conductive material is a hollow nanometer material.
- the hole transport material and the heat conducting material form a mixed material body.
- At least part of the thermally conductive material forms an independent material body on a side of the hole transport layer close to the light emitting layer.
- the hole transport layer includes a stacked hole transport film layer and a thermally conductive modification layer, and the hole transport film layer is formed of the hole transport material;
- the thermally conductive modification layer is formed of the thermally conductive material; the thermally conductive modification layer is located between the hole transport film layer and the light emitting layer.
- the step of preparing the thermally conductive modification layer includes: providing a solution of hollow nanomaterials, and disposing the solution of hollow nanomaterials on the hole transport film layer or the The surface of the light-emitting layer forms the heat-conducting modified layer; wherein, the concentration of the solution of the hollow nanomaterial is 3-10 mg/mL.
- after disposing the solution of the hollow nanomaterial on the surface of the hole transport film layer further includes: annealing at 60-100° C. for 10-60 minutes .
- the light-emitting diode is a positive light-emitting diode
- the semi-finished device includes an anode
- the formation of a stacked hole transport layer and a light-emitting layer on the semi-finished device includes: Forming the hole transport film layer, the thermally conductive modification layer, and the light-emitting layer sequentially on the semi-finished device; after forming the stacked hole transport layer and the light-emitting layer on the semi-finished device, it also includes: A cathode is formed on the light emitting layer.
- the light-emitting diode is an inverted light-emitting diode
- the semi-finished device includes a cathode
- the forming a stacked hole transport layer and a light-emitting layer on the semi-finished device includes: Forming the light-emitting layer, the thermally conductive modification layer and the hole transport film layer sequentially on the semi-finished device; after forming the stacked hole transport layer and light-emitting layer on the semi-finished device, further comprising: A cathode is formed on the hole transport film layer.
- a heat-conducting material is added to the material of the hole transport layer stacked with the light-emitting layer to realize rapid heat dissipation in the light-emitting region of the device under working conditions, and reduce the temperature rise of the light-emitting region under working conditions.
- the effect of the hole transport layer; and the thermal conductive material adopts hollow nanomaterials, because the nanomaterials with hollow structures have high thermal stability, and at the same time, through the thermal conductive materials, it is easy to realize the rapid transfer of heat generated by the light-emitting layer and reduce the impact on hole transport.
- the destruction of the material further improves the heat dissipation of the light-emitting area of the device, thereby more effectively reducing the damage to the hole transport layer caused by the temperature rise of the light-emitting area of the device under working conditions.
- FIG. 1 is a schematic flow chart of a method for preparing a light-emitting diode provided in an embodiment of the present application
- Fig. 2 is a schematic structural diagram of a light emitting diode provided in Embodiment 1 of the present application;
- Figure 3 is a schematic structural view of the hollow nickel oxide nanoparticles provided in Example 1 of the present application.
- a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
- At least one means one or more, and “multiple” means two or more.
- At least one means two or more.
- At least one means two or more.
- At least one means two or more.
- At least one means two or more.
- At least one means two or more.
- At least one means two or more.
- At least one means two or more.
- At least one means two or more.
- At least one means two or more.
- At least one means two or more.
- the present application provides a light-emitting diode, including a hole transport layer and a light-emitting layer that are stacked, and the material of the hole transport layer includes a hole transport material and a thermally conductive material; the thermally conductive material is a hollow nanomaterial;
- At least part of the thermally conductive material forms a separate material body on the side of the hole transport layer close to the light emitting layer.
- the mixed material body in this application refers to a structural layer in which materials are randomly distributed and not layered, formed after at least two materials are mixed.
- An independent material body refers to a structural layer formed by one material, and the structural layer has a clear interface with the adjacent structural layer.
- forming a mixed material body with a hole transport material and a heat conduction material should be understood as: a heat conduction material is mixed with a hole transport material to form a single-layer structure layer, and a hole transport layer doped with a heat conduction material is obtained.
- the thermally conductive material can form a path for heat transfer in the hole transport layer, and the heat generated by the light-emitting layer under working conditions can transfer heat through the heat transfer path formed by the thermally conductive material.
- at least part of the thermally conductive material forms an independent material body on the side of the hole transport layer close to the light-emitting layer.
- a structural layer with an obvious interface with the adjacent structural layer is formed, that is, part or all of the heat-conducting material is located between the light-emitting layer and the layer structure formed by the hole-transporting material.
- the rest of the heat-conducting material can be dispersed in the hole-transporting layer to form a mixed material body with the hole-transporting material.
- the thermally conductive material is doped in the hole transport layer formed by the hole transport material, and the thermally conductive material forms a path in the hole transport layer that can be used for heat transmission.
- the thermally conductive material can be uniformly distributed in the hole transport layer, or can be distributed on the interface between the hole transport layer and the light emitting layer and in the hole transport layer.
- the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the material of the hole transport film layer is formed by a hole transport material; the thermally conductive modification layer is formed by a thermally conductive material; the thermally conductive modification layer is located in the hole transport Between the film layer and the light-emitting layer. That is: the hole transport layer is a composite layer formed by a hole transport film layer and a thermally conductive modified layer. The thermally conductive modified layer formed by a thermally conductive material is located between the hole transport layer and the light-emitting layer, and the heat-conductive material is in contact with the light-emitting layer. The heat generated under the working conditions of the device can be quickly transferred through the thermally conductive modification layer based on the thermally conductive material, which improves the heat dissipation effect and improves the stability of the device.
- the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the hole transport film layer is formed of a hole transport material and a thermally conductive material; the thermally conductive modification layer is formed of a thermally conductive material; the thermally conductive modification layer is located in the hole Between the transmission film layer and the light-emitting layer.
- the hole transport layer is a composite layer formed by a hole transport film layer and a thermally conductive modified layer, and the thermally conductive modified layer formed by a thermally conductive material is located between the hole transport layer and the light-emitting layer, so that the heat generated by the light-emitting layer under device working conditions It can be quickly transferred through the heat-conducting modification layer based on heat-conducting materials; at the same time, the hole-transporting film layer is also doped with heat-conducting materials, which can form a heat transfer path in the hole-transporting film layer, so that the heat generated by the light-emitting layer under working conditions The heat is quickly transferred to the electrodes of the light-emitting diode, so that the device can dissipate heat quickly and improve the stability of the device.
- the hollow nanomaterials can be nanotubes or hollow nanoparticles, wherein the nanotubes are hollow one-dimensional nanomaterials, which can be selected from carbon nanotubes, polypropylene nanofibers, and polyvinylpyrrolidone nanofibers.
- hollow nanoparticles are hollow zero-dimensional nanomaterials, which can be hollow non-oxide nanoparticles or hollow metal oxide nanoparticles or hollow non-metal oxide nanoparticles; wherein the hollow metal oxide nanoparticles can be selected from One or more of NiO y , MoO y , WO y , CuO y , wherein 1 ⁇ y ⁇ 3; the non-metal oxide nanoparticles can be selected from one or more of SiO 2 and the like.
- the diameter of the nanotube can be 5-20 nm, so that the thickness of the thermally conductive modification layer is controlled at 20-60 nm, so as to avoid affecting the hole transport layer due to the excessive thickness of the thermally conductive modification layer. and the transfer of charge carriers between the light-emitting layers.
- the particle size of the hollow nanoparticle is 10-50 nm, so as to avoid the poor film-forming property of the thermally conductive modification layer and the thin film layer due to the large particle size of the hollow nanoparticle. Thick, affecting charge transport; at the same time avoiding the difficulty of preparation and the increase of preparation cost due to the small particle size of hollow nanoparticles.
- the hollow nanoparticles are hollow nanocrystalline particles.
- the thermal conductivity of the hollow nanomaterial is above 2W/(m ⁇ K) or 2W ⁇ m ⁇ 1 ⁇ K ⁇ 1 or 2 W/m ⁇ degree, so that the hollow nanomaterial has better thermal conductivity, Play a better heat dissipation effect.
- the hole mobility of the hollow nanomaterial is 1 ⁇ 10 -5 cm 2 ⁇ V -1 ⁇ s -1 or 1 ⁇ 10 -5 cm 2 /(V ⁇ s) or 1 ⁇ 10 -5 Centimeter 2 / (volt ⁇ second) above.
- the carrier transport theory holes are mainly transported in the highest occupied molecular orbital between molecules, so the hole transport capability of the hole transport layer is closely related to the composition of the highest occupied molecular orbital.
- the highest occupied molecular orbital energy level of the hole transport layer is usually above 5.3eV, which has a certain gap compared with the valence band energy level of the light-emitting layer.
- the holes in the hole transport layer need a higher voltage to cross the potential barrier and reach the recombination region of holes and electrons, so a higher voltage needs to be applied to the device, and the high voltage will lead to the A further increase in operating temperature will more easily lead to irreversible damage to the material of the hole transport layer. Therefore, adding a thermally conductive material with an energy level between the hole transport material and the material of the light-emitting layer in the hole transport layer can reduce the potential barrier of the hole transport layer while achieving a good heat dissipation effect, thereby reducing the device The temperature of the glowing area.
- the hole transport layer is a composite layer formed by a hole transport film layer and a thermally conductive modification layer
- the energy level of the thermally conductive modification layer is between the hole transport layer and the light-emitting layer, it is possible to optimize the light-emitting layer and the hole transport layer.
- the energy level of the device is matched, so that the holes are transported step by step, thereby reducing the temperature of the light-emitting region of the device, while not affecting the charge transport between the hole-transport layer and the light-emitting layer.
- an electron transport layer is provided on the side of the light-emitting layer away from the hole transport layer; the carrier mobility of the electron transport layer is higher than that of the hole transport layer; the thermally conductive material is a hollow metal oxide matter nanoparticles.
- the energy level of the thermally conductive material is between the energy level of the hole transport material and the energy level of the material of the light-emitting layer, when the thermally conductive material is doped into the hole transport layer based on the hole transport material or in the hole transport based
- a thermally conductive modification layer is formed between the hole transport layer of the material and the light-emitting layer, so the energy level matching between the hole transport layer and the light-emitting layer is optimized , improving the carrier mobility of the hole transport layer, thereby reducing the carrier mobility difference between the hole transport layer and the electron transport layer, and improving the electron-hole injection imbalance of the device.
- the hollow metal oxide nanoparticles are used as the thermally conductive material, it can simultaneously play a good heat dissipation effect and optimize the energy level matching between the hole transport layer and the light-emitting layer, and the role played by the organic hole transport layer The heat dissipation effect obtained is more obvious. Therefore, in this application, the hollow metal oxide nanoparticles are used as a heat-conducting material, which can further improve the performance of the light-emitting diode.
- the hole transport material may be an organic hole transport material or an inorganic hole transport material, specifically, an organic hole transport material. This is because organic hole transport materials are less chemically stable and thermally stable than inorganic hole transport materials. Therefore, under device conditions, organic hole transport layers based on organic hole transport materials are easier to It is damaged due to temperature rise, so adding a thermally conductive material to the organic hole transport layer can more significantly improve the heat dissipation between the organic hole transport layer and the light-emitting layer, thereby significantly improving the stability of the device.
- the light-emitting diode provided in this application can be any light-emitting diode that includes a hole transport layer and a light-emitting layer, and the hole transport layer and the light-emitting layer are stacked, such as an inorganic light-emitting diode that is stacked with a hole transport layer and a light-emitting layer.
- the material of the hole transport layer of quantum dot light-emitting diodes is mostly organic semiconductors, such as PEDOT:PSS, TFB, Poly-TPD; and the material of the electron transport layer is mostly ZnO, and the carrier migration of ZnO
- the rate is much greater than the carrier mobility of the hole transport layer, resulting in the electron-hole injection imbalance of the quantum dot light-emitting diode. Therefore, in order to improve the electron-hole injection imbalance of the quantum dot light-emitting diode, it is necessary to improve the hole transport layer. carrier mobility or reduce the carrier mobility of the electron transport layer.
- thermally conductive materials that can reduce the energy level of the hole transport layer in the hole transport layer can optimize the energy level matching between the hole transport layer and the light-emitting layer, improve the carrier mobility of the hole transport layer, and improve the quantum dot luminescence
- the electron-hole injection of the diode is unbalanced; at the same time, the thermally conductive material can also have a good heat dissipation effect.
- QLEDs can give full play to the superior photoelectric properties and excellent solution processability of the colloidal quantum dots used in them, they are expected to become a new generation of high-performance, large-area, and low-cost electroluminescent devices, so for this application to provide
- the structure of the light-emitting diode and the preparation method of the light-emitting diode have a better application prospect in quantum dot light-emitting diodes.
- the material of the electron transport layer can be selected from non-doped metal oxide or doped metal oxide, wherein the non-doped metal oxide can be selected from ZnO, TiO 2 , SnO, SnO 2 , MgO, Ta 2 O 3
- doped metal oxide can be selected from aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide, copper doped zinc oxide, yttrium doped oxide Zinc, cobalt-doped zinc oxide, manganese-doped zinc oxide, cadmium-doped zinc oxide, lithium-doped zinc oxide, aluminum-doped titanium oxide, gallium-doped titanium oxide, indium-doped titanium oxide, magnesium-doped titanium oxide, One of copper-doped titanium oxide, yttrium-doped titanium oxide, cobalt-doped titanium oxide, manganese-doped titanium oxide, cadmium-doped titanium oxide, lithium-doped zinc oxide, aluminum-
- the material of the organic hole transport layer can be selected from poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl) diphenylamine) (TFB), polyvinylcarbazole (PVK) , poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine)(poly-TPD), poly(9,9-dioctylfluorene-co-bis -N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4'-tris(carbazol-9-yl)triphenylamine (TCTA), 4,4'-di( 9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N,N
- the material of the light emitting layer is an inorganic material.
- Inorganic materials can choose ZnS:Mn, ZnS:Tb, ZnS:Tb/CdS, SiO 2 :Ge, SiO 2 :Er, SrS:Ce, CaGa 2 S 4 :Ce, SrGa 2 S 4 :Ce, SrS:Cu, GaN, ZnS:Tm, Zn 2 SiO 2 :Ca or other phosphor materials; here, ":” means doping; "/" means cladding.
- the material of the light emitting layer is a small molecule organic material.
- small molecule organic material can choose 4-(dinitrile methyl)-2-butyl-6-(1,1,7,7-tetramethyljuronesidine-9-vinyl)-4H-pyran (DCJTB), 9,10-bis( ⁇ -naphthyl)anthracene (ADN), 4,4'-bis(9-ethyl-3-carbazolevinyl)-1,1'-biphenyl (BCzVBi) Or 8-hydroxyquinoline aluminum or other small molecule organic light-emitting materials.
- the material of the light-emitting layer is a polymer organic material.
- the high molecular organic material can choose polyparaphenylene, polythiophene, polyaniline, polycarbazole or other high molecular organic light-emitting materials.
- the material of the light emitting layer is a quantum dot material.
- the quantum dot material can choose CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe or other quantum dots to emit light Material.
- the thickness of the thermally conductive modification layer is 20-60 nm, so as to avoid affecting the charge transport due to the thickness of the thermally conductive modification layer being too thick.
- the thickness of the hole transport layer is 20-60 nm.
- the thickness of the light-emitting layer is 20-60 nm.
- the thickness of the top electrode is 40-80 nm.
- the light emitting diodes may be upright light emitting diodes or inverted light emitting diodes.
- the positive light-emitting diode includes a stacked anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode, the anode is arranged on the substrate, and the cathode is used as the top electrode; when emitting light
- the diode is an inverted light-emitting diode
- the inverted light-emitting diode includes a stacked cathode, an electron transport layer, a light-emitting layer, a hole transport layer and an anode, the cathode is arranged on the substrate, and the anode is used as a top electrode.
- the anode material can be selected from one or more of ITO, FTO, ZTO; the cathode material can be selected from one or more of Al, Ag, Au, Cu, Mo and their alloys; the substrate can be Rigid substrate, flexible substrate can also be used.
- the rigid substrate can be selected from one or more of glass and metal foil;
- the flexible substrate can be selected from polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polyetheretherketone (PEEK), polystyrene (PS), polyethersulfone (PES), polycarbonate (PC), polyarylate (PAT), polyarylate (PAR), poly One or more of imide (PI), polyvinyl chloride (PV), polyethylene (PE), polyvinylpyrrolidone (PVP), and textile fibers.
- PET polyethylene terephthalate
- PEN polyethylene terephthalate
- PEEK polyetheretherketone
- PS polystyrene
- PS polyethersulfone
- PC polycarbonate
- PAT polyarylate
- PAR polyarylate
- PI imide
- PV polyvinyl chloride
- PE polyethylene
- PVP polyvinylpyrrolidone
- the electron transport layer has a thickness of 20-60 nm.
- an electron functional layer such as an electron injection layer may be disposed between the electron transport layer and the cathode; a hole functional layer such as a hole injection layer may also be disposed between the hole transport layer and the anode.
- the light emitting diode further includes functional layers such as a hole blocking layer and an electron blocking layer.
- FIG. 1 is a schematic flow chart of a method for preparing a light-emitting diode provided in an embodiment of the present application, including:
- Step S11 providing a semi-finished device
- Step S12 laminating and forming a hole transport layer and a light emitting layer on the semi-finished device
- the material of the hole transport layer includes a hole transport material and a thermally conductive material;
- the thermally conductive material is a hollow nanomaterial; wherein, the hole transport material and the thermally conductive material form a mixed material body; or
- At least part of the thermally conductive material forms a separate material body on the side of the hole transport layer close to the light emitting layer.
- forming a hole-transporting layer and a light-emitting layer on a semi-finished device means laminating a hole-transporting layer and a light-emitting layer on the surface of a semi-finished device;
- the formation sequence is not limited, and the formation sequence of the hole transport layer and the light emitting layer can be adjusted according to the type of the light emitting diode to be prepared.
- the hole transport layer and the light-emitting layer are sequentially deposited on the semi-finished device; when the prepared light-emitting diode is a reverse light-emitting diode, the light-emitting layer, the hole transport layer.
- the semi-finished device in this application may include a substrate, an electrode, or may include a substrate, an electrode, and a functional layer, or a semi-finished device with electrodes and a functional layer deposited on its surface.
- the electrode mentioned here can be a cathode or an anode; it is adjusted according to the type of light-emitting diode prepared; the functional layer mentioned here can include a hole injection layer, or an electron injection layer or an electron injection layer. transport layer.
- the hole transport layer is deposited using a solution containing a hole transport material and a thermally conductive material; the light emitting layer is deposited using a solution containing a light emitting material.
- the hole transport layer is formed of a hole transport material and a thermally conductive material, ie, the hole transport material and the thermally conductive material form a mixed material body of the hole transport layer.
- the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the material of the hole transport film layer is formed by a hole transport material; the thermally conductive modification layer is formed by a thermally conductive material; the thermally conductive modification layer is located in the hole transport Between the film layer and the light-emitting layer; that is, all the heat-conducting materials form an independent material body of a heat-conducting modification layer on the side of the hole-transporting layer close to the light-emitting layer.
- the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the material of the hole transport film layer is formed by a hole transport material and a thermally conductive material; the thermally conductive modification layer is formed by a thermally conductive material; the thermally conductive modification layer is located at Between the hole transport film layer and the light-emitting layer; that is, part of the heat-conducting material forms an independent material body of a heat-conducting modification layer on the side of the hole-transport layer close to the light-emitting layer, and the remaining part of the heat-conducting material is doped in the hole transport film layer , forming the mixed material body of the hole transport film layer.
- forming a hole transport layer, a thermally conductive modification layer, and a light-emitting layer on a semi-finished device refers to forming a layered hole transport layer, a heat-conductive modification layer, and a light-emitting layer on the surface of a semi-finished device.
- the formation order of the hole transport layer, the thermally conductive modification layer, and the light-emitting layer, and the formation order of the hole transport layer, the heat-conductive modification layer, and the light-emitting layer can be adjusted according to the type of the light-emitting diode to be prepared.
- the prepared light-emitting diode is a positive light-emitting diode, a hole transport layer, a thermally conductive modification layer, and a light-emitting layer are sequentially deposited on the semi-finished device; when the prepared light-emitting diode is a reverse light-emitting diode, the light-emitting layer is sequentially deposited on the semi-finished device , thermally conductive modification layer, hole transport layer.
- the thermally conductive modification layer is deposited indirectly or directly on the surface of the hole transport layer or the light-emitting layer, that is, other functional layers can be arranged between the heat-conductive modification layer and the hole-transport film layer, and between the light-emitting layer and the thermally conductive modification layer.
- the semi-finished device in this application may include a substrate, an electrode, or may include a substrate, an electrode, and a functional layer, or a semi-finished device with electrodes and a functional layer deposited on its surface.
- the electrode mentioned here can be a cathode or an anode; it is adjusted according to the type of light-emitting diode prepared; the functional layer mentioned here can include a hole injection layer, or an electron injection layer or an electron injection layer. transport layer.
- the hole transport film layer, the heat-conducting modification layer, and the light-emitting layer are respectively deposited using corresponding solutions including hole-transport materials, heat-conducting materials, and light-emitting materials.
- the thermally conductive modification layer is deposited by using a hollow nanomaterial solution with a concentration of 3-10 mg/mL.
- the thermally conductive modification layer is deposited by using a solution formed of hollow nanomaterials and hole transport materials with a concentration of 3-10 mg/mL, respectively.
- the spin-coating time of the solution used to form the thermally conductive modification layer is 30 s-120 s, and the annealing time is 10-30 min.
- the method of depositing the solution containing hole transport material, thermal conductive material and luminescent material on the semi-finished device can be spin coating method, printing method, printing method, dipping and pulling method, soaking method, spraying method , roll coating method, pouring method, slit coating method, strip coating method, electrodeposition method, etc. any one of the commonly used methods in this field.
- the thermally conductive modification layer can be prepared by the following methods:
- hollow nanomaterials and hole transport material solutions with concentrations of 3 to 10 mg/mL
- drop the solutions containing hollow nanomaterials and hole transport materials on the surface of the hole transport film and Spin-coating is performed at a rotating speed, and after 15-120 seconds of spin-coating, annealing treatment is performed at 60-100° C. for 10-60 minutes to obtain a heat-conducting modified layer.
- the thermally conductive modification layer can be prepared by the following methods:
- a solution with a hollow nanomaterial concentration of 3-10mg/mL drop the solution containing the hollow nanomaterial on the surface of the hole transport film, and spin-coat at a speed of 2000-4000rpm/min for 15-120s Afterwards, annealing treatment is performed at 60-100° C. for 10-60 minutes to obtain a thermally conductive modified layer.
- the hollow metal oxide nanoparticle is obtained by performing a hydrothermal reaction with a metal source and an alkali solution.
- the metal source is selected from nickel chloride, nickel nitrate, nickel acetylacetonate, molybdenum chloride, ammonium molybdate tetrahydrate, ammonium thiomolybdate, molybdenum acetylacetonate, tungsten chloride, tungsten acetylacetonate, copper chloride, copper nitrate, One or more of copper sulfate and other compounds that can provide metal ions.
- the alkali solution can be one or more of sodium hydroxide solution, potassium hydroxide solution, and ammonia water.
- the hydrothermal reaction adopts microwave heating, the heating effect is simple and efficient, the reaction system is evenly heated, and the particle size of the obtained hollow metal oxide nanoparticles is relatively uniform.
- the preparation steps of hollow metal oxide nanoparticles include:
- the solution B is heated by microwave to react to obtain hollow metal oxide nanoparticles.
- the obtained hollow metal oxide nanoparticles are dispersed with a solvent and then separated to obtain hollow metal oxide nanoparticles with a particle size of 15-50 nm.
- the solvent adopted for dispersing can be one or more in ethylene glycol, glycerol, DMF, DMSO; Wherein, separation can adopt any one in the commonly used method in this field such as ultracentrifugation method, membrane separation method .
- the molar ratio of the solute to the metal source in the alkaline solution is 1 ⁇ 2:1.
- the alkaline solution is added dropwise to the precursor solution A, and the stirring is continued during the dropwise addition.
- the solvent of the precursor solution A is an organic solvent, wherein the organic solvent can be selected from one or more of ethylene glycol, glycerol, DMF, and DMSO.
- the microwave heating temperature is 120-240° C.
- the heating time is 10-60 minutes.
- ultrasonic dispersion is used for dispersion, and the dispersion time is 10 to 120 minutes, so that the dispersion effect is better, and it is beneficial to obtain smaller and uniform hollow metal oxide nanoparticles. matter nanoparticles.
- ultracentrifugation is used for separation, and the rotation speed is 4000-12000 rpm.
- the preparation of hollow nickel oxide nanoparticles 20 specifically comprises the following steps:
- the hollow nickel oxide nanoparticles 20 are hollow nanospheres formed by nickel oxide nanocrystals 201 .
- the specific preparation steps are as follows:
- a substrate 101 is provided, and ITO is deposited on the substrate 101 as the bottom electrode 102 to obtain an ITO substrate.
- the ITO substrate is cleaned with a cleaning agent to initially remove the stains on the surface, and then deionized water, isopropanol, and Ultrasonic cleaning in acetone and deionized water for 20 minutes respectively to remove impurities on the surface, and finally drying with high-purity nitrogen to obtain the ITO substrate;
- the ITO substrate is fixed on the coater, and the solution of the prepared TFB hole transport material is spin-coated on the ITO substrate to form a film, and annealed to complete the preparation of the hole transport layer 103;
- the substrate prepared by the hole transport layer 103 was fixed on a homogenizer, and the prepared hollow nickel oxide nanoparticles 20 was spin-coated at a speed of 3000 rpm/min to form a film on the substrate with a solution having a concentration of 8 mg/mL. Annealing at 80° C. for 10 minutes to complete the preparation of the thermally conductive modification layer 104 ;
- the substrate on which each functional layer has been deposited is placed in an evaporation chamber and a layer of metallic silver is thermally evaporated through a mask plate as the top electrode 107 to obtain a quantum dot light-emitting diode A, see FIG. 2 .
- the preparation of hollow molybdenum trioxide nanoparticles specifically comprises the following steps:
- the hollow molybdenum trioxide nanoparticles were formulated into a solution with a concentration of 5 mg/mL, and the hollow molybdenum trioxide nanoparticles prepared in this example were used as the heat-conducting
- the material of the modification layer is prepared to obtain the quantum dot light-emitting diode B.
- the preparation of hollow tungsten trioxide nanoparticles specifically comprises the following steps:
- the hollow tungsten trioxide nanoparticles were prepared into a solution with a concentration of 5 mg/mL, and the hollow tungsten trioxide nanoparticles prepared in this example were used as a heat-conducting
- the material of the modification layer is prepared to obtain the quantum dot light-emitting diode C.
- Example 1 Compared with Example 1, in this example, the material of the hole transport layer is replaced by CuO, the material of the quantum dot light-emitting layer is replaced by InP, the material of the electron transport layer is replaced by SnO, and the rest of the materials are the same as in Example 1, and adopt the same method as in Example 1.
- Quantum dot light-emitting diode A was prepared in the same method as in Example 1, and quantum dot light-emitting diode D was prepared by using the hollow tungsten trioxide nanoparticles prepared in this example as the material of the thermally conductive modification layer.
- Example 1 Compared with Example 1, in this example, hollow nickel oxide nanoparticles with a particle size of 15 nm were added to the solution of the hole transport material to form hollow nickel oxide nanoparticles containing TFB hole transport material and 8 mg/mL
- the remaining materials are the same as in Example 1, and on the basis of Example 1, III: the step of preparation of the thermally conductive modification layer is removed, and the remaining steps are the same as in Example 1.
- the preparation method of diode A is the same, and quantum dot light-emitting diode E is prepared.
- Example 1 Compared with Example 1, in this example, hollow nickel oxide nanoparticles with a particle size of 30 nm were added to the solution of the hole transport material to form hollow nickel oxide nanoparticles containing TFB hole transport material and 8 mg/mL
- the remaining materials are the same as in Example 1, and on the basis of Example 1, III: the step of preparation of the thermally conductive modification layer is removed, and the remaining steps are the same as in Example 1.
- the preparation method of diode A is the same, and quantum dot light-emitting diode F is prepared.
- Example 1 Compared with Example 1, the material of the thermally conductive modification layer in this example is replaced by carbon nanotubes with a diameter of 5 nm, and the rest of the materials are the same as in Example 1, and the same preparation method as that of the quantum dot light-emitting diode A in Example 1 is adopted. Quantum dot light-emitting diode G was prepared by the method.
- the quantum dot light-emitting diode prepared in this comparative example 1 was prepared without the thermally conductive modification layer, and the rest of the preparation steps were the same as the preparation method of the quantum dot light-emitting diode in Example 1 to obtain the quantum dot light-emitting diode DB1.
- the material of the thermally conductive modification layer prepared in this comparative example adopts conventional nickel oxide nanoparticles (solid structure) with a particle size of 15-50 nm, and adopts the same method as that used in the preparation of quantum dot light-emitting diode A in Example 1.
- Method The same method was used to prepare the quantum dot light-emitting diode DB2 by using conventional nickel oxide nanoparticles as the material of the thermally conductive modification layer.
- conventional nickel oxide nanoparticles were purchased from Sigma Company.
- Example 7 Compared with Example 7, conventional nickel oxide nanoparticles (solid structure) with a particle size of 30nm are added to the solution of the hole transport layer in this comparative example to replace the hollow nickel oxide nanoparticles;
- the method for preparing diode G is the same as that of using conventional nickel oxide nanoparticles as a heat-conducting material to obtain quantum dot light-emitting diode DB3.
- conventional nickel oxide nanoparticles were purchased from Sigma Company.
- the light-emitting diodes provided in Examples 1 to 7 of the present application use a hole transport layer added with a thermally conductive material (hollow nanomaterial) or a hole transport layer combined with a hole transport film layer and a thermally conductive modification layer.
- the temperature of the light-emitting region of the light-emitting diode is significantly lower than that of the light-emitting diode whose hole transport layer does not contain hollow nanomaterials (comparative example 1), and the life of the light-emitting diode is compared with that of the hole transport layer that does not contain hollow nanomaterials.
- the LED of the material (Comparative Example 1) is significantly elongated.
- the addition of hollow nanomaterials to the hole transport layer can effectively reduce the operating temperature of the device, improve the damage to the hole transport layer caused by high temperature, and increase the life of the device. It can also be seen from Table 1 that the quantum dot light-emitting diodes provided in Examples 1 to 6 of the present application use hollow metal oxide nanoparticles as the heat-conducting material in the hole transport layer, and the obtained quantum dot light-emitting diodes not only reduce the temperature of the light-emitting region , and the luminous efficiency is also significantly higher than that of quantum dot light-emitting diodes that do not contain thermally conductive materials in the hole transport layer.
- hollow metal oxide nanoparticles as thermally conductive materials can effectively reduce the operating temperature of the device, and at the same time achieve The charges of the hole transport layer and the light-emitting layer are transported step by step, and the energy level matching between the hole transport layer and the light-emitting layer is optimized.
- metal oxide nanoparticles Comparative Examples 2-3
- Examples 1-7 of the present application use hollow nano-materials as the heat-conducting material, and the heat dissipation effect is better.
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Abstract
Disclosed in the present application are a light-emitting diode and a preparation method therefor. The light-emitting diode comprises a hole transport layer and a light-emitting layer, which are arranged in a stacked manner, wherein the material of the hole transport layer comprises a hole transport material and a heat conduction material, and the heat conduction material is a hollow nano-material. The hollow nano-material having a heat dissipation effect is added to the hole transport layer, such that heat dissipation of a light-emitting area of a device is realized.
Description
本申请要求于2021年11月12日在中国专利局提交的、申请号为202111341189.7、申请名称为“一种发光二极管及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202111341189.7 and the application title "A Light-Emitting Diode and Its Preparation Method" filed at the China Patent Office on November 12, 2021, the entire contents of which are hereby incorporated by reference In this application.
本申请涉及显示技术领域，具体涉及一种发光二极管及其制备方法。The present application relates to the field of display technology, in particular to a light emitting diode and a preparation method thereof.
发光二极管(Light Emitting Diode,LED)是一种可以把电能转化为光能的固态半导体点光源器件。根据发光层采用的材料不同，发光二极管主要包括无机发光二极管(Inorganic Light Emitting Diode,iLED)、高分子发光二极管(Polymer Light Emitting Diode,PLED)、有机发光二极管(Organic Light Emitting Diode,OLED)和量子点发光二极管(Quantum Dots Light Emitting Doides,QLEDs)。目前，发光二极管的结构通常采用包括透明阳极/空穴传输层(HTL)/发光层(EML)/电子传输层(ETL)/金属阴极的多层结构；因此，在器件工况下，发光区域发光时所产生的热量会对空穴传输层造成影响，导致空穴传输层被损坏。因此，为得到性能更好的发光二极管，仍需要对发光二极管的各层材料或器件结构进行优化。Light Emitting Diode (LED) is a solid-state semiconductor point light source device that can convert electrical energy into light energy. According to the different materials used in the light-emitting layer, light-emitting diodes mainly include inorganic light-emitting diodes (Inorganic Light Emitting Diode, iLED), polymer light-emitting diodes (Polymer Light Emitting Diode, PLED), organic light-emitting diodes (Organic Light Emitting Diode, OLED) and quantum Quantum Dots Light Emitting Doides (QLEDs). At present, the structure of light-emitting diodes usually adopts a multi-layer structure including transparent anode/hole transport layer (HTL)/emissive layer (EML)/electron transport layer (ETL)/metal cathode; therefore, under device operating conditions, the light-emitting area The heat generated during light emission affects the hole transport layer, resulting in damage to the hole transport layer. Therefore, in order to obtain a light-emitting diode with better performance, it is still necessary to optimize the materials of each layer of the light-emitting diode or the device structure.
在器件工况下，发光区域发光时所产生的热量会对空穴传输层造成影响，导致空穴传输层被损坏，影响发光二极管的性能。Under the working condition of the device, the heat generated when the light-emitting region emits light will affect the hole transport layer, resulting in damage to the hole transport layer and affecting the performance of the light-emitting diode.
本申请提供一种发光二极管及其制备方法。The application provides a light emitting diode and a preparation method thereof.
本申请提供一种发光二极管，包括层叠设置的空穴传输层和发光层，所述空穴传输层的材料包括空穴传输材料和导热材料；所述导热材料为空心纳米材 料。The present application provides a light-emitting diode, comprising a hole transport layer and a light-emitting layer stacked. The material of the hole transport layer includes a hole transport material and a thermally conductive material; the thermally conductive material is a hollow nanomaterial.
可选的，在本申请的一些实施例中，所述空穴传输材料与所述导热材料形成混合材料体。Optionally, in some embodiments of the present application, the hole transport material and the heat conducting material form a mixed material body.
可选的，在本申请的一些实施例中，至少部分所述导热材料在所述空穴传输层的靠近所述发光层的一侧形成独立材料体。Optionally, in some embodiments of the present application, at least part of the thermally conductive material forms an independent material body on a side of the hole transport layer close to the light emitting layer.
可选的，在本申请的一些实施例中，所述空穴传输层包括空穴传输膜层和导热修饰层；所述空穴传输膜层由所述空穴传输材料形成；所述导热修饰层由所述导热材料形成；所述导热修饰层设置于所述空穴传输膜层与所述发光层之间。Optionally, in some embodiments of the present application, the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the hole transport film layer is formed of the hole transport material; the thermally conductive modification The layer is formed by the heat-conducting material; the heat-conducting modification layer is arranged between the hole transport film layer and the light-emitting layer.
可选的，在本申请的一些实施例中，所述空心纳米材料的导热系数在2W/m
-1·K
-1以上。
Optionally, in some embodiments of the present application, the thermal conductivity of the hollow nanomaterial is above 2 W/m −1 ·K −1 .
可选的，在本申请的一些实施例中，所述空心纳米材料的空穴迁移率在1×10
-5cm
2·V
-1·s
-1以上。
Optionally, in some embodiments of the present application, the hole mobility of the hollow nanomaterial is above 1×10 -5 cm 2 ·V -1 ·s -1 .
可选的，在本申请的一些实施例中，所述空心纳米材料为空心金属氧化物纳米颗粒。Optionally, in some embodiments of the present application, the hollow nanomaterials are hollow metal oxide nanoparticles.
可选的，在本申请的一些实施例中，所述空心金属氧化物纳米颗粒选自NiO
y、MoO
y、WO
y、CuO
y中的一种或多种，其中，1≤y≤3。
Optionally, in some embodiments of the present application, the hollow metal oxide nanoparticles are selected from one or more of NiO y , MoO y , WO y , and CuO y , wherein 1≤y≤3.
可选的，在本申请的一些实施例中，所述空心纳米材料的粒径为10～50nm。Optionally, in some embodiments of the present application, the particle size of the hollow nanomaterial is 10-50 nm.
可选的，在本申请的一些实施例中，所述导热修饰层的厚度为20～60nm。Optionally, in some embodiments of the present application, the thickness of the thermally conductive modification layer is 20-60 nm.
可选的，在本申请的一些实施例中，所述发光二极管还包括电子传输层；所述电子传输层设置于所述发光层的远离所述空穴传输层的一侧；所述电子传输层的载流子迁移率高于所述空穴传输层的载流子迁移率。Optionally, in some embodiments of the present application, the light-emitting diode further includes an electron transport layer; the electron transport layer is disposed on a side of the light-emitting layer away from the hole transport layer; the electron transport The carrier mobility of the layer is higher than the carrier mobility of the hole transport layer.
可选的，在本申请的一些实施例中，所述空穴传输材料选自有机空穴传输材料或无机空穴传输材料；其中，所述有机空穴传输材料选自于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、聚乙烯咔唑、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)、4,4',4'-三(咔唑-9-基)三苯胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺、N,N'-二苯基-N,N’-(1-萘基)-1,1'-联苯-4,4’-二胺、掺杂石墨烯、非掺杂石墨烯、C60中的一种或多种；所述无机空穴传输材料选自于掺杂或非 掺杂金属氧化物、掺杂或非掺杂金属硫化物、掺杂或非掺杂金属硒化物，所述非掺杂金属氧化物选自ZnO、MoO
x、VO
x、WO
x、CrO
x、CuO、NiO
x中的一种或多种，所述非掺杂金属硫化物选自MoS
x、WS
x、CuS
x、MoS
x中的一种或多种，所述非掺杂金属硒化物选自MoSe
x、WSe
x、的一种或多种，其中1≤x≤3；所述掺杂金属氧化物包括所述非掺杂金属氧化物和掺杂元素，所述掺杂金属硫化物包括所述非掺杂金属硫化物和掺杂元素，所述掺杂金属硒化物包括所述非掺杂金属硒化物和掺杂元素，所述掺杂元素选自铝、镓、铟、镁、铜、钇、钴、锰、镉、锂中的一种或多种；所述电子传输层的材料选自非掺杂金属氧化物或掺杂金属氧化物，其中，所述非掺杂金属氧化物选自于ZnO、TiO
2、SnO、SnO
2、MgO、Ta
2O
3中的一种或多种，所述掺杂金属氧化物选自于铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌、铜掺杂氧化锌、钇掺杂氧化锌、钴掺杂氧化锌、锰掺杂氧化锌、镉掺杂氧化锌、锂掺杂氧化锌、铝掺杂氧化钛、镓掺杂氧化钛、铟掺杂氧化钛、镁掺杂氧化钛、铜掺杂氧化钛、钇掺杂氧化钛、钴掺杂氧化钛、锰掺杂氧化钛、镉掺杂氧化钛、锂掺杂氧化钛、锌掺杂氧化锡、铝掺杂氧化镁中的一种或多种；所述发光层的材料选自无机材料、小分子有机材料、高分子有机材料和量子点材料中的一种或多种，所述无机材料选自ZnS:Mn、ZnS:Tb、ZnS:Tb/CdS、SiO
2:Ge、SiO
2:Er、SrS:Ce、CaGa
2S
4:Ce、SrGa
2S
4:Ce、SrS:Cu、GaN、ZnS:Tm、Zn
2SiO
2:Ca中的一种或多种，所述小分子有机材料选自4-(二腈甲基)-2-丁基-6-(1,1,7,7-四甲基久洛呢啶-9-乙烯基)-4H-吡喃、9,10-二(β-萘基)蒽、4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯或8-羟基喹啉铝中的一种或多种，所述高分子有机材料选自聚对苯乙烯撑、聚噻吩、聚苯胺、聚咔唑中的一种或多种，所述量子点材料选自CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe中的一种或多种；所述发光二极管还包括阴极和阳极，所述阳极设置在所述空穴传输层远离所述发光层一侧，所述阴极设置在所述电子传输层远离所述发光层一侧，其中，所述阳极的材料选自ITO、FTO、ZTO中的一种或多种，所述阴极的材料选自Al、Ag、Au、Cu、Mo及其合金中的一种或多种。
Optionally, in some embodiments of the present application, the hole transport material is selected from organic hole transport materials or inorganic hole transport materials; wherein, the organic hole transport material is selected from poly(9,9 -dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), polyvinylcarbazole, poly(N,N'bis(4-butylphenyl)-N,N'-bis( phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine), 4,4',4'-tris(carbazole -9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1 '-Biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, One or more of doped graphene, non-doped graphene, C60; the inorganic hole transport material is selected from doped or non-doped metal oxide, doped or non-doped metal sulfide, Doped or non-doped metal selenide, the non-doped metal oxide is selected from one or more of ZnO, MoO x , VO x , WO x , CrO x , CuO, NiO x , the non-doped The heterometallic sulfide is selected from one or more of MoS x , WS x , CuS x , MoS x , and the non-doped metal selenide is selected from one or more of MoS x , WS x , wherein 1 ≤x≤3; the doped metal oxide includes the non-doped metal oxide and a doping element, the doped metal sulfide includes the non-doped metal sulfide and a doping element, the doped Heterometal selenides include said non-doped metal selenides and doping elements, said doping elements being selected from one or more of aluminum, gallium, indium, magnesium, copper, yttrium, cobalt, manganese, cadmium, lithium The material of the electron transport layer is selected from non-doped metal oxides or doped metal oxides, wherein the non-doped metal oxides are selected from ZnO, TiO 2 , SnO, SnO 2 , MgO, Ta One or more of 2 O 3 , the doped metal oxide is selected from aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide, copper doped zinc oxide , yttrium-doped zinc oxide, cobalt-doped zinc oxide, manganese-doped zinc oxide, cadmium-doped zinc oxide, lithium-doped zinc oxide, aluminum-doped titanium oxide, gallium-doped titanium oxide, indium-doped titanium oxide, magnesium Doped titanium oxide, copper doped titanium oxide, yttrium doped titanium oxide, cobalt doped titanium oxide, manganese doped titanium oxide, cadmium doped titanium oxide, lithium doped titanium oxide, zinc doped tin oxide, aluminum doped One or more in magnesium oxide; The material of the light-emitting layer is selected from one or more of inorganic materials, small molecule organic materials, polymer organic materials and quantum dot materials, and the inorganic materials are selected from ZnS: Mn, ZnS:Tb, ZnS:Tb/CdS, SiO 2 :Ge, SiO 2 :Er, SrS:Ce, CaGa 2 S 4 :Ce, SrGa 2 S 4 :Ce, SrS:Cu, GaN, ZnS:Tm, Zn 2 SiO 2 : one or more of Ca, the small molecule organic material is selected from 4-(dinitrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Julomedine-9-vinyl)-4H-pyran, 9,10-bis(β-naphthyl)anthracene, 4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , one or more of 1'-biphenyl or 8-hydroxyquinoline aluminum, and the polymer organic material is selected from one or more of poly-p-phenylene, polythiophene, polyaniline, and polycarbazole The quantum dot material is selected from CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe One or more; the light-emitting diode also includes a cathode and an anode, the anode is arranged on the side of the hole transport layer away from the light-emitting layer, and the cathode is arranged on the electron-transport layer away from the light-emitting layer One side, wherein, the material of the anode is selected from one or more of ITO, FTO, ZTO, and the material of the cathode is selected from one or more of Al, Ag, Au, Cu, Mo and their alloys kind.
相应的，本申请还提供一种发光二极管的制备方法，包括：提供半成品器 件；在所述半成品器件上形成层叠的空穴传输层和发光层；其中，所述空穴传输层的材料包括空穴传输材料和导热材料，所述导热材料为空心纳米材料。Correspondingly, the present application also provides a method for preparing a light-emitting diode, including: providing a semi-finished device; forming a stacked hole transport layer and a light-emitting layer on the semi-finished device; wherein, the material of the hole transport layer includes A hole transport material and a thermally conductive material, the thermally conductive material is a hollow nanometer material.
可选的，在本申请的一些实施例中，所述空穴传输材料与所述导热材料形成混合材料体。Optionally, in some embodiments of the present application, the hole transport material and the heat conducting material form a mixed material body.
可选的，在本申请的一些实施例中，至少部分所述导热材料在所述空穴传输层的靠近所述发光层的一侧形成独立材料体。Optionally, in some embodiments of the present application, at least part of the thermally conductive material forms an independent material body on a side of the hole transport layer close to the light emitting layer.
可选的，在本申请的一些实施例中，所述空穴传输层包括层叠设置的空穴传输膜层和导热修饰层，所述空穴传输膜层由所述空穴传输材料形成；所述导热修饰层由所述导热材料形成；所述导热修饰层位于所述空穴传输膜层与所述发光层之间。Optionally, in some embodiments of the present application, the hole transport layer includes a stacked hole transport film layer and a thermally conductive modification layer, and the hole transport film layer is formed of the hole transport material; The thermally conductive modification layer is formed of the thermally conductive material; the thermally conductive modification layer is located between the hole transport film layer and the light emitting layer.
可选的，在本申请的一些实施例中，制备所述导热修饰层的步骤包括：提供空心纳米材料的溶液，将所述空心纳米材料的溶液设置到所述空穴传输膜层或所述发光层的表面，形成所述导热修饰层；其中，所述空心纳米材料的溶液的浓度为3～10mg/mL。Optionally, in some embodiments of the present application, the step of preparing the thermally conductive modification layer includes: providing a solution of hollow nanomaterials, and disposing the solution of hollow nanomaterials on the hole transport film layer or the The surface of the light-emitting layer forms the heat-conducting modified layer; wherein, the concentration of the solution of the hollow nanomaterial is 3-10 mg/mL.
可选的，在本申请的一些实施例中，所述将所述空心纳米材料的溶液设置到所述空穴传输膜层的表面之后，还包括：在60～100℃下退火处理10～60min。Optionally, in some embodiments of the present application, after disposing the solution of the hollow nanomaterial on the surface of the hole transport film layer, further includes: annealing at 60-100° C. for 10-60 minutes .
可选的，在本申请的一些实施例中，所述发光二极管为正置发光二极管，所述半成品器件包括阳极；所述在所述半成品器件上形成层叠的空穴传输层和发光层包括：在所述半成品器件上依次形成所述空穴传输膜层、所述导热修饰层和所述发光层；所述在所述半成品器件上形成层叠的空穴传输层和发光层之后，还包括：在所述发光层上形成阴极。Optionally, in some embodiments of the present application, the light-emitting diode is a positive light-emitting diode, and the semi-finished device includes an anode; the formation of a stacked hole transport layer and a light-emitting layer on the semi-finished device includes: Forming the hole transport film layer, the thermally conductive modification layer, and the light-emitting layer sequentially on the semi-finished device; after forming the stacked hole transport layer and the light-emitting layer on the semi-finished device, it also includes: A cathode is formed on the light emitting layer.
可选的，在本申请的一些实施例中，所述发光二极管为倒置发光二极管，所述半成品器件包括阴极；所述在所述半成品器件上形成层叠的空穴传输层和发光层包括：在所述半成品器件上依次形成所述发光层、所述导热修饰层和所述空穴传输膜层；所述在所述半成品器件上形成层叠的空穴传输层和发光层之后，还包括：在所述空穴传输膜层上形成阴极。Optionally, in some embodiments of the present application, the light-emitting diode is an inverted light-emitting diode, and the semi-finished device includes a cathode; the forming a stacked hole transport layer and a light-emitting layer on the semi-finished device includes: Forming the light-emitting layer, the thermally conductive modification layer and the hole transport film layer sequentially on the semi-finished device; after forming the stacked hole transport layer and light-emitting layer on the semi-finished device, further comprising: A cathode is formed on the hole transport film layer.
本申请提供的一种发光二极管，在与发光层层叠设置的空穴传输层的材料 中加入导热材料，实现器件发光区域在工况下快速散热，降低发光区域在工况下温度升高对空穴传输层的影响；且该导热材料采用空心纳米材料，由于空心结构的纳米材料具有较高的热稳定性，同时通过导热材料，易于实现发光层产生的热量的快速传递，减少对空穴传输材料的破坏，进一步提高器件发光区域的散热，进而更有效降低器件在工况下发光区域温度升高对空穴传输层的损坏。In the light-emitting diode provided by the present application, a heat-conducting material is added to the material of the hole transport layer stacked with the light-emitting layer to realize rapid heat dissipation in the light-emitting region of the device under working conditions, and reduce the temperature rise of the light-emitting region under working conditions. The effect of the hole transport layer; and the thermal conductive material adopts hollow nanomaterials, because the nanomaterials with hollow structures have high thermal stability, and at the same time, through the thermal conductive materials, it is easy to realize the rapid transfer of heat generated by the light-emitting layer and reduce the impact on hole transport. The destruction of the material further improves the heat dissipation of the light-emitting area of the device, thereby more effectively reducing the damage to the hole transport layer caused by the temperature rise of the light-emitting area of the device under working conditions.
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.
图1为本申请实施例提供的一种发光二极管的制备方法的流程示意图；FIG. 1 is a schematic flow chart of a method for preparing a light-emitting diode provided in an embodiment of the present application;
图2是本申请实施例1提供的发光二极管的结构示意图；Fig. 2 is a schematic structural diagram of a light emitting diode provided in Embodiment 1 of the present application;
图3是本申请实施例1提供的空心氧化镍纳米颗粒的结构示意图；Figure 3 is a schematic structural view of the hollow nickel oxide nanoparticles provided in Example 1 of the present application;
其中，101-衬底，102-底电极，103-空穴传输膜层，104-导热修饰层，105-量子点发光层，106-电子传输层，107-顶电极；20-空心氧化镍纳米颗粒；201-纳米晶。Among them, 101-substrate, 102-bottom electrode, 103-hole transport film layer, 104-thermally conductive modification layer, 105-quantum dot luminescent layer, 106-electron transport layer, 107-top electrode; 20-hollow nickel oxide nano Particles; 201-nanocrystals.
本申请的实施方式Embodiment of this application
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本申请保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the application with reference to the drawings in the embodiments of the application. Apparently, the described embodiments are only some of the embodiments of the application, not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts belong to the scope of protection of this application.
此外，应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。在本申请中，在未作相反说明的情况下，使用的方位词如“上”和“下”具体为附图中的图面方向。另外，在本申请的描述中，术语“包括”是指“包括但不限于”。本申请的各种实施例可以以一个范围的形式存在；应当理解，以一范围形式的描述仅仅是因为方便及简洁，不应理解为对本 申请范围的硬性限制；因此，应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如，应当认为从1到6的范围描述已经具体公开子范围，例如从1到3，从1到4，从1到5，从2到4，从2到6，从3到6等，以及所述范围内的单一数字，例如1、2、3、4、5及6，此不管范围为何皆适用。另外，每当在本文中指出数值范围，是指包括所指范围内的任何引用的数字(分数或整数)。In addition, it should be understood that the specific implementations described here are only used to illustrate and explain the present application, and are not intended to limit the present application. In the present application, unless otherwise stated, the used orientation words such as "upper" and "lower" specifically refer to the direction of the drawings in the drawings. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the application; therefore, the described range should be regarded as The description has specifically disclosed all possible subranges as well as individual values within that range. For example, a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
在本申请中，“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。In this application, "and/or" describes the association relationship of associated objects, indicating that there may be three types of relationships, for example, A and/or B, which may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural.
在本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“至少一种”、“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。In this application, "at least one" means one or more, and "multiple" means two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of a single item or a plurality of items. For example, "at least one item (unit) of a, b, or c", or "at least one item (unit) of a, b, and c" can mean: a, b, c, a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.
第一方面，本申请提供一种发光二极管，包括层叠设置的空穴传输层和发光层，空穴传输层的材料包括空穴传输材料和导热材料；导热材料为空心纳米材料；In a first aspect, the present application provides a light-emitting diode, including a hole transport layer and a light-emitting layer that are stacked, and the material of the hole transport layer includes a hole transport material and a thermally conductive material; the thermally conductive material is a hollow nanomaterial;
其中，空穴传输材料与导热材料形成混合材料体；或者wherein the hole transport material and the thermally conductive material form a mixed material body; or
至少部分导热材料在空穴传输层的靠近发光层的一侧形成独立材料体。At least part of the thermally conductive material forms a separate material body on the side of the hole transport layer close to the light emitting layer.
需要说明的是，本申请中的混合材料体是指至少两种材料混合后形成的材料无序分布且不分层的结构层。独立材料体是指一种材料形成的结构层，且该结构层与相邻结构层具有明显界面。在本申请中，空穴传输材料导热材料形成混合材料体应当理解为：导热材料与空穴传输材料混合形成单层结构层，得到导热材料掺杂的空穴传输层。在该空穴传输层中，导热材料在空穴传输层中可以形成用于热量传输的通路，发光层在工况下产生的热量可以经由导热材料形成的热量传输的通路传递热量。在本申请中，至少部分导热材料在空穴传输层的靠近发光层的一侧形成独立材料体应当理解为：空穴传输层中部分或者全部导热材料聚集在空穴传输层靠近发光层的一侧，形成一层与相邻结构层具有明显界面的结构层，即部分或者全部的导热材料位于发光层和空穴传输材料形成 的层结构之间。当部分导热材料在空穴传输层靠近发光层的一侧形成一层结构层时，剩余部分的导热材料可以分散在空穴传输层中，与空穴传输材料形成混合材料体。It should be noted that the mixed material body in this application refers to a structural layer in which materials are randomly distributed and not layered, formed after at least two materials are mixed. An independent material body refers to a structural layer formed by one material, and the structural layer has a clear interface with the adjacent structural layer. In this application, forming a mixed material body with a hole transport material and a heat conduction material should be understood as: a heat conduction material is mixed with a hole transport material to form a single-layer structure layer, and a hole transport layer doped with a heat conduction material is obtained. In the hole transport layer, the thermally conductive material can form a path for heat transfer in the hole transport layer, and the heat generated by the light-emitting layer under working conditions can transfer heat through the heat transfer path formed by the thermally conductive material. In this application, at least part of the thermally conductive material forms an independent material body on the side of the hole transport layer close to the light-emitting layer. On the other hand, a structural layer with an obvious interface with the adjacent structural layer is formed, that is, part or all of the heat-conducting material is located between the light-emitting layer and the layer structure formed by the hole-transporting material. When part of the heat-conducting material forms a structural layer on the side of the hole-transporting layer close to the light-emitting layer, the rest of the heat-conducting material can be dispersed in the hole-transporting layer to form a mixed material body with the hole-transporting material.
在一些实施例中，导热材料掺杂在空穴传输材料形成的空穴传输层中，导热材料在空穴传输层中形成可以用于热量传输的通路，通过导热材料良好的导热性，使发光层在器件工况下产生的热量可以被快速传递至发光二极管的电极，提高散热效果，进而改善发光二极管的稳定性。其中，导热材料在空穴传输层中可以均匀分布，也可以分布在空穴传输层与发光层的界面上以及空穴传输层中。In some embodiments, the thermally conductive material is doped in the hole transport layer formed by the hole transport material, and the thermally conductive material forms a path in the hole transport layer that can be used for heat transmission. Through the good thermal conductivity of the thermally conductive material, the luminescent The heat generated by the layer under the working condition of the device can be quickly transferred to the electrodes of the light-emitting diode, thereby improving the heat dissipation effect and further improving the stability of the light-emitting diode. Wherein, the thermally conductive material can be uniformly distributed in the hole transport layer, or can be distributed on the interface between the hole transport layer and the light emitting layer and in the hole transport layer.
在一些实施例中，空穴传输层包括空穴传输膜层和导热修饰层；空穴传输膜层的材料由空穴传输材料形成；导热修饰层由导热材料形成；导热修饰层位于空穴传输膜层与发光层之间。即：空穴传输层为空穴传输膜层与导热修饰层形成的复合层，导热材料形成的导热修饰层位于空穴传输层与发光层之间，导热材料与发光层接触，使发光层在器件工况下产生的热量可以经由基于导热材料的导热修饰层快速传递，提高散热效果，提高器件的稳定性。In some embodiments, the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the material of the hole transport film layer is formed by a hole transport material; the thermally conductive modification layer is formed by a thermally conductive material; the thermally conductive modification layer is located in the hole transport Between the film layer and the light-emitting layer. That is: the hole transport layer is a composite layer formed by a hole transport film layer and a thermally conductive modified layer. The thermally conductive modified layer formed by a thermally conductive material is located between the hole transport layer and the light-emitting layer, and the heat-conductive material is in contact with the light-emitting layer. The heat generated under the working conditions of the device can be quickly transferred through the thermally conductive modification layer based on the thermally conductive material, which improves the heat dissipation effect and improves the stability of the device.
在一些实施例中，空穴传输层包括空穴传输膜层和导热修饰层；空穴传输膜层由空穴传输材料和导热材料形成；导热修饰层由导热材料形成；导热修饰层位于空穴传输膜层与发光层之间。即：空穴传输层为空穴传输膜层与导热修饰层形成的复合层，导热材料形成的导热修饰层位于空穴传输层与发光层之间，使发光层在器件工况下产生的热量可以经由基于导热材料的导热修饰层快速传递；同时，空穴传输膜层中还掺杂有导热材料，可以在空穴传输膜层中形成热量传递的通路，使发光层在工况时产生的热快速传递到发光二极管的电极，使器件快速散热，提高器件的稳定性。In some embodiments, the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the hole transport film layer is formed of a hole transport material and a thermally conductive material; the thermally conductive modification layer is formed of a thermally conductive material; the thermally conductive modification layer is located in the hole Between the transmission film layer and the light-emitting layer. That is: the hole transport layer is a composite layer formed by a hole transport film layer and a thermally conductive modified layer, and the thermally conductive modified layer formed by a thermally conductive material is located between the hole transport layer and the light-emitting layer, so that the heat generated by the light-emitting layer under device working conditions It can be quickly transferred through the heat-conducting modification layer based on heat-conducting materials; at the same time, the hole-transporting film layer is also doped with heat-conducting materials, which can form a heat transfer path in the hole-transporting film layer, so that the heat generated by the light-emitting layer under working conditions The heat is quickly transferred to the electrodes of the light-emitting diode, so that the device can dissipate heat quickly and improve the stability of the device.
需要说明的是，空心纳米材料可以为纳米管或者空心纳米颗粒，其中纳米管为中空的一维纳米材料，可以选自于碳纳米管、聚丙烯纳米纤维、聚乙烯吡咯烷酮纳米纤维中的一种或多种；空心纳米颗粒为中空的零维纳米材料，可以为空心非氧化物纳米颗粒或空心金属氧化物纳米颗粒或空心非金属氧化物纳米颗粒；其中，空心金属氧化物纳米颗粒可以选自于NiO
y、MoO
y、WO
y、CuO
y中的一种或多种，其中，1≤y≤3；非金属氧化物纳米颗粒可以选自于SiO
2等中 的一种或多种。
It should be noted that the hollow nanomaterials can be nanotubes or hollow nanoparticles, wherein the nanotubes are hollow one-dimensional nanomaterials, which can be selected from carbon nanotubes, polypropylene nanofibers, and polyvinylpyrrolidone nanofibers. or multiple; hollow nanoparticles are hollow zero-dimensional nanomaterials, which can be hollow non-oxide nanoparticles or hollow metal oxide nanoparticles or hollow non-metal oxide nanoparticles; wherein the hollow metal oxide nanoparticles can be selected from One or more of NiO y , MoO y , WO y , CuO y , wherein 1≤y≤3; the non-metal oxide nanoparticles can be selected from one or more of SiO 2 and the like.
在一些实施例中，当空心纳米材料为纳米管时，纳米管的直径可以为5～20nm，使导热修饰层厚度控制在20～60nm，避免因为导热修饰层厚度过厚而影响空穴传输层和发光层之间的带载流子迁移。In some embodiments, when the hollow nanomaterial is a nanotube, the diameter of the nanotube can be 5-20 nm, so that the thickness of the thermally conductive modification layer is controlled at 20-60 nm, so as to avoid affecting the hole transport layer due to the excessive thickness of the thermally conductive modification layer. and the transfer of charge carriers between the light-emitting layers.
在一些实施例中，当空心纳米材料为空心纳米颗粒时，空心纳米颗粒的粒径为10～50nm，避免因为空心纳米颗粒粒径过大导致导热修饰层的成膜性较差、膜层较厚，影响电荷传输；同时避免因为空心纳米颗粒粒径较小导致制备困难、制备成本增加。In some embodiments, when the hollow nanomaterial is a hollow nanoparticle, the particle size of the hollow nanoparticle is 10-50 nm, so as to avoid the poor film-forming property of the thermally conductive modification layer and the thin film layer due to the large particle size of the hollow nanoparticle. Thick, affecting charge transport; at the same time avoiding the difficulty of preparation and the increase of preparation cost due to the small particle size of hollow nanoparticles.
在一些实施例中，当空心纳米颗粒为空心纳米晶颗粒。In some embodiments, when the hollow nanoparticles are hollow nanocrystalline particles.
在一些实施例中，空心纳米材料的导热系数在2W/(m·K)或2W·m
-1·K
-1或2瓦/米·度以上，使空心纳米材料具有较好的导热性能，起到更好的散热效果。
In some embodiments, the thermal conductivity of the hollow nanomaterial is above 2W/(m·K) or 2W·m −1 ·K −1 or 2 W/m·degree, so that the hollow nanomaterial has better thermal conductivity, Play a better heat dissipation effect.
在一些实施例中，空心纳米材料的空穴迁移率在1×10
-5cm
2·V
-1·s
-1或1×10
-5cm
2/(V·s)或1×10
-5厘米2/(伏·秒)以上。根据载流子传输理论，空穴主要在分子间的最高占据分子轨道中传输，因此空穴传输层的空穴传输能力与最高占据分子轨道组成密切相关。目前，空穴传输层的最高占据分子轨道能级通常在5.3eV以上，相较于发光层的价带能级，存在一定差距。因此，在器件工况下，空穴传输层的空穴需要更高的电压才能越过势垒到达空穴和电子的复合区域，故需要对器件施加更高的电压，而高电压会导致器件的工况温度进一步升高，如此，就更容易导致空穴传输层的材料产生不可逆的损坏。因此，在空穴传输层中添加能级介于空穴传输材料和发光层的材料之间的导热材料，可以在起到良好散热效果的同时，降低空穴传输层的势垒，进而降低器件发光区域的温度。而当空穴传输层为空穴传输膜层和导热修饰层形成的复合层时，由于导热修饰层的能级介于空穴传输层与发光层之间，可以使优化发光层与空穴传输层的能级匹配，使空穴逐级传输，进而降低器件发光区域的温度，同时不影响空穴传输层与发光层之间的电荷传输。
In some embodiments, the hole mobility of the hollow nanomaterial is 1×10 -5 cm 2 ·V -1 ·s -1 or 1×10 -5 cm 2 /(V·s) or 1×10 -5 Centimeter 2 / (volt · second) above. According to the carrier transport theory, holes are mainly transported in the highest occupied molecular orbital between molecules, so the hole transport capability of the hole transport layer is closely related to the composition of the highest occupied molecular orbital. At present, the highest occupied molecular orbital energy level of the hole transport layer is usually above 5.3eV, which has a certain gap compared with the valence band energy level of the light-emitting layer. Therefore, under the working conditions of the device, the holes in the hole transport layer need a higher voltage to cross the potential barrier and reach the recombination region of holes and electrons, so a higher voltage needs to be applied to the device, and the high voltage will lead to the A further increase in operating temperature will more easily lead to irreversible damage to the material of the hole transport layer. Therefore, adding a thermally conductive material with an energy level between the hole transport material and the material of the light-emitting layer in the hole transport layer can reduce the potential barrier of the hole transport layer while achieving a good heat dissipation effect, thereby reducing the device The temperature of the glowing area. And when the hole transport layer is a composite layer formed by a hole transport film layer and a thermally conductive modification layer, since the energy level of the thermally conductive modification layer is between the hole transport layer and the light-emitting layer, it is possible to optimize the light-emitting layer and the hole transport layer. The energy level of the device is matched, so that the holes are transported step by step, thereby reducing the temperature of the light-emitting region of the device, while not affecting the charge transport between the hole-transport layer and the light-emitting layer.
在一些实施例中，发光层远离空穴传输层的一侧设置有电子传输层；电子传输层的载流子迁移率高于空穴传输层的载流子迁移率；导热材料为空心金属氧化物纳米颗粒。由于导热材料的能级介于空穴传输材料的能级与发光层的材料的能级之间，因此，当导热材料掺杂进入基于空穴传输材料的空穴传输层或 者在基于空穴传输材料的空穴传输膜层与发光层之间形成导热修饰层时，空穴传输层与发光层之间的能极差被降低，因此空穴传输层与发光层之间的能级匹配得到优化，提高了空穴传输层的载流子迁移率，进而降低空穴传输层与电子传输层的载流子迁移率差值，改善器件的电子-空穴注入不平衡。In some embodiments, an electron transport layer is provided on the side of the light-emitting layer away from the hole transport layer; the carrier mobility of the electron transport layer is higher than that of the hole transport layer; the thermally conductive material is a hollow metal oxide matter nanoparticles. Since the energy level of the thermally conductive material is between the energy level of the hole transport material and the energy level of the material of the light-emitting layer, when the thermally conductive material is doped into the hole transport layer based on the hole transport material or in the hole transport based When a thermally conductive modification layer is formed between the hole transport layer of the material and the light-emitting layer, the energy gap between the hole transport layer and the light-emitting layer is reduced, so the energy level matching between the hole transport layer and the light-emitting layer is optimized , improving the carrier mobility of the hole transport layer, thereby reducing the carrier mobility difference between the hole transport layer and the electron transport layer, and improving the electron-hole injection imbalance of the device.
如上述所言，采用空心金属氧化物纳米颗粒作为导热材料时，可以同时起到良好的散热效果和优化空穴传输层与发光层的能级匹配的作用，且对于有机空穴传输层所起到的散热效果更加明显，因此在本申请中空心金属氧化物纳米颗粒作为导热材料，可以进一步提升发光二极管的性能。As mentioned above, when the hollow metal oxide nanoparticles are used as the thermally conductive material, it can simultaneously play a good heat dissipation effect and optimize the energy level matching between the hole transport layer and the light-emitting layer, and the role played by the organic hole transport layer The heat dissipation effect obtained is more obvious. Therefore, in this application, the hollow metal oxide nanoparticles are used as a heat-conducting material, which can further improve the performance of the light-emitting diode.
需要说明的是，空穴传输材料可以为有机空穴传输材料或无机空穴传输材料，具体的，可以为有机空穴传输材料。这是因为有机空穴传输材料相较于无机空穴传输材料，其化学稳定性和热稳定性更差，因此，在器件工况下，基于有机空穴传输材料的有机空穴传输层更容易因温度升高而受到损伤，因此在有机空穴传输层中加入导热材料，可以更加明显地改善有机空穴传输层和发光层之间的散热，进而明显改善器件的稳定性。It should be noted that the hole transport material may be an organic hole transport material or an inorganic hole transport material, specifically, an organic hole transport material. This is because organic hole transport materials are less chemically stable and thermally stable than inorganic hole transport materials. Therefore, under device conditions, organic hole transport layers based on organic hole transport materials are easier to It is damaged due to temperature rise, so adding a thermally conductive material to the organic hole transport layer can more significantly improve the heat dissipation between the organic hole transport layer and the light-emitting layer, thereby significantly improving the stability of the device.
需要说明的是，本申请提供的发光二极管可以为任意包括空穴传输层和发光层，且空穴传输层与发光层层叠设置的发光二极管，如层叠设置有空穴传输层和发光层的无机发光二极管、有机发光二极管、高分子发光二极管、量子点发光二极管；尤其适用于量子点发光二极管。这是因为量子点发光二极管的空穴传输层的材料多以有机半导体为主，如PEDOT:PSS、TFB、Poly-TPD；且电子传输层材料多以ZnO为主，而ZnO的载流子迁移率远大于空穴传输层的载流子迁移率，导致量子点发光二极管的电子-空穴注入不平衡，因此为了改善量子点发光二极管的电子-空穴注入不平衡，需要提高空穴传输层的载流子迁移率或者降低电子传输层的载流子迁移率。因此，在空穴传输层中加入可以降低空穴传输层能级导热材料，可以优化空穴传输层与发光层的能级匹配、提高空穴传输层的载流子迁移率，改善量子点发光二极管的电子-空穴注入不平衡；同时，导热材料还可以起到良好的散热效果。此外，由于QLEDs能够充分发挥其所采用的胶体量子点的优越的光电性能和优异的溶液加工性，因而有望成为新一代高性能、大面积、低成本的电致发光器件，故对于本申请提供的发光二极管的结构及该发光二极管的制备方法在量子点发光二极管中的应用前景更 佳。其中，电子传输层的材料可以选择非掺杂金属氧化物或掺杂金属氧化物，其中非掺杂金属氧化物可以选自于ZnO、TiO
2、SnO、SnO
2、MgO、Ta
2O
3中的一种或多种，掺杂金属氧化物可以选自于铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌、铜掺杂氧化锌、钇掺杂氧化锌、钴掺杂氧化锌、锰掺杂氧化锌、镉掺杂氧化锌、锂掺杂氧化锌、铝掺杂氧化钛、镓掺杂氧化钛、铟掺杂氧化钛、镁掺杂氧化钛、铜掺杂氧化钛、钇掺杂氧化钛、钴掺杂氧化钛、锰掺杂氧化钛、镉掺杂氧化钛、锂掺杂氧化钛、锌掺杂氧化锡、铝掺杂氧化镁中的一种或多种。
It should be noted that the light-emitting diode provided in this application can be any light-emitting diode that includes a hole transport layer and a light-emitting layer, and the hole transport layer and the light-emitting layer are stacked, such as an inorganic light-emitting diode that is stacked with a hole transport layer and a light-emitting layer. Light-emitting diodes, organic light-emitting diodes, polymer light-emitting diodes, quantum dot light-emitting diodes; especially suitable for quantum dot light-emitting diodes. This is because the material of the hole transport layer of quantum dot light-emitting diodes is mostly organic semiconductors, such as PEDOT:PSS, TFB, Poly-TPD; and the material of the electron transport layer is mostly ZnO, and the carrier migration of ZnO The rate is much greater than the carrier mobility of the hole transport layer, resulting in the electron-hole injection imbalance of the quantum dot light-emitting diode. Therefore, in order to improve the electron-hole injection imbalance of the quantum dot light-emitting diode, it is necessary to improve the hole transport layer. carrier mobility or reduce the carrier mobility of the electron transport layer. Therefore, adding thermally conductive materials that can reduce the energy level of the hole transport layer in the hole transport layer can optimize the energy level matching between the hole transport layer and the light-emitting layer, improve the carrier mobility of the hole transport layer, and improve the quantum dot luminescence The electron-hole injection of the diode is unbalanced; at the same time, the thermally conductive material can also have a good heat dissipation effect. In addition, because QLEDs can give full play to the superior photoelectric properties and excellent solution processability of the colloidal quantum dots used in them, they are expected to become a new generation of high-performance, large-area, and low-cost electroluminescent devices, so for this application to provide The structure of the light-emitting diode and the preparation method of the light-emitting diode have a better application prospect in quantum dot light-emitting diodes. Among them, the material of the electron transport layer can be selected from non-doped metal oxide or doped metal oxide, wherein the non-doped metal oxide can be selected from ZnO, TiO 2 , SnO, SnO 2 , MgO, Ta 2 O 3 One or more, doped metal oxide can be selected from aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide, copper doped zinc oxide, yttrium doped oxide Zinc, cobalt-doped zinc oxide, manganese-doped zinc oxide, cadmium-doped zinc oxide, lithium-doped zinc oxide, aluminum-doped titanium oxide, gallium-doped titanium oxide, indium-doped titanium oxide, magnesium-doped titanium oxide, One of copper-doped titanium oxide, yttrium-doped titanium oxide, cobalt-doped titanium oxide, manganese-doped titanium oxide, cadmium-doped titanium oxide, lithium-doped titanium oxide, zinc-doped tin oxide, aluminum-doped magnesium oxide one or more species.
其中，有机空穴传输层的材料可以选自于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(TFB)、聚乙烯咔唑(PVK)、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(poly-TPD)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)(PFB)、4,4',4'-三(咔唑-9-基)三苯胺(TCTA)、4,4'-二(9-咔唑)联苯(CBP)、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺(TPD)、N,N'-二苯基-N,N’-(1-萘基)-1,1'-联苯-4,4’-二胺(NPB)、掺杂石墨烯、非掺杂石墨烯、C60中的一种或多种；无机空穴传输层的材料可以选自于掺杂或非掺杂的金属氧化物、掺杂或非掺杂的金属硫化物、掺杂或非掺杂的金属硒化物，如：ZnO、MoO
x、VO
x、WO
x、CrO
x、CuO、NiO
x、MoS
x、MoSe
x、WS
x、WSe
x、CuS
x、MoS
x的一种或多种，其中1≤x≤3；其中，掺杂的方式包括但不限于铝掺杂、镓掺杂、铟掺杂、镁掺杂、铜掺杂、钇掺杂、钴掺杂、锰掺杂、镉掺杂、锂掺杂。
Wherein, the material of the organic hole transport layer can be selected from poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl) diphenylamine) (TFB), polyvinylcarbazole (PVK) , poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine)(poly-TPD), poly(9,9-dioctylfluorene-co-bis -N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4'-tris(carbazol-9-yl)triphenylamine (TCTA), 4,4'-di( 9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), doped graphene, non One or more in doped graphene, C60; The material of inorganic hole transport layer can be selected from the metal oxide of doping or non-doping, the metal sulfide of doping or non-doping, doping or Non-doped metal selenides, such as one of ZnO, MoO x , VO x , WO x , CrO x , CuO, NiO x , MoS x , MoS x , WS x , WS x , CuS x , MoS x Various, where 1≤x≤3; wherein, the doping methods include but not limited to aluminum doping, gallium doping, indium doping, magnesium doping, copper doping, yttrium doping, cobalt doping, manganese doping hetero, cadmium doped, lithium doped.
需要说明的是，当发光二极管为无机发光二极管时，其发光层的材料为无机材料。无机材料可以选择ZnS:Mn、ZnS:Tb、ZnS:Tb/CdS、SiO
2:Ge、SiO
2:Er、SrS:Ce、CaGa
2S
4:Ce、SrGa
2S
4:Ce、SrS:Cu、GaN、ZnS:Tm、Zn
2SiO
2:Ca或其他无机发光材料；此处，“:”表示掺杂；“/”表示包覆。
It should be noted that when the light emitting diode is an inorganic light emitting diode, the material of the light emitting layer is an inorganic material. Inorganic materials can choose ZnS:Mn, ZnS:Tb, ZnS:Tb/CdS, SiO 2 :Ge, SiO 2 :Er, SrS:Ce, CaGa 2 S 4 :Ce, SrGa 2 S 4 :Ce, SrS:Cu, GaN, ZnS:Tm, Zn 2 SiO 2 :Ca or other phosphor materials; here, ":" means doping; "/" means cladding.
当发光二极管为有机发光二极管时，其发光层的材料为小分子有机材料。其小分子有机材料可以选择4-(二腈甲基)-2-丁基-6-(1,1,7,7-四甲基久洛呢啶-9-乙烯基)-4H-吡喃(DCJTB)、9,10-二(β-萘基)蒽(ADN)、4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯(BCzVBi)或8-羟基喹啉铝或其他小分子有机发光材料。When the light emitting diode is an organic light emitting diode, the material of the light emitting layer is a small molecule organic material. Its small molecule organic material can choose 4-(dinitrile methyl)-2-butyl-6-(1,1,7,7-tetramethyljuronesidine-9-vinyl)-4H-pyran (DCJTB), 9,10-bis(β-naphthyl)anthracene (ADN), 4,4'-bis(9-ethyl-3-carbazolevinyl)-1,1'-biphenyl (BCzVBi) Or 8-hydroxyquinoline aluminum or other small molecule organic light-emitting materials.
当发光二极管为高分子发光二极管时，其发光层的材料为高分子有机材 料。其高分子有机材料可以选择聚对苯乙烯撑、聚噻吩、聚苯胺、聚咔唑或其他高分子有机发光材料。When the light-emitting diode is a polymer light-emitting diode, the material of the light-emitting layer is a polymer organic material. The high molecular organic material can choose polyparaphenylene, polythiophene, polyaniline, polycarbazole or other high molecular organic light-emitting materials.
当发光二极管为量子点发光二极管时，其发光层的材料为量子点材料。其量子点材料可以选择CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe或其他量子点发光材料。When the light emitting diode is a quantum dot light emitting diode, the material of the light emitting layer is a quantum dot material. The quantum dot material can choose CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe or other quantum dots to emit light Material.
在一些实施例中，导热修饰层的厚度为20～60nm，避免因为导热修饰层的厚度过厚而影响电荷传输。In some embodiments, the thickness of the thermally conductive modification layer is 20-60 nm, so as to avoid affecting the charge transport due to the thickness of the thermally conductive modification layer being too thick.
在一些实施例中，空穴传输层的厚度为20～60nm。In some embodiments, the thickness of the hole transport layer is 20-60 nm.
在一些实施例中，发光层的厚度为20～60nm。In some embodiments, the thickness of the light-emitting layer is 20-60 nm.
在一些实施例中，顶电极的厚度为40～80nm。In some embodiments, the thickness of the top electrode is 40-80 nm.
需要说明的是，发光二级管可以是正置发光二极管，也可以是倒置发光二极管。当发光二级管为正置发光二极管时，正置发光二极管包括层叠设置的阳极、空穴传输层、发光层、电子传输层和阴极，阳极设置在衬底上，阴极作为顶电极；当发光二极管为倒置发光二极管时，倒置发光二极管包括层叠设置的阴极、电子传输层、发光层、空穴传输层和阳极，阴极设置在衬底上，阳极作为顶电极。其中阳极材料可选自于ITO、FTO、ZTO中的一种或多种；阴极材料可以选自于Al、Ag、Au、Cu、Mo及其合金中的一种或多种；衬底可以采用刚性衬底，也可以采用柔性衬底。其中，刚性衬底可选自于玻璃、金属箔片中的一种或多种；柔性衬底选自于聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸乙二醇酯(PEN)、聚醚醚酮(PEEK)、聚苯乙烯(PS)、聚醚砜(PES)、聚碳酸酯(PC)、聚芳基酸酯(PAT)、聚芳酯(PAR)、聚酰亚胺(PI)、聚氯乙烯(PV)、聚乙烯(PE)、聚乙烯吡咯烷酮(PVP)、纺织纤维中的一种或多种。It should be noted that the light emitting diodes may be upright light emitting diodes or inverted light emitting diodes. When the light-emitting diode is a positive light-emitting diode, the positive light-emitting diode includes a stacked anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode, the anode is arranged on the substrate, and the cathode is used as the top electrode; when emitting light When the diode is an inverted light-emitting diode, the inverted light-emitting diode includes a stacked cathode, an electron transport layer, a light-emitting layer, a hole transport layer and an anode, the cathode is arranged on the substrate, and the anode is used as a top electrode. Wherein the anode material can be selected from one or more of ITO, FTO, ZTO; the cathode material can be selected from one or more of Al, Ag, Au, Cu, Mo and their alloys; the substrate can be Rigid substrate, flexible substrate can also be used. Among them, the rigid substrate can be selected from one or more of glass and metal foil; the flexible substrate can be selected from polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polyetheretherketone (PEEK), polystyrene (PS), polyethersulfone (PES), polycarbonate (PC), polyarylate (PAT), polyarylate (PAR), poly One or more of imide (PI), polyvinyl chloride (PV), polyethylene (PE), polyvinylpyrrolidone (PVP), and textile fibers.
在一些实施例中，电子传输层的厚度为20～60nm。In some embodiments, the electron transport layer has a thickness of 20-60 nm.
在一些实施例中，电子传输层与阴极之间还可以设置电子注入层等电子功能层；空穴传输层与阳极之间还可以设置空穴注入层等空穴功能层。In some embodiments, an electron functional layer such as an electron injection layer may be disposed between the electron transport layer and the cathode; a hole functional layer such as a hole injection layer may also be disposed between the hole transport layer and the anode.
在一些实施例中，发光二极管还包括空穴阻挡层、电子阻挡层等功能层。In some embodiments, the light emitting diode further includes functional layers such as a hole blocking layer and an electron blocking layer.
第二方面，本申请还提供了一种发光二极管的制备方法，参阅图1，图1为本申请实施例提供的一种发光二极管的制备方法的流程示意图，包括：In the second aspect, the present application also provides a method for preparing a light-emitting diode, refer to FIG. 1 , and FIG. 1 is a schematic flow chart of a method for preparing a light-emitting diode provided in an embodiment of the present application, including:
步骤S11：提供半成品器件；Step S11: providing a semi-finished device;
步骤S12：在半成品器件上层叠形成空穴传输层、发光层；Step S12: laminating and forming a hole transport layer and a light emitting layer on the semi-finished device;
其中，空穴传输层的材料包括空穴传输材料和导热材料；导热材料为空心纳米材料；其中，空穴传输材料与导热材料形成混合材料体；或者Wherein, the material of the hole transport layer includes a hole transport material and a thermally conductive material; the thermally conductive material is a hollow nanomaterial; wherein, the hole transport material and the thermally conductive material form a mixed material body; or
至少部分导热材料在空穴传输层的靠近发光层的一侧形成独立材料体。At least part of the thermally conductive material forms a separate material body on the side of the hole transport layer close to the light emitting layer.
需要说明的是，本申请中的在半成品器件上层叠形成空穴传输层、发光层是指在半成品器件的表面层叠形成空穴传输膜层、发光层；其对空穴传输层和发光层的形成顺序不做限定，空穴传输层、发光层的形成顺序根据所制备的发光二极管的类型进行调整。It should be noted that, in the present application, forming a hole-transporting layer and a light-emitting layer on a semi-finished device means laminating a hole-transporting layer and a light-emitting layer on the surface of a semi-finished device; The formation sequence is not limited, and the formation sequence of the hole transport layer and the light emitting layer can be adjusted according to the type of the light emitting diode to be prepared.
当所制备的发光二极管为正置发光二极管时，在半成品器件上依次沉积空穴传输层、发光层；当所制备的发光二极管为反置发光二极管时，在半成品器件上依次沉积发光层、空穴传输层。When the prepared light-emitting diode is a positive light-emitting diode, the hole transport layer and the light-emitting layer are sequentially deposited on the semi-finished device; when the prepared light-emitting diode is a reverse light-emitting diode, the light-emitting layer, the hole transport layer.
其中，本申请中的半成品器件可以包括衬底、电极，也可以包括衬底、电极和功能层或者表面沉积有电极和功能层的半成品器件。此处所提及的电极可以为阴极也可以为阳极；其根据所制备的发光二极管的类型进行调整；此处所提及的功能层可以包括空穴注入层，也可以包括电子注入层或电子传输层。Wherein, the semi-finished device in this application may include a substrate, an electrode, or may include a substrate, an electrode, and a functional layer, or a semi-finished device with electrodes and a functional layer deposited on its surface. The electrode mentioned here can be a cathode or an anode; it is adjusted according to the type of light-emitting diode prepared; the functional layer mentioned here can include a hole injection layer, or an electron injection layer or an electron injection layer. transport layer.
在一些实施例中，空穴传输层利用含有空穴传输材料和导热材料的溶液来沉积；发光层利用含有发光材料的溶液沉积。In some embodiments, the hole transport layer is deposited using a solution containing a hole transport material and a thermally conductive material; the light emitting layer is deposited using a solution containing a light emitting material.
在一些实施例中，空穴传输层由空穴传输材料和导热材料形成，即空穴传输材料和导热材料形成空穴传输层这一混合材料体。In some embodiments, the hole transport layer is formed of a hole transport material and a thermally conductive material, ie, the hole transport material and the thermally conductive material form a mixed material body of the hole transport layer.
在一些实施例中，空穴传输层包括空穴传输膜层和导热修饰层；空穴传输膜层的材料由空穴传输材料形成；导热修饰层由导热材料形成；导热修饰层位于空穴传输膜层与发光层之间；即全部导热材料在空穴传输层的靠近发光层的一侧形成导热修饰层这一独立材料体。In some embodiments, the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the material of the hole transport film layer is formed by a hole transport material; the thermally conductive modification layer is formed by a thermally conductive material; the thermally conductive modification layer is located in the hole transport Between the film layer and the light-emitting layer; that is, all the heat-conducting materials form an independent material body of a heat-conducting modification layer on the side of the hole-transporting layer close to the light-emitting layer.
在一些实施例中，空穴传输层包括空穴传输膜层和导热修饰层；空穴传输膜层的材料由空穴传输材料和导热材料形成；导热修饰层由导热材料形成；导热修饰层位于空穴传输膜层与发光层之间；即部分导热材料在空穴传输层的靠近发光层的一侧形成导热修饰层这一独立材料体，剩余部分导热材料掺杂在空穴传输膜层中，形成空穴传输膜层这一混合材料体。In some embodiments, the hole transport layer includes a hole transport film layer and a thermally conductive modification layer; the material of the hole transport film layer is formed by a hole transport material and a thermally conductive material; the thermally conductive modification layer is formed by a thermally conductive material; the thermally conductive modification layer is located at Between the hole transport film layer and the light-emitting layer; that is, part of the heat-conducting material forms an independent material body of a heat-conducting modification layer on the side of the hole-transport layer close to the light-emitting layer, and the remaining part of the heat-conducting material is doped in the hole transport film layer , forming the mixed material body of the hole transport film layer.
需要说明的是，本申请中的在半成品器件上层叠形成空穴传输膜层、导热修饰层、发光层是指在半成品器件的表面形成层叠设置的空穴传输层、导热修饰层、发光层，其对空穴传输层、导热修饰层、发光层的形成顺序不做限定，空穴传输层、导热修饰层、发光层的形成顺序根据所制备的发光二极管的类型进行调整。It should be noted that, in the present application, forming a hole transport layer, a thermally conductive modification layer, and a light-emitting layer on a semi-finished device refers to forming a layered hole transport layer, a heat-conductive modification layer, and a light-emitting layer on the surface of a semi-finished device. There is no limitation on the formation order of the hole transport layer, the thermally conductive modification layer, and the light-emitting layer, and the formation order of the hole transport layer, the heat-conductive modification layer, and the light-emitting layer can be adjusted according to the type of the light-emitting diode to be prepared.
当所制备的发光二极管为正置发光二极管时，在半成品器件上依次沉积空穴传输层、导热修饰层、发光层；当所制备的发光二极管为反置发光二极管时，在半成品器件上依次沉积发光层、导热修饰层、空穴传输层。导热修饰层间接沉积或者直接沉积在空穴传输层或发光层的表面，即导热修饰层与空穴传输膜层之间、发光层与导热修饰层之间可以设置其他功能层。其中，本申请中的半成品器件可以包括衬底、电极，也可以包括衬底、电极和功能层或者表面沉积有电极和功能层的半成品器件。此处所提及的电极可以为阴极也可以为阳极；其根据所制备的发光二极管的类型进行调整；此处所提及的功能层可以包括空穴注入层，也可以包括电子注入层或电子传输层。When the prepared light-emitting diode is a positive light-emitting diode, a hole transport layer, a thermally conductive modification layer, and a light-emitting layer are sequentially deposited on the semi-finished device; when the prepared light-emitting diode is a reverse light-emitting diode, the light-emitting layer is sequentially deposited on the semi-finished device , thermally conductive modification layer, hole transport layer. The thermally conductive modification layer is deposited indirectly or directly on the surface of the hole transport layer or the light-emitting layer, that is, other functional layers can be arranged between the heat-conductive modification layer and the hole-transport film layer, and between the light-emitting layer and the thermally conductive modification layer. Wherein, the semi-finished device in this application may include a substrate, an electrode, or may include a substrate, an electrode, and a functional layer, or a semi-finished device with electrodes and a functional layer deposited on its surface. The electrode mentioned here can be a cathode or an anode; it is adjusted according to the type of light-emitting diode prepared; the functional layer mentioned here can include a hole injection layer, or an electron injection layer or an electron injection layer. transport layer.
在一些实施例中，空穴传输膜层、导热修饰层、发光层分别利用对应的包括了空穴传输材料、导热材料、发光材料的溶液来沉积。In some embodiments, the hole transport film layer, the heat-conducting modification layer, and the light-emitting layer are respectively deposited using corresponding solutions including hole-transport materials, heat-conducting materials, and light-emitting materials.
在一些实施例中，导热修饰层利用空心纳米材料浓度为3～10mg/mL的溶液沉积得到。In some embodiments, the thermally conductive modification layer is deposited by using a hollow nanomaterial solution with a concentration of 3-10 mg/mL.
在一些实施例中，导热修饰层利用浓度分别为3～10mg/mL的空心纳米材料、空穴传输材料形成的溶液沉积得到。In some embodiments, the thermally conductive modification layer is deposited by using a solution formed of hollow nanomaterials and hole transport materials with a concentration of 3-10 mg/mL, respectively.
在一些实施例中，用于形成导热修饰层的溶液的旋涂时间为30s～120s，退火时间为10～30min。In some embodiments, the spin-coating time of the solution used to form the thermally conductive modification layer is 30 s-120 s, and the annealing time is 10-30 min.
需要说明的是，本申请中含有空穴传输材料、导热材料、发光材料的溶液沉积在半成品器件上的方法可以为旋涂法、印刷法、打印法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇筑法、狭缝式涂布法、条状涂布法、电沉积法等本领域常用方法中的任一种。It should be noted that, in this application, the method of depositing the solution containing hole transport material, thermal conductive material and luminescent material on the semi-finished device can be spin coating method, printing method, printing method, dipping and pulling method, soaking method, spraying method , roll coating method, pouring method, slit coating method, strip coating method, electrodeposition method, etc. any one of the commonly used methods in this field.
在一些实施例中，导热修饰层可以通过以下方法制备：In some embodiments, the thermally conductive modification layer can be prepared by the following methods:
提供空心纳米材料、空穴传输材料浓度分别为3～10mg/mL的溶液，将含有空心纳米材料、空穴传输材料的溶液滴加在空穴传输膜层表面，并在 2000～4000rpm/min的转速下进行旋涂，旋涂15～120s后，在60～100℃下退火处理10～60min，得到导热修饰层。Provide hollow nanomaterials and hole transport material solutions with concentrations of 3 to 10 mg/mL, drop the solutions containing hollow nanomaterials and hole transport materials on the surface of the hole transport film, and Spin-coating is performed at a rotating speed, and after 15-120 seconds of spin-coating, annealing treatment is performed at 60-100° C. for 10-60 minutes to obtain a heat-conducting modified layer.
在一些实施例中，导热修饰层可以通过以下方法制备：In some embodiments, the thermally conductive modification layer can be prepared by the following methods:
提供空心纳米材料浓度为3～10mg/mL的溶液，将含有空心纳米材料的溶液滴加在空穴传输膜层表面，并在2000～4000rpm/min的转速下进行旋涂，旋涂15～120s后，在60～100℃下退火处理10～60min，得到导热修饰层。Provide a solution with a hollow nanomaterial concentration of 3-10mg/mL, drop the solution containing the hollow nanomaterial on the surface of the hole transport film, and spin-coat at a speed of 2000-4000rpm/min for 15-120s Afterwards, annealing treatment is performed at 60-100° C. for 10-60 minutes to obtain a thermally conductive modified layer.
在一些实施例中，当空心纳米材料为空心金属氧化物纳米颗粒时，空心金属氧化物纳米颗粒利用金属源和碱溶液进行水热反应得到。金属源选自于氯化镍、硝酸镍、乙酰丙酮镍、氯化钼、四水钼酸铵、硫钼酸铵、乙酰丙酮钼、氯化钨、乙酰丙酮钨、氯化铜、硝酸铜、硫酸铜以及其他可以提供金属离子的化合物中的一种或多种。碱溶液可以为氢氧化钠溶液、氢氧化钾溶液、氨水中的一种或多种。水热反应采用微波加热，其加热效果简便高效，反应体系受热均匀，得到的空心金属氧化物纳米颗粒粒径较为均匀。In some embodiments, when the hollow nanomaterial is a hollow metal oxide nanoparticle, the hollow metal oxide nanoparticle is obtained by performing a hydrothermal reaction with a metal source and an alkali solution. The metal source is selected from nickel chloride, nickel nitrate, nickel acetylacetonate, molybdenum chloride, ammonium molybdate tetrahydrate, ammonium thiomolybdate, molybdenum acetylacetonate, tungsten chloride, tungsten acetylacetonate, copper chloride, copper nitrate, One or more of copper sulfate and other compounds that can provide metal ions. The alkali solution can be one or more of sodium hydroxide solution, potassium hydroxide solution, and ammonia water. The hydrothermal reaction adopts microwave heating, the heating effect is simple and efficient, the reaction system is evenly heated, and the particle size of the obtained hollow metal oxide nanoparticles is relatively uniform.
在一些实施例中，空心金属氧化物纳米颗粒的制备步骤包括：In some embodiments, the preparation steps of hollow metal oxide nanoparticles include:
提供碱溶液和含有金属源的前驱体溶液A；Provide an alkaline solution and a precursor solution A containing a metal source;
将碱溶液与前驱体溶液A混合，反应，得到溶液B；Mix the alkali solution with the precursor solution A and react to obtain solution B;
将溶液B微波加热，反应得到空心金属氧化物纳米颗粒。The solution B is heated by microwave to react to obtain hollow metal oxide nanoparticles.
在一些实施例中，将得到的空心金属氧化物纳米颗粒利用溶剂分散后再分离得到粒径为15～50nm的空心金属氧化物纳米颗粒。其中，分散所采用的溶剂可以为乙二醇、丙三醇、DMF、DMSO中的一种或多种；其中，分离可以采用超速离心法、膜分离法等本领域常用方法中的任一种。In some embodiments, the obtained hollow metal oxide nanoparticles are dispersed with a solvent and then separated to obtain hollow metal oxide nanoparticles with a particle size of 15-50 nm. Wherein, the solvent adopted for dispersing can be one or more in ethylene glycol, glycerol, DMF, DMSO; Wherein, separation can adopt any one in the commonly used method in this field such as ultracentrifugation method, membrane separation method .
在一些实施例中，碱溶液的溶质与金属源的摩尔比为1～2：1。In some embodiments, the molar ratio of the solute to the metal source in the alkaline solution is 1˜2:1.
在一些实施例中，碱溶液通过滴加的方式加入前驱体溶液A中，并在滴加的过程中持续搅拌。In some embodiments, the alkaline solution is added dropwise to the precursor solution A, and the stirring is continued during the dropwise addition.
在一些实施例中，前驱体溶液A的溶剂为有机溶剂，其中有机溶剂可以选自于乙二醇、丙三醇、DMF、DMSO中的一种或多种。In some embodiments, the solvent of the precursor solution A is an organic solvent, wherein the organic solvent can be selected from one or more of ethylene glycol, glycerol, DMF, and DMSO.
在一些实施例中，微波加热温度为120～240℃，加热时间为10～60min。In some embodiments, the microwave heating temperature is 120-240° C., and the heating time is 10-60 minutes.
在一些实施例中，空心金属氧化物纳米颗粒的分散过程中，分散采用超声波分散，其分散时间为10～120min，使其分散效果更佳，有利于获得粒径较小 且均一的空心金属氧化物纳米颗粒。In some embodiments, during the dispersion process of hollow metal oxide nanoparticles, ultrasonic dispersion is used for dispersion, and the dispersion time is 10 to 120 minutes, so that the dispersion effect is better, and it is beneficial to obtain smaller and uniform hollow metal oxide nanoparticles. matter nanoparticles.
在一些实施例中，空心金属氧化物纳米颗粒的分离过程中，采用超速离心法分离，其转速为4000～12000rpm。In some embodiments, during the separation process of the hollow metal oxide nanoparticles, ultracentrifugation is used for separation, and the rotation speed is 4000-12000 rpm.
为使本申请上述实施细节和操作能清楚地被本领域技术人员理解，以及本申请实施例对应的发光二极管的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。In order to make the above-mentioned implementation details and operations of the present application clearly understood by those skilled in the art, and to realize the remarkable improvement of the performance of the light-emitting diodes corresponding to the embodiments of the present application, the above-mentioned technical solutions are exemplified below through multiple embodiments.
实施例1Example 1
空心氧化镍纳米颗粒20的制备，具体包括以下步骤：The preparation of hollow nickel oxide nanoparticles 20 specifically comprises the following steps:
S1：将六水合硝酸镍超声溶解分散于乙二醇中，形成0.2mol/L前驱体溶液A；S1: Ultrasonic dissolution and dispersion of nickel nitrate hexahydrate in ethylene glycol to form a 0.2mol/L precursor solution A;
S2：将浓氨水加入至去离子水当中，形成氨浓度为2mol/L的碱溶液；按照金属源与氨的摩尔比为1:1.25的比例将碱溶液滴加到前驱体溶液A中，搅拌1小时，得到溶液B。S2: Add concentrated ammonia water to deionized water to form an alkali solution with an ammonia concentration of 2mol/L; add the alkali solution dropwise to the precursor solution A according to the ratio of the metal source to ammonia molar ratio of 1:1.25, and stir After 1 hour, solution B was obtained.
S3：将溶液B转移至反应釜中，微波加热220℃，加热20min，得到空心氧化镍纳米颗粒20，分散于乙醇中。S3: Transfer the solution B to a reaction kettle, heat it with microwave at 220° C. for 20 minutes, and obtain hollow nickel oxide nanoparticles 20 , which are dispersed in ethanol.
S4：将上述空心氧化镍纳米颗20溶液超声处理2h，然后以6000rpm/min的转速离心，收集上层溶液，重复离心两次，得到粒径为15～50nm、壁厚5～25nm的空心氧化镍纳米颗粒20，参阅图3，该空心氧化镍纳米颗粒20为氧化镍纳米晶201形成的空心纳米球。S4: ultrasonically treat the above-mentioned hollow nickel oxide nanoparticle 20 solution for 2 hours, then centrifuge at a speed of 6000rpm/min, collect the upper layer solution, and repeat the centrifugation twice to obtain hollow nickel oxide with a particle size of 15-50nm and a wall thickness of 5-25nm Nanoparticles 20 , referring to FIG. 3 , the hollow nickel oxide nanoparticles 20 are hollow nanospheres formed by nickel oxide nanocrystals 201 .
以上述得到的空心氧化镍纳米颗粒20为导热修饰层的材料，并制备基于导热修饰层的量子点发光二极管，其具体制备步骤如下：Using the hollow nickel oxide nanoparticles 20 obtained above as the material of the thermally conductive modification layer, and preparing a quantum dot light-emitting diode based on the thermally conductive modification layer, the specific preparation steps are as follows:
I：提供ITO基板I: Provide ITO substrate
首先，提供衬底101，并在衬底101上沉积ITO作为底电极102，得到ITO基板，将ITO基板用清洁剂清洗，初步去除表面存在的污渍，随后依次在去离子水、异丙醇、丙酮、去离子水中分别超声清洗20min，以除去表面存在的杂质，最后用高纯氮气吹干，即可得到ITO基板；First, a substrate 101 is provided, and ITO is deposited on the substrate 101 as the bottom electrode 102 to obtain an ITO substrate. The ITO substrate is cleaned with a cleaning agent to initially remove the stains on the surface, and then deionized water, isopropanol, and Ultrasonic cleaning in acetone and deionized water for 20 minutes respectively to remove impurities on the surface, and finally drying with high-purity nitrogen to obtain the ITO substrate;
II：空穴传输层103的制备II: Preparation of hole transport layer 103
将ITO基板固定在匀胶机上，用配制好的TFB空穴传输材料的溶液在ITO基板上旋涂成膜，并退火处理，完成空穴传输层103制备；The ITO substrate is fixed on the coater, and the solution of the prepared TFB hole transport material is spin-coated on the ITO substrate to form a film, and annealed to complete the preparation of the hole transport layer 103;
III：导热修饰层104的制备III: Preparation of thermally conductive modification layer 104
将完成空穴传输层103制备的基片固定在匀胶机上，用配制好的空心氧化镍纳米颗粒20浓度为8mg/mL的溶液在基片上以3000rpm/min的转速旋涂成膜，并在80℃退火处理10min，完成导热修饰层104的制备；The substrate prepared by the hole transport layer 103 was fixed on a homogenizer, and the prepared hollow nickel oxide nanoparticles 20 was spin-coated at a speed of 3000 rpm/min to form a film on the substrate with a solution having a concentration of 8 mg/mL. Annealing at 80° C. for 10 minutes to complete the preparation of the thermally conductive modification layer 104 ;
IV：量子点发光层105制备IV: Preparation of Quantum Dot Light-emitting Layer 105
将完成导热修饰层104制备的基片固定在匀胶机上，用配制好的CdSe溶液在基片上旋涂成膜，并退火处理，完成量子点发光层105制备；Fix the substrate prepared by the thermally conductive modification layer 104 on a glue spreader, spin-coat the substrate with the prepared CdSe solution to form a film, and anneal to complete the preparation of the quantum dot light-emitting layer 105;
V：电子传输层106制备V: Preparation of electron transport layer 106
将完成量子点发光层105制备的基片固定在匀胶机上，用配制好的氧化锌纳米颗粒的溶液在基片上旋涂成膜，并退火处理，完成电子传输层106制备；Fix the substrate prepared by the quantum dot light-emitting layer 105 on a homogenizer, spin-coat the substrate with a prepared solution of zinc oxide nanoparticles to form a film, and anneal to complete the preparation of the electron transport layer 106;
VI:顶电极107制备VI: Preparation of top electrode 107
将沉积完各功能层的基片置于蒸镀仓中通过掩膜板热蒸镀一层金属银作为顶电极107，得到量子点发光二极管A，参阅图2。The substrate on which each functional layer has been deposited is placed in an evaporation chamber and a layer of metallic silver is thermally evaporated through a mask plate as the top electrode 107 to obtain a quantum dot light-emitting diode A, see FIG. 2 .
实施例2Example 2
空心三氧化钼纳米颗粒的制备，具体包括以下步骤：The preparation of hollow molybdenum trioxide nanoparticles specifically comprises the following steps:
S1：将四水合钼酸铵超声溶解分散于乙醇中，形成0.2mol/L前驱体溶液A；S1: Ultrasonic dissolution and dispersion of ammonium molybdate tetrahydrate in ethanol to form a 0.2mol/L precursor solution A;
S2：将浓氨水加入至去离子水当中，形成氨浓度为2mol/L的碱溶液；按照金属源与氨的摩尔比为1:1的比例将碱溶液滴加到前驱体溶液A中，搅拌1小时，得到溶液B。S2: Add concentrated ammonia water to deionized water to form an alkali solution with an ammonia concentration of 2mol/L; add the alkali solution dropwise to the precursor solution A according to the molar ratio of the metal source to ammonia at a ratio of 1:1, and stir After 1 hour, solution B was obtained.
S3：将溶液B转移至反应釜中，微波加热180℃，加热30min，得到空心三氧化钼纳米颗粒，分散于乙醇中。S3: Transfer the solution B to a reaction kettle, heat it with microwave at 180° C. for 30 minutes, and obtain hollow molybdenum trioxide nanoparticles, which are dispersed in ethanol.
S4：将上述空心三氧化钼纳米颗溶液超声处理2h，然后以6000rpm/min的转速离心，收集上层溶液，重复离心两次，得到空心三氧化钼纳米颗粒。S4: ultrasonically treat the above hollow molybdenum trioxide nanoparticle solution for 2 hours, then centrifuge at a speed of 6000 rpm/min, collect the upper layer solution, and repeat the centrifugation twice to obtain hollow molybdenum trioxide nanoparticle.
将空心三氧化钼纳米颗粒配制成浓度为5mg/mL的溶液，并采用与实施例1中量子点发光二极管A的制备方法相同的方法将本实施例制备得到的空心三氧化钼纳米颗粒作为导热修饰层的材料制备得到量子点发光二极管B。The hollow molybdenum trioxide nanoparticles were formulated into a solution with a concentration of 5 mg/mL, and the hollow molybdenum trioxide nanoparticles prepared in this example were used as the heat-conducting The material of the modification layer is prepared to obtain the quantum dot light-emitting diode B.
实施例3Example 3
空心三氧化钨纳米颗粒的制备，具体包括以下步骤：The preparation of hollow tungsten trioxide nanoparticles specifically comprises the following steps:
S1：将六氯化钨超声溶解分散于乙二醇中，形成0.2mol/L前驱体溶液A；S1: ultrasonically dissolve and disperse tungsten hexachloride in ethylene glycol to form a 0.2mol/L precursor solution A;
S2：将浓氨水加入至去离子水当中，形成氨浓度为2mol/L的碱溶液；按照金属源与氨的摩尔比为1:1.5的比例将碱溶液滴加到前驱体溶液A中，搅拌1小时，得到溶液B。S2: Add concentrated ammonia water to deionized water to form an alkali solution with an ammonia concentration of 2mol/L; add the alkali solution dropwise to the precursor solution A according to the ratio of the metal source to ammonia molar ratio of 1:1.5, and stir After 1 hour, solution B was obtained.
S3：将溶液B转移至反应釜中，微波加热200℃，加热20min，得到空心三氧化钼纳米颗粒，分散于乙醇中。S3: Transfer the solution B to a reaction kettle, heat it with microwave at 200° C. for 20 minutes, and obtain hollow molybdenum trioxide nanoparticles, which are dispersed in ethanol.
S4：将上述空心三氧化钨纳米颗溶液超声处理2h，然后以6000rpm/min的转速离心，收集上层溶液，重复离心两次，得到空心三氧化钼纳米颗粒。S4: The above hollow tungsten trioxide nanoparticle solution was sonicated for 2 hours, and then centrifuged at a speed of 6000 rpm/min to collect the upper layer solution, and the centrifugation was repeated twice to obtain hollow molybdenum trioxide nanoparticles.
将空心三氧化钨纳米颗粒配制成浓度为5mg/mL的溶液，并采用与实施例1中量子点发光二极管A的制备方法相同的方法将本实施例制备得到的空心三氧化钨纳米颗粒作为导热修饰层的材料制备得到量子点发光二极管C。The hollow tungsten trioxide nanoparticles were prepared into a solution with a concentration of 5 mg/mL, and the hollow tungsten trioxide nanoparticles prepared in this example were used as a heat-conducting The material of the modification layer is prepared to obtain the quantum dot light-emitting diode C.
实施例4Example 4
相较于实施例1，本实施例中空穴传输层的材料替换为CuO，量子点发光层的材料替换为InP，电子传输层的材料替换为SnO，其余材料与实施例1相同，并采用与实施例1中量子点发光二极管A的制备方法相同的方法将本实施例制备得到的空心三氧化钨纳米颗粒作为导热修饰层的材料制备得到量子点发光二极管D。Compared with Example 1, in this example, the material of the hole transport layer is replaced by CuO, the material of the quantum dot light-emitting layer is replaced by InP, the material of the electron transport layer is replaced by SnO, and the rest of the materials are the same as in Example 1, and adopt the same method as in Example 1. Quantum dot light-emitting diode A was prepared in the same method as in Example 1, and quantum dot light-emitting diode D was prepared by using the hollow tungsten trioxide nanoparticles prepared in this example as the material of the thermally conductive modification layer.
实施例5Example 5
相较于实施例1，本实施例中将粒径为15nm的空心氧化镍纳米颗粒，添加至空穴传输材料的溶液中，形成包含TFB空穴传输材料和8mg/mL的空心氧化镍纳米颗粒的复合溶液作为制备空穴传输层的溶液，其余材料与实施例1相同，并在实施例1的基础上去掉III：导热修饰层的制备这一步骤，其余步骤与实施例1中量子点发光二极管A的制备方法相同，制备得到量子点发光二极管E。Compared with Example 1, in this example, hollow nickel oxide nanoparticles with a particle size of 15 nm were added to the solution of the hole transport material to form hollow nickel oxide nanoparticles containing TFB hole transport material and 8 mg/mL As the solution for preparing the hole transport layer, the remaining materials are the same as in Example 1, and on the basis of Example 1, III: the step of preparation of the thermally conductive modification layer is removed, and the remaining steps are the same as in Example 1. The preparation method of diode A is the same, and quantum dot light-emitting diode E is prepared.
实施例6Example 6
相较于实施例1，本实施例中将粒径为30nm的空心氧化镍纳米颗粒，添加至空穴传输材料的溶液中，形成包含TFB空穴传输材料和8mg/mL的空心氧化镍纳米颗粒的复合溶液作为制备空穴传输层的溶液，其余材料与实施例1相同，并在实施例1的基础上去掉III：导热修饰层的制备这一步骤，其余步骤与实施例1中量子点发光二极管A的制备方法相同，制备得到量子点发光 二极管F。Compared with Example 1, in this example, hollow nickel oxide nanoparticles with a particle size of 30 nm were added to the solution of the hole transport material to form hollow nickel oxide nanoparticles containing TFB hole transport material and 8 mg/mL As the solution for preparing the hole transport layer, the remaining materials are the same as in Example 1, and on the basis of Example 1, III: the step of preparation of the thermally conductive modification layer is removed, and the remaining steps are the same as in Example 1. The preparation method of diode A is the same, and quantum dot light-emitting diode F is prepared.
实施例7Example 7
相较于实施例1，本实施例中导热修饰层的材料替换为直径为5nm的碳纳米管，其余材料与实施例1相同，并采用与实施例1中量子点发光二极管A的制备方法相同的方法制备得到量子点发光二极管G。Compared with Example 1, the material of the thermally conductive modification layer in this example is replaced by carbon nanotubes with a diameter of 5 nm, and the rest of the materials are the same as in Example 1, and the same preparation method as that of the quantum dot light-emitting diode A in Example 1 is adopted. Quantum dot light-emitting diode G was prepared by the method.
对比例1Comparative example 1
相较于实施例1，本对比例1中制备的量子点发光二极管去掉导热修饰层的制备，其余制备步骤与实施例1中量子点发光二极管的制备方法相同，得到量子点发光二极管DB1。Compared with Example 1, the quantum dot light-emitting diode prepared in this comparative example 1 was prepared without the thermally conductive modification layer, and the rest of the preparation steps were the same as the preparation method of the quantum dot light-emitting diode in Example 1 to obtain the quantum dot light-emitting diode DB1.
对比例2Comparative example 2
相较于实施例1，本对比例中制备的导热修饰层的材料采用粒径为15～50nm的常规氧化镍纳米颗粒(实心结构)，并采用与实施例1中量子点发光二极管A的制备方法相同的方法将常规氧化镍纳米颗粒作为导热修饰层的材料制备得到量子点发光二极管DB2。其中，常规氧化镍纳米颗粒购自于Sigma公司。Compared with Example 1, the material of the thermally conductive modification layer prepared in this comparative example adopts conventional nickel oxide nanoparticles (solid structure) with a particle size of 15-50 nm, and adopts the same method as that used in the preparation of quantum dot light-emitting diode A in Example 1. Method The same method was used to prepare the quantum dot light-emitting diode DB2 by using conventional nickel oxide nanoparticles as the material of the thermally conductive modification layer. Wherein, conventional nickel oxide nanoparticles were purchased from Sigma Company.
对比例3Comparative example 3
相较于实施例7，本对比例中空穴传输层的溶液中加入粒径为30nm的常规氧化镍纳米颗粒(实心结构)，替换空心氧化镍纳米颗粒；并采用与实施例7中量子点发光二极管G的制备方法相同的方法将常规氧化镍纳米颗粒作为导热材料制备得到量子点发光二极管DB3。其中，常规氧化镍纳米颗粒购自于Sigma公司。Compared with Example 7, conventional nickel oxide nanoparticles (solid structure) with a particle size of 30nm are added to the solution of the hole transport layer in this comparative example to replace the hollow nickel oxide nanoparticles; The method for preparing diode G is the same as that of using conventional nickel oxide nanoparticles as a heat-conducting material to obtain quantum dot light-emitting diode DB3. Wherein, conventional nickel oxide nanoparticles were purchased from Sigma Company.
将实施例1～9、对比例1～3制备得到的量子点发光二极管进行性能测试，其检测结果如表1所示：The quantum dot light-emitting diodes prepared in Examples 1-9 and Comparative Examples 1-3 were tested for performance, and the test results are shown in Table 1:
表1Table 1
从表1可以看出，本申请实施例1～7提供的发光二极管采用加入了导热材料(空心纳米材料)的空穴传输层或者采用了空穴传输膜层和导热修饰层复合的空穴传输层后，其发光二极管的发光区温度相较于空穴传输层未包含空心纳米材料(对比例1)的发光二极管有明显的下降，而发光二极管寿命相较于空穴传输层未包含空心纳米材料(对比例1)的发光二极管则明显延长。由此可见，空穴传输层中加入空心纳米材料能有效降低器件工况温度、改善高温对空穴传输层的损坏，提高器件寿命。从表1还可以看出，本申请实施例1～6提供的量子点发光二极管以空心金属氧化物纳米颗粒作为空穴传输层中的导热材料，其得到的量子点发光二极管不仅发光区域温度下降，且发光效率相较于空穴传输层未包含导热材料的量子点发光二极管也明显上升，由此可见，采用空心金属氧化物纳米颗粒作为导热材料可以有效降低器件工况温度，同时还能实现空穴传输层与发光层的电荷逐级传输，优化空穴传输层与发光层的能级匹配。此外，相较于金属氧化物纳米颗粒(对比例2～3)作为导热材料，本申请实施例1～7采用空心纳米材料作为导热材料，其散热效果更好。It can be seen from Table 1 that the light-emitting diodes provided in Examples 1 to 7 of the present application use a hole transport layer added with a thermally conductive material (hollow nanomaterial) or a hole transport layer combined with a hole transport film layer and a thermally conductive modification layer. After layering, the temperature of the light-emitting region of the light-emitting diode is significantly lower than that of the light-emitting diode whose hole transport layer does not contain hollow nanomaterials (comparative example 1), and the life of the light-emitting diode is compared with that of the hole transport layer that does not contain hollow nanomaterials. The LED of the material (Comparative Example 1) is significantly elongated. It can be seen that the addition of hollow nanomaterials to the hole transport layer can effectively reduce the operating temperature of the device, improve the damage to the hole transport layer caused by high temperature, and increase the life of the device. It can also be seen from Table 1 that the quantum dot light-emitting diodes provided in Examples 1 to 6 of the present application use hollow metal oxide nanoparticles as the heat-conducting material in the hole transport layer, and the obtained quantum dot light-emitting diodes not only reduce the temperature of the light-emitting region , and the luminous efficiency is also significantly higher than that of quantum dot light-emitting diodes that do not contain thermally conductive materials in the hole transport layer. It can be seen that the use of hollow metal oxide nanoparticles as thermally conductive materials can effectively reduce the operating temperature of the device, and at the same time achieve The charges of the hole transport layer and the light-emitting layer are transported step by step, and the energy level matching between the hole transport layer and the light-emitting layer is optimized. In addition, compared with metal oxide nanoparticles (Comparative Examples 2-3) as the heat-conducting material, Examples 1-7 of the present application use hollow nano-materials as the heat-conducting material, and the heat dissipation effect is better.
以上对本申请实施例所提供的一种发光二极管及其制备方法进行了详细介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本申请的方法及其核心思想；同时，对于本领域 的技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本申请的限制。A light-emitting diode provided by the embodiment of the present application and its preparation method have been introduced in detail above. In this paper, the principle and implementation of the present application have been explained by using specific examples. The description of the above embodiment is only used to help understand the present application. The method of application and its core idea; at the same time, for those skilled in the art, according to the idea of this application, there will be changes in the specific implementation and scope of application. In summary, the content of this specification should not be understood as Limitations on this Application.
Claims (20)
- 一种发光二极管，其中，包括：A light emitting diode, comprising:层叠设置的空穴传输层和发光层，所述空穴传输层的材料包括空穴传输材料和导热材料；所述导热材料为空心纳米材料。A hole transport layer and a light-emitting layer are stacked, and the material of the hole transport layer includes a hole transport material and a thermally conductive material; the thermally conductive material is a hollow nano material.
- 根据权利要求1所述的发光二极管，其中，所述空穴传输材料与所述导热材料形成混合材料体。The light emitting diode according to claim 1, wherein the hole transport material and the thermally conductive material form a mixed material body.
- 根据权利要求1所述的发光二极管，其中，至少部分所述导热材料在所述空穴传输层的靠近所述发光层的一侧形成独立材料体。The light emitting diode according to claim 1, wherein at least part of the thermally conductive material forms an independent material body on a side of the hole transport layer close to the light emitting layer.
- 根据权利要求3所述的发光二极管，其中，所述空穴传输层包括空穴传输膜层和导热修饰层；所述空穴传输膜层由所述空穴传输材料形成；所述导热修饰层由所述导热材料形成；The light emitting diode according to claim 3, wherein the hole transport layer comprises a hole transport film layer and a thermally conductive modification layer; the hole transport film layer is formed of the hole transport material; the thermally conductive modification layer formed from said thermally conductive material;所述导热修饰层设置于所述空穴传输膜层与所述发光层之间。The thermally conductive modification layer is disposed between the hole transport film layer and the light emitting layer.
- 根据权利要求1所述的发光二极管，其中，所述空心纳米材料的导热系数在2W/m -1·K -1以上。 The light emitting diode according to claim 1, wherein the thermal conductivity of the hollow nanomaterial is above 2W/m -1 ·K -1 .
- 根据权利要求1所述的发光二极管，其中，所述空心纳米材料的空穴迁移率在1×10 -5cm 2·V -1·s -1以上。 The light emitting diode according to claim 1, wherein the hole mobility of the hollow nanomaterial is above 1×10 -5 cm 2 ·V -1 ·s -1 .
- 根据权利要求1所述的发光二极管，其中，所述空心纳米材料为空心金属氧化物纳米颗粒。The light emitting diode according to claim 1, wherein the hollow nanomaterials are hollow metal oxide nanoparticles.
- 根据权利要求1所述的发光二极管，其中，所述空心金属氧化物纳米颗粒选自NiO y、MoO y、WO y、CuO y中的一种或多种，其中，1≤y≤3。 The light emitting diode according to claim 1, wherein the hollow metal oxide nanoparticles are selected from one or more of NiO y , MoO y , WO y , CuO y , wherein 1≤y≤3.
- 根据权利要求1所述的发光二极管，其中，所述空心纳米材料的粒径为10～50nm。The light emitting diode according to claim 1, wherein the particle size of the hollow nanomaterial is 10-50 nm.
- 根据权利要求4所述的发光二极管，其中，所述导热修饰层的厚度为20～60nm。The light emitting diode according to claim 4, wherein the thickness of the thermally conductive modification layer is 20-60 nm.
- 根据权利要求1所述的发光二极管，其中，所述发光二极管还包括电子传输层；所述电子传输层设置于所述发光层的远离所述空穴传输层的一侧；所述电子传输层的载流子迁移率高于所述空穴传输层的载流子迁移率。The light emitting diode according to claim 1, wherein the light emitting diode further comprises an electron transport layer; the electron transport layer is disposed on a side of the light emitting layer away from the hole transport layer; the electron transport layer The carrier mobility of is higher than that of the hole transport layer.
- 根据权利要求11所述的发光二极管，其中，The light emitting diode according to claim 11, wherein,所述空穴传输材料选自有机空穴传输材料或无机空穴传输材料；其中，所述有机空穴传输材料选自于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、聚乙烯咔唑、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)、4,4',4'-三(咔唑-9-基)三苯胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺、N,N'-二苯基-N,N’-(1-萘基)-1,1'-联苯-4,4’-二胺、掺杂石墨烯、非掺杂石墨烯、C60中的一种或多种；所述无机空穴传输材料选自于掺杂或非掺杂金属氧化物、掺杂或非掺杂金属硫化物、掺杂或非掺杂金属硒化物，所述非掺杂金属氧化物选自ZnO、MoO x、VO x、WO x、CrO x、CuO、NiO x中的一种或多种，所述非掺杂金属硫化物选自MoS x、WS x、CuS x、MoS x中的一种或多种，所述非掺杂金属硒化物选自MoSe x、WSe x、的一种或多种，其中1≤x≤3；所述掺杂金属氧化物包括所述非掺杂金属氧化物和掺杂元素，所述掺杂金属硫化物包括所述非掺杂金属硫化物和掺杂元素，所述掺杂金属硒化物包括所述非掺杂金属硒化物和掺杂元素，所述掺杂元素选自铝、镓、铟、镁、铜、钇、钴、锰、镉、锂中的一种或多种； The hole-transporting material is selected from organic hole-transporting materials or inorganic hole-transporting materials; wherein, the organic hole-transporting material is selected from poly(9,9-dioctylfluorene-CO-N-(4- Butylphenyl) diphenylamine), polyvinylcarbazole, poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9- Dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine), 4,4',4'-tris(carbazol-9-yl)triphenylamine, 4,4'- Bis(9-carbazole)biphenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, doped graphene, non-doped graphene, C60 One or more of; the inorganic hole transport material is selected from doped or non-doped metal oxide, doped or non-doped metal sulfide, doped or non-doped metal selenide, the non-doped The doped metal oxide is selected from one or more of ZnO, MoO x , VO x , WO x , CrO x , CuO, NiO x , and the non-doped metal sulfide is selected from MoS x , WS x , CuS One or more of x , MoS x , the non-doped metal selenide is selected from one or more of MoS x , WS x , wherein 1≤x≤3; the doped metal oxide includes The non-doped metal oxide and doping element, the doped metal sulfide includes the non-doped metal sulfide and the doping element, the doped metal selenide includes the non-doped metal selenide And a doping element, the doping element is selected from one or more of aluminum, gallium, indium, magnesium, copper, yttrium, cobalt, manganese, cadmium, lithium;所述电子传输层的材料选自非掺杂金属氧化物或掺杂金属氧化物，其中，所述非掺杂金属氧化物选自于ZnO、TiO 2、SnO、SnO 2、MgO、Ta 2O 3中的一种或多种，所述掺杂金属氧化物选自于铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌、铜掺杂氧化锌、钇掺杂氧化锌、钴掺杂氧化锌、锰掺杂氧化锌、镉掺杂氧化锌、锂掺杂氧化锌、铝掺杂氧化钛、镓掺杂氧化钛、铟掺杂氧化钛、镁掺杂氧化钛、铜掺杂氧化钛、钇掺杂氧化钛、钴掺杂氧化钛、锰掺杂氧化钛、镉掺杂氧化钛、锂掺杂氧化钛、锌掺杂氧化锡、铝掺杂氧化镁中的一种或多种； The material of the electron transport layer is selected from non-doped metal oxides or doped metal oxides, wherein the non-doped metal oxides are selected from ZnO, TiO 2 , SnO, SnO 2 , MgO, Ta 2 O One or more of 3 , the doped metal oxide is selected from aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide, copper doped zinc oxide, yttrium Doped zinc oxide, cobalt doped zinc oxide, manganese doped zinc oxide, cadmium doped zinc oxide, lithium doped zinc oxide, aluminum doped titanium oxide, gallium doped titanium oxide, indium doped titanium oxide, magnesium doped Titanium oxide, copper-doped titanium oxide, yttrium-doped titanium oxide, cobalt-doped titanium oxide, manganese-doped titanium oxide, cadmium-doped titanium oxide, lithium-doped titanium oxide, zinc-doped tin oxide, aluminum-doped magnesium oxide one or more of所述发光层的材料选自无机材料、小分子有机材料、高分子有机材料和量子点材料中的一种或多种，所述无机材料选自ZnS:Mn、ZnS:Tb、ZnS:Tb/CdS、SiO 2:Ge、SiO 2:Er、SrS:Ce、CaGa 2S 4:Ce、SrGa 2S 4:Ce、SrS:Cu、GaN、ZnS:Tm、Zn 2SiO 2:Ca中的一种或多种，所述小分子有机材料选自4-(二腈甲基)-2-丁基-6-(1,1,7,7-四甲基久洛呢啶-9-乙烯基)-4H-吡喃、9,10-二(β-萘基)蒽、4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯或8-羟基喹啉铝中的一种或多种，所述高分子有机材料选自聚对苯乙烯撑、聚噻吩、聚苯胺、聚咔唑中的一种或多种，所述量 子点材料选自CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe中的一种或多种； The material of the light-emitting layer is selected from one or more of inorganic materials, small molecule organic materials, polymer organic materials and quantum dot materials, and the inorganic materials are selected from ZnS:Mn, ZnS:Tb, ZnS:Tb/ One of CdS, SiO 2 :Ge, SiO 2 :Er, SrS:Ce, CaGa 2 S 4 :Ce, SrGa 2 S 4 :Ce, SrS:Cu, GaN, ZnS:Tm, Zn 2 SiO 2 :Ca or more, the small molecule organic material is selected from 4-(dinitrile methyl)-2-butyl-6-(1,1,7,7-tetramethyljulonesidine-9-vinyl) -4H-pyran, 9,10-bis(β-naphthyl)anthracene, 4,4'-bis(9-ethyl-3-carbazolevinyl)-1,1'-biphenyl or 8-hydroxyl One or more of quinoline aluminum, the polymer organic material is selected from one or more of polyphenylene, polythiophene, polyaniline, polycarbazole, and the quantum dot material is selected from CdS , CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe one or more;所述发光二极管还包括阴极和阳极，所述阳极设置在所述空穴传输层远离所述发光层一侧，所述阴极设置在所述电子传输层远离所述发光层一侧，其中，所述阳极的材料选自ITO、FTO、ZTO中的一种或多种，所述阴极的材料选自Al、Ag、Au、Cu、Mo及其合金中的一种或多种。The light-emitting diode further includes a cathode and an anode, the anode is arranged on the side of the hole transport layer away from the light-emitting layer, and the cathode is arranged on the side of the electron-transport layer away from the light-emitting layer, wherein the The material of the anode is selected from one or more of ITO, FTO, ZTO, and the material of the cathode is selected from one or more of Al, Ag, Au, Cu, Mo and their alloys.
- 一种发光二极管的制备方法，其中，包括：A method of manufacturing a light emitting diode, comprising:提供半成品器件；Provide semi-finished devices;在所述半成品器件上形成层叠的空穴传输层和发光层；forming a laminated hole transport layer and light emitting layer on the semi-finished device;其中，所述空穴传输层的材料包括空穴传输材料和导热材料，所述导热材料为空心纳米材料。Wherein, the material of the hole transport layer includes a hole transport material and a thermally conductive material, and the thermally conductive material is a hollow nanomaterial.
- 根据权利要求13所述的发光二极管的制备方法，其中，所述空穴传输材料与所述导热材料形成混合材料体。The method for manufacturing a light emitting diode according to claim 13, wherein the hole transport material and the heat conducting material form a mixed material body.
- 根据权利要求13所述的发光二极管的制备方法，其中，至少部分所述导热材料在所述空穴传输层的靠近所述发光层的一侧形成独立材料体。The method for manufacturing a light emitting diode according to claim 13, wherein at least part of the thermally conductive material forms an independent material body on a side of the hole transport layer close to the light emitting layer.
- 根据权利要求15所述的发光二极管的制备方法，其中，所述空穴传输层包括层叠设置的空穴传输膜层和导热修饰层，所述空穴传输膜层由所述空穴传输材料形成；所述导热修饰层由所述导热材料形成；所述导热修饰层位于所述空穴传输膜层与所述发光层之间。The method for preparing a light-emitting diode according to claim 15, wherein the hole transport layer comprises a hole transport film layer and a thermally conductive modification layer stacked, and the hole transport film layer is formed of the hole transport material ; The thermally conductive modification layer is formed by the thermally conductive material; The thermally conductive modification layer is located between the hole transport film layer and the light-emitting layer.
- 根据权利要求16所述的发光二极管的制备方法，其中，制备所述导热修饰层的步骤包括：The method for preparing a light emitting diode according to claim 16, wherein the step of preparing the thermally conductive modification layer comprises:提供空心纳米材料的溶液，将所述空心纳米材料的溶液设置到所述空穴传输膜层或所述发光层的表面，形成所述导热修饰层；其中，所述空心纳米材料的溶液的浓度为3～10mg/mL。A solution of hollow nanomaterials is provided, and the solution of hollow nanomaterials is set on the surface of the hole transport film layer or the light-emitting layer to form the thermally conductive modification layer; wherein, the concentration of the solution of hollow nanomaterials 3~10mg/mL.
- 根据权利要求17所述的发光二极管的制备方法，其中，所述将所述空心纳米材料的溶液设置到所述空穴传输膜层的表面之后，还包括：在60～100℃下退火处理10～60min。The method for preparing a light-emitting diode according to claim 17, wherein, after the solution of the hollow nanomaterial is placed on the surface of the hole transport film layer, further comprising: annealing at 60-100° C. for 10 ~60min.
- 根据权利要求16所述的发光二极管的制备方法，其中，所述发光二 极管为正置发光二极管，所述半成品器件包括阳极；The method for preparing a light-emitting diode according to claim 16, wherein the light-emitting diode is a positive light-emitting diode, and the semi-finished device includes an anode;所述在所述半成品器件上形成层叠的空穴传输层和发光层包括：在所述半成品器件上依次形成所述空穴传输膜层、所述导热修饰层和所述发光层；The forming the stacked hole transport layer and the light-emitting layer on the semi-finished device includes: sequentially forming the hole transport layer, the thermally conductive modification layer and the light-emitting layer on the semi-finished device;所述在所述半成品器件上形成层叠的空穴传输层和发光层之后，还包括：在所述发光层上形成阴极。After forming the stacked hole transport layer and light-emitting layer on the semi-finished device, the method further includes: forming a cathode on the light-emitting layer.
- 根据权利要求16所述的发光二极管的制备方法，其中，所述发光二极管为倒置发光二极管，所述半成品器件包括阴极；The method for preparing a light-emitting diode according to claim 16, wherein the light-emitting diode is an inverted light-emitting diode, and the semi-finished device includes a cathode;所述在所述半成品器件上形成层叠的空穴传输层和发光层包括：在所述半成品器件上依次形成所述发光层、所述导热修饰层和所述空穴传输膜层；The forming the laminated hole transport layer and the light-emitting layer on the semi-finished device includes: sequentially forming the light-emitting layer, the thermally conductive modification layer and the hole transport film layer on the semi-finished device;所述在所述半成品器件上形成层叠的空穴传输层和发光层之后，还包括：在所述空穴传输膜层上形成阴极。After forming the stacked hole transport layer and light-emitting layer on the semi-finished device, the method further includes: forming a cathode on the hole transport film layer.
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| WO2020108073A1 (en) * | 2018-11-28 | 2020-06-04 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN111261793A (en) * | 2020-01-20 | 2020-06-09 | Tcl华星光电技术有限公司 | Display panel, preparation method thereof and display device |
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| CN103771470A (en) * | 2014-01-20 | 2014-05-07 | 绍兴文理学院 | Synthesis method for aluminium oxide nano hollow ball-in-ball |
| WO2020108073A1 (en) * | 2018-11-28 | 2020-06-04 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
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