CN104183705A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN104183705A CN104183705A CN201310188033.9A CN201310188033A CN104183705A CN 104183705 A CN104183705 A CN 104183705A CN 201310188033 A CN201310188033 A CN 201310188033A CN 104183705 A CN104183705 A CN 104183705A
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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
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
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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 electroluminescent device which comprises the components of: an anode substrate, a light emitting functional layer, a cathode and a packaging layer; wherein the anode structure, the light emitting functional layer, the cathode 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 mixed barrier layer and an inorganic barrier layer which are successively laminated. The mixed barrier layer is made of a mixed material which is formed through mixing an organic material, a first inorganic material and a second inorganic material. The organic material is TAPC, NPB, Alq3, m-MTDATA, BCP or TPBi. The first inorganic material is magnesium fluoride, aluminum fluoride or sodium fluoroaluminate. The second inorganic material is lanthanide metal fluoride. 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 organic electroluminescent 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.And existing organic electroluminescence device can not provide good light transmittance conventionally.
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 mixing barrier layer and the inorganic barrier layer stacking gradually
The material on described mixing barrier layer is organic material, the composite material that the first inorganic material and the second inorganic material three are mixed to form, described organic material is 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 the first inorganic material is magnesium fluoride, aluminum fluoride or hexafluoro sodium aluminate, described the second inorganic material is lanthanide series metal fluoride, in the material on described mixing barrier layer, described the first inorganic material accounts for 10%～20% of described mixing barrier layer gross mass, and described the second inorganic material accounts for 10%～20% of described mixing barrier layer gross mass,
The material of described inorganic barrier layer is titanium oxide, magnesium oxide, silicon dioxide, zirconia, zinc oxide or aluminium oxide.
Preferably, anode substrate is conducting glass substrate or organic PETG substrate that conducts electricity.
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.
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.).Be preferably transparent cathode.
Encapsulated layer unit comprises mixing barrier layer and inorganic barrier layer successively.
The material of mixing barrier layer is the composite material that organic material, the first inorganic material and the second inorganic material three are mixed to form.
Organic material is 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 existence of organic material can effectively improve the evenness of the whole rete that mixes barrier layer, prevents that encapsulated layer from existing gap.
The first inorganic material is short period metal fluoride, is magnesium fluoride (MgF
2), aluminum fluoride (AlF
3) or hexafluoro sodium aluminate (Na
3alF
6).Short period metal fluoride has stronger Corrosion Protection, thereby can effectively improve the anti-extraneous corrosive nature of the whole rete that mixes barrier layer.
The second inorganic material is lanthanide series metal fluoride.Preferably, lanthanide series metal fluoride is lanthanum fluoride (LaF
3), neodymium fluoride (NdF
3) or gadolinium fluoride (GdF).Lanthanide series metal fluoride refractive index is high, and stress is little, is combined with the first inorganic material of low-refraction, can effectively make up space defect.
Mix barrier layer and adopt the evaporation preparation altogether of above-mentioned three kinds of material mixing and dopings, gained rete thermal stability is high, and compactness is high, and evenness is good, thereby can effectively stop extraneous water, the erosion of oxygen isoreactivity material to organic electroluminescence device, extends device useful life.
Inorganic barrier layer is deposited on mixing barrier layer surface by the mode of magnetron sputtering.
The material of inorganic barrier layer is titanium oxide (TiO
2), magnesium oxide (MgO), silicon dioxide (SiO
2), zirconia (ZrO
2), zinc oxide (ZnO) or aluminium oxide (Al
2o
3).
Inorganic barrier layer is high water suction oxygen uptake material rete, and its existence can protect negative electrode to exempt from destruction under subsequent operation condition, extends water, oxygen permeation pathway, effectively reduces outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device.
Preferably, the thickness that mixes barrier layer is 100～200nm, and the thickness of inorganic barrier layer is 50～100nm.
Preferably, described encapsulated layer unit repeats to arrange 4～6 times.
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 mixing barrier layer and the inorganic barrier layer stacking gradually,
The material on described mixing barrier layer is organic material, the composite material that the first inorganic material and the second inorganic material three are mixed to form, described organic material is 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 the first inorganic material is magnesium fluoride, aluminum fluoride or hexafluoro sodium aluminate, described the second inorganic material is lanthanide series metal fluoride, in the material on described mixing barrier layer, described the first inorganic material accounts for 10%～20% of described mixing barrier layer gross mass, and described the second inorganic material accounts for 10%～20% of described mixing barrier layer gross mass, described mixing barrier layer adopts 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 inorganic barrier layer is titanium oxide, magnesium oxide, silicon dioxide, zirconia, zinc oxide or aluminium oxide, and described inorganic barrier layer adopts the mode of magnetron sputtering to prepare, and the base vacuum degree in described magnetron sputtering process is 1 * 10
-5pa～1 * 10
-3pa, sputter procedure passes into argon gas and ammonia, and it is 5～15sccm that argon gas passes into flow, and it is 10～20sccm that ammonia passes into flow.
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, 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, 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.).Be preferably transparent cathode.Negative electrode adopts the mode of vacuum evaporation to prepare.
Encapsulated layer unit comprises mixing barrier layer and 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 and mix barrier layer, then on mixing barrier layer, adopt the mode of magnetron sputtering to prepare 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 4～6 times.
The material of mixing barrier layer is the composite material that organic material, the first inorganic material and the second inorganic material three are mixed to form.
Organic material is 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 existence of organic material can effectively improve the evenness of the whole rete that mixes barrier layer, reduces encapsulated layer and has gap.
The first inorganic material is short period metal fluoride, can be magnesium fluoride (MgF
2), aluminum fluoride (AlF
3) or hexafluoro sodium aluminate (Na
3alF
6).Short period metal fluoride has stronger Corrosion Protection, thereby can effectively improve the anti-extraneous corrosive nature of the whole rete that mixes barrier layer.
The second inorganic material is lanthanide series metal fluoride.Preferably, lanthanide series metal fluoride is lanthanum fluoride (LaF
3), neodymium fluoride (NdF
3) or gadolinium fluoride (GdF).Lanthanide series metal fluoride refractive index is high, and stress is little, is combined with the first inorganic material of low-refraction, can effectively make up space defect.
Mix barrier layer adopt above-mentioned three kinds of materials to mix after evaporation preparation, gained rete thermal stability is high, compactness is high, thereby can effectively stop extraneous water, the erosion of oxygen isoreactivity material to organic electroluminescence device, extends device useful life.
Vacuum degree in the evaporation preparation process on mixing barrier layer is 1 * 10
-5pa～1 * 10
-3pa, evaporation rate is
The material of inorganic barrier layer is titanium oxide (TiO
2), magnesium oxide (MgO), silicon dioxide (SiO
2), zirconia (ZrO
2), zinc oxide (ZnO) or aluminium oxide (Al
2o
3).
Inorganic barrier layer is high water suction oxygen uptake material rete, and its existence can protect negative electrode to exempt from destruction under subsequent operation condition, extends water, oxygen permeation pathway, effectively reduces outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device
Preferably, the thickness that mixes barrier layer is 100～200nm, and the thickness of inorganic barrier layer is 50～100nm.
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) organic electroluminescence device of the present invention repeats the mixing barrier layer and the inorganic barrier layer that arrange, can effectively reduce the erosion to organic electroluminescence device such as steam, oxygen, can protect light emitting functional layer and negative electrode to exempt from destruction, thereby significantly improve the life-span of organic electroluminescence device simultaneously;
(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 5000 hours, encapsulating face light transmittance can reach more than 50%;
(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 ZnS/Ag/ZnS, ZnS thickness 30nm, Ag thickness 10nm, vacuum degree is 1 * 10
-5pa, evaporation rate is
(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 mixing barrier layer and the inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare the mixing barrier layer that a layer thickness is 120nm; The material of mixing barrier layer is TPBi, MgF
2the composite material being mixed to form with GdF, in composite material, MgF
2be 12% with the shared mass fraction of GdF, the vacuum degree of evaporate process is 1 * 10
-3pa, evaporation rate is
B. by the mode of magnetron sputtering, on mixing barrier layer, prepare the TiO that thickness is 70nm
2layer is as inorganic barrier layer, and the base vacuum degree in magnetron sputtering process is 1 * 10
-3pa, passes into Ar and NH
3, Ar flow is 8sccm, NH
3flow is 15sccm;
C. repeat step a, b 3 times, form the composite package layer with 4 encapsulated layer unit, obtain organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 6.5 * 10
-4, life-span (T701000cd/m
2) be 4985 hours, light transmittance is 63%.
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.Ito glass substrate 1 and encapsulated layer 8 form an enclosure space by epoxy sealing, and hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6 and negative electrode 7 are contained in this enclosure space.Described encapsulated layer 8 comprises that 4 layer thicknesses are the mixing barrier layer 81,83,85 of 120nm and the inorganic barrier layer 82,84,86 and 88 that 87,4 layer thicknesses are 70nm successively.
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 5 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises mixing barrier layer and the inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare the mixing barrier layer that a layer thickness is 200nm; The material of mixing barrier layer is NPB, AlF
3and NdF
3the composite material being mixed to form, in composite material, AlF
3shared mass fraction is 20%, NdF
3shared mass fraction is 10%, and the vacuum degree of evaporate process is 1 * 10
-5pa, evaporation rate is
B. the mode by magnetron sputtering mix on barrier layer, prepare thickness be the ZnO layer of 100nm as inorganic barrier layer, the base vacuum degree in magnetron sputtering process is 1 * 10
-5pa, passes into Ar and NH
3, Ar flow is 10sccm, NH
3flow is 10sccm;
C. repeat step a, b 4 times, form the composite package layer with 5 encapsulated layer unit, obtain organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 4.8 * 10
-4, life-span (T701000cd/m
2) be 5074 hours, light transmittance is 55%.
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 5 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises mixing barrier layer and the inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare the mixing barrier layer that a layer thickness is 100nm;
The material of mixing barrier layer is Alq3, MgF
2the composite material being mixed to form with GdF, in composite material, MgF
2shared mass fraction is that the shared mass fraction of 10%, GdF is 20%, and the vacuum degree of evaporate process is 1 * 10
-5pa, evaporation rate is
B. by the mode of magnetron sputtering, on mixing barrier layer, prepare the ZrO that thickness is 50nm
2layer is as inorganic barrier layer, and the base vacuum degree in magnetron sputtering process is 1 * 10
-5pa, passes into Ar and NH
3, Ar flow is 5sccm, NH
3flow is 15sccm;
C. repeat step a, b 4 times, form the composite package layer with 5 encapsulated layer unit, obtain organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 5.1 * 10
-4, life-span (T701000cd/m
2) be 5060 hours, light transmittance is 56%.
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 5 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises mixing barrier layer and the inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare the mixing barrier layer that a layer thickness is 130nm; The material of mixing barrier layer is m-MTDATA, Na
3alF
6and LaF
3the composite material being mixed to form, in composite material, Na
3alF
6shared mass fraction is 16%, LaF
3shared mass fraction is 13%, and the vacuum degree of evaporate process is 5 * 10
-5pa, evaporation rate is
B. by the mode of magnetron sputtering, on mixing barrier layer, prepare the SiO that thickness is 70nm
2layer is as inorganic barrier layer, and the base vacuum degree in magnetron sputtering process is 5 * 10
-5pa, passes into Ar and NH
3, Ar flow is 9sccm, NH
3flow is 17sccm;
C. repeat step a, b 4 times, form the composite package layer with 5 encapsulated layer unit, obtain organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 5.4 * 10
-4, life-span (T701000cd/m
2) be 5045 hours, light transmittance is 57%.
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 5 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises mixing barrier layer and the inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare the mixing barrier layer that a layer thickness is 140nm; The material of mixing barrier layer comprises BCP, AlF
3and NdF
3the composite material being mixed to form, in composite material, AlF
3shared mass fraction is 16%, NdF
3shared mass fraction is 11%, and the vacuum degree of evaporate process is 5 * 10
-5pa, evaporation rate is
B. the mode by magnetron sputtering mix on barrier layer, prepare thickness be the MgO layer of 60nm as inorganic barrier layer, the base vacuum degree in magnetron sputtering process is 5 * 10
-5pa, passes into Ar and NH
3, Ar flow is 7sccm, NH
3flow is 12sccm;
C. repeat step a, b 4 times, form the composite package layer with 5 encapsulated layer unit, obtain 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 5025 hours, light transmittance is 59%.
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 6 times, form the encapsulated layer with composite construction, obtain organic electroluminescence device;
Described encapsulated layer unit comprises mixing barrier layer and the inorganic barrier layer stacking gradually;
A. by the mode of vacuum evaporation, at cathode surface, prepare the mixing barrier layer that a layer thickness is 200nm; The material of mixing barrier layer comprises TAPC, Na
3alF
6and LaF
3the composite material being mixed to form, in composite material, Na
3alF
6shared mass fraction is 15%, LaF
3shared mass fraction is 15%, and the vacuum degree of evaporate process is 1 * 10
-5pa, evaporation rate is
B. by the mode of magnetron sputtering, on mixing barrier layer, prepare the Al that thickness is 80nm
2o
3layer is as inorganic barrier layer, and the base vacuum degree in magnetron sputtering process is 1 * 10
-5pa, passes into Ar and NH
3, Ar flow is 8sccm, NH
3flow is 20sccm;
C. repeat step a, b 5 times, form the composite package layer with 6 encapsulated layer unit, obtain organic electroluminescence device.
The water resistance of the organic electroluminescence device after the present embodiment composite package (WVTR, cc/m
2day) be 4.2 * 10
-4, life-span (T701000cd/m
2) be 5112 hours, light transmittance is 52%.
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; improve significantly the life-span of organic electroluminescence device; and can protect light emitting functional layer and negative electrode to exempt from destruction, improve the light transmittance of encapsulating face simultaneously.
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 mixing barrier layer and the inorganic barrier layer stacking gradually
The material on described mixing barrier layer is organic material, the composite material that the first inorganic material and the second inorganic material three are mixed to form, described organic material is 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 the first inorganic material is magnesium fluoride, aluminum fluoride or hexafluoro sodium aluminate, described the second inorganic material is lanthanide series metal fluoride, in the material on described mixing barrier layer, described the first inorganic material accounts for 10%～20% of described mixing barrier layer gross mass, and described the second inorganic material accounts for 10%～20% of described mixing barrier layer gross mass,
The material of described inorganic barrier layer is titanium oxide, magnesium oxide, silicon dioxide, zirconia, zinc oxide or aluminium oxide.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described lanthanide series metal fluoride is lanthanum fluoride, neodymium fluoride or gadolinium fluoride.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness on described mixing barrier layer is 100～200nm, and the thickness of described inorganic barrier layer is 50～100nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described encapsulated layer unit repeats to arrange 4～6 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 mixing barrier layer and the inorganic barrier layer stacking gradually,
The material on described mixing barrier layer is organic material, the composite material that the first inorganic material and the second inorganic material three are mixed to form, described organic material is 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 the first inorganic material is magnesium fluoride, aluminum fluoride or hexafluoro sodium aluminate, described the second inorganic material is lanthanide series metal fluoride, in the material on described mixing barrier layer, described the first inorganic material accounts for 10%～20% of described mixing barrier layer gross mass, and described the second inorganic material accounts for 10%～20% of described mixing barrier layer gross mass, described mixing barrier layer adopts 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 inorganic barrier layer is titanium oxide, magnesium oxide, silicon dioxide, zirconia, zinc oxide or aluminium oxide, and described inorganic barrier layer adopts the mode of magnetron sputtering to prepare, and the base vacuum degree in described magnetron sputtering process is 1 * 10
-5pa～1 * 10
-3pa, sputter procedure passes into argon gas and ammonia, and it is 5～15sccm that argon gas passes into flow, and it is 10～20sccm that ammonia passes into flow.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described lanthanide series metal fluoride is lanthanum fluoride, neodymium fluoride or gadolinium fluoride.
8. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thickness on described mixing barrier layer is 100～200nm, and the thickness of described inorganic barrier layer is 50～100nm.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described encapsulated layer unit repeats to arrange 4～6 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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