CN113594381B - Light emitting device, method of manufacturing the same, and light emitting apparatus - Google Patents
Light emitting device, method of manufacturing the same, and light emitting apparatus Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a light-emitting device, a preparation method thereof and a light-emitting device. The light-emitting device comprises a cathode, an inorganic electron transport layer, a light-emitting layer and an anode which are arranged in a stacked manner; the inorganic electron transport layer is an n-type doping element doped zirconium dioxide layer, and the n-type doping element is selected from at least one of F, cl, br and I elements. The luminescent device takes the zirconium dioxide layer which has lower conduction band bottom energy level and is doped with n-type doping elements as an inorganic electron transmission layer, the zirconium dioxide layer is close to LUMO or conduction band bottom energy levels of other organic functional layers in the luminescent device, the electronic conductivity is good, the electron transmission of the luminescent device is facilitated, and the luminescent performance of the luminescent device is improved.
Description
Technical Field
The invention relates to the technical field of display and illumination, in particular to a light-emitting device, a preparation method thereof and a light-emitting device.
Background
Organic Light Emitting Diode (OLED) and quantum dot light emitting diode (QLED) display devices have been drawing attention and research in the business and academic circles due to their advantages of self-luminescence, flexibility, foldability, lightness, thinness, good shock resistance, large viewing angle, high sensitivity, and the like.
The structures of OLEDs and QLEDs can be divided into two types, right side up and down, where the down-side structure has some special advantages, such as: the bottom cathode and the n-channel TFT driving unit can be better combined, and the service life of the device has greater potential. Currently, in inverted structure OLEDs and QLEDs, n-type metal oxides (e.g., znO, tiO) 2 Etc.) are widely used as electron injection layer or electron transport layer materials because n-type metal oxides generally have excellent electron conductivity, stability, etc., which facilitates device structure design, device stability improvement, etc. However, most n-type metal oxides (e.g., znO, tiO) 2 Etc.) has a conduction band bottom level of about-4 eV to-4.5 eV, and although it contributes to ohmic contact with an electrode, it has a large electron barrier (usually, a large electron barrier between the Lowest Unoccupied Molecular Orbital (LUMO) level or the conduction band bottom level of an organic electron transport material, an organic light emitting material, a high energy quantum dot, etc. (i.e., a large electron barrier between the Lowest Unoccupied Molecular Orbital (LUMO) level and the conduction band bottom level of a high energy quantum dot, etc.)>1 eV), which restricts the development of inverted structure OLEDs and QLEDs, affecting the light emission performance.
Thus, there is a need for further improvements and enhancements in the art.
Disclosure of Invention
In view of this, it is necessary to provide a light-emitting device capable of effectively improving light-emitting performance.
The invention provides a light-emitting device, which comprises a cathode, an inorganic electron transport layer, a light-emitting layer and an anode which are arranged in a stacked manner;
wherein the inorganic electron transport layer is n-type doped element-doped zirconium dioxide (ZrO) 2 ) A layer, the n-type doping element being selected from at least one of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I) elements.
The light emitting device is formed by ZrO doped with n-type doping element and having lower conduction band bottom energy level 2 The (zirconium dioxide) layer is used as an inorganic electron transport layer and is close to the bottom energy level of a conduction band of an organic luminescent material or LUMO of a quantum dot material of a luminescent layer in a luminescent device, so that the electron injection barrier between a cathode and the luminescent layer is reduced, and the ZrO is improved by doping n-type doping elements 2 Thereby contributing to promotion of electron transport of the light emitting device and further improving the light emitting performance of the light emitting device.
In some of these embodiments, the light-emitting layer has a conduction band bottom level of from-3 eV to-3.5 eV or a LUMO of the light-emitting layer of from-2.5 eV to-3 eV.
In some of these embodiments, the n-type dopant-doped zirconium dioxide layer has a conduction band bottom level in the range of-2.8 eV to-3.0 eV.
In some of these embodiments, the n-type doping element is present in an amount of 0.1wt% to 15wt%, based on the total mass of the inorganic electron transporting layer.
Further, the n-type doping element isChlorine。
Further, the content of the n-type doping element is 5wt% to 15wt% based on the total mass of the inorganic electron transport layer.
In some embodiments, the light-emitting device further comprises a hole transport layer disposed between the anode and the light-emitting layer; the material of the hole transport layer is selected from at least one of CDBP, mCBP, CBP, mCP, TCTA, TAPC, NPB and alpha-NPD.
In some embodiments, the light-emitting device further comprises a hole injection layer disposed between the anode and the hole transport layer, the hole injection layer being made of a material selected from HAT-CN, F 4 -TCNQ、MoO 3 、V 2 O 5 、WO 3 And ReO 3 At least one of (1).
In some of these embodiments, the light emitting device is an OLED device or a QLED device.
In some embodiments, the OLED device further comprises an organic electron transport layer disposed between the inorganic electron transport layer and the light emitting layer, and the material of the organic electron transport layer is selected from at least one of TPBi, tmPyPb, BCP, balq, bphen, tmPyTz, and B3 PYMPM.
Another object of the present invention is to provide a method for manufacturing a light emitting device, for manufacturing the above light emitting device, the method comprising the steps of:
forming a cathode, and sequentially laminating an inorganic electron transport layer, a light emitting layer and an anode on the cathode; or alternatively
Forming an anode, and sequentially laminating a light-emitting layer, an electron transport layer and a cathode on the anode;
the inorganic electron transport layer is an n-type doped element doped zirconium dioxide layer, and the n-type doped element is at least one selected from fluorine, chlorine, bromine and iodine elements.
In some of these embodiments, the method of forming the inorganic electron transport layer is a hydrothermal method, a coating method, or an ink jet printing method.
The invention further aims to provide a light-emitting device which comprises the light-emitting device or the light-emitting device prepared by the preparation method.
It is to be noted that the light-emitting device may be a display device or an illumination device. The display device may be a flat panel display, a television display, an electronic paper, a logic and memory circuit, a flexible display, or the like.
Drawings
Fig. 1 is a schematic structural diagram of a light emitting device according to an embodiment of the present invention.
Detailed Description
In order that the invention may be more fully understood, a more complete description of the invention, and a preferred embodiment of the invention, is now provided. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In order to solve the problem that the performance improvement of OLED and QLED devices is restricted by the existence of a large electron barrier between a traditional n-type metal oxide electron injection/transmission layer and an organic electron transmission layer, an organic light emitting layer or a high-energy quantum dot light emitting layer, most of the prior proposals are to embed an interface dipole layer capable of reducing the surface work function between the n-type metal oxide layer and the organic functional layer to reduce the electron barrier, but the method has poor applicability in large-scale mass production. Accordingly, the skilled person selects n-type doped ZrO having a lower conduction band energy level 2 As the material of the electron transport layer or the electron injection layer, the structure of the device is simplified, the mass production is facilitated, and the ZrO is improved by doping n dopant 2 The electron conductivity of (2) promotes the development of light emitting devices such as OLEDs and QLEDs.
As shown in fig. 1, an embodiment of the present invention provides a light emitting device 100 including a substrate 10, and a cathode 20, an inorganic electron transport layer 30, a light emitting layer 50, and an anode 80, which are stacked on the substrate 10.
It is understood that the light emitting device 100 of the present embodiment is an inverted type structure. In other embodiments, the light emitterThe member may be of a positive type, and the layer structure is changed accordingly. Wherein the bottom level of the conduction band of the light emitting layer 50 is-3 eV to-3.5 eV, or the LUMO of the light emitting layer 50 is-2.5 eV to-3 eV. The inorganic electron transport layer 30 is n-type doped zirconium dioxide (ZrO) 2 ) A layer, the n-type doping element being at least one selected from fluorine (F), chlorine (Cl), bromine (Br), and iodine (I); the conduction band bottom energy level of the n-type dopant-doped zirconium dioxide layer is-2.8 eV to-3.0 eV.
The light emitting device 100 described above has the inorganic electron transport layer 30 provided between the cathode 20 and the light emitting layer 50, the inorganic electron transport layer 30 being ZrO doped with an n-type doping element 2 A layer in which a bottom conduction band level of the n-type dopant-doped zirconium dioxide layer is-2.8 eV to-3.0 eV, and the n-type dopant-doped zirconium dioxide layer can reduce a barrier for injecting electrons from the cathode 20 so that the electrons can be efficiently injected into the light emitting layer 50; and, in ZrO 2 In the crystal lattice, the outermost O atom layer has 6 valence electrons, the outermost n-type doped halogen elements, such as fluorine, chlorine, bromine, iodine, etc., has 7 valence electrons, and when the halogen atoms replace the O atom position, the excessive valence electrons are generated to form free electrons in the crystal lattice, so as to raise the ZrO content 2 The electron conductivity of the inorganic electron transport layer 30 can be increased, and the electron transport rate can be increased, so that the light emitting device 100 has a simple structure, is beneficial to large-scale mass production, and has good electron transport performance.
In the present invention, zrO doped with an n-type doping element 2 The layer has both an electron transporting function and an electron injecting function, that is, the inorganic electron transporting layer 30 corresponds to an electron transporting layer and an electron injecting layer. In some embodiments, the n-type doping element is present in an amount of 0.1wt% to 15wt%, based on the total mass of the inorganic electron transporting layer 30. It can be understood that when the content of the n-type doping element exceeds 15wt%, the scattering phenomenon of the light emitting device is severe, and the electron mobility is significantly reduced, which is not favorable for improving the electron conductivity; and as the concentration of the dopant increases, the scattering phenomenon becomes more and more severe.
Further, the n-type doping element is chlorine.
Further, the content of the n-type doping element is 5wt% to 15wt% based on the total mass of the inorganic electron transporting layer 30. More specifically, it may be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 1wt%, 13wt%, 14wt%, 15wt%, etc.
In some embodiments, the inorganic electron transport layer has a thickness of 10nm to 20nm.
The substrate 10 may be a flexible substrate such as polyimide or polyester, or may be a rigid substrate such as glass.
The material of the cathode 20 may be ITO, IZO, IGZO, or the like.
The material of the anode 80 may be Ag, al, or Mg, or a low work function composite metal formed of these metals, such as Mg — Ag alloy, or the like.
In some embodiments, light emitting device 100 further comprises a hole transport layer 60 disposed between anode 80 and light emitting layer 50.
Further, the material of the hole transport layer 60 is selected from at least one of CDBP (4,4 '-bis (9-carbazolyl) -2,2' -dimethylbiphenyl), mCBP (3,3 '-bis (N-carbazolyl) -1,1' -biphenyl), CBP (4,4 '-bis (9-carbazole) biphenyl), mCP (9,9' - (1,3-phenyl) bis-9H-carbazole), TCTA (4,4 ',4 ″ -tris (carbazol-9-yl) triphenylamine), TAPC (4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ]), NPB (N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4,4' -diamine), α -NPD, and the like.
In an embodiment, the light emitting device 100 further includes a hole injection layer 70 disposed between the anode 80 and the hole transport layer 60.
Further, the material of the hole injection layer 70 is selected from HAT-CN (2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene), F 4 -TCNQ (tetrafluorotetracyanoquinodimethane), moO 3 (molybdenum trioxide), V 2 O 5 (vanadium pentoxide), WO 3 (tungsten trioxide) and ReO 3 (rhenium trioxide) and the like.
In this particular embodiment, the light emitting layer 150 of the light emitting device 100 is an organic light emitting layer, i.e. the light emitting device 100 is an OLED device.
Further, the material of the organic light emitting layer is selected fromIr(piq) 3 、Ir(ppy) 3 、C545T、Ir(ppy) 2 (acac), firpic, and DCJTB.
In other embodiments, the light emitting layer of the light emitting device may be a quantum dot light emitting layer, i.e. the light emitting device is a QLED device.
Further, the material of the quantum dot light emitting layer may be selected from group II-VI compound semiconductors including, but not limited to CdS, cdSe, cdS/ZnS, cdSe/ZnS, znCdS/ZnS, cdSe/CdS/ZnS; and may also be selected from group III-V or group IV-VI compound semiconductors including, but not limited to, inP, inAs, inP, inAsP, gaAs, pbS/ZnS, pbSe/ZnS; and may be selected from group I-III-VI semiconductor nanocrystals.
In this embodiment, the light emitting device 100 further includes an organic electron transport layer 40, the organic electron transport layer 40 being disposed between the light emitting layer 50 and the inorganic electron transport layer 30.
Further, the material of the organic electron transport layer 40 is selected from at least one of TPBi (1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene), tmPyPb (1,3,5-tris [ (3-pyridyl) -3-phenyl ] benzene), BCP (2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline), balq (2-methyl-8-hydroxyquinoline p-hydroxybiphenylaluminum), bphen (4,7-diphenyl-1,10-phenanthroline), pytz (2,4,6-tris (3- (pyridyl) phenyl) -1,3,5-triazine), and B3PYMPM (4,6-bis (3,5-bis (3-pyridyl) phenyl) -2-methylpyrimidine), and the like.
In some embodiments, the organic electron transport layer 40 has a thickness of 10nm to 200nm.
An embodiment of the present invention provides a method for manufacturing a light emitting device, including the steps of:
forming a cathode, and sequentially laminating an inorganic electron transport layer, a light emitting layer and an anode on the cathode;
alternatively, an anode is formed, and a light-emitting layer, an inorganic electron-transporting layer, and a cathode are sequentially stacked over the anode.
The inorganic electron transport layer is an n-type doped element-doped zirconium dioxide layer, and the n-type doped element is at least one selected from fluorine, chlorine, bromine and iodine elements.
In some embodiments, the n-type doping element is present in an amount of 0.1wt% to 15wt%, based on the total mass of the inorganic electron transporting layer.
In some embodiments, the method of forming the inorganic electron transport layer is a hydrothermal method, a coating method, or an ink jet printing method.
Wherein, the hydrothermal method is adopted to directly prepare ZrO on the cathode 2 A thin film layer, or preparing n-type doped ZrO 2 Nanoparticles and then ZrO doped with the resulting n-type doping element 2 Preparing ZrO from nano particles by coating method or ink-jet printing method 2 A thin film layer.
In some embodiments, the halogen element as a doping source in a hydrothermal process is derived from hydrohalic acids (e.g., hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid), halide salts (e.g., ammonium fluoride, ammonium chloride, ammonium bromide, etc.), halide salts (e.g., sodium chlorate, sodium bromate, etc.), and the like.
In some embodiments, n-type doping element doped ZrO 2 The preparation method of the nano-particles comprises the following steps:
dissolving a halogen source and an alkali in ethanol to obtain a first mixed solution, wherein the halogen source is selected from at least one of halogen acid, halide salt or halide salt, and the alkali is selected from at least one of tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide;
heating the dimethyl sulfoxide solution of zirconium salt to 55-65 ℃, dripping the dimethyl sulfoxide solution into the first mixed solution, uniformly mixing, and reacting for 1.5-2.5 h; after the reaction is finished, centrifuging, and cleaning and precipitating by using normal hexane to obtain the ZrO doped with the halogen element 2 Nanoparticles, wherein the zirconium salt is selected from at least one of zirconium isopropoxide, zirconium acetate and zirconium chloride.
Still another embodiment of the present invention also provides a light emitting apparatus including the above light emitting device.
In some embodiments, the light emitting device may be a display device or an illumination device. The display device includes, but is not limited to, a flat panel display, a television display, an electronic paper, a logic and memory circuit, a flexible display, and the like.
The following are specific examples
EXAMPLE 1 hydrothermal preparation of F (10 wt%) -doped ZrO 2 Nanoparticles
(1) 5mmol of zirconium isopropoxide is dissolved in 30ml of dimethyl sulfoxide;
(2) Dissolving 1mmol of hydrofluoric acid and 10mmol of tetramethylammonium hydroxide in ethanol;
(3) Stirring the mixed solution in the step (1), and heating to 60 ℃;
(4) Dropwise adding the solution in the step (2) into the mixed solution in the step (3), and reacting for 2 hours;
(5) After the reaction is finished, centrifuging, and cleaning a resultant by using normal hexane to obtain F-dot ZrO 2 。
EXAMPLE 2 OLED of inverted Structure
(1) Taking a transparent conductive film ITO as a cathode, wherein the thickness is 50nm;
(2) Solution deposition of F (5 wt%) -dots ZrO on ITO 2 The nano particles are used as an electron injection/transmission layer and have the thickness of 60nm;
(3) Depositing Bphen on the electron injection/transmission layer by a solution method to be used as an organic electron transmission layer, wherein the thickness is 30nm;
(4) Co-depositing CBP Ir (piq) on the organic electron transport layer by evaporation 3 (5 wt%) as a light-emitting layer, having a thickness of 25nm;
(5) Depositing TCTA as a hole transport layer on the luminescent layer by an evaporation method, wherein the thickness of the TCTA is 30nm;
(6) Depositing HAT-CN on the hole transport layer by an evaporation method to form a hole injection layer with the thickness of 10nm;
(7) Al is deposited as an anode on the hole injection layer by evaporation to a thickness of 120nm.
Example 3: QLED with inverted structure
(1) Taking a transparent conductive film ITO as a cathode, wherein the thickness is 50nm;
(2) Depositing F (on ITO) by solution method5wt％)-doped ZrO 2 The nano particles are used as an electron injection/transmission layer and have the thickness of 90nm;
(3) Depositing ZnCdS/ZnS on the electron injection/transmission layer by a solution method to be used as a quantum dot light-emitting layer, wherein the thickness is 20nm;
(4) Depositing TCTA as a hole transport layer on the quantum dot light-emitting layer by using an evaporation method, wherein the thickness of the TCTA is 30nm;
(5) Deposition of MoO on hole transport layer by evaporation 3 As a hole injection layer, the thickness is 10nm;
(6) Al was deposited as an anode on the hole injection layer by an evaporation method to a thickness of 120nm.
EXAMPLE 4 OLED of inverted structure
(1) Taking a transparent conductive film ITO as a cathode, wherein the thickness is 50nm;
(2) Solution deposition of Cl (10 wt%) -dot ZrO on ITO 2 The nano particles are used as an electron injection/transmission layer and have the thickness of 60nm;
(3) Depositing Bphen on the electron injection/transmission layer by a solution method to be used as an organic electron transmission layer, wherein the thickness is 30nm;
(4) Co-depositing CBP Ir (piq) on the organic electron transport layer by evaporation 3 (5 wt%) as a light-emitting layer, having a thickness of 25nm;
(5) Depositing TCTA as a hole transport layer on the luminescent layer by an evaporation method, wherein the thickness of the TCTA is 30nm;
(6) Depositing HAT-CN on the hole transport layer by an evaporation method to form a hole injection layer with the thickness of 10nm;
(7) Al is deposited as an anode on the hole injection layer by evaporation to a thickness of 120nm.
Embodiment 5 QLED of inverted structure
(1) Taking a transparent conductive film ITO as a cathode, wherein the thickness is 50nm;
(2) Deposition of Cl (10 wt%) -coped ZrO on ITO by solution method 2 The nano particles are used as an electron injection/transmission layer and have the thickness of 90nm;
(3) Depositing ZnCdS/ZnS on the electron injection/transmission layer by a solution method to be used as a quantum dot light-emitting layer, wherein the thickness of the ZnCdS/ZnS is 20nm;
(4) Depositing TCTA as a hole transport layer on the quantum dot light-emitting layer by using an evaporation method, wherein the thickness of the TCTA is 30nm;
(5) By evaporation on the hole transport layerMethod for depositing MoO 3 As a hole injection layer, the thickness is 10nm;
(6) Al is deposited as an anode on the hole injection layer by evaporation to a thickness of 120nm.
EXAMPLE 6 OLED of inverted Structure
(1) Taking a transparent conductive film ITO as a cathode, wherein the thickness is 50nm;
(2) Deposition of Br (10 wt%) -coped ZrO on ITO by solution method 2 The nano particles are used as an electron injection/transmission layer and have the thickness of 60nm;
(3) Depositing Bphen on the electron injection/transmission layer by a solution method to be used as an organic electron transmission layer, wherein the thickness is 30nm;
(4) Co-depositing CBP Ir (piq) on the organic electron transport layer by evaporation 3 (5 wt%) as a light-emitting layer, having a thickness of 25nm;
(5) Depositing TCTA as a hole transport layer on the luminescent layer by an evaporation method, wherein the thickness of the TCTA is 30nm;
(6) Depositing HAT-CN on the hole transport layer by an evaporation method to form a hole injection layer with the thickness of 10nm;
(7) Al is deposited as an anode on the hole injection layer by evaporation to a thickness of 120nm.
Example 7: QLED with inverted structure
(1) Taking a transparent conductive film ITO as a cathode, wherein the thickness is 50nm;
(2) Deposition of Br (10 wt%) -coped ZrO on ITO by solution method 2 The nano particles are used as an electron injection/transmission layer and have the thickness of 90nm;
(3) Depositing ZnCdS/ZnS on the electron injection/transmission layer by a solution method to be used as a quantum dot light-emitting layer, wherein the thickness of the ZnCdS/ZnS is 20nm;
(4) Depositing TCTA as a hole transport layer on the quantum dot light-emitting layer by using an evaporation method, wherein the thickness of the TCTA is 30nm;
(5) Deposition of MoO on hole transport layer by evaporation 3 As a hole injection layer, 10nm thick;
(6) Al is deposited as an anode on the hole injection layer by evaporation to a thickness of 120nm.
Comparative example 1 an inverted OLED
(1) Taking a transparent conductive film ITO as a cathode, wherein the thickness is 50nm;
(2) Solution deposition of ZrO on ITO 2 The nano particles are used as an electron injection/transmission layer and have the thickness of 60nm;
(3) Depositing Bphen on the electron injection/transmission layer by a solution method to be used as an organic electron transmission layer, wherein the thickness is 30nm;
(4) Co-depositing CBP Ir (piq) on the organic electron transport layer by evaporation 3 (5 wt%) as a light-emitting layer, having a thickness of 25nm;
(5) Depositing TCTA as a hole transport layer on the luminescent layer by an evaporation method, wherein the thickness of the TCTA is 30nm;
(6) Depositing HAT-CN as a hole injection layer on the hole transport layer by using an evaporation method, wherein the thickness is 10nm;
(7) Al was deposited as an anode on the hole injection layer by an evaporation method to a thickness of 120nm.
Comparative example 2 QLED of inverted structure
(1) Taking a transparent conductive film ITO as a cathode, wherein the thickness is 50nm;
(2) Solution deposition of ZrO on ITO 2 The nano particles are used as an electron injection/transmission layer and have the thickness of 90nm;
(3) Depositing ZnCdS/ZnS on the electron injection/transmission layer by a solution method to be used as a quantum dot light-emitting layer, wherein the thickness of the ZnCdS/ZnS is 20nm;
(4) Depositing TCTA as a hole transport layer on the quantum dot light-emitting layer by using an evaporation method, wherein the thickness of the TCTA is 30nm;
(5) Deposition of MoO on hole transport layer by evaporation 3 As a hole injection layer, the thickness is 10nm;
(6) Al is deposited as an anode on the hole injection layer by evaporation to a thickness of 120nm.
Performance detection
The OLED devices or QLEDs of examples 2 to 7 and comparative examples 1 to 2 were tested for their properties such as driving voltage, external Quantum Efficiency (EQE), and luminance degradation, and the results are shown in table 1 below.
TABLE 1
| V(v)@10mA/cm 2 | EQE(％)@10mA/cm 2 | T 95 (h)@1000cd/m 2 | |
| Comparative example 1 | 5.3 | 15 | 1200 |
| Comparative example 2 | 5.6 | 12 | 5 |
| Example 2 | 4.6 | 18 | 2600 |
| Example 3 | 4.8 | 14 | 15 |
| Example 4 | 4.3 | 20 | 3100 |
| Example 5 | 4.6 | 15 | 30 |
| Example 6 | 4.7 | 17 | 2500 |
| Example 7 | 5.0 | 14 | 13 |
Note: v @10mA/cm 2 Indicates a current density of 10mA/cm 2 The corresponding driving voltage;
EQE@10mA/cm 2 indicates a current density of 10mA/cm 2 The corresponding EQE;
T 95 (h)@1000cd/m 2 indicating that the device had an initial luminance of 1000cd/m 2 The next continuous lighting, when the luminance decays to 95% of the initial luminance (here, 950 cd/m) 2 ) The elapsed time.
As can be seen from Table 1, the QLED or OLED devices of examples 2-7 of the present application are doped with ZrO of halogen elements such as F, cl, br, I 2 As an electron injection layer and an electron transmission layer, the electron barrier between the organic functional layer and the quantum dot light-emitting layer is effectively reduced, the conductivity of the electron injection/transmission layer is improved, the driving voltage of the device is reduced, and the brightness decay life of the device is prolonged; and simplifies the structure and preparation process of the device.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A light emitting device, comprising:
a cathode, an inorganic electron transport layer, a light emitting layer, and an anode, which are stacked;
the inorganic electron transport layer is an n-type doping element doped zirconium dioxide layer, and the n-type doping element is selected from at least one of fluorine, chlorine, bromine and iodine elements;
the conduction band bottom energy level of the light-emitting layer is-3 eV to-3.5 eV, or the LUMO of the light-emitting layer is-2.5 eV to-3 eV;
the conduction band bottom energy level of the n-type doping element doped zirconium dioxide layer is-2.8 eV to-3.0 eV.
2. The light-emitting device according to claim 1, wherein the n-type doping element is present in an amount of 0.1wt% to 15wt% based on the total mass of the inorganic electron transport layer.
3. The light-emitting device according to claim 2, wherein the n-type doping element is chlorine; and/or
Based on the total mass of the inorganic electron transmission layer, the content of the n-type doping element is 5wt% -15 wt%.
4. The light-emitting device according to claim 1, further comprising:
a hole transport layer disposed between the anode and the light emitting layer; the material of the hole transport layer is selected from at least one of CDBP, mCBP, CBP, mCP, TCTA, TAPC, NPB and alpha-NPD.
5. The light-emitting device according to claim 4, further comprising:
a hole injection layer arranged between the anode and the hole transport layer, wherein the hole injection layer is made of materials selected from HAT-CN and F 4 -TCNQ、MoO 3 、V 2 O 5 、WO 3 And ReO 3 At least one of (1).
6. The light-emitting device of any one of claims 1~5 which is an OLED device or a QLED device.
7. The light-emitting device according to claim 6, wherein the OLED device further comprises an organic electron transport layer disposed between the inorganic electron transport layer and the light-emitting layer, and wherein the material of the organic electron transport layer is at least one selected from TPBi, tmPyPb, BCP, balq, bphen, tmPyTz and B3 PYMPM.
8. A method for manufacturing a light emitting device, comprising the steps of:
forming a cathode, and sequentially laminating an inorganic electron transport layer, a light-emitting layer and an anode on the cathode; or
Forming an anode, and sequentially laminating a light-emitting layer, an inorganic electron transport layer and a cathode on the anode;
wherein the conduction band bottom energy level of the light-emitting layer is-3 eV to-3.5 eV, or the LUMO of the light-emitting layer is-2.5 eV to-3 eV;
the inorganic electron transport layer is an n-type doped element-doped zirconium dioxide layer, and the n-type doped element is at least one of fluorine, chlorine, bromine and iodine; the conduction band bottom energy level of the n-type doping element doped zirconium dioxide layer is-2.8 eV to-3.0 eV.
9. The production method according to claim 8, wherein a method of forming the inorganic electron transport layer is a hydrothermal method, a coating method, or an ink-jet printing method.
10. The method of claim 9, wherein the halogen element as a doping source in the hydrothermal process is selected from the group consisting of a halogen acid, a halide salt, and a halide salt.
11. A light-emitting device, comprising:
a light emitting device as claimed in any one of claims 1-7; alternatively, a light-emitting device obtained by the production method according to claims 8 to 10.
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