CN101651184B - Organic electroluminescence device and preparation method thereof - Google Patents
Organic electroluminescence device and preparation method thereof Download PDFInfo
- Publication number
- CN101651184B CN101651184B CN200910090378A CN200910090378A CN101651184B CN 101651184 B CN101651184 B CN 101651184B CN 200910090378 A CN200910090378 A CN 200910090378A CN 200910090378 A CN200910090378 A CN 200910090378A CN 101651184 B CN101651184 B CN 101651184B
- Authority
- CN
- China
- Prior art keywords
- ion
- metal complex
- type
- 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.)
- Active
Links
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic electroluminescence device and a preparation method thereof, belonging to the field of electrooptical technologies. The organic electroluminescence device comprises an anode, a cathode and an organic electroluminescence layer arranged between the anode and the cathode. The electroluminescence layer comprises main materials and object materials, wherein the main materials adopt small molecule materials; and the object materials adopt ionic type phosphorescent materials. By adopting a wet method to prepare the electroluminescence layer of the device, the invention greatly simplifies the preparation process and obtains monochrome devices and white devices with high efficiency, high color purity, fast response and long service life.
Description
Technical field
The present invention relates to a kind of novel electroluminescent device and preparation method thereof, belong to field of photoelectric technology.
Background technology
A series of advantages such as display of organic electroluminescence has from main light emission, low-voltage DC driven, solidifies entirely, the visual angle is wide, color is abundant; Compare with LCD; Display of organic electroluminescence does not need backlight, has that the visual angle is big, power is low, response speed is fast, lower-cost characteristics.Therefore, display of organic electroluminescence has broad application prospects, and is counted as one of following flat panel display that is rich in competitiveness.
The luminous main body of organic electroluminescence device is an organic solid material, and the minimum energy excitation state in the organic solid is divided into singlet and triplet state, and the former causes fluorescent emission, and the latter causes phosphorescent emissions.According to the electron spin statistical estimation, it is 25% that hole and electronics combine the highest probability of formation singlet exciton, and promptly the highest internal quantum efficiency of fluorescent material is 25%; And in some phosphor material, triplet state can release energy with the form of recombination radiation, and the highest internal quantum efficiency of phosphor material can reach 100% like this.In actual conditions; Because device interfaces refraction etc., the probability of photon effusion device is 20% to the maximum, therefore uses the external quantum efficiency of the organic electroluminescence device of fluorescent material to be up to 5%; And the external quantum efficiency of phosphor material device is up to 20%, can reach 4 times of fluorescent material.
The most representative in the ion-type phosphor material is exactly the ion-type transient metal complex; It has numerous advantages; As: be easy to synthetic and purification, the ion characteristic of intrinsic, abundant tunable optical physics and electrochemical properties; In the polar solvent even the aqueous solution, having fine solubility can wait, and begins to cause people's attention in recent years.At present; In the organic electroluminescent field; The ion-type transient metal complex is mainly used in organic electrochemistry pond luminescent device, and has obtained device efficient, high color purity, but also has problems such as luminescent layer concentration essence is gone out seriously, the response time long, device lifetime is short.Also handlebar ion-type transient metal complex is applied to the polymer organic electroluminescence device as phosphorescent dopants; It can be through the preparation of wet methods such as spin coating or inkjet printing, and technology is simpler, but high molecular polymer itself is synthetic and purification difficult; There is not definite molecular structure; And compare with the micromolecule organic electroluminescence device, the polymer organic electroluminescence device efficiency is lower, and the life-span is shorter.
Compare with the polymer organic electroluminescence device, the micromolecule organic electroluminescence device mainly adopts the micromolecule functional material, and the method through vapor deposition obtains usually.Small molecule material is prone to synthetic; It is also fairly simple to purify, and adopts the method for vapor deposition to be easy to realize the device architecture of multi-functional layer simultaneously, thereby can realize efficiently that charge carrier injects and transmission; Reach carrier balance with the raising device efficiency, so micromolecule vapor deposition device has very high efficient.But evaporation process is complicated, needs high-vacuum technology, and cost is higher.
Therefore, research and development can be passed through the significant as the micromolecule organic electroluminescence device of phosphorescent dopants with the ion-type transient metal complex of wet method preparation.
Summary of the invention
The objective of the invention is to propose a kind of novel organic electroluminescence device and preparation method thereof, prepare the micromolecule organic electroluminescence device of dopant ion type phosphor material through wet method.
The present invention proposes a kind of organic electroluminescence device; Comprise anode, negative electrode and the organic luminous layer between two electrodes; Comprise material of main part and guest materials in the organic luminous layer; Wherein material of main part adopts triplet energy level greater than 2.0eV, the glass transition temperature small molecule material greater than 50 ℃, and guest materials adopts the ion-type phosphor material.
Material of main part in the above-mentioned organic luminous layer has good wet method filming performance, and not only has the hole transport function but also have the electric transmission function.
The aforementioned body material is a kind of, and this material has hole transport function and electric transmission function simultaneously.This material of main part is selected from the substituted indeno pyridazine class of carbazyl derivative, and concrete material is selected from 5, and 5-is two, and [(4-(3; 6-di-t-butyl-9-carbazyl) phenyl] indeno [1,2-c] pyridazine or 9,9-is two, and [(4-(3; 6-di-t-butyl-9-carbazyl) phenyl] indeno [1,2-d] pyridazine.
Material of main part in the above-mentioned organic luminous layer can be two kinds, and a kind of have a hole transport function, is selected from fluorene derivative or carbazoles derivative; Another kind has the electric transmission function, Xuan Zi oxadiazole analog derivative.
Above-mentioned have a hole transport materials with function, is selected from N, N '-two carbazyl-1,4-dimethylene benzene, 9,9-two [(4-(3,6-di-t-butyl-9-carbazyl) phenyl] fluorenes or 9, two [4-(9-carbazyl) phenyl]-2 of 9-, 7-di-tert-butyl-fluorene.
Above-mentioned have the electric transmission materials with function and be selected from 1, two [(4-tert-butyl-phenyl)-1,3, the 4-oxadiazole base] benzene of 3-or 2-(4-diphenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole.
The weight ratio that possesses the hole transport materials with function in the aforementioned body material and possess the electric transmission materials with function is between 10: 1～1: 10.
Guest materials in the above-mentioned organic luminous layer is selected from the ion-type transient metal complex of phosphorescent emissions, is central metal ion ion-type complex with Ir especially.
Guest materials is selected from the ion-type Ir metal complex of red emission in the organic luminous layer of ruddiness monochrome devices provided by the invention, and concrete material is selected from two (2-phenylpyridine) iridium (III) (2-(1-phenyl-2-benzimidazolyl) quinoline) hexafluorophosphates.
Guest materials is selected from the ion-type Ir metal complex of green emission in the organic luminous layer of green glow monochrome devices provided by the invention; Concrete material is selected from two (2-(2, the 4-difluorophenyl) pyridine) iridium (III) (1-phenyl-2-(2-pyridine radicals) benzimidazole) hexafluorophosphates.
Guest materials is selected from the ion-type Ir metal complex of blue emission in the organic luminous layer of blue light monochrome devices provided by the invention; Concrete material is selected from two (2-(2, the 4-difluorophenyl) pyridine) iridium (III) (2-(N-pyrazolyl) pyridine) hexafluorophosphates or two (2-phenylpyridine) iridium (III) (2-(N-pyrazolyl) pyridine) hexafluorophosphate.
Guest materials in the organic luminous layer of white light parts provided by the invention can be two kinds, is selected from the ion-type Ir metal complex of red emission and the ion-type Ir metal complex of blue emission respectively.
The ion-type Ir metal complex of used red emission is selected from two (2-phenylpyridine) iridium (III) (2-(1-phenyl-2-benzimidazolyl) quinoline) hexafluorophosphates in the above-mentioned guest materials, and the ion-type Ir metal complex of used blue emission is selected from two (2-phenylpyridine) iridium (III) (2-(N-pyrazolyl) pyridine) hexafluorophosphates.
The ion-type Ir metal complex weight ratio of the ion-type Ir metal complex of used red emission and blue emission is between 1: 20～1: 100 in the above-mentioned guest materials.
Guest materials in the organic luminous layer of white light parts provided by the invention also can be three kinds, is selected from the ion-type Ir metal complex of red emission, the ion-type Ir metal complex of green emission and the ion-type Ir metal complex of blue emission respectively.
The ion-type Ir metal complex of used red emission is selected from two (2-phenylpyridine) iridium (III) (2-(1-phenyl-2-benzimidazolyl) quinoline) hexafluorophosphates in the above-mentioned guest materials; The ion-type Ir metal complex of used green emission is selected from that two (2-(2; The 4-difluorophenyl) iridium (III) (1-phenyl-2-(2-pyridine radicals) benzimidazole) hexafluorophosphate pyridine); The ion-type Ir metal complex of used blue emission is selected from two (2-(2, the 4-difluorophenyl) pyridine) iridium (III) (2-(N-pyrazolyl) pyridine) hexafluorophosphates.
The weight ratio of the ion-type Ir metal complex of the ion-type Ir metal complex of the ion-type Ir metal complex of used red emission, green emission and blue emission is between 1: 0.01: 100～1: 0.5: 20 in the above-mentioned guest materials.
The thickness of above-mentioned organic luminous layer is 80nm～120nm.
Organic electroluminescence device provided by the invention is provided with the anode modification layer between anode and organic luminous layer, its material is PEDOT:PSS, and its thickness is 20nm～60nm.
Organic electroluminescence device provided by the invention, negative electrode adopts composite construction, and material is selected from Cs
2CO
3With Al, Cs
2CO
3With Ag, CsF and Al or CsF and Ag.
Organic electroluminescence device provided by the invention is provided with electron transfer layer between negative electrode and organic luminous layer, its material is selected from 1,3,5-three (1-phenyl-2-benzimidazolyl) benzene.
A kind of method for preparing above-mentioned organic electroluminescence device, the organic luminous layer of employing wet method fabricate devices adopts the method for vacuum evaporation to prepare negative electrode.
A kind of method for preparing above-mentioned organic electroluminescence device adopts anode modification layer and organic luminous layer in the wet method fabricate devices, adopts the method for vacuum evaporation to prepare negative electrode.
A kind of method for preparing above-mentioned organic electroluminescence device adopts the organic luminous layer in the wet method fabricate devices, adopts the method for vacuum evaporation to prepare electron transfer layer and negative electrode.
Adopt the micromolecule organic electroluminescence device of the dopant ion type phosphor material of above-mentioned wettable method preparation, not only simplified preparation technology greatly, and obtained high efficiency, high color purity, response and long-life monochrome devices and white light parts fast.
Embodiment
The preparation method of micromolecule organic electroluminescence device: on glass substrate, prepare anode, organic function layer and negative electrode successively.
(1) step: preparation anode layer: anode layer is generally the higher metals of work function such as metal oxide such as ITO, zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as.
(2) step: preparation organic luminous layer: luminescent layer adopts the micromolecule material of main part to mix as the dyestuff of guest materials, through the method preparation of spin coating.Comprise in the material of main part: have hole transport materials with function such as TBCPF, DCB, CPTBF and have the electric transmission materials with function such as OXD-7, PBD.The guest materials of selecting for use is selected from Ir-qlbi like red ion-type phosphor material, and green ion-type phosphor material is selected from Irdf-pybi, and blue ion-type phosphor material is selected from Irdf-pzpy or Ir-pzpy.
Before (2) step, can also prepare the anode modification layer earlier, adopt the organic conductive polymer as the anode modification layer material, the organic conductive polymer is preferably polythiophene/polyvinylbenzenesulfonic acid sodium (PEDOT:PSS).
(3) step: the preparation negative electrode: cathode layer adopts composite construction, and through the method preparation of vacuum evaporation, material is selected from Cs
2CO
3With Al, Cs
2CO
3With Ag, CsF and Al, perhaps CsF and Ag.
Before (3) step, can also prepare electron transfer layer earlier, adopt to have electric transmission function, the triplet energy level organic material more than 2.7eV, be preferably 1,3,5-three (1-phenyl-2-benzimidazolyl) benzene (TPBI).
The particular compound title and the molecular structural formula of material of main part and guest materials is as follows in the above-mentioned luminescent layer:
Embodiment 1
The cleaning that step (1) is carved with ito glass substrate in advance: the washing agent of utilization heat is ultrasonic to be cleaned the transparent conduction base sheet ito glass with the ultrasonic method of deionized water; Place it in oven dry under the infrared lamp after the cleaning; Then the ito substrate of oven dry is carried out the preliminary treatment of low energy oxygen ion beam bombardment; The square resistance of ITO film is 15 Ω, and thickness is 150nm.Continue preparation anode modification layer then, the method through spin coating on pretreated glass substrate prepares the PEDOT:PSS film as the anode modification layer, on 200 ℃ hot plate, carries out annealing in process 10min, and thickness is 40nm.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; OXD-7 and blue ion-type phosphor material Irdf-pzpy are dissolved in 1 according to weight ratio at 6: 3: 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
The preparation of step (3) negative electrode: aforesaid substrate is sent in the vapor deposition chamber, on above-mentioned organic layer, deposits Cs successively
2CO
3With Al, evaporation rate is respectively 0.02nm/s and 0.5-1nm/s, and thickness is respectively 3nm and 150nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
Embodiment 2
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; OXD-7 and blue ion-type phosphor material Ir-pzpy are dissolved in 1 according to weight ratio at 6: 3: 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 3
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 2 prepares organic luminous layer.
The preparation of step (3) negative electrode: aforesaid substrate is sent in the vapor deposition chamber, on above-mentioned organic membrane, deposits Cs successively
2CO
3With Ag, evaporation rate is respectively 0.02nm/s and 0.1nm/s, and thickness is respectively 3nm and 120nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
Embodiment 4
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 2 prepares organic luminous layer.
The preparation of step (3) negative electrode: aforesaid substrate is sent in the vapor deposition chamber; On above-mentioned organic membrane, deposit CsF and Al successively; Evaporation rate is respectively 0.02nm/s and 0.5-1nm/s, and thickness is respectively 1nm and 150nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
Embodiment 5
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 2 prepares organic luminous layer.
The preparation of step (3) negative electrode: aforesaid substrate is sent in the vapor deposition chamber, on above-mentioned organic membrane, deposits CsF and Ag successively, evaporation rate is respectively 0.02nm/s and 0.1nm/s, and thickness is respectively 1nm and 120nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
Embodiment 6
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 2 prepares organic luminous layer.
The preparation of step (3) electron transfer layer: aforesaid substrate is sent in the organic vapor deposition chamber, on above-mentioned organic membrane, deposits TPBI, evaporation rate is 0.1-0.2nm/s, and thickness is 20nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
The preparation of step (4) negative electrode: under high vacuum state, aforesaid substrate is sent in the metal evaporation chamber, on above-mentioned electron transfer layer, deposits Cs successively
2CO
3With Al, evaporation rate is respectively 0.02nm/s and 0.5-1nm/s, and thickness is respectively 3nm and 150nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
Embodiment 7
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 2 prepares organic luminous layer.
The preparation of step (3) electron transfer layer: aforesaid substrate is sent in the organic vapor deposition chamber, on above-mentioned organic membrane, deposits TPBI, evaporation rate is 0.1-0.2nm/s, and thickness is 30nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 8
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 2 prepares organic luminous layer.
The preparation of step (3) electron transfer layer: aforesaid substrate is sent in the organic vapor deposition chamber, on above-mentioned organic membrane, deposits TPBI, evaporation rate is 0.1-0.2nm/s, and thickness is 40nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 9
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 2 prepares organic luminous layer.
The preparation of step (3) electron transfer layer: aforesaid substrate is sent in the organic vapor deposition chamber, on above-mentioned organic membrane, deposits TPBI, evaporation rate is 0.1-0.2nm/s, and thickness is 50nm, keeps chamber vacuum degree 3 * 10 in the evaporate process
-4Pa.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 10
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; OXD-7 and green ion-type phosphor material Irdf-pybi are dissolved in 1 according to weight ratio at 6: 3: 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 11
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 10 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 12
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; OXD-7 and red ion-type phosphor material Ir-qlbi are dissolved in 1 according to weight ratio at 6.34: 3.16: 0.5, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 13
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 12 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 14
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; OXD-7 and blue ion-type phosphor material Ir-pzpy, red ion-type phosphor material Ir-qlbi were according to weight ratio 6: 3: 1: 0.2 is dissolved in 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 15
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 14 prepares luminescent layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 16
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; OXD-7 and blue ion-type phosphor material Ir-pzpy, red ion-type phosphor material Ir-qlbi were according to weight ratio 6: 3: 1: 0.25 is dissolved in 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 17
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 16 prepares luminescent layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 18
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; OXD-7 and blue ion-type phosphor material Ir-pzpy, red ion-type phosphor material Ir-qlbi were according to weight ratio 6: 3: 1: 0.33 is dissolved in 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 19
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 18 prepares luminescent layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 20
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; OXD-7 and blue ion-type phosphor material Ir-pzpy, green ion-type phosphor material Irdf-pybi; Red ion-type phosphor material Ir-qlbi was according to weight ratio 6: 3: 1: be dissolved in 1 at 0.05: 0.2, in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 21
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 20 prepares luminescent layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 22
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part DCB; OXD-7 and blue ion-type phosphor material Ir-pzpy are dissolved in 1 according to weight ratio at 6: 3: 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 50 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 23
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 22 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 24
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part CPTBF; OXD-7 and blue ion-type phosphor material Ir-pzpy are dissolved in 1 according to weight ratio at 6: 3: 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 25
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 24 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 26
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part TBCPF; PBD and green ion-type phosphor material Irdf-pybi are dissolved in 1 according to weight ratio at 6: 3: 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 27
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 26 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 28
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; Micromolecule material of main part TBCPIPDI and blue ion-type phosphor material Ir-pzpy are dissolved in 1 according to weight ratio at 9: 1; In the 2-dichloroethanes; Spin coating obtains luminescent layer on aforesaid substrate then, on 80 ℃ hot plate, carries out annealing in process 30min, and thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 29
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 28 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 30
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; Micromolecule material of main part TBCPIPDA and blue ion-type phosphor material Ir-pzpy are dissolved in 1 according to weight ratio at 9: 1; In the 2-dichloroethanes; Spin coating obtains luminescent layer on aforesaid substrate then, on 80 ℃ hot plate, carries out annealing in process 30min, and thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 31
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 30 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 32
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part DCB; OXD-7 and blue ion-type phosphor material Ir-pzpy, red ion-type phosphor material Ir-qlbi were according to weight ratio 6: 3: 1: 0.25 is dissolved in 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 50 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 33
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 32 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 34
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; With micromolecule material of main part CPTBF; OXD-7 and blue ion-type phosphor material Ir-pzpy, red ion-type phosphor material Ir-qlbi were according to weight ratio 6: 3: 1: 0.25 is dissolved in 1, and in the 2-dichloroethanes, spin coating obtains luminescent layer on aforesaid substrate then; On 80 ℃ hot plate, carry out annealing in process 30min, thickness is 80-100nm.
Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 35
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 34 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 36
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; Micromolecule material of main part TBCPIPDI and blue ion-type phosphor material Ir-pzpy, red ion-type phosphor material Ir-qlbi are dissolved in 1 according to weight ratio at 9: 1: 0.25; In the 2-dichloroethanes; Spin coating obtains luminescent layer on aforesaid substrate then, on 80 ℃ hot plate, carries out annealing in process 30min, and thickness is 80-100nm.Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 37
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 36 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
Embodiment 38
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
The preparation of step (2) organic luminous layer: above-mentioned substrate through anode modification is sent in the glove box of nitrogen protection; Micromolecule material of main part TBCPIPDA and blue ion-type phosphor material Ir-pzpy, red ion-type phosphor material Ir-qlbi are dissolved in 1 according to weight ratio at 9: 1: 0.25; In the 2-dichloroethanes; Spin coating obtains luminescent layer on aforesaid substrate then, on 80 ℃ hot plate, carries out annealing in process 30min, and thickness is 80-100nm.Method according to the step (3) of embodiment 1 prepares negative electrode.
Embodiment 39
Method according to the step (1) of embodiment 1 prepares anode on glass substrate.
Method according to the step (2) of embodiment 38 prepares organic luminous layer.
Method according to the step (3) of embodiment 7 prepares electron transfer layer.
Method according to the step (4) of embodiment 6 prepares negative electrode.
The performance of device sees following table for details among the foregoing description 1-39:
| The embodiment numbering | High-high brightness [cdm -2] | Maximal efficiency [cdA -1] | Chromaticity coordinates [x, y] | Color rendering index (to white light parts) |
| 1 | 1950 | 2.3 | (0.16，0.25) | - |
| 2 | 11500 | 10.2 | (0.18，0.45) | - |
| 3 | 9800 | 9.8 | (0.18，0.45) | - |
| 4 | 12700 | 9.5 | (0.18，0.46) | - |
| 5 | 7600 | 7.4 | (0.19，0.46) |
| 6 | 14000 | 13.3 | (0.18，0.45) | - |
| 7 | 17700 | 19.8 | (0.19，0.46) | - |
| 8 | 21300 | 20.5 | (0.19，0.48) | - |
| 9 | 19300 | 21.4 | (0.21，0.52) | - |
| 10 | 3400 | 1.5 | (0.46，0.52) | - |
| 11 | 26500 | 22.1 | (0.46，0.52) | - |
| 12 | 1900 | 1.1 | (0.65，0.35) | - |
| 13 | 5700 | 3.4 | (0.66，0.34) | - |
| 14 | 9800 | 6.5 | (0.35，0.44) | 67 |
| 15 | 17000 | 11.1 | (0.34，0.44) | 67 |
| 16 | 7700 | 6.2 | (0.37，0.44) | 71 |
| 17 | 19000 | 12.4 | (0.35，0.44) | 68 |
| 18 | 5800 | 4.9 | (0.42，0.43) | 75 |
| 19 | 18000 | 11.2 | (0.39，0.43) | 73 |
| 20 | 12500 | 10.4 | (0.42，0.45) | 84 |
| 21 | 27000 | 19.7 | (0.43，0.45) | 85 |
| 22 | 8700 | 7.8 | (0.19，0.46) | - |
| 23 | 15800 | 16.4 | (0.19，0.46) | - |
| 24 | 10800 | 9.3 | (0.18，0.45) | - |
| 25 | 16900 | 17.9 | (0.19，0.46) | - |
| 26 | 2900 | 1.3 | (0.46，0.52) | - |
| 27 | 27000 | 23.4 | (0.46，0.52) | - |
| 28 | 6500 | 5.3 | (0.19，0.46) | - |
| 29 | 14500 | 12.6 | (0.20，0.48) | - |
| 30 | 7200 | 6.7 | (0.19，0.46) | - |
| 31 | 15400 | 13.9 | (0.20，0.48) | - |
| 32 | 6300 | 4.5 | (0.38，0.44) | 70 |
| 33 | 18700 | 8.7 | (0.38，0.44) | 71 |
| 34 | 7100 | 5.8 | (0.37，0.44) | 70 |
| 35 | 19400 | 10.8 | (0.37，0.44) | 70 |
| 36 | 4300 | 3.9 | (0.38，0.44) | 69 |
| 37 | 9600 | 8.1 | (0.38，0.44) | 70 |
| 38 | 5600 | 4.2 | (0.39，0.44) | 71 |
| 39 | 11200 | 9.5 | (0.39，0.44) | 71 |
Claims (16)
1. organic electroluminescence device; Comprise anode, negative electrode and the organic luminous layer between two electrodes; Comprise material of main part and guest materials in the said organic luminous layer; Wherein material of main part adopts triplet energy level greater than 2.0eV, the glass transition temperature small molecule material greater than 50 ℃; It is characterized in that guest materials is selected from the ion-type Ir metal complex of red emission, the ion-type Ir metal complex of said red emission is selected from two (2-phenylpyridine) iridium (III) (2-(1-phenyl-2-benzimidazolyl) quinoline) hexafluorophosphates; Perhaps
Be selected from the ion-type Ir metal complex of green emission, the ion-type Ir metal complex of said green emission is selected from two (2-(2, the 4-difluorophenyl) pyridine) iridium (III) (1-phenyl-2-(2-pyridine radicals) benzimidazole) hexafluorophosphates; Perhaps
Be selected from the ion-type Ir metal complex of blue emission; The ion-type Ir metal complex of said blue emission is selected from two (2-(2, the 4-difluorophenyl) pyridine) iridium (III) (2-(N-pyrazolyl) pyridine) hexafluorophosphates or two (2-phenylpyridine) iridium (III) (2-(N-pyrazolyl) pyridine) hexafluorophosphate; Perhaps
When organic electroluminescence device is a kind of white light parts; Said guest materials is two kinds; Be selected from the ion-type Ir metal complex of red emission and the ion-type Ir metal complex of blue emission respectively; The ion-type Ir metal complex of said red emission is selected from two (2-phenylpyridine) iridium (III) (2-(1-phenyl-2-benzimidazolyl) quinoline) hexafluorophosphates, and the ion-type Ir metal complex of used blue emission is selected from two (2-phenylpyridine) iridium (III) (2-(N-pyrazolyl) pyridine) hexafluorophosphates; Perhaps
When organic electroluminescence device is a kind of white light parts; Said guest materials is three kinds; Be selected from the ion-type Ir metal complex of red emission, the ion-type Ir metal complex of green emission and the ion-type Ir metal complex of blue emission respectively; The ion-type Ir metal complex of described red emission is selected from two (2-phenylpyridine) iridium (III) (2-(1-phenyl-2-benzimidazolyl) quinoline) hexafluorophosphates; The ion-type Ir metal complex of used green emission is selected from that two (2-(2; The 4-difluorophenyl) iridium (III) (1-phenyl-2-(2-pyridine radicals) benzimidazole) hexafluorophosphate pyridine), the ion-type Ir metal complex of used blue emission are selected from two (2-(2, the 4-difluorophenyl) pyridine) iridium (III) (2-(N-pyrazolyl) pyridine) hexafluorophosphates.
2. organic electroluminescence device according to claim 1 is characterized in that, said material of main part has good wet method filming performance, and not only has the hole transport function but also have the electric transmission function.
3. organic electroluminescence device according to claim 2 is characterized in that, said material of main part is a kind of, and this material has hole transport function and electric transmission function simultaneously, is selected from the substituted indeno pyridazine class of carbazyl derivative.
4. organic electroluminescence device according to claim 3 is characterized in that said material of main part is selected from 5; 5-pair [(4-(3,6-di-t-butyl-9-carbazyl) phenyl] indeno [1,2-c] pyridazine or 9; 9-pair [(4-(3,6-di-t-butyl-9-carbazyl) phenyl] indeno [1,2-d] pyridazine.
5. organic electroluminescence device according to claim 2 is characterized in that, said material of main part is two kinds; A kind of for having the hole transport materials with function; Be selected from fluorene derivative or carbazoles derivative, another kind of for having the electric transmission materials with function, Xuan Zi oxadiazole analog derivative.
6. organic electroluminescence device according to claim 5 is characterized in that, said have a hole transport materials with function, is selected from N; N '-two carbazyl-1,4-dimethylene benzene, 9,9-is two, and [(4-(3; 6-di-t-butyl-9-carbazyl) phenyl] fluorenes, 9, two [4-(9-carbazyl) phenyl]-2 of 9-, 7-di-tert-butyl-fluorene; Said have the electric transmission materials with function and be selected from 1, two [(the 4-tert-butyl-phenyls)-1,3 of 3-; 4-oxadiazole base] benzene, 2-(4-diphenyl)-5-(4-tert-butyl-phenyl)-1,3, the 4-oxadiazole.
7. organic electroluminescence device according to claim 5 is characterized in that, in the said material of main part, the weight ratio that possesses the hole transport materials with function and possess the electric transmission materials with function is between 10: 1～1: 10.
8. organic electroluminescence device according to claim 1; It is characterized in that; When organic electroluminescence device is a kind of white light parts; When said guest materials was two kinds, the ion-type Ir metal complex weight ratio of the ion-type Ir metal complex of the red emission that said guest materials is used and blue emission was between 1: 20～1: 100.
9. organic electroluminescence device according to claim 1; It is characterized in that; When organic electroluminescence device is a kind of white light parts; When said guest materials was three kinds, the weight ratio of the ion-type Ir metal complex of the ion-type Ir metal complex of the red emission that said guest materials is used, the ion-type Ir metal complex of green emission and blue emission was between 1: 0.01: 100～1: 0.5: 20.
10. organic electroluminescence device according to claim 1 is characterized in that, said organic light emission layer thickness is 80nm～120nm.
11. organic electroluminescence device according to claim 1 is characterized in that, between anode and organic luminous layer, is provided with the anode modification layer, its material is PEDOT:PSS, and its thickness is 20nm～60nm.
12. organic electroluminescence device according to claim 1 is characterized in that, said negative electrode adopts composite construction, and material is selected from Cs
2CO
3With Al, Cs
2CO
3With Ag, CsF and Al or CsF and Ag.
13. organic electroluminescence device according to claim 1 is characterized in that, between negative electrode and organic luminous layer, is provided with electron transfer layer, material is selected from 1,3,5-three (1-phenyl-2-benzimidazolyl) benzene.
14. a method for preparing the described organic electroluminescence device of claim 1, the organic luminous layer of employing wet method fabricate devices adopts the method for vacuum evaporation to prepare negative electrode.
15. a method for preparing the described organic electroluminescence device of claim 11 adopts anode modification layer and organic luminous layer in the wet method fabricate devices, adopts the method for vacuum evaporation to prepare negative electrode.
16. a method for preparing the described organic electroluminescence device of claim 13 adopts the organic luminous layer in the wet method fabricate devices, adopts the method for vacuum evaporation to prepare electron transfer layer and negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910090378A CN101651184B (en) | 2009-08-07 | 2009-08-07 | Organic electroluminescence device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910090378A CN101651184B (en) | 2009-08-07 | 2009-08-07 | Organic electroluminescence device and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101651184A CN101651184A (en) | 2010-02-17 |
| CN101651184B true CN101651184B (en) | 2012-09-05 |
Family
ID=41673359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910090378A Active CN101651184B (en) | 2009-08-07 | 2009-08-07 | Organic electroluminescence device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101651184B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408448B (en) * | 2010-09-21 | 2015-04-15 | 中国科学院福建物质结构研究所 | Phosphorescence material for detecting hypochlorite |
| CN104250248A (en) * | 2013-06-26 | 2014-12-31 | 海洋王照明科技股份有限公司 | Bipolar blue phosphorescent compound, preparation method thereof and organic electroluminescent device |
| KR101880595B1 (en) * | 2015-12-10 | 2018-07-20 | 성균관대학교산학협력단 | Organic electroluminescent compound, producing method of the same and organic electroluminescent device including the same |
| CN107452884B (en) * | 2017-07-04 | 2019-08-09 | 华南师范大学 | Phosphorescent molecules sensitization multilayered structure light emitting diode with quantum dots of whole soln processing and preparation method thereof |
| CN108933201B (en) * | 2017-12-12 | 2020-03-20 | 广东聚华印刷显示技术有限公司 | Light emitting device and method of manufacturing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101452999A (en) * | 2008-12-31 | 2009-06-10 | 清华大学 | A white light organic electroluminescent devices |
-
2009
- 2009-08-07 CN CN200910090378A patent/CN101651184B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101452999A (en) * | 2008-12-31 | 2009-06-10 | 清华大学 | A white light organic electroluminescent devices |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101651184A (en) | 2010-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100448058C (en) | Organic electroluminescent device | |
| CN100586243C (en) | A kind of red organic electroluminescence device and preparation method thereof | |
| CN103137881B (en) | Organnic electroluminescent device and preparation method thereof | |
| CN101740724B (en) | Organic electroluminescent device and preparation method thereof | |
| CN101651184B (en) | Organic electroluminescence device and preparation method thereof | |
| CN102097594A (en) | Organic light-emitting device | |
| CN110335954B (en) | Efficient and stable white light organic electroluminescent device and preparation method thereof | |
| CN101159315A (en) | Red organic electroluminescent device and method for fabricating the same | |
| CN105826483A (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN101262045B (en) | An organic EL part and its making method | |
| CN102683608B (en) | Organic electroluminescent device and preparation method of organic electroluminescent device | |
| CN101452999B (en) | A white light organic electroluminescent devices | |
| CN101114699A (en) | Novel electroluminescent device and method for producing the same | |
| CN106340594A (en) | White-light organic electroluminescent device and preparation method thereof | |
| CN103137876B (en) | Organnic electroluminescent device and preparation method thereof | |
| CN105870350B (en) | Organic luminescent device | |
| CN101022156A (en) | Blue organic electroluminescent device and producing method thereof | |
| CN101051673B (en) | Organic electroluminescence device capable of emitting green light, purple light and white light | |
| CN101740723B (en) | Organic electroluminescent device and preparation method thereof | |
| Yin et al. | High performance solution-processed red phosphorescent organic light-emitting diodes by co-doping europium complex as sensitizer | |
| CN100448051C (en) | Organic electroluminescence device | |
| CN1976085B (en) | Organic electroluminescent device and producing method thereof | |
| CN103594660A (en) | Organic electroluminescent device and preparation method thereof | |
| CN103137887B (en) | A kind of electroluminescent device and preparation method thereof | |
| CN1964096A (en) | An organic electroluminescent device and its manufacture method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |