CN104051638A - Organic light-emitting device and preparation method thereof - Google Patents

Organic light-emitting device and preparation method thereof Download PDF

Info

Publication number
CN104051638A
CN104051638A CN201310077729.4A CN201310077729A CN104051638A CN 104051638 A CN104051638 A CN 104051638A CN 201310077729 A CN201310077729 A CN 201310077729A CN 104051638 A CN104051638 A CN 104051638A
Authority
CN
China
Prior art keywords
layer
hole
thickness
organic electroluminescence
electroluminescence device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310077729.4A
Other languages
Chinese (zh)
Inventor
周明杰
王平
黄辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201310077729.4A priority Critical patent/CN104051638A/en
Publication of CN104051638A publication Critical patent/CN104051638A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active 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
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures

Abstract

The invention provides an organic light-emitting device and a preparation method thereof. The organic light-emitting device comprises a charge generating layer including an n type doping layer, a metal layer and a hole generating layer, wherein the n type doping layer, the metal layer and the hole generating layer are successively laminated. The n type doping layer is made of a material based on a mixture of inorganic metal oxide and lithium salt and the electron transport rate of the material is higher than that of the organic material, thereby improving the electron transport rate; and the formed nano particle has the scattering effect on the light. And because of the metal in the metal layer, the light transmissivity of the charge generating layer can be improved. According to the invention, the preparation method is simple and easy control and operation are realized; and the raw material is easy to access.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind ofly to take organic material as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, in fields such as demonstration, illuminations, has application prospect very widely.
The structure of organic electroluminescence device is sandwich structure, and in containing the device of sandwich construction, inner side, the two poles of the earth mainly comprises luminescent layer, implanted layer and transport layer.Organic electroluminescence device is carrier injection type luminescent device, at the two poles of the earth, add after operating voltage, hole and electronics are injected into the organic material layer of device work from the two poles of the earth respectively, and it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode.
At present, in order to improve luminosity and luminous efficiency, increasing research is to take laminated device as main, this structure normally uses charge generation layer as articulamentum, several light emitting functional layer (luminescence unit) to be together in series, compare with unit component, multilayer devices often has current efficiency and luminosity at double.In laminated device, conventionally utilize two or more material with hole injectability or electronic injection ability as charge generation layer (as Cs:BCP/V 2o 5), or utilize N-shaped and p-type doped layer as charge generation layer (as N-shaped (Alq 3: Li) and p-type (NPB:FeCl 3)) be linked in sequence a plurality of luminescence units and form, but adopt the luminous efficiency of this charge generation layer laminated organic electroluminescent device lower.
Summary of the invention
In order to address the above problem, the present invention aims to provide a kind of organic electroluminescence device having compared with high light-emitting efficiency.The present invention also provides a kind of preparation method of organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, comprises the conductive anode substrate of glass, the first light emitting functional layer, charge generation layer, the second light emitting functional layer and the negative electrode that stack gradually;
Described charge generation layer comprises that the N-shaped doped layer, metal level and the hole that stack gradually produce layer; The material of described N-shaped doped layer is the mixture that N-shaped metal oxide and lithium salts form, and the mass fraction that described lithium salts accounts for N-shaped metal oxide is 20～60%; The material of described metal level is aluminium or noble metal; The material that described hole produces layer is hole mobile material;
Described N-shaped metal oxide is zinc oxide or titanium dioxide; Described lithium salts is a kind of in lithium carbonate, lithium fluoride and lithia; Described noble metal is a kind of in silver, platinum and gold; Described hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) 4, two (9H-carbazole-9-yl) biphenyl (CBP) and 9 of 4'-, a kind of in 9'-(1,3-phenyl) two-9H-carbazole (mCP).
Preferably, the material of conductive anode substrate of glass is a kind of in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).More preferably, the material of conductive anode substrate of glass is ITO.
The first light emitting functional layer is arranged in conductive anode substrate of glass.
The first light emitting functional layer comprises the first luminescent layer, also comprises at least one in the first hole injection layer, the first hole transmission layer and the first electron transfer layer.
Preferably, the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stacking gradually.
Preferably, the material of the first hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in a kind of.More preferably, the material of the first hole injection layer is WO 3.
Preferably, the thickness of the first hole injection layer is 20～80nm.More preferably, the thickness of the first hole injection layer is 40nm.
Preferably, the material of the first hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of the first hole transmission layer is TAPC.
Preferably, the thickness of the first hole transmission layer is 20～60nm.More preferably, the thickness of the first hole transmission layer is 40nm.
Preferably, the material of the first luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in a kind of.More preferably, the material of the first luminescent layer is Alq 3.
Preferably, the thickness of the first luminescent layer is 5～40nm.More preferably, the thickness of the first luminescent layer is 30nm.
Preferably, the material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the first electron transfer layer is Bphen.
Preferably, the thickness of the first electron transfer layer is 40～200nm.More preferably, the thickness of the first electron transfer layer is 180nm.
In the first light emitting functional layer, set gradually N-shaped doped layer, metal level and hole and produce layer.
In the present invention, it is charge generation layer that N-shaped doped layer, metal level and hole produce layer.
The material of N-shaped doped layer is the mixture that N-shaped metal oxide and lithium salts form, and wherein, lithium salts is guest materials, and N-shaped metal oxide is material of main part.
In the material of N-shaped doped layer, the quality of guest materials is 20～60% of material of main part quality, and to account for the mass fraction of N-shaped metal oxide be 20～60% to lithium salts.
Lithium salts is a kind of in lithium carbonate, lithium fluoride and lithia.
N-shaped metal oxide is zinc oxide or titanium dioxide.
Preferably, the particle diameter of zinc oxide is 50～200nm.
Titanium dioxide (the TiO that the present invention uses 2) be common rutile type titanium dioxide, porosity is higher, and specific area is larger, and light is had to stronger scattering process, is a kind of good electron transport material.
Preferably, the particle diameter of titanium dioxide is 20～200nm
Preferably, the thickness of N-shaped doped layer is 20～60nm.
The material of metal level is aluminium or noble metal, and wherein, noble metal is selected from a kind of in silver, platinum and gold.
Preferably, the thickness of metal level is 1～10nm.
The material that hole produces layer is hole mobile material, and hole mobile material is to have good hole migration ability, the effective organic molecule material of conduction hole.
The hole mobile material that the present invention adopts is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) 4, two (9H-carbazole-9-yl) biphenyl (CBP) and 9 of 4'-, a kind of in 9'-(1,3-phenyl) two-9H-carbazole (mCP).
Preferably, the thickness of hole generation layer is 20～80nm.
Charge generation layer produces layer by the N-shaped doped layer stacking gradually, metal level and hole and forms, what the material of N-shaped doped layer adopted is the mixture of inorganic, metal oxide and lithium salts, electric transmission speed ratio organic material is high, can farthest improve electric transmission speed, and the nano particle forming has scattering process to light, meanwhile, N-shaped layer metal level can improve the transmitance of charge generation layer, improves the light extraction efficiency of device; And the existence of metal in metal level can improve the light transmission rate of charge generation layer; Hole produces layer can improve regeneration and the transmittability in hole.
The second light emitting functional layer is arranged on hole and produces on layer.
The second light emitting functional layer comprises the second luminescent layer, also comprises at least one in the second hole transmission layer, the second electron transfer layer and the second electron injecting layer.
Preferably, the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer stacking gradually.
Preferably, the material of the second hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of the second hole transmission layer is TCTA.
Preferably, the thickness of the second hole transmission layer is 20～60nm.More preferably, the thickness of the second hole transmission layer is 40nm.
Preferably, the material of the second luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in a kind of.More preferably, the material of the second luminescent layer is Alq 3.
Preferably, the thickness of the second luminescent layer is 5～40nm.More preferably, the thickness of the second luminescent layer is 25nm.
Preferably, the material of the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the second electron transfer layer is TPBi.
Preferably, the thickness of the second electron transfer layer is 40～200nm.More preferably, the thickness of the second electron transfer layer is 80nm.
Preferably, the material of the second electron injecting layer is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) in a kind of.More preferably, the material of the second electron injecting layer is LiF.
Preferably, the thickness of the second electron injecting layer is 0.5～10nm.More preferably, the thickness of the second electron injecting layer is 1nm.
Negative electrode is arranged in the second light emitting functional layer.
Preferably, the material of negative electrode is a kind of in silver, aluminium, platinum and gold.More preferably, the material of negative electrode is silver.
Preferably, the thickness of negative electrode is 60～300nm.More preferably, the thickness of negative electrode is 120nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
Conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared the first light emitting functional layer, charge generation layer, the second light emitting functional layer and negative electrode successively, obtains organic electroluminescence device;
Described charge generation layer comprises that the N-shaped doped layer, metal level and the hole that stack gradually produce layer, and the material of described N-shaped doped layer is the mixture that N-shaped metal oxide and lithium salts form, and the mass fraction that described lithium salts accounts for N-shaped metal oxide is 20～60%; The material of described metal level is aluminium or noble metal; The material that described hole produces layer is hole mobile material;
Described N-shaped metal oxide is zinc oxide or titanium dioxide; Described lithium salts is a kind of in lithium carbonate, lithium fluoride and lithia; Described noble metal is a kind of in silver, platinum and gold; Described hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) 4, two (9H-carbazole-9-yl) biphenyl (CBP) and 9 of 4'-, a kind of in 9'-(1,3-phenyl) two-9H-carbazole (mCP).
By the cleaning to conductive anode substrate of glass, remove the organic pollution of conductive anode glass basic surface.
Particularly, the clean operation of conductive anode substrate of glass is: conductive anode substrate of glass is used to distilled water, alcohol flushing successively, then be placed on soaked overnight in isopropyl alcohol, remove the organic pollution of conductive anode glass surface, obtain clean conductive anode substrate of glass.
Preferably, the material of conductive anode substrate of glass is a kind of in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).More preferably, the material of conductive anode substrate of glass is ITO.
The first light emitting functional layer is arranged in conductive anode substrate of glass by the method for thermal resistance evaporation.
When preferably, thermal resistance evaporation is prepared the first light emitting functional layer, condition is pressure 2 * 10 -4～5 * 10 -3pa, speed 0.1～1nm/s.
The first light emitting functional layer comprises the first luminescent layer, also comprises at least one in the first hole injection layer, the first hole transmission layer and the first electron transfer layer.
Preferably, the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stacking gradually.
Preferably, the material of the first hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in a kind of.More preferably, the material of the first hole injection layer is WO 3.
Preferably, the thickness of the first hole injection layer is 20～80nm.More preferably, the thickness of the first hole injection layer is 40nm.
Preferably, the material of the first hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of the first hole transmission layer is TAPC.
Preferably, the thickness of the first hole transmission layer is 20～60nm.More preferably, the thickness of the first hole transmission layer is 40nm.
Preferably, the material of the first luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in a kind of.More preferably, the material of the first luminescent layer is Alq 3.
Preferably, the thickness of the first luminescent layer is 5～40nm.More preferably, the thickness of the first luminescent layer is 30nm.
Preferably, the material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the first electron transfer layer is Bphen.
Preferably, the thickness of the first electron transfer layer is 40～200nm.More preferably, the thickness of the first electron transfer layer is 180nm.
In the first light emitting functional layer, thermal resistance evaporation arranges N-shaped doped layer, metal level and hole and produces layer successively.
In the present invention, it is charge generation layer that N-shaped doped layer, metal level and hole produce layer.
When preferably, thermal resistance evaporation is prepared N-shaped doped layer and metal level, condition is pressure 2 * 10 -4～5 * 10 -3pa, speed 1～10nm/s.
The material of N-shaped doped layer is the mixture that N-shaped metal oxide and lithium salts form, and wherein, lithium salts is guest materials, and N-shaped metal oxide is material of main part.
In the material of N-shaped doped layer, the quality of guest materials is 20～60% of material of main part quality, and to account for the mass fraction of N-shaped metal oxide be 20～60% to lithium salts.
Lithium salts is a kind of in lithium carbonate, lithium fluoride and lithia.
N-shaped metal oxide is zinc oxide or titanium dioxide.
Preferably, the particle diameter of zinc oxide is 50～200nm.
Titanium dioxide (the TiO that the present invention uses 2) be common rutile type titanium dioxide, porosity is higher, and specific area is larger, and light is had to stronger scattering process, is a kind of good electron transport material.
Preferably, the particle diameter of titanium dioxide is 20～200nm
Preferably, the thickness of N-shaped doped layer is 20～60nm.
The material of metal level is aluminium or noble metal, and wherein, noble metal is selected from a kind of in silver, platinum and gold.
Preferably, the thickness of metal level is 1～10nm.
When preferably, thermal resistance evaporation is prepared hole generation layer, condition is pressure 2 * 10 -4～5 * 10 -3pa, speed 0.1～1nm/s.
The material that hole produces layer is hole mobile material, and hole mobile material is to have good hole migration ability, the effective organic molecule material of conduction hole.
The hole mobile material that the present invention adopts is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) 4, two (9H-carbazole-9-yl) biphenyl (CBP) and 9 of 4'-, a kind of in 9'-(1,3-phenyl) two-9H-carbazole (mCP).
Preferably, the thickness of hole generation layer is 20～80nm.
Charge generation layer produces layer by the N-shaped doped layer stacking gradually, metal level and hole and forms, what the material of N-shaped doped layer adopted is the mixture of inorganic, metal oxide and lithium salts, electric transmission speed ratio organic material is high, can farthest improve electric transmission speed, and the nano particle forming has scattering process to light, meanwhile, N-shaped layer metal level can improve the transmitance of charge generation layer, improves the light extraction efficiency of device; And the existence of metal in metal level can improve the light transmission rate of charge generation layer; Hole produces layer can improve regeneration and the transmittability in hole.
The second light emitting functional layer is arranged on hole by thermal resistance evaporation and produces on layer.
When preferably, thermal resistance evaporation is prepared the second light emitting functional layer, condition is pressure 2 * 10 -4～5 * 10 -3pa, speed 0.1～1nm/s.
The second light emitting functional layer comprises the second luminescent layer, also comprises at least one in the second hole transmission layer, the second electron transfer layer and the second electron injecting layer.
Preferably, the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer stacking gradually.
Preferably, the material of the second hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of the second hole transmission layer is TCTA.
Preferably, the thickness of the second hole transmission layer is 20～60nm.More preferably, the thickness of the second hole transmission layer is 40nm.
Preferably, the material of the second luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in a kind of.More preferably, the material of the second luminescent layer is Alq 3.
Preferably, the thickness of the second luminescent layer is 5～40nm.More preferably, the thickness of the second luminescent layer is 25nm.
Preferably, the material of the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the second electron transfer layer is TPBi.
Preferably, the thickness of the second electron transfer layer is 40～200nm.More preferably, the thickness of the second electron transfer layer is 80nm.
Preferably, the material of the second electron injecting layer is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) in a kind of.More preferably, the material of the second electron injecting layer is LiF.
Preferably, the thickness of the second electron injecting layer is 0.5～10nm.More preferably, the thickness of the second electron injecting layer is 1nm.
Negative electrode is arranged in the second light emitting functional layer by thermal resistance evaporation.
When preferably, thermal resistance evaporation is prepared negative electrode, condition is pressure 2 * 10 -4～5 * 10 -3pa, speed 1～10nm/s.
Preferably, the material of negative electrode is a kind of in silver, aluminium, platinum and gold.More preferably, the material of negative electrode is silver.
Preferably, the thickness of negative electrode is 60～300nm.More preferably, the thickness of negative electrode is 120nm.
The present invention has following beneficial effect:
Organic electroluminescence device prepared by the present invention, charge generation layer produces layer by the N-shaped doped layer stacking gradually, metal level and hole and forms, what the material of N-shaped doped layer adopted is the mixture of inorganic, metal oxide and lithium salts, electric transmission speed ratio organic material is high, can farthest improve electric transmission speed, and the nano particle forming has scattering process to light, simultaneously, N-shaped layer metal level can improve the transmitance of charge generation layer, improves the light extraction efficiency of device; And the existence of metal in metal level can improve the light transmission rate of charge generation layer; Hole produces layer can improve regeneration and the transmittability in hole.
Meanwhile, preparation method of the present invention is simple, be easy to control and operation, and raw material easily obtains.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structure chart of the organic electroluminescence device that provides of the embodiment of the present invention 1;
Fig. 2 is organic electroluminescence device and the current density of comparative example and the graph of a relation of current efficiency that the embodiment of the present invention 1 provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10 -4under the condition of Pa, with evaporation speed thermal resistance evaporation in clean ito glass substrate of 0.6nm/s, prepare the first light emitting functional layer, comprise the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually;
Particularly, the material of the first hole injection layer is WO 3, thickness is 40nm; The material of the first hole transmission layer is TAPC, and thickness is 40nm; The material of the first luminescent layer is Alq 3, thickness is 30nm; The material of the first electron transfer layer is Bphen, and thickness is 180nm;
(3) at pressure, be 5 * 10 -4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared N-shaped doped layer, metal level and hole generation layer as charge generation layer successively, wherein, with evaporation speed evaporating n type doped layer and the metal level of 6nm/s, with the evaporation speed evaporation hole of 0.6nm/s, produce layer:
Particularly, the material of N-shaped doped layer is the mixture of LiF and ZnO, and the mass fraction that LiF accounts for ZnO is 50%, and thickness is 25nm; The material of metal level is Ag, and thickness is 2nm; The material that hole produces layer is mCP, and thickness is 15nm;
(4) at pressure, be 5 * 10 -4under the condition of Pa, evaporation speed thermal resistance evaporation on hole generation layer with 0.6nm/s is prepared the second light emitting functional layer, comprise the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stack gradually, evaporation speed evaporation on the second electron injecting layer with 6nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is TCTA, and thickness is 40nm; The material of the second luminescent layer is Alq 3, thickness is 30nm; The material of the second electron transfer layer is TPBi, and thickness is 80nm; The material of the second electron injecting layer is LiF, and thickness is 1nm; The material of negative electrode is Ag, and thickness is 120nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ito glass/WO 3/ TAPC/Alq 3/ Bphen/ZnO:LiF/Ag/mCP/TCTA/Alq 3/ TPBi/LiF/Ag.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises that the conductive anode substrate of glass 10, the second light emitting functional layer 20(that stack gradually comprise the first hole injection layer 201, the first hole transport 202, the first luminescent layer 203 and the first electron transfer layer 204), charge generation layer 30(comprises that N-shaped doped layer 301, metal level 302, hole produce layer 303), the second light emitting functional layer 40(comprises the second hole transmission layer 401, the second luminescent layer 402, the second electron transfer layer 403 and the second electron injecting layer 404) and negative electrode 50.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 2 * 10 -4under the condition of Pa, with evaporation speed thermal resistance evaporation in clean AZO substrate of glass of 1nm/s, prepare the first light emitting functional layer, comprise the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually;
Particularly, the material of the first hole injection layer is V 2o 5, thickness is 80nm; The material of the first hole transmission layer is NPB, and thickness is 60nm; The material of the first luminescent layer is ADN, and thickness is 5nm; The material of the first electron transfer layer is TAZ, and thickness is 40nm;
(3) at pressure, be 2 * 10 -4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared N-shaped doped layer, metal level and hole generation layer as charge generation layer wherein successively, with evaporation speed evaporating n type doped layer and the metal level of 10nm/s, with the evaporation speed evaporation hole generation layer of 1nm/s;
Particularly, the material of N-shaped doped layer is Li 2cO 3and TiO 2mixture, Li 2cO 3account for TiO 2mass fraction be 20%, thickness is 20nm; The material of metal level is Pt, and thickness is 1nm; The material that hole produces layer is m-MTDATA, and thickness is 20nm;
(4) at pressure, be 2 * 10 -4under the condition of Pa, evaporation speed thermal resistance evaporation on hole generation layer with 1nm/s is prepared the second light emitting functional layer, comprise the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stack gradually, evaporation speed evaporation on the second electron injecting layer with 10nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is TCTA, and thickness is 20nm; The material of the second luminescent layer is BCzVBi, and thickness is 40nm; The material of the second electron transfer layer is Bphen, and thickness is 200nm; The material of the second electron injecting layer is LiF, and thickness is 0.5nm; The material of negative electrode is Pt, and thickness is 60nm;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: AZO glass/V 2o 5/ NPB/ADN/TAZ/TiO 2: Li 2cO 3/ Pt/m-MTDATA/TCTA/BCzVBi/Bphen/LiF/Pt.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10 -3under the condition of Pa, with evaporation speed thermal resistance evaporation in clean IZO substrate of glass of 0.1nm/s, prepare the first light emitting functional layer, comprise the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually;
Particularly, the material of the first hole injection layer is V 2o 5, thickness is 20nm; The material of the first hole transmission layer is TAPC, and thickness is 30nm; The material of the first luminescent layer is DCJTB, and thickness is 10nm; The material of the first electron transfer layer is TPBi, and thickness is 200nm;
(3) at pressure, be 5 * 10 -3under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared N-shaped doped layer, metal level and hole generation layer as charge generation layer wherein successively, with evaporation speed evaporating n type doped layer and the metal level of 1nm/s, with the evaporation speed evaporation hole generation layer of 0.1nm/s;
Particularly, the material of N-shaped doped layer is Li 2o and TiO 2the mixture forming, Li 2o accounts for TiO 2mass fraction be 60%, thickness is 60nm; The material of metal level is Al, and thickness is 10nm; The material that hole produces layer is CBP, and thickness is 80nm;
(4) at pressure, be 5 * 10 -3under the condition of Pa, evaporation speed thermal resistance evaporation on hole generation layer with 0.1nm/s is prepared the second light emitting functional layer, comprise the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer that stack gradually, evaporation speed evaporation on the second electron injecting layer with 1nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is TAPC, and thickness is 60nm; The material of the second luminescent layer is ADN, and thickness is 5nm; The material of the second electron transfer layer is Bphen, and thickness is 40nm; The material of the second electron injecting layer is Bphen, and thickness is 10nm; The material of negative electrode is Al, and thickness is 300nm;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO glass/V 2o 5/ TAPC/DCJTB/TPBi/TiO 2: Li 2o/Al/CBP/TAPC/ADN/Bphen/Bphen/Al.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10 -4under the condition of Pa, with evaporation speed thermal resistance evaporation in clean IZO substrate of glass of 0.5nm/s, prepare the first light emitting functional layer, comprise the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually;
Particularly, the material of the first hole injection layer is MoO 3, thickness is 30nm; The material of the first hole transmission layer is NPB, and thickness is 50nm; The material of the first luminescent layer is BCzVBi, and thickness is 40nm; The material of the first electron transfer layer is Bphen, and thickness is 40nm;
(3) at pressure, be 5 * 10 -4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared N-shaped doped layer, metal level and hole generation layer as charge generation layer wherein successively, with evaporation speed evaporating n type doped layer and the metal level of 5nm/s, with the evaporation speed evaporation hole generation layer of 0.5nm/s;
Particularly, the material of N-shaped doped layer is ZnO and Li 2cO 3the mixture forming, Li 2cO 3the mass fraction that accounts for ZnO is 30%, and thickness is 35nm; The material of metal level is Au, and thickness is 4nm; The material that hole produces layer is CBP, and thickness is 70nm;
(4) at pressure, be 5 * 10 -4under the condition of Pa, evaporation speed thermal resistance evaporation on hole generation layer with 0.5nm/s is prepared the second light emitting functional layer, comprise the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stack gradually, evaporation speed evaporation on the second electron injecting layer with 5nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is NPB, and thickness is 50nm; The material of the second luminescent layer is BCzVBi, and thickness is 25nm; The material of the second electron transfer layer is Bphen, and thickness is 100nm; The material of the second electron injecting layer is CsF, and thickness is 2nm; The material of negative electrode is Au, and thickness is 180nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO glass/MoO 3/ NPB/BCzVBi/Bphen/ZnO:Li 2cO 3/ Au/CBP/NPB/BCzVBi/Bphen/CsF/Au.
Comparative example
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10 -4under the condition of Pa, with the evaporation speed of 0.6nm/s in clean ito glass substrate successively thermal resistance evaporation prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, with evaporation speed evaporation on electron injecting layer of 6nm/s, prepare negative electrode;
Particularly, the material of hole injection layer is WO 3, thickness is 40nm; The material of hole transmission layer is TAPC, and thickness is 40nm; The material of luminescent layer is Alq 3, thickness is 30nm; The material of electron transfer layer is Bphen, and thickness is 180nm; The material of electron injecting layer is LiF, and thickness is 1nm; The material of negative electrode is Ag, and thickness is 120nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ito glass/WO 3/ TAPC/Alq 3/ Bphen/LiF/Ag.
Utilize the Keithley2400 test electric property of U.S. Keithley company, colorimeter (Japanese Konica Minolta company, model: CS-100A) test brightness and colourity.
Fig. 2 is the graph of a relation of the organic electroluminescence device of the present embodiment and the current density of comparative example and current efficiency.Wherein, curve 1 is the present embodiment the current density of organic electroluminescence device and the graph of a relation of current efficiency; For comparative example, (structure is specifically expressed as curve 2: ito glass/WO 3/ TAPC/Alq 3/ Bphen/LiF/Ag) current density and the graph of a relation of current efficiency.
As can see from Figure 2, under different current densities, the current efficiency of embodiment 1 is large than comparative example all, maximum current efficiency is 22.3cd/A, and that comparative example is only 18.2cd/A, this explanation, prepared by the present invention produces by N-shaped doped layer, metal level and hole the charge generation layer that layer forms, N-shaped doped layer can farthest improve electric transmission speed, and light is had to scattering process, improves light extraction efficiency.This laminated device can effectively improve luminous efficiency.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (9)

1. an organic electroluminescence device, is characterized in that, comprises the conductive anode substrate of glass, the first light emitting functional layer, charge generation layer, the second light emitting functional layer and the negative electrode that stack gradually;
Described charge generation layer comprises that the N-shaped doped layer, metal level and the hole that stack gradually produce layer; The material of described N-shaped doped layer is the mixture that N-shaped metal oxide and lithium salts form, and the mass fraction that described lithium salts accounts for described N-shaped metal oxide is 20～60%; The material of described metal level is aluminium or noble metal; The material that described hole produces layer is hole mobile material;
Described N-shaped metal oxide is a kind of in zinc oxide and titanium dioxide; Described lithium salts is a kind of in lithium carbonate, lithium fluoride and lithia; Described noble metal is a kind of in silver, platinum and gold; Described hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) 4, two (9H-carbazole-9-yl) biphenyl (CBP) and 9 of 4'-, a kind of in 9'-(1,3-phenyl) two-9H-carbazole (mCP).
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described N-shaped doped layer is 20～60nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described metal level is 1～10nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness that described hole produces layer is 20～80nm.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared the first light emitting functional layer, charge generation layer, the second light emitting functional layer and negative electrode successively, obtains organic electroluminescence device;
Described charge generation layer comprises that the N-shaped doped layer, metal level and the hole that stack gradually produce layer; The material of described N-shaped doped layer is the mixture that N-shaped metal oxide and lithium salts form, and the mass fraction that described lithium salts accounts for described N-shaped metal oxide is 20～60%; The material of described metal level is aluminium or noble metal; The material that described hole produces layer is hole mobile material;
Described N-shaped metal oxide is a kind of in zinc oxide and titanium dioxide; Described lithium salts is a kind of in lithium carbonate, lithium fluoride and lithia; Described noble metal is a kind of in silver, platinum and gold; Described hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) 4, two (9H-carbazole-9-yl) biphenyl (CBP) and 9 of 4'-, a kind of in 9'-(1,3-phenyl) two-9H-carbazole (mCP).
6. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, pressure prepared by described thermal resistance evaporation is 2 * 10 -4～5 * 10 -3pa.
7. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described N-shaped doped layer is 20～60nm; The thickness of described metal level is 1～10nm; The thickness that described hole produces layer is 20～80nm.
8. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, described the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stacking gradually.
9. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer stacking gradually.
CN201310077729.4A 2013-03-12 2013-03-12 Organic light-emitting device and preparation method thereof Pending CN104051638A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310077729.4A CN104051638A (en) 2013-03-12 2013-03-12 Organic light-emitting device and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310077729.4A CN104051638A (en) 2013-03-12 2013-03-12 Organic light-emitting device and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104051638A true CN104051638A (en) 2014-09-17

Family

ID=51504237

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310077729.4A Pending CN104051638A (en) 2013-03-12 2013-03-12 Organic light-emitting device and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104051638A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016074277A1 (en) * 2014-11-14 2016-05-19 深圳市华星光电技术有限公司 Tandem organic light-emitting diode and display

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060157728A1 (en) * 2005-01-14 2006-07-20 Au Optronics Corp. Organic light-emitting device
JP2007059848A (en) * 2005-08-26 2007-03-08 Dainippon Printing Co Ltd Organic electroluminescent element
CN100550465C (en) * 2004-08-20 2009-10-14 伊斯曼柯达公司 White OLED with multiple white electroluminescent units
CN101562236A (en) * 2004-08-04 2009-10-21 株式会社半导体能源研究所 Light-emitting element, display device, and electronic appliance
CN102842682A (en) * 2011-06-21 2012-12-26 海洋王照明科技股份有限公司 Stacked organic electroluminescence device and manufacturing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101562236A (en) * 2004-08-04 2009-10-21 株式会社半导体能源研究所 Light-emitting element, display device, and electronic appliance
CN100550465C (en) * 2004-08-20 2009-10-14 伊斯曼柯达公司 White OLED with multiple white electroluminescent units
US20060157728A1 (en) * 2005-01-14 2006-07-20 Au Optronics Corp. Organic light-emitting device
JP2007059848A (en) * 2005-08-26 2007-03-08 Dainippon Printing Co Ltd Organic electroluminescent element
CN102842682A (en) * 2011-06-21 2012-12-26 海洋王照明科技股份有限公司 Stacked organic electroluminescence device and manufacturing method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016074277A1 (en) * 2014-11-14 2016-05-19 深圳市华星光电技术有限公司 Tandem organic light-emitting diode and display

Similar Documents

Publication Publication Date Title
CN104051639A (en) Organic light-emitting device and preparation method thereof
CN103972413A (en) Organic light-emitting device and production method thereof
CN104051638A (en) Organic light-emitting device and preparation method thereof
CN104124365A (en) Organic light-emitting device and preparation method thereof
CN104051661A (en) Organic electroluminescent device and manufacturing method thereof
CN104124361A (en) Organic light-emitting device and preparation method thereof
CN104218166A (en) Organic light-emitting device and preparation method thereof
CN103972408A (en) Organic light-emitting device and method for manufacturing same
CN104253243A (en) Organic electroluminescent device and preparation method thereof
CN103972421A (en) Organic light-emitting device and production method thereof
CN104009179A (en) Organic electroluminescent device and preparation method
CN104124352A (en) Organic light-emitting device and preparation method thereof
CN104124393A (en) Organic light-emitting device and preparation method thereof
CN104051640A (en) Organic electroluminescent device and manufacturing method thereof
CN104124356A (en) Organic light-emitting device and preparation method thereof
CN103824954A (en) Organic electroluminescent device and preparation method thereof
CN104124395A (en) Organic light-emitting device and preparation method thereof
CN104009164A (en) Organic electroluminescent device and preparation method
CN103972409A (en) Organic light-emitting device and method for manufacturing same
CN104124392A (en) Organic light-emitting device and preparation method thereof
CN103972411A (en) Organic light-emitting device and production method thereof
CN104009168A (en) Organic electroluminescent device and preparation method
CN103824956A (en) Organic electroluminescent device and preparation method thereof
CN104078568A (en) Organic light-emitting diode and preparation method thereof
CN103824955A (en) Organic electroluminescent device and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140917