CN104183742A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN104183742A CN104183742A CN201310188056.XA CN201310188056A CN104183742A CN 104183742 A CN104183742 A CN 104183742A CN 201310188056 A CN201310188056 A CN 201310188056A CN 104183742 A CN104183742 A CN 104183742A
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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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, 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 by doping an organic material, a metal oxide and a metal. The metal oxide is molybdena, vanadic anhydride, tungsten trioxide, cesium oxide, nickel oxide or manganese dioxide. The inorganic barrier layer is made of a mixed material which is formed by a metal fluoride and a metal sulfide. The metal fluoride is lithium fluoride, cesium fluoride, magnesium fluoride, aluminum fluoride, calcium fluoride or barium fluoride. The metal sulfide is cadmium sulfide, lead sulfide, iron disulfide, copper sulfide, zinc sulfide or nickel sulfide. 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 when applying between electrode after certain voltage, 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, ultraviolet polymerization resin sealing for its edge, 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 the flexible organic electroluminescent device of preparing as substrate taking plastics or metal.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, encapsulated layer is to repeat to arrange by encapsulated layer unit the composite construction forming, encapsulated layer unit comprises the mixing barrier layer and the inorganic barrier layer that stack gradually
The material on described mixing barrier layer is the composite material that organic material blended metal oxide and metal form, and described metal oxide accounts for 30%～50% of described mixing barrier layer gross mass, and described metal accounts for 10%～30% of described mixing barrier layer gross mass; 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 metal oxide is molybdenum oxide, vanadic oxide, tungstic acid, cesium oxide, nickel oxide or manganese dioxide; Described metal is silver, aluminium, nickel, gold, copper or platinum;
The material of described inorganic barrier layer is the composite material that metal fluoride and metal sulfide are mixed to form, and the mol ratio of described metal fluoride and metal sulfide is 0.3～0.5: 1; Described metal fluoride is lithium fluoride, cesium fluoride, magnesium fluoride, aluminum fluoride, calcirm-fluoride or barium fluoride, and described metal sulfide is cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide or nickel sulfide.
Preferably, anode substrate is conducting glass substrate or organic PETG substrate that conducts electricity.
Preferably, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack 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 blended metal oxide and metal 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.
Metal oxide is molybdenum oxide (MoO
3), vanadic oxide (V
2o
5), tungstic acid (WO
3), cesium oxide (Cs
2o), nickel oxide (Ni
2or manganese dioxide (MnO O)
2); Metal is silver (Ag), aluminium (Al), nickel (Ni), gold (Au), copper (Cu) or platinum (Pt).The existence of metal oxide can make the rete density of mixing barrier layer improve, main landing low stress effect.The high rete waterproof ability that causes of its hardness of because of metal and density is strong, and plasticity and thermal conductivity strengthen simultaneously.
Mix barrier layer and adopt organic material and metal oxide and the preparation of metal mixed evaporation, 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, extend device useful life.
Inorganic barrier layer is deposited on mixing barrier layer surface by the mode of vacuum evaporation.
The material of inorganic barrier layer is the composite material that metal fluoride and metal sulfide are mixed to form.
Described metal fluoride is lithium fluoride (LiF), cesium fluoride (CeF
2), magnesium fluoride (MgF
2), aluminum fluoride (AlF
3), calcirm-fluoride (CaF
2) or barium fluoride (BaF
2).Metal sulfide is CdS, PbS, FeS
2, CuS, ZnS or NiS.Metal fluoride and metal sulfide all have stronger Corrosion Protection, and it is good that both steam standby mixed membranous layer compactness altogether, can effectively prevent extraneous water, the erosion of oxygen isoreactivity material to device.
Preferably, the thickness on mixing barrier layer is 200～300nm.
Preferably, the thickness of inorganic barrier layer is 100～200nm.
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;
Prepare encapsulated layer at described cathode surface, 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 the mixing barrier layer and the inorganic barrier layer that stack gradually,
The material on described mixing barrier layer is the composite material that organic material blended metal oxide and metal form, and described metal oxide accounts for 30%～50% of described mixing barrier layer gross mass, and described metal accounts for 10%～30% of described mixing barrier layer gross mass; 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 metal oxide is molybdenum oxide, vanadic oxide, tungstic acid, cesium oxide, nickel oxide or manganese dioxide; Described metal is silver, aluminium, nickel, gold, copper or platinum; 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 the composite material that metal fluoride and metal sulfide are mixed to form, and the mol ratio of described metal fluoride and metal sulfide is 0.3～0.5: 1; Described metal fluoride is lithium fluoride, cesium fluoride, magnesium fluoride, aluminum fluoride, calcirm-fluoride or barium fluoride, described metal sulfide is cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide or nickel sulfide, described inorganic 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
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 clean with supersonic wave cleaning machine, 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 the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Preferably, light emitting functional layer is by the method for vacuum evaporation or the method setting of 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 adopt the mode of vacuum evaporation to prepare at cathode surface 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 blended metal oxide and metal 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.
Metal oxide is molybdenum oxide (MoO
3), vanadic oxide (V
2o
5), tungstic acid (WO
3), cesium oxide (Cs
2o), nickel oxide (Ni
2or manganese dioxide (MnO O)
2); Metal is silver (Ag), aluminium (Al), nickel (Ni), gold (Au), copper (Cu) or platinum (Pt).The existence of metal oxide can make the rete density of mixing barrier layer improve, main landing low stress effect.The high rete waterproof ability that causes of its hardness of because of metal and density is strong, and plasticity and thermal conductivity strengthen simultaneously.
Mix barrier layer and adopt organic material and metal oxide and the preparation of metal mixed evaporation, 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, extend device useful life.
Inorganic barrier layer is deposited on mixing barrier layer surface by the mode of vacuum evaporation.
The material of inorganic barrier layer is the composite material that metal fluoride and metal sulfide are mixed to form.
Described metal fluoride is lithium fluoride (LiF), cesium fluoride (CeF
2), magnesium fluoride (MgF
2), aluminum fluoride (AlF
3), calcirm-fluoride (CaF
2) or barium fluoride (BaF
2).Metal sulfide is cadmium sulfide (CdS), vulcanized lead (PbS), ferrous disulfide (FeS
2), copper sulfide (CuS), zinc sulphide (ZnS) or nickel sulfide (NiS).Metal fluoride and metal sulfide all have stronger Corrosion Protection, and it is good that both steam standby mixed membranous layer compactness altogether, can effectively prevent extraneous water, the erosion of oxygen isoreactivity material to device.
Preferably, the thickness on mixing barrier layer is 200～300nm.
Preferably, the thickness of inorganic barrier layer is 100～200nm.
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 3700 hours, encapsulating face light transmittance can reach more than 50%;
(3) the inventive method is applicable to the organic electroluminescence device prepared taking electro-conductive glass as anode substrate of encapsulation, is also applicable to the flexible organic electroluminescent device that encapsulation is prepared as anode substrate taking plastics or metal.The inventive method is particularly useful for encapsulating flexible organic electroluminescent device;
(4) organic electroluminescence device material cheapness of the present invention, method for packing technique is simple, and easily large area preparation is suitable for large-scale industrialization and uses.
Brief description of the drawings
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, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, 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 clean with supersonic wave cleaning machine, 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 the mixing barrier layer and the inorganic barrier layer that stack gradually;
A. be prepared with at cathode surface the mixing barrier layer that a layer thickness is 220nm by the mode of vacuum evaporation, the material of mixing barrier layer is TPBi doped with Mn O
2with the composite material of Pt formation, in composite material, MnO
2shared mass fraction is that the shared mass fraction of 40%, Pt is 25%, and the vacuum degree of evaporate process is 1 × 10
-3pa, evaporation rate is
B. on mixing barrier layer, prepare the inorganic barrier layer that thickness is 150nm by the mode of vacuum evaporation; The material of inorganic barrier layer is BaF
2with the composite material that NiS is mixed to form, BaF
2with the mol ratio of NiS be 0.5:1, the vacuum degree of evaporate process is 1 × 10
-3pa, evaporation rate is
C. repeat step a, b 3 times, form the composite package layer with 4 encapsulated layer unit, obtain organic electroluminescence device.
Water resistance (WVTR, the cc/m of the organic electroluminescence device after the present embodiment composite package
2day) be 8.5 × 10
-4, life-span (T701000cd/m
2) be 3786 hours, light transmittance is 61%.
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 inorganic barrier layer 82,84,86 and 88 that mixing barrier layer 81,83,85 and 87,4 layer thicknesses of 220nm are 150nm 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 the mixing barrier layer and the inorganic barrier layer that stack gradually;
A. be prepared with at cathode surface the mixing barrier layer that a layer thickness is 300nm by the mode of vacuum evaporation, the material of mixing barrier layer is NPB doping V
2o
5with the composite material of Al formation, in composite material, V
2o
5shared mass fraction is that the shared mass fraction of 40%, Al is 30%, and the vacuum degree of evaporate process is 5 × 10
-5pa, evaporation rate is
B. on mixing barrier layer, prepare the inorganic barrier layer that thickness is 100nm by the mode of vacuum evaporation; The material of inorganic barrier layer is CeF
2with the composite material that PbS is mixed to form, CeF
2with the mol ratio of PbS be 0.45:1, the vacuum degree of evaporate process is 5 × 10
-5pa, evaporation rate is
C. repeat step a, b 4 times, form the composite package layer with 5 encapsulated layer unit, obtain organic electroluminescence device.
Water resistance (WVTR, the cc/m of the organic electroluminescence device after the present embodiment composite package
2day) be 7.1 × 10
-4, life-span (T701000cd/m
2) be 3855 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 the mixing barrier layer and the inorganic barrier layer that stack gradually;
A. be prepared with at cathode surface the mixing barrier layer that a layer thickness is 200nm by the mode of vacuum evaporation, the material of mixing barrier layer is Alq3 doping WO
3with the composite material of Ni formation, in composite material, WO
3shared mass fraction is that the shared mass fraction of 30%, Ni is 10%, and the vacuum degree of evaporate process is 5 × 10
-5pa, evaporation rate is
B. on mixing barrier layer, prepare the inorganic barrier layer that thickness is 200nm by the mode of vacuum evaporation; The material of inorganic barrier layer is MgF
2and FeS
2the composite material being mixed to form, MgF
2with FeS
2mol ratio be 0.45:1, the vacuum degree of evaporate process is 5 × 10
-5pa, evaporation rate is
C. repeat step a, b 4 times, form the composite package layer with 5 encapsulated layer unit, obtain organic electroluminescence device.
Water resistance (WVTR, the cc/m of the organic electroluminescence device after the present embodiment composite package
2day) be 7.3 × 10
-4, life-span (T701000cd/m
2) be 3840 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 the mixing barrier layer and the inorganic barrier layer that stack gradually;
A. be prepared with at cathode surface the mixing barrier layer that a layer thickness is 240nm by the mode of vacuum evaporation, the material of mixing barrier layer is m-MTDATA doping Cs
2the composite material that O and Au form, in composite material, Cs
2the shared mass fraction of O is that the shared mass fraction of 50%, Au is 15%, and the vacuum degree of evaporate process is 5 × 10
-5pa, evaporation rate is
B. on mixing barrier layer, prepare the inorganic barrier layer that thickness is 200nm by the mode of vacuum evaporation; The material of inorganic barrier layer is AlF
3with the composite material that CuS is mixed to form, AlF
3with the mol ratio of CuS be 0.4:1, the vacuum degree of evaporate process is 5 × 10
-5pa, evaporation rate is
C. repeat step a, b 4 times, form the composite package layer with 5 encapsulated layer unit, obtain organic electroluminescence device.
Water resistance (WVTR, the cc/m of the organic electroluminescence device after the present embodiment composite package
2day) be 7.43 × 10
-4, life-span (T701000cd/m
2) be 3825 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 the mixing barrier layer and the inorganic barrier layer that stack gradually;
A. be prepared with at cathode surface the mixing barrier layer that a layer thickness is 240nm by the mode of vacuum evaporation, the material of mixing barrier layer is BCP Ni doped
2the composite material that O and Cu form, in composite material, Ni
2the shared mass fraction of O is that the shared mass fraction of 45%, Cu is 19%, and the vacuum degree of evaporate process is 5 × 10
-5pa, evaporation rate is
B. on mixing barrier layer, prepare the inorganic barrier layer that thickness is 140nm by the mode of vacuum evaporation; The material of inorganic barrier layer is CaF
2with the composite material that ZnS is mixed to form, CaF
2with the mol ratio of ZnS be 0.4:1, the vacuum degree of evaporate process is 5 × 10
-5pa, evaporation rate is
C. repeat step a, b 4 times, form the composite package layer with 5 encapsulated layer unit, obtain organic electroluminescence device.
Water resistance (WVTR, the cc/m of the organic electroluminescence device after the present embodiment composite package
2day) be 7.6 × 10
-4, life-span (T701000cd/m
2) be 3810 hours, light transmittance is 58%.
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 the mixing barrier layer and the inorganic barrier layer that stack gradually;
A. be prepared with at cathode surface the mixing barrier layer that a layer thickness is 250nm by the mode of vacuum evaporation, the material of mixing barrier layer is TAPC doping MoO
3with the composite material of Ag formation, in composite material, MoO
3shared mass fraction is that the shared mass fraction of 40%, Ag is 20%, and the vacuum degree of evaporate process is 1 × 10
-5pa, evaporation rate is
B. on mixing barrier layer, prepare the inorganic barrier layer that thickness is 150nm by the mode of vacuum evaporation; The material of inorganic barrier layer is the composite material that LiF and CdS are mixed to form, and the mol ratio of LiF and CdS is 0.4:1, and the vacuum degree of evaporate process is 1 × 10
-5pa, evaporation rate is
C. repeat step a, b 5 times, form the composite package layer with 6 encapsulated layer unit, obtain organic electroluminescence device.
Water resistance (WVTR, the cc/m of the organic electroluminescence device after the present embodiment composite package
2day) be 6.7 × 10
-4, life-span (T701000cd/m
2) be 3911 hours, light transmittance is 51%.
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 negative electrode to exempt from destruction, improve the light transmittance of encapsulating face.
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, encapsulated layer is to repeat to arrange by encapsulated layer unit the composite construction forming, encapsulated layer unit comprises the mixing barrier layer and the inorganic barrier layer that stack gradually
The material on described mixing barrier layer is the composite material that organic material blended metal oxide and metal form, and described metal oxide accounts for 30%～50% of described mixing barrier layer gross mass, and described metal accounts for 10%～30% of described mixing barrier layer gross mass; 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 metal oxide is molybdenum oxide, vanadic oxide, tungstic acid, cesium oxide, nickel oxide or manganese dioxide; Described metal is silver, aluminium, nickel, gold, copper or platinum;
The material of described inorganic barrier layer is the composite material that metal fluoride and metal sulfide are mixed to form, and the mol ratio of described metal fluoride and metal sulfide is 0.3～0.5: 1; Described metal fluoride is lithium fluoride, cesium fluoride, magnesium fluoride, aluminum fluoride, calcirm-fluoride or barium fluoride, and described metal sulfide is cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide or nickel sulfide.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness on described mixing barrier layer is 200～300nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described inorganic barrier layer is 100～200nm.
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 the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack 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;
Prepare encapsulated layer at described cathode surface, 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 the mixing barrier layer and the inorganic barrier layer that stack gradually,
The material on described mixing barrier layer is the composite material that organic material blended metal oxide and metal form, and described metal oxide accounts for 30%～50% of described mixing barrier layer gross mass, and described metal accounts for 10%～30% of described mixing barrier layer gross mass; 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 metal oxide is molybdenum oxide, vanadic oxide, tungstic acid, cesium oxide, nickel oxide or manganese dioxide; Described metal is silver, aluminium, nickel, gold, copper or platinum; 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 the composite material that metal fluoride and metal sulfide are mixed to form, and the mol ratio of described metal fluoride and metal sulfide is 0.3～0.5: 1; Described metal fluoride is lithium fluoride, cesium fluoride, magnesium fluoride, aluminum fluoride, calcirm-fluoride or barium fluoride, described metal sulfide is cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide or nickel sulfide, described inorganic 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
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thickness on described mixing 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 inorganic barrier layer is 100～200nm.
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 the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
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