CN104167493A - Organic light emitting device and preparation method thereof - Google Patents
Organic light emitting device and preparation method thereof Download PDFInfo
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- CN104167493A CN104167493A CN201310187384.8A CN201310187384A CN104167493A CN 104167493 A CN104167493 A CN 104167493A CN 201310187384 A CN201310187384 A CN 201310187384A CN 104167493 A CN104167493 A CN 104167493A
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- 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
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Abstract
The invention provides an organic light emitting device comprising an anode substrate, a light emitting function layer, a cathode and an encapsulation layer which are stacked sequentially. The encapsulation layer is of a composite structure formed by repeatedly arranging an encapsulation layer unit. Each encapsulation layer unit includes a first organic barrier layer, a first inorganic barrier layer, a second organic barrier layer and a second inorganic barrier layer which are stacked sequentially, wherein the first organic barrier layer and the second organic barrier layer are made of a mixed material formed by mixing a first organic material and a second organic material, the first inorganic barrier layer is made of a mixed material formed by doping an oxide of rhenium in a metal nitride, and the second inorganic barrier layer is made of a mixed material formed by doping a carbide in an oxide of rhenium. The invention further provides a preparation method of the organic light emitting device. The method can effectively reduce erosion of water and oxygen to the device and increase the service life of the device.
Description
Technical field
The present invention relates to organic electroluminescence device, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is between transparent anode and metallic cathode, to accompany multilayer organic material film (hole injection layer, hole transmission layer, luminescent layer, electron supplying layer and electron injecting layer), and after applying certain voltage between electrode, luminescent layer will be luminous.In recent years, organic electroluminescence device because cost of manufacture own is low, the response time is short, luminosity is high, the feature such as wide visual angle, low driving voltage and energy-conserving and environment-protective has been subject to extensive concern in fields such as panchromatic demonstration, backlight and illuminations, and has been considered to be most likely at the device of new generation that occupies dominance on following illumination and display device market.
At present, the problem that organic electroluminescence device average life is shorter, this is mainly because organic material film is very loose, occurs rapidly aging after easily being infiltrated by compositions such as airborne steam and oxygen.Therefore, organic electroluminescence device must encapsulate before entering actual use, and the quality of encapsulation is directly connected to the life-span of organic electroluminescence device.
In conventional art, adopt glass cover or crown cap to encapsulate, its edge is resin-sealed by ultraviolet polymerization, but the glass cover using in this method or crown cap volume are often larger, increased the weight of device, and the method can not be applied to the give out light encapsulation of device of flexible organic electroluminescence.
Summary of the invention
For overcoming the defect of above-mentioned prior art, the invention provides a kind of organic electroluminescence device and preparation method thereof.This preparation method can reduce water, the erosion of oxygen isoreactivity material to organic electroluminescence device, the life-span of improving significantly organic electroluminescence device effectively.The organic electroluminescence device that the inventive method is applicable to prepare with conducting glass substrate, is also applicable to take the flexible organic electroluminescent device that plastics or metal are prepared as substrate.The inventive method is particularly useful for encapsulating flexible organic electroluminescent device.
On the one hand, the invention provides a kind of organic electroluminescence device, comprise the anode substrate, light emitting functional layer, negative electrode and the encapsulated layer that are cascading, described encapsulated layer is to repeat to arrange by encapsulated layer unit the composite construction forming, described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually
The material on described first organic barrier layer and second organic barrier layer is the composite material that the first organic material and the second organic material are mixed to form, and the mol ratio of described the first organic material and the second organic material is 0.4~0.6:1; Described the first organic material is N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-4,4 '-benzidine (TPD), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines (NPB), 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene (MADN), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA) or 1,3-bis-(9H-carbazole-9-yl) benzene (mCP); Described the second organic material is 4,7-diphenyl Phen (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), oxine aluminium (Alq3), two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium (Balq) or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole (TAZ);
The material of described the first inorganic barrier layer is the composite material that the oxide of metal nitride doping rhenium forms, and the doping mass fraction of the oxide of described rhenium is 10~30%; The material of described the second inorganic barrier layer is the composite material that the oxide-doped carbide of rhenium forms, and the doping mass fraction of described carbide is 10~30%; Described metal nitride is aluminium nitride (AlN), titanium nitride (TiN), vanadium nitride (VN), niobium nitride (NbN), zirconium nitride (ZrN), tantalum nitride (TaN); The oxide of described rhenium is Re
2o, ReO, Re
2o
3, ReO
2, Re
2o
5or ReO
3; Described carbide is carborundum (SiC), tungsten carbide (WC), ramet (TaC), boron carbide (BC), titanium carbide (TiC) or hafnium carbide (HfC).
Preferably, the thickness on described first organic barrier layer is 200~300nm, and the thickness on described second organic barrier layer is 200~300nm.
Preferably, the thickness of described the first inorganic barrier layer is 100~150nm, and the thickness of described the second inorganic barrier layer is 100~150nm.
Preferably, described encapsulated layer unit repeats to arrange 2~4 times.
Preferably, described light emitting functional layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually.
Preferably, anode substrate is conducting glass substrate or organic PETG substrate that conducts electricity.
In the present invention, the material of hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer and luminescent layer is not done concrete restriction, and this area current material is all applicable to the present invention.
Negative electrode can be non-transparent metals negative electrode (aluminium, silver, gold etc.), can be also transparent cathode (dielectric layer/metal level/dielectric layer structure that dielectric layer tramp metal layer forms etc.).
Encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer successively.
Wherein, in organic barrier layer, the first organic material is hole transport shaped material, the second organic material is electric transmission shaped material, a kind of electrophilic material, a kind of electronics material that obtains, the organic barrier layer that adopts above-mentioned two kinds of organic materials to be mixed with, rete evenness improves.The composite material preparation that the first inorganic barrier layer adopts the oxide of metal nitride doping rhenium to form, metal nitride has very strong hardness and durability, and waterproof oxygen ability is strong, and the oxide of rhenium can reduce nitride hardness, reduces fragility; The second inorganic barrier layer adopts the oxide-doped carbide preparation of rhenium, and the oxide stress of rhenium is less, and carbide evenness is good, and two kinds of materials are in conjunction with the rete that has evenness and barrier concurrently can be provided.The present invention adopts organic barrier layer and inorganic barrier layer alternately to repeat to arrange the encapsulated layer of formation, finally can effectively stop extraneous water, the erosion of oxygen isoreactivity material to organic electroluminescence device, extends device useful life.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise the following steps:
On anode substrate, prepare successively light emitting functional layer and negative electrode;
At described cathode surface, prepare encapsulated layer, obtain organic electroluminescence device, described encapsulated layer is to repeat to arrange by encapsulated layer unit the composite construction forming, and described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually;
The material on described first organic barrier layer and second organic barrier layer is the composite material that the first organic material and the second organic material are mixed to form, and the mol ratio of described the first organic material and the second organic material is 0.4~0.6:1; Described the first organic material is N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-4,4 '-benzidine, N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines, 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines or 1,3-bis-(9H-carbazole-9-yl) benzene; Described the second organic material is 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole; Described first organic barrier layer and second organic barrier layer all adopt the mode of vacuum evaporation to prepare, and the vacuum degree in described vacuum evaporation process is 1 * 10
-5pa~1 * 10
-3pa, evaporation rate is
The material of described the first inorganic barrier layer is the composite material that the oxide of metal nitride doping rhenium forms, and the doping mass fraction of the oxide of described rhenium is 10~30%; The material of described the second inorganic barrier layer is the composite material that the oxide-doped carbide of rhenium forms, and the doping mass fraction of described carbide is 10~30%; Described metal nitride is aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, zirconium nitride, tantalum nitride; The oxide of described rhenium is Re
2o, ReO, Re
2o
3, ReO
2, Re
2o
5or ReO
3; Described carbide is carborundum, tungsten carbide, ramet, boron carbide, titanium carbide or hafnium carbide; Described the first inorganic barrier layer and the second inorganic barrier layer all adopt the mode of electron beam evaporation plating to prepare, and in described electron beam evaporation plating process, vacuum degree is 1 * 10
-5~1 * 10
-3pa.
Preferably, the thickness on described first organic barrier layer is 200~300nm, and the thickness on described second organic barrier layer is 200~300nm.
Preferably, the thickness of described the first inorganic barrier layer is 100~150nm, and the thickness of described the second inorganic barrier layer is 100~150nm.
Preferably, described encapsulated layer unit repeats to arrange 2~4 times.
Preferably, described light emitting functional layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually.
Preferably, anode substrate is conducting glass substrate or organic PETG substrate that conducts electricity.
Preferably, anode substrate is carried out to following clean: carry out successively acetone cleaning, ethanol cleaning, pure water cleaning and ethanol and clean, all with supersonic wave cleaning machine, clean, each washing adopts cleans 5 minutes, and then stand-by by oven for drying, then the anode substrate after cleaning is carried out to surface activation process.
Preferably, light emitting functional layer arranges by the method for vacuum evaporation or the method for solution coating.In the present invention, the material of hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer and luminescent layer is not done concrete restriction, and this area current material is all applicable to the present invention.
Negative electrode can be non-transparent metals negative electrode (aluminium, silver, gold etc.), can be also transparent cathode (dielectric layer/metal level/dielectric layer structure that dielectric layer tramp metal layer forms etc.).Negative electrode adopts the mode of vacuum evaporation to prepare.
Encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer successively.
Particularly, the preparation process of encapsulated layer unit comprises: first at cathode surface, adopt the mode of vacuum evaporation to prepare first organic barrier layer, then on described first organic barrier layer, adopt the mode of electron beam evaporation plating to prepare the first inorganic barrier layer, at the first inorganic barrier layer, adopt the mode of vacuum evaporation to prepare second organic barrier layer again, then on second organic barrier layer, adopt the mode of electron beam evaporation plating to prepare the second inorganic barrier layer.Repeatedly prepare according to this encapsulated layer unit, form the encapsulated layer with composite construction.Preferably, described encapsulated layer unit repeats to arrange 2~4 times.
Wherein, in organic barrier layer, the first organic material is hole transport shaped material, the second organic material is electric transmission shaped material, a kind of electrophilic material, a kind of electronics material that obtains, the organic barrier layer that adopts above-mentioned two kinds of organic materials to be mixed with, rete evenness improves.The composite material preparation that the first inorganic barrier layer adopts the oxide of metal nitride doping rhenium to form, metal nitride has very strong hardness and durability, and waterproof oxygen ability is strong, and the oxide of rhenium can reduce nitride hardness, reduces fragility; The second inorganic barrier layer adopts the oxide-doped carbide preparation of rhenium, and the oxide stress of rhenium is less, and carbide evenness is good, and two kinds of materials are in conjunction with the rete that has evenness and barrier concurrently can be provided.The present invention adopts organic barrier layer and inorganic barrier layer alternately to repeat to arrange the encapsulated layer of formation, finally can effectively stop extraneous water, the erosion of oxygen isoreactivity material to organic electroluminescence device, extends device useful life.
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) encapsulated layer of organic electroluminescence device of the present invention has composite construction, by organic barrier layer and inorganic barrier layer, alternately repeated to arrange to form, this encapsulated layer good airproof performance, can effectively reduce water, the erosion of oxygen isoreactivity material to organic electroluminescence device, effectively defencive function layer and negative electrode exempt from destruction in subsequent operation process simultaneously, thereby significantly improve the life-span of organic electroluminescence device;
(2) water resistance of organic electroluminescence device of the present invention (WVTR) reaches 10
-4g/m
2day, device lifetime (T70@1000cd/m
2) reach more than 6500 hours;
(3) the inventive method is applicable to encapsulation and take the organic electroluminescence device that electro-conductive glass prepared as anode substrate, also be applicable to encapsulation and take the flexible organic electroluminescent device that plastics or metal prepared as anode substrate, the inventive method is particularly useful for encapsulating flexible organic electroluminescent device;
(4) organic electroluminescence device material of the present invention is cheap, and method for packing technique is simple, and easily large area preparation is suitable for large-scale industrialization and uses.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device that makes of the embodiment of the present invention 1.
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) on anode substrate, prepare light emitting functional layer and negative electrode
A. the pre-treatment of conducting glass substrate
Get ito glass substrate, carry out successively acetone cleaning, ethanol cleaning, pure water cleaning and ethanol and clean, all with supersonic wave cleaning machine, clean, each washing employing cleaning 5 minutes, after oven dry, carries out surface activation process to the ito glass substrate after cleaning; ITO thickness 100nm;
B. the preparation of light emitting functional layer and negative electrode
Adopt the method for vacuum evaporation on ito glass substrate, to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode;
The preparation of hole injection layer: by MoO
3be doped into N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, in 4 '-diamines (NPB), as hole injection layer material, doping mass concentration is 30%, thickness is 10nm, vacuum degree 3 * 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) is as hole mobile material, vacuum degree 3 * 10
-5pa, evaporation rate
evaporation thickness 30nm;
The preparation of luminescent layer: material of main part adopts 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), guest materials adopts three (2-phenylpyridines) to close iridium (Ir (ppy)
3), guest materials doping mass concentration is 5%, will after material of main part and guest materials mixing and doping, steam altogether, vacuum degree is 3 * 10
-5pa, evaporation rate is
evaporation thickness 20nm;
The preparation of electron transfer layer: adopt 4,7-diphenyl-1,10-phenanthroline (Bphen) is as electron transport material, vacuum degree 3 * 10
-5pa, evaporation rate
evaporation thickness 10nm;
The preparation of electron injecting layer: by CsN
3mix 4,7-diphenyl-1, in 10-phenanthroline (Bphen) as electronic injection layer material, doping mass concentration 30%, vacuum degree 3 * 10
-5pa, evaporation rate
evaporation thickness 20nm;
The preparation of negative electrode: negative electrode adopts metal A l, thickness 100nm, vacuum degree is 3 * 10
-5pa, evaporation rate is
(2) on negative electrode, repeat to prepare encapsulated layer unit 2 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare first organic barrier layer that a layer thickness is 250nm, the material on first organic barrier layer is mCP and the TAZ composite material that 0.4:1 is mixed to form in molar ratio, vacuum degree 1 * 10
-3pa, evaporation rate
B. adopt the mode of electron beam evaporation plating on first organic barrier layer, to prepare the first inorganic barrier layer that a layer thickness is 130nm; The material of the first inorganic barrier layer is TaN doping ReO
3the composite material forming, ReO
3doping mass fraction be 20%, the base vacuum degree in electron beam evaporation plating process is 1 * 10
-3pa;
C. adopt the mode of vacuum evaporation on the first inorganic barrier layer, to prepare second organic barrier layer that a layer thickness is 250nm, material is mCP and the TAZ composite material that 0.4:1 is mixed to form in molar ratio, vacuum degree 1 * 10
-3pa, evaporation rate
D. adopt the mode of electron beam evaporation plating on second organic barrier layer, to prepare the second inorganic barrier layer that a layer thickness is 100nm, the material of the second inorganic barrier layer is ReO
3the composite material that doping HfC forms, the doping mass fraction of HfC is 15%, the base vacuum degree in electron beam evaporation plating process is 1 * 10
-3pa;
E, repetition 1 step a, b, c, d, form the composite package layer with 2 encapsulated layer unit, obtains organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 4.3 * 10
-4, life-span (T70@1000cd/m
2) be 6504 hours.
Fig. 1 is the structural representation of the organic electroluminescence device that makes of the embodiment of the present invention 1.As shown in Figure 1, the present embodiment organic electroluminescence device, comprises ito glass substrate 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6, negative electrode 7 and encapsulated layer 8 successively.Described encapsulated layer 8 comprises two encapsulated layer unit, comprise that 2 layer thicknesses are first organic barrier layer 81 and 85 of 250nm, 2 layer thicknesses are the first inorganic barrier layer 82 and 86 of 130nm, 2 layer thicknesses are second organic barrier layer 83 of 250nm and the second inorganic barrier layer 84 and 88 that 87,2 layer thicknesses are 100nm.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer and negative electrode
Same with embodiment 1.
(2) on negative electrode, repeat to prepare encapsulated layer unit 3 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare the first organic stopping that a layer thickness is 250nm
Layer, the material on first organic barrier layer is NPB and the BCP composite material that 0.5:1 is mixed to form in molar ratio, vacuum degree 5 * 10
-5pa, evaporation rate
B. adopt the mode of electron beam evaporation plating on first organic barrier layer, to prepare the first inorganic barrier layer that a layer thickness is 100nm; The material of the first inorganic barrier layer is the composite material that TiN doping ReO forms, and the doping mass fraction of ReO is 10%, and the base vacuum degree in electron beam evaporation plating process is 5 * 10
-5pa;
C. adopt the mode of vacuum evaporation on the first inorganic barrier layer, to prepare second organic barrier layer that a layer thickness is 250nm, material is NPB and the BCP composite material that 0.5:1 is mixed to form in molar ratio, vacuum degree 5 * 10
-5pa, evaporation rate
D. adopt the mode of electron beam evaporation plating on second organic barrier layer, to prepare the second inorganic barrier layer that a layer thickness is 120nm, the material of the second inorganic barrier layer is the composite material that ReO doping WC forms, the doping mass fraction of WC is 20%, and the base vacuum degree in electron beam evaporation plating process is 1 * 10
-5pa;
E, repetition 2 step a, b, c, d, form the composite package layer with 3 encapsulated layer unit, obtains organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 3.5 * 10
-4, life-span (T70@1000cd/m
2) be 6586 hours.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer and negative electrode
Same with embodiment 1.
(2) on negative electrode, repeat to prepare encapsulated layer unit 3 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare first organic barrier layer that a layer thickness is 200nm, the material on first organic barrier layer is TAPC and the TPBi composite material that 0.5:1 is mixed to form in molar ratio, vacuum degree 5 * 10
-5pa, evaporation rate
B. adopt the mode of electron beam evaporation plating on first organic barrier layer, to prepare the first inorganic barrier layer that a layer thickness is 150nm; The material of the first inorganic barrier layer is VN doping Re
2o
3the composite material forming, Re
2o
3doping mass fraction be 30%, the base vacuum degree in electron beam evaporation plating process is 5 * 10
-5pa;
C. adopt the mode of vacuum evaporation on the first inorganic barrier layer, to prepare second organic barrier layer that a layer thickness is 200nm, material is TAPC and the TPBi composite material that 0.5:1 is mixed to form in molar ratio, vacuum degree 5 * 10
-5pa, evaporation rate
D. adopt the mode of electron beam evaporation plating on second organic barrier layer, to prepare the second inorganic barrier layer that a layer thickness is 120nm, the material of the second inorganic barrier layer is Re
2o
3the composite material that doping TaC forms, the doping mass fraction of TaC is 10%, the base vacuum degree in electron beam evaporation plating process is 1 * 10
-5pa;
E, repetition 2 step a, b, c, d, form the composite package layer with 3 encapsulated layer unit, obtains organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 3.6 * 10
-4, life-span (T70@1000cd/m
2) be 6567 hours.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer and negative electrode
Same with embodiment 1.
(2) on negative electrode, repeat to prepare encapsulated layer unit 3 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare first organic barrier layer that a layer thickness is 250nm, the material on first organic barrier layer is MADN and the Alq3 composite material that 0.6:1 is mixed to form in molar ratio, vacuum degree 5 * 10
-5pa, evaporation rate
B. adopt the mode of electron beam evaporation plating on first organic barrier layer, to prepare the first inorganic barrier layer that a layer thickness is 120nm; The material of the first inorganic barrier layer is NbN doping ReO
2the composite material forming, ReO
2doping mass fraction be 20%, the base vacuum degree in electron beam evaporation plating process is 5 * 10
-5pa;
C. adopt the mode of vacuum evaporation on the first inorganic barrier layer, to prepare second organic barrier layer that a layer thickness is 250nm, material is MADN and the Alq3 composite material that 0.6:1 is mixed to form in molar ratio, vacuum degree 5 * 10
-5pa, evaporation rate
D. adopt the mode of electron beam evaporation plating on second organic barrier layer, to prepare the second inorganic barrier layer that a layer thickness is 100nm, the material of the second inorganic barrier layer is ReO
2the composite material that doping BC forms, the doping mass fraction of BC is 12%, the base vacuum degree in electron beam evaporation plating process is 1 * 10
-5pa;
E, repetition 2 step a, b, c, d, form the composite package layer with 3 encapsulated layer unit, obtains organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 3.7 * 10
-4, life-span (T70@1000cd/m
2) be 6545 hours.
Embodiment 5
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer and negative electrode
Same with embodiment 1.
(2) on negative electrode, repeat to prepare encapsulated layer unit 3 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare first organic barrier layer that a layer thickness is 250nm, the material on first organic barrier layer is TCTA and the Balq composite material that 0.5:1 is mixed to form in molar ratio, vacuum degree 5 * 10
-5pa, evaporation rate
B. adopt the mode of electron beam evaporation plating on first organic barrier layer, to prepare the first inorganic barrier layer that a layer thickness is 120nm; The material of the first inorganic barrier layer is ZrN doping Re
2o
5the composite material forming, Re
2o
5doping mass fraction be 20%, the base vacuum degree in electron beam evaporation plating process is 5 * 10
-5pa;
C. adopt the mode of vacuum evaporation on the first inorganic barrier layer, to prepare second organic barrier layer that a layer thickness is 250nm, material is TCTA and the Balq composite material that 0.5:1 is mixed to form in molar ratio, vacuum degree 5 * 10
-5pa, evaporation rate
D. adopt the mode of electron beam evaporation plating on second organic barrier layer, to prepare the second inorganic barrier layer that a layer thickness is 110nm, the material of the second inorganic barrier layer is Re
2o
5the composite material that doped Ti C forms, the doping mass fraction of TiC is 15%, the base vacuum degree in electron beam evaporation plating process is 1 * 10
-4pa;
E, repetition 2 step a, b, c, d, form the composite package layer with 3 encapsulated layer unit, obtains organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 3.9 * 10
-4, life-span (T70@1000cd/m
2) be 6530 hours.
Embodiment 6
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer and negative electrode
Same with embodiment 1.
(2) on negative electrode, repeat to prepare encapsulated layer unit 4 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare first organic barrier layer that a layer thickness is 300nm, the material on first organic barrier layer is TPD and the Bphen composite material that 0.55:1 is mixed to form in molar ratio, vacuum degree 1 * 10
-5pa, evaporation rate
B. adopt the mode of electron beam evaporation plating on first organic barrier layer, to prepare the first inorganic barrier layer that a layer thickness is 125nm; The material of the first inorganic barrier layer is AlN doping Re
2the composite material that O forms, Re
2the doping mass fraction of O is 20%, and the base vacuum degree in electron beam evaporation plating process is 1 * 10
-5pa;
C. adopt the mode of vacuum evaporation on the first inorganic barrier layer, to prepare second organic barrier layer that a layer thickness is 300nm, material is TPD and the Bphen composite material that 0.55:1 is mixed to form in molar ratio, vacuum degree 1 * 10
-5pa, evaporation rate
D. adopt the mode of electron beam evaporation plating on second organic barrier layer, to prepare the second inorganic barrier layer that a layer thickness is 150nm, the material of the second inorganic barrier layer is Re
2the composite material that O doped SIC forms, the doping mass fraction of SiC is 30%, the base vacuum degree in electron beam evaporation plating process is 1 * 10
-5pa;
E, repetition 3 step a, b, c, d, form the composite package layer with 4 encapsulated layer unit, obtains organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 3.1 * 10
-4, life-span (T70@1000cd/m
2) be 6609 hours.
To sum up, the preparation method of organic electroluminescence device provided by the invention can reduce steam and the erosion of oxygen to organic electroluminescence device effectively, the life-span of improving significantly organic electroluminescence device, and can protect light emitting functional layer and negative electrode to exempt from destruction.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, comprise the anode substrate, light emitting functional layer, negative electrode and the encapsulated layer that are cascading, it is characterized in that, described encapsulated layer is to repeat to arrange by encapsulated layer unit the composite construction forming, described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually
The material on described first organic barrier layer and second organic barrier layer is the composite material that the first organic material and the second organic material are mixed to form, and the mol ratio of described the first organic material and the second organic material is 0.4~0.6:1; Described the first organic material is N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-4,4 '-benzidine, N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines, 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines or 1,3-bis-(9H-carbazole-9-yl) benzene; Described the second organic material is 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole;
The material of described the first inorganic barrier layer is the composite material that the oxide of metal nitride doping rhenium forms, and the doping mass fraction of the oxide of described rhenium is 10~30%; The material of described the second inorganic barrier layer is the composite material that the oxide-doped carbide of rhenium forms, and the doping mass fraction of described carbide is 10~30%; Described metal nitride is aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, zirconium nitride, tantalum nitride; The oxide of described rhenium is Re
2o, ReO, Re
2o
3, ReO
2, Re
2o
5or ReO
3; Described carbide is carborundum, tungsten carbide, ramet, boron carbide, titanium carbide or hafnium carbide.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness on described first organic barrier layer is 200~300nm, and the thickness on described second organic barrier layer is 200~300nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the first inorganic barrier layer is 100~150nm, and the thickness of described the second inorganic barrier layer is 100~150nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described encapsulated layer unit repeats to arrange 2~4 times.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, described light emitting functional layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
On anode substrate, prepare successively light emitting functional layer and negative electrode;
At described cathode surface, prepare encapsulated layer, obtain organic electroluminescence device, described encapsulated layer is to repeat to arrange by encapsulated layer unit the composite construction forming, and described encapsulated layer unit comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually;
The material on described first organic barrier layer and second organic barrier layer is the composite material that the first organic material and the second organic material are mixed to form, and the mol ratio of described the first organic material and the second organic material is 0.4~0.6:1; Described the first organic material is N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-4,4 '-benzidine, N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines, 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines or 1,3-bis-(9H-carbazole-9-yl) benzene; Described the second organic material is 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole; Described first organic barrier layer and second organic barrier layer all adopt the mode of vacuum evaporation to prepare, and the vacuum degree in described vacuum evaporation process is 1 * 10
-5pa~1 * 10
-3pa, evaporation rate is
The material of described the first inorganic barrier layer is the composite material that the oxide of metal nitride doping rhenium forms, and the doping mass fraction of the oxide of described rhenium is 10~30%; The material of described the second inorganic barrier layer is the composite material that the oxide-doped carbide of rhenium forms, and the doping mass fraction of described carbide is 10~30%; Described metal nitride is aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, zirconium nitride, tantalum nitride; The oxide of described rhenium is Re
2o, ReO, Re
2o
3, ReO
2, Re
2o
5or ReO
3; Described carbide is carborundum, tungsten carbide, ramet, boron carbide, titanium carbide or hafnium carbide; Described the first inorganic barrier layer and the second inorganic barrier layer all adopt the mode of electron beam evaporation plating to prepare, and in described electron beam evaporation plating process, vacuum degree is 1 * 10
-5~1 * 10
-3pa.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thickness on described first organic barrier layer is 200~300nm, and the thickness on described second organic barrier layer is 200~300nm.
8. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thickness of described the first inorganic barrier layer is 100~150nm, and the thickness of described the second inorganic barrier layer is 100~150nm.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described encapsulated layer unit repeats to arrange 2~4 times.
10. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described light emitting functional layer comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer stacking gradually.
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