CN104183787A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN104183787A CN104183787A CN201310188054.0A CN201310188054A CN104183787A CN 104183787 A CN104183787 A CN 104183787A CN 201310188054 A CN201310188054 A CN 201310188054A CN 104183787 A CN104183787 A CN 104183787A
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Abstract
The invention provides an organic electroluminescent device which comprises the components of: an anode substrate, a light emitting functional layer, a cathode and a packaging layer; wherein the anode substrate, the light emitting functional layer and the packaging layer are successively laminated. The packaging layer has a composite structure which is formed through repeatedly arranging packaging layer units. Each packaging layer unit comprises a first organic barrier layer, a first inorganic barrier layer, a second organic barrier layer and a second inorganic barrier layer; wherein the first organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are successively laminated. The first inorganic barrier layer is made of a mixed material which is formed through mixing metal silicide and metal nitride. The second inorganic barrier layer is made of a mixed material which is formed through mixing a metal silicide and a metal oxide. The invention further provides a preparation method for the organic electroluminescent device. The preparation method can effectively reduce erosion of water and oxygen to the device and prolongs service life of the organic electroluminescent 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 all selected from 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq3), 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 4,7-diphenyl-1,10-Phen (BCP) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi);
The material of described the first inorganic barrier layer is the composite material that metal silicide and metal nitride are mixed to form, and described metal silicide accounts for 10～30% of the first inorganic barrier layer gross mass; The material of described the second inorganic barrier layer is the composite material that metal silicide and metal oxide are mixed to form, and described metal silicide accounts for 10～30% of the second inorganic barrier layer gross mass; Described metal silicide is two chromium silicide (CrSi
2), tantalum silicide (TaSi
2), two hafnium suicide (HfSi
2), titanium disilicide (TiSi
2), molybdenum disilicide (MoSi
2) or tungsten silicide (WSi
2), described metal nitride is aluminium nitride (AlN), titanium nitride (TiN), vanadium nitride (VN), niobium nitride (NbN), zirconium nitride (ZrN) or tantalum nitride (TaN), described metal oxide is magnesium oxide (MgO), aluminium oxide (Al
2o
3), titanium dioxide (TiO
2), zirconia (ZrO
2), hafnium oxide (HfO
2) or tantalum oxide (Ta
2o
5).
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, the evenness of the rete of whole encapsulated layer can be effectively improved on organic barrier layer, prevents that encapsulated layer from existing gap.The composite material preparation that the first inorganic barrier layer adopts metal silicide and metal nitride to be mixed to form, metal silicide good insulating, have metal and nonmetallic feature concurrently, to reducing nitride stress, there is certain effect, metal nitride has very strong hardness and durability, waterproof oxygen ability is strong, but its stress is large, and metal silicide can have certain alleviation by counter stress; The composite material preparation that the second inorganic barrier layer adopts metal silicide and metal oxide to be mixed to form, the existence of metal oxide can make the rete density on barrier layer improve.High by the prepared inorganic barrier film thermal stability of composite material, compactness is high, and evenness is good.The present invention adopts organic barrier layer and inorganic barrier layer alternately to overlap 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 all selected from 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; 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 metal silicide and metal nitride are mixed to form, and described metal silicide accounts for 10～30% of the first inorganic barrier layer gross mass; The material of described the second inorganic barrier layer is the composite material that metal silicide and metal oxide are mixed to form, and described metal silicide accounts for 10～30% of the second inorganic barrier layer gross mass; Described metal silicide is two chromium silicides, tantalum silicide, two hafnium suicide, titanium disilicide, molybdenum disilicide or tungsten silicide, described metal nitride is aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, zirconium nitride or tantalum nitride, and described metal oxide is magnesium oxide, aluminium oxide, titanium dioxide, zirconia, hafnium oxide or tantalum oxide; Described the first inorganic barrier layer and the second inorganic barrier layer all adopt the mode of magnetron sputtering to prepare, in described magnetron sputtering process, and base vacuum degree 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 magnetron sputtering 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 magnetron sputtering 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, the evenness of the rete of whole encapsulated layer can be effectively improved on organic barrier layer, prevents that encapsulated layer from existing gap.The composite material preparation that the first inorganic barrier layer adopts metal silicide and metal nitride to be mixed to form, metal silicide good insulating, have metal and nonmetallic feature concurrently, to reducing nitride stress, there is certain effect, metal nitride has very strong hardness and durability, waterproof oxygen ability is strong, but its stress is large, and metal silicide can have certain alleviation by counter stress; The composite material preparation that the second inorganic barrier layer adopts metal silicide and metal oxide to be mixed to form, the existence of metal oxide can make the rete density on barrier layer improve.High by the prepared inorganic barrier film thermal stability of composite material, compactness is high, and evenness is good.The present invention adopts organic barrier layer and inorganic barrier layer alternately to overlap 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 overlap and 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 (T701000cd/m
2) reach more than 5400 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, material is TPBi, vacuum degree 1 * 10
-3pa, evaporation rate
B. adopt the mode of magnetron sputtering 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 CrSi
2with the composite material that TaN forms, CrSi
2shared mass fraction is 15%, and the base vacuum degree in magnetron sputtering 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 TPBi, vacuum degree 1 * 10
-3pa, evaporation rate
D. adopt the mode of magnetron sputtering 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 WSi
2with Ta
2o
5the composite material forming, WSi
2shared mass fraction is 20%, and the base vacuum degree in magnetron sputtering 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 6.6 * 10
-4, life-span (T701000cd/m
2) be 5491 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 120nm, 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 first organic barrier layer that a layer thickness is 250nm, material is NPB, vacuum degree 5 * 10
-5pa, evaporation rate
B. adopt the mode of magnetron sputtering 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 MoSi
2with the composite material that TiN forms, MoSi
2shared mass fraction is 30%, and the base vacuum degree in magnetron sputtering 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 250nm, material is NPB, vacuum degree 5 * 10
-5pa, evaporation rate
D. adopt the mode of magnetron sputtering 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 TaSi
2with Al
2o
3the composite material forming, TaSi
2shared mass fraction is 10%, and the base vacuum degree in magnetron sputtering 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 5.5 * 10
-4, life-span (T701000cd/m
2) be 5590 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, material is Alq3, vacuum degree 5 * 10
-5pa, evaporation rate
B. adopt the mode of magnetron sputtering 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 TiSi
2with the composite material that VN forms, TiSi
2shared mass fraction is 10%, and the base vacuum degree in magnetron sputtering 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 Alq3, vacuum degree 5 * 10
-5pa, evaporation rate
D. adopt the mode of magnetron sputtering 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 HfSi
2with TiO
2the composite material forming, HfSi
2shared mass fraction is 20%, and the base vacuum degree in magnetron sputtering 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 5.6 * 10
-4, life-span (T701000cd/m
2) be 5566 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, material is m-MTDATA, vacuum degree 5 * 10
-5pa, evaporation rate
B. adopt the mode of magnetron sputtering 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 HfSi
2with the composite material that NbN forms, HfSi
2shared mass fraction is 20%, and the base vacuum degree in magnetron sputtering 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 m-MTDATA, vacuum degree 5 * 10
-5pa, evaporation rate
D. adopt the mode of magnetron sputtering 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 TiSi
2with ZrO
2the composite material forming, TiSi
2shared mass fraction is 15%, and the base vacuum degree in magnetron sputtering 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 5.7 * 10
-4, life-span (T701000cd/m
2) be 5550 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, material is BCP, vacuum degree 5 * 10
-5pa, evaporation rate
B. adopt the mode of magnetron sputtering 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 TaSi
2with the composite material that ZrN forms, TaSi
2shared mass fraction is 15%, and the base vacuum degree in magnetron sputtering 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 BCP, vacuum degree 5 * 10
-5pa, evaporation rate
D. adopt the mode of magnetron sputtering 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 MoSi
2with HfO
2the composite material forming, MoSi
2shared mass fraction is 17%, and the base vacuum degree in magnetron sputtering 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 5.9 * 10
-4, life-span (T701000cd/m
2) be 5524 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, material is TAPC, vacuum degree 1 * 10
-5pa, evaporation rate
B. adopt the mode of magnetron sputtering 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 WSi
2with the composite material that AlN forms, WSi
2shared mass fraction is 20%, and the base vacuum degree in magnetron sputtering 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 TAPC, vacuum degree 1 * 10
-5pa, evaporation rate
D. adopt the mode of magnetron sputtering 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 CrSi
2with the composite material that MgO forms, CrSi
2shared mass fraction is 30%, and the base vacuum degree in magnetron sputtering 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 5.0 * 10
-4, life-span (T701000cd/m
2) be 5623 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 all selected from 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described the first inorganic barrier layer is the composite material that metal silicide and metal nitride are mixed to form, and described metal silicide accounts for 10～30% of the first inorganic barrier layer gross mass; The material of described the second inorganic barrier layer is the composite material that metal silicide and metal oxide are mixed to form, and described metal silicide accounts for 10～30% of the second inorganic barrier layer gross mass; Described metal silicide is two chromium silicides, tantalum silicide, two hafnium suicide, titanium disilicide, molybdenum disilicide or tungsten silicide, described metal nitride is aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, zirconium nitride or tantalum nitride, and described metal oxide is magnesium oxide, aluminium oxide, titanium dioxide, zirconia, hafnium oxide or tantalum oxide.
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 all selected from 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; 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 metal silicide and metal nitride are mixed to form, and described metal silicide accounts for 10～30% of the first inorganic barrier layer gross mass; The material of described the second inorganic barrier layer is the composite material that metal silicide and metal oxide are mixed to form, and described metal silicide accounts for 10～30% of the second inorganic barrier layer gross mass; Described metal silicide is two chromium silicides, tantalum silicide, two hafnium suicide, titanium disilicide, molybdenum disilicide or tungsten silicide, described metal nitride is aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, zirconium nitride or tantalum nitride, and described metal oxide is magnesium oxide, aluminium oxide, titanium dioxide, zirconia, hafnium oxide or tantalum oxide; Described the first inorganic barrier layer and the second inorganic barrier layer all adopt the mode of magnetron sputtering to prepare, in described magnetron sputtering process, and base vacuum degree 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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Application publication date: 20141203 |