CN103730605A

CN103730605A - Preparation method of organic electroluminescence display device

Info

Publication number: CN103730605A
Application number: CN201410037092.0A
Authority: CN
Inventors: 刘小燕; 刘仁玉
Original assignee: NANTONG XIANGYANG OPTICAL ELEMENT CO Ltd
Current assignee: NANTONG XIANGYANG OPTICAL ELEMENT CO Ltd
Priority date: 2014-01-26
Filing date: 2014-01-26
Publication date: 2014-04-16
Anticipated expiration: 2034-01-26
Also published as: CN103730605B

Abstract

The invention relates to a preparation method of an organic electroluminescence display device. The preparation method is characterized by comprising the following steps: 1, printing an ITO (Indium Tin Oxide) positive electrode pattern on a substrate, respectively performing ultrasonic cleaning on the substrate printed with the ITO positive electrode pattern by using methylbenzene, alcohol and acetone; 2, evaporating a mixture of 1,3,5-triphenyl (diphenylamine) and SiCl4 and a polyazomethine polymer on the substrate printed with the indium tin oxide (ITO) by using a vacuum evaporation method, wherein the deposition rate is 0.6-1.0nm/s and the mass percent is (1.0-3.5):(2.0-5.5):(97.0-94.0); 3, vacuum-evaporating an organic luminescent material on SiCl4. Negative electrode materials LiF and Al are evaporated by adopting the vacuum evaporation method so that a mixed negative electrode is prepared, the system vacuum degree is maintained to be 1*10<-6>Pa, the deposition rate of the negative electrode material is 1.5nm/s, and the thicknesses of the LiF and the Al are respectively about 0.3nm and about 40nm.

Description

A kind of preparation method of organic elctroluminescent device

Technical field

The invention belongs to organic functional molecular material and electroluminescent organic material technical field, be specifically related to class efficient hole material and a preparation method, and the application in organic electroluminescence device.

Background technology

Electroluminescent organic material is the material foundation of OLED device.OLED basic device structure generally includes transparent anode, hole transmission layer, luminescent layer, electron transfer layer and metal negative electrode etc.The effect of hole transmission layer is to improve the efficiency of transmission of hole in device, electronics is blocked in luminescent layer effectively, and the maximum that realizes charge carrier is compound, and reduce hole inject time energy barrier, improve hole injection efficiency, improve brightness, efficiency and the life-span of device.Meanwhile, it is a major reason of component failure that hole transmission layer lost efficacy under heat effect, and the thermal stability of raising hole mobile material can effectively prevent that this inefficacy from occurring.

Summary of the invention

The present invention prepares and contains 1,3,5-tri-(hexichol amido) benzene and SiCl4 and poly methylene imine as hole mobile material.The preparation method of the display of organic electroluminescence that contains this material comprises: 1) on substrate, print ito anode figure, the substrate of the ito anode figure printing is carried out to ultrasonic cleaning with toluene, ethanol and acetone respectively; 2) with method evaporation 1 on the substrate that prints tin indium oxide ito anode figure of vacuum evaporation, 3, the mixture of 5-tri-(hexichol amido) benzene and SiCl4 and poly methylene imine polymer, deposition rate is 0.6-1.0nm/s, and mass percent is 1.0-3.5: 2.0-5.5: 97.0-94.0; 3) vacuum evaporation plating machine luminescent material on SiCL4; The method evaporation cathode material Li and the Al mixing negative electrode that adopt vacuum evaporation, system vacuum degree maintains 1 × 10-6Pa, and the deposition rate of cathode material is 1.5nm/s, and the thickness of LiF and Al is respectively about 0.3nm and about 40nm.

Wherein, the preparation method of poly methylene imine is:

Take diamine monomer and dialdehyde monomer as reaction monomers, the mol ratio of diamine monomer and dialdehyde monomer is 1～1.01, take anhydrous calcium chloride or anhydrous Lithium chloride as catalyst, catalyst and reaction monomers mass ratio are 0～0.023: 1, take anhydrous 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF) or dimethylacetylamide (DMAc) as solvent, solid content is 10wt%～15wt%; Being equipped with in the three-necked bottle of stirrer, nitrogen protection, add reaction monomers, catalysts and solvents, in temperature, be to react 24～36 hours under the boiling point condition of 20 ℃～solvent; Then discharging is in absolute ethyl alcohol, ethanol extracting 12 hours for the solid obtaining, and dry 7～9 hours of 70 ℃, vacuum, obtains solid powdery poly methylene imine material.

The hole mobility of the application's who is recorded by time-of-flight method hole transmission layer is 0.96 × 10-4～4.0 × 10-4cm2V-1s-1, it has good dissolubility when having higher vitrification point Tg and good thermal stability, meet the requirement of hole mobile material, technique is simple, practical.

Accompanying drawing explanation

Fig. 1 is the pattern sectional view that represents organic EL one example of the 1st execution mode.

Substrate, 2-hole injecting electrode, 3-hole injection layer

4-hole transporting layer, 5-luminescent layer, 6-hole trapping layer

7-electron injecting layer

8-electron injection electrode

100 organic electroluminescent devices

206: crown cap

Embodiment

Embodiment 1,

On substrate, print ito anode figure, the substrate of the ito anode figure printing is carried out to ultrasonic cleaning with toluene, ethanol and acetone respectively; 2, with method evaporation 1 on the substrate that prints tin indium oxide ito anode figure of vacuum evaporation, 3, the mixture of 5-tri-(hexichol amido) benzene and SiCl4 and poly methylene imine polymer, deposition rate is 0.6-1.0nm/s, and mass percent is 1.0-3.5: 2.0-5.5: 97.0-94.0; 3, vacuum evaporation plating machine luminescent material on SiCL4; Adopt method evaporation cathode material Li and the Al mixing negative electrode of vacuum evaporation, maintain × 10-6Pa of system vacuum degree, the deposition rate of cathode material is 1.5nm/s, the thickness of LiF and Al is 0.3nm and 40nm respectively; 4) device is carried out to overall package.

Wherein, the preparation method of poly methylene imine polymer is: take diamine monomer and dialdehyde monomer as reaction monomers, the mol ratio of diamine monomer and dialdehyde monomer is 1, take anhydrous calcium chloride or anhydrous Lithium chloride as catalyst, catalyst and reaction monomers mass ratio are 0～0.02: 1, take anhydrous 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF) or dimethylacetylamide (DMAc) as solvent, solid content is 10wt%; Being equipped with in the three-necked bottle of stirrer, nitrogen protection, add reaction monomers, catalysts and solvents, in temperature, be to react 36 hours under the boiling point condition of 20 ℃～solvent; Then discharging is in absolute ethyl alcohol, ethanol extracting 12 hours for the solid obtaining, and dry 7 hours of 70 ℃, vacuum, obtains poly methylene imine material.

Fig. 1 is the pattern sectional view that represents an example of the organic EL of the 1st execution mode.Organic EL 100, has the laminar structure that lamination hole injecting electrode 2 (anode), organic compound layer 10 and electron injection electrode 8 (negative electrode) form successively on substrate 1.Organic compound layer 10 is to consist of hole injection layer 3, hole transmission layer 4 (mixture described in the application), luminescent layer 5, hole trapping layer 6 and electron injecting layer 7.

Substrate 1 is the transparency carrier consisting of glass or plastics etc.Hole injecting electrode 2 is transparency electrode or the semitransparent electrodes that consist of metal or alloy such as metallic compound, the silver such as indium-tin-oxide (hereinafter to be referred as ITO).Negative electrode 8 is by the metallic compounds such as magnesium-indium alloy or ITO or Li and Al mixing negative electrode, can be transparency electrode, semitransparent electrode or opaque electrode.Wherein, during evaporation cathode material, system vacuum degree maintains 1 × 10-6Pa, and the deposition rate of cathode material is 1.5nm/s, and the thickness of LiF and Al is respectively about 0.3nm and about 40nm.

The evaporation of hole transmission layer is 1 × 10-6Pa and substrate 1 is not carried out carrying out under temperature controlled condition in vacuum degree.

Hole injection layer 3 can consist of copper phthalocyanine.

Luminescent layer 5 consists of main material described later, light-emitting dopant and auxiliary dopant.Luminescent layer 5 is by the main material consisting of CBP, and the auxiliary dopant that interpolation consists of Ir (ppy) 3 generates.The ratio of the light-emitting dopant adding to luminescent layer 5 is 2 % by weight of luminescent layer.The thickness of the luminescent layer 5 forming is 250nm.The evaporation condition of luminescent layer 5 is identical with the evaporation condition of hole injection layer 3.

On the surface of formed luminescent layer 5, by vacuum vapour deposition, form the electron supplying layer being formed by BCP.The thickness of the electron supplying layer forming is 200.The evaporation condition of electron supplying layer is identical with the evaporation condition of hole injection layer 3.

And luminescent layer can contain make triplet excitation power conversion become luminous light-emitting dopant, by the auxiliary dopant that makes triplet excitation power conversion become luminous material to form and triplet excitation energy is helped out to the movement of described light-emitting dopant.For example: in luminescent layer, further contain main material, between the highest occupied MO energy level H2 of the highest occupied MO energy level H0 of described main material and the highest occupied MO energy level H1 of described light-emitting dopant and described auxiliary dopant, there is the relation of H0 > H2 > H1, between the energy level L2 of the energy level L1 of the energy level L0 of the lowest unoccupied molecular orbital (LUMO) of described main material and the lowest unoccupied molecular orbital (LUMO) of described light-emitting dopant and the lowest unoccupied molecular orbital (LUMO) of described auxiliary dopant, there is the relation of L0 > L2 > L1.

By light-emitting dopant, make triplet excitation power conversion become luminous, can obtain thus high-luminous-efficiency.No matter in addition, by auxiliary dopant, triplet excitation energy is moved to light-emitting dopant, therefore, be which kind of color the illuminant colour of light-emitting dopant is, can both obtain higher luminous efficiency.

For example, luminescent layer main material is: the organic materials such as 4,4 '-bis-(carbazole-9-yl)-biphenyl (4,4 '-Bis (carbazol-9-yl)-biphenyl) (being called for short CPB) form.As light-emitting dopant D1, can use two (2-phenyl benzo thiozolato-N, C2) iridium (acetylacetonate), or the triplet organic material of similar ortho-metalated complex.

Electron injecting layer by as three (8-hydroxyl quinolinato) aluminium Tris (8-hydroxyquinolinato) aluminum) organic material such as (be called for short Alq) forms.

Finally, on the electron supplying layer surface forming, by vacuum vapour deposition, form the composite electron injecting electrode 8 being formed by LiF, Al.The thickness of LiF and Al is respectively about 0.3nm and about 40nm.

Claims

1. a preparation method for organic elctroluminescent device, is characterized in that, comprises the steps: 1) on substrate, print ito anode figure, the substrate of the ito anode figure printing is carried out to ultrasonic cleaning with toluene, ethanol and acetone respectively; 2) with method evaporation 1 on the substrate that prints tin indium oxide ito anode figure of vacuum evaporation, 3, the mixture of 5-tri-(hexichol amido) benzene and SiCl4 and poly methylene imine polymer, deposition rate is 0.6-1.0nm/s, and mass percent is 1.0-3.5: 2.0-5.5: 97.0-94.0; 3) vacuum evaporation plating machine luminescent material on SiCL4; The method evaporation cathode material LiF and the Al mixing negative electrode that adopt vacuum evaporation, system vacuum degree maintains 1 × 10-6Pa, and the deposition rate of cathode material is 1.5nm/s, and the thickness of LiF and Al is respectively about 0.3nm and about 40nm.

2. one kind adopts the organic elctroluminescent device that as claimed in claim 1 prepared by method