CN104638117A - Organic light-emitting device and preparation method thereof - Google Patents

Organic light-emitting device and preparation method thereof Download PDF

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Publication number
CN104638117A
CN104638117A CN201310561328.6A CN201310561328A CN104638117A CN 104638117 A CN104638117 A CN 104638117A CN 201310561328 A CN201310561328 A CN 201310561328A CN 104638117 A CN104638117 A CN 104638117A
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inorganic barrier
barrier layer
layer
organic electroluminescence
electroluminescence device
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周明杰
钟铁涛
王平
冯小明
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Publication of CN104638117A publication Critical patent/CN104638117A/en
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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
    • 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
    • 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

Abstract

The invention provides an organic light-emitting device. The organic light-emitting device comprises an anode conductive substrate, an organic light-emitting functional layer, a cathode and a packaging layer in sequentially overlapped arrangement. The packaging layer comprises inorganic barrier layers and organic barrier layers, and the inorganic barrier layers and the organic barrier layers are sequentially overlapped on the surface of the cathode. The inorganic barrier layers are made of TiO2:Cl, ZrO2:Cl or HfO2:Cl. The organic barrier layers are made of loop-chain borane with a structural formula shown in the original text, wherein R1 refers to same or different naphthene bases, branched alkyls or straight-chain alkyls with carbon number being 1-6, l refers to an integer ranging from 1 to 10, m refers to an integer ranging from 5 to 15, and n refers to an integer ranging from 0 to m-1. The packaging layer is high in compactness, so that service lives of devices, especially flexible devices, can be prolonged to be longer than 11500 hours (T701000cd/m<2>). The invention further provides a preparation method of the organic light-emitting device.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic electroluminescence device technical field, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
At present, there is life-span shorter problem in organic electroluminescence device (OLED), and this is mainly because the oxygen that invades and steam cause.On the one hand, oxygen is quencher, and luminous quantum efficiency can be made significantly to decline, meanwhile, oxygen can with luminescent layer generation oxidation, the carbonyls of generation is also effective quencher; On the other hand, the impact of steam is more apparent, and its main failure mode is the organic compound generation hydrolysis made in device, also can react with metallic cathode simultaneously, its stability is declined greatly, thus causes component failure, reduce useful life.Therefore; in order to effectively suppress the degeneration of organic electroluminescence device (OLED) in long-term work process and inefficacy; with the life-span making steady operation reach enough; the encapsulation technology playing seal protection effect has just become a break-through point of solution organic electroluminescence device (OLED) life problems; meanwhile, this proposes high requirement to the barrier of encapsulating material.
The encapsulation technology of conventional organic electroluminescence device (OLED) is in substrate, adopt cover plate to encapsulate, and cover plate encapsulation also needs to seal cover plate and substrate with fluid sealant.The porousness of fluid sealant makes oxygen and steam be easy to infiltrate device inside, therefore adopts during this packaged type and generally also needs to add drier in device.Along with the drier in device adsorbs a large amount of oxygen and steam, make drier lose absorbability at short notice, cause in device, building up oxygen and steam, thus the life-span of device is significantly declined; The glass cover-plate wherein usually adopted or metal cover board are fragile material, and easily crack, obtained device can seem very thick and heavy, is not suitable for flexible device.Therefore, how to reduce oxygen and steam to the infiltration of device, improve the life-span of device, the life-span of especially improving flexible device become current technical staff one of the problem that will solve in a hurry.
Summary of the invention
For solving the problem, first aspect present invention provides a kind of organic electroluminescence device, namely on cathode surface, arranges encapsulated layer; Encapsulated layer provided by the invention has very high compactness, and water resistance (WVTR) reaches 4.16 × 10 -6g/m 2about day; effectively reduce outside oxygen, steam isoreactivity material to the erosion of the organic compound in organic electroluminescence device and electrode; thus effective protection is defined to device; improve the life-span of device; especially the life-span of flexible device, the life-span of device is made to reach more than 11500 hours (T70@1000cd/m 2); Second aspect present invention additionally provides a kind of preparation method of organic electroluminescence device, and this preparation method's technique is simple, easy large area preparation, and the thickness of the film made, compactness and uniformity are good, avoid the pollution of harmful substance simultaneously.
First aspect, the invention provides a kind of organic electroluminescence device, the organic luminescence function layer, negative electrode and the encapsulated layer that comprise anode conducting substrate and be cascading on the surface of described anode conducting substrate; Described encapsulated layer is included in inorganic barrier layer and inorganic barrier layer that the surface of described negative electrode is cascading; The material of described inorganic barrier layer is the titanium oxide (TiO of chlorine doping 2: Cl), chlorine doping zirconia (ZrO 2: Cl) or chlorine doping hafnium oxide (HfO 2: Cl); The material of described inorganic barrier layer is cycloalkanyl boron, and the structural formula of described cycloalkanyl boron is as shown in P: wherein R 1to be identical or different carbon number be 1 ~ 6 straight chained alkyl, branched alkyl or cycloalkyl, l is the integer of 1 ~ 10, and m is the integer of 5 ~ 15, and n is the integer of 0 ~ m-1.
Adulterate in the material of inorganic barrier layer chlorine, the compactness of rete can be improved, and hydrate can be formed by the steam entered with the external world, steam is stoped to enter in device, in inorganic barrier layer, the oxygen ion vacancy of oxide inside can catch oxygen simultaneously, and therefore inorganic barrier layer has good oxygen and the obstructing capacity of steam; Organic substance in inorganic barrier layer has adhesive and pliability, the while of can improving inorganic barrier layer adhering, effectively can also reduce the stress between rete.
Preferably, the thickness of described inorganic barrier layer is 15nm ~ 20nm; The thickness of described inorganic barrier layer is 200nm ~ 300nm.
Preferably, described inorganic barrier layer and described inorganic barrier layer form an encapsulation unit, and described encapsulated layer is laminated by 4 ~ 6 described encapsulation units.
Encapsulated layer comprises multiple encapsulation unit be made up of inorganic barrier layer and inorganic barrier layer, add the average length of the pin hole of inorganic matter in inorganic barrier layer, organic substance cycloalkanyl boron in inorganic barrier layer has also more effectively filled up the pin hole of inorganic matter in inorganic barrier layer, because this reducing the impact of pin hole for encapsulation, make encapsulated layer be provided with very high compactness, more effectively improve the barrier of encapsulated layer.
Preferably, described anode conducting substrate is electro-conductive glass substrate, conducting metal substrate or conductive plastics substrate.
More preferably, the material of described electro-conductive glass substrate is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO);
The material of described conductive plastics substrate is PETG (PET), polysulfones ether (PES), polyethylene naphthalate (PEN) or polyimides (PI).
Encapsulated layer can to rigid basement (substrate of glass, metallic substrates) and flexible substrates (plastic-substrates); especially flexible substrates is encapsulated; this is because the organic substance in thin layer has pliability; what can realize flexible device can tortuosity, thus can form effective protection to flexible device.
Preferably, described organic luminescence function layer comprises luminescent layer, and comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer;
Hole injection layer adopts common used material in industry, be preferably N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) and be entrained in N, N'-diphenyl-N, molybdenum trioxide (MoO in N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) 3);
Hole transmission layer adopts common used material in industry, is preferably 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA);
Luminescent layer adopts common used material in industry, and preferably, material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium [Ir (ppy) 3];
Electron transfer layer adopts common used material in industry, is preferably 4,7-diphenyl-1,10-phenanthroline (Bphen);
Electron injecting layer adopts common used material in industry, the cesium azide (CsN being preferably 4,7-diphenyl-1,10-phenanthroline (Bphen) and being entrained in 4,7-diphenyl-1,10-phenanthroline (Bphen) 3);
Negative electrode can be non-transparent metals negative electrode (aluminium, silver, gold etc.), also can be transparent cathode (dielectric layer/metal level/dielectric layer structure etc. that dielectric layer tramp metal layer is formed).
Preferably, the material of negative electrode is aluminium (Al), silver (Ag), gold (Au).
Preferably, the material of negative electrode is the sandwich that tin indium oxide (ITO)/silver (Ag)/tin indium oxide (ITO) or zinc sulphide (ZnS)/silver (Ag)/zinc sulphide (ZnS) are formed.
Second aspect, present invention also offers a kind of preparation method of organic electroluminescence device, comprises the steps:
(1) anode pattern first preparing organic electroluminescence device on the surface of the conductive substrates of cleaning forms anode conducting substrate, then adopts the method for vacuum evaporation to stack gradually on the surface of described anode conducting substrate and prepares organic luminescence function layer and negative electrode;
(2) on the surface of described negative electrode, prepare encapsulated layer, described encapsulated layer is included in inorganic barrier layer and inorganic barrier layer that the surface of described negative electrode is cascading, and preparation method is as follows:
A) preparation of inorganic barrier layer: adopt atomic layer deposition method to prepare inorganic barrier layer on the surface of described negative electrode, the operating pressure of described ald is 10Pa ~ 50Pa, and temperature is 40 DEG C ~ 60 DEG C; The material of described inorganic barrier layer is the titanium oxide (TiO of chlorine doping 2: Cl), chlorine doping zirconia (ZrO 2: Cl) or chlorine doping hafnium oxide (HfO 2: Cl); The presoma adopted in the process of described deposition inorganic barrier layer is four (dichloromethyl amido) titanium [Ti (N (CH 2cl) 2) 4], four (dichloromethyl amido) zirconium [Zr (N (CH 2cl) 2) 4] or four (dichloromethyl amido) hafnium [Hf (N (CH 2cl) 2) 4] in a kind of amido thing and steam; The injection length of described amido thing is 0.2s ~ 1s, and the injection length of described steam is 20ms ~ 40ms, injects described amido thing and to inject between described steam interval 5s ~ 10s nitrogen injection as Purge gas; The flow of described amido thing, described steam and described nitrogen is 10sccm ~ 20sccm; Described four (dichloromethyl amido) titanium [Ti (N (CH 2cl) 2) 4], described four (dichloromethyl amido) zirconium [Zr (N (CH 2cl) 2) 4] and described four (dichloromethyl amido) hafnium [Hf (N (CH 2cl) 2) 4] structural formula respectively shown in following A, B, C:
B) preparation of inorganic barrier layer: adopt the method for magnetron sputtering to prepare inorganic barrier layer on the surface of described inorganic barrier layer, the vacuum degree of described magnetron sputtering is 1 × 10 -5pa ~ 1 × 10 -3pa, accelerating voltage is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2; The material of described inorganic barrier layer is cycloalkanyl boron, and the structural formula of described cycloalkanyl boron is as shown in P: wherein R 1to be identical or different carbon number be 1 ~ 6 straight chained alkyl, branched alkyl or cycloalkyl, l is the integer of 1 ~ 10, and m is the integer of 5 ~ 15, and n is the integer of 0 ~ m-1.
Technique for atomic layer deposition accurately can control thickness and the composition of film, avoids the pollution of harmful substance simultaneously, has good step coverage and large area thickness evenness, can provide level and smooth, continuous and fine and close film.
Preferably, the thickness of described inorganic barrier layer is 15nm ~ 20nm; The thickness of described inorganic barrier layer is 200nm ~ 300nm.
Preferably, described inorganic barrier layer and described inorganic barrier layer form an encapsulation unit, repeat step (2) 4 ~ 6 times successively, prepare the encapsulated layer being repeated to be formed by 4 ~ 6 described encapsulation units by step (a) and (b) sequence alternate.
Preferably, described anode conducting substrate is electro-conductive glass substrate, conducting metal substrate or conductive plastics substrate.
Preferably, described organic luminescence function layer comprises luminescent layer, and comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer;
Hole injection layer adopts common used material in industry, be preferably N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) and be entrained in N, N'-diphenyl-N, molybdenum trioxide (MoO in N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) 3);
Hole transmission layer adopts common used material in industry, is preferably 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA);
Luminescent layer adopts common used material in industry, and preferably, material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium [Ir (ppy) 3];
Electron transfer layer adopts common used material in industry, is preferably 4,7-diphenyl-1,10-phenanthroline (Bphen);
Electron injecting layer adopts common used material in industry, the cesium azide (CsN being preferably 4,7-diphenyl-1,10-phenanthroline (Bphen) and being entrained in 4,7-diphenyl-1,10-phenanthroline (Bphen) 3);
Negative electrode can be non-transparent metals negative electrode (aluminium, silver, gold etc.), also can be transparent cathode (dielectric layer/metal level/dielectric layer structure etc. that dielectric layer tramp metal layer is formed).
Preferably, the material of negative electrode is aluminium (Al), silver (Ag), gold (Au).
Preferably, the material of negative electrode is the sandwich that tin indium oxide (ITO)/silver (Ag)/tin indium oxide (ITO) or zinc sulphide (ZnS)/silver (Ag)/zinc sulphide (ZnS) are formed.
Obtain described organic electroluminescence device by above-mentioned steps, comprise the anode conducting substrate, light emitting functional layer, negative electrode and the encapsulated layer that are cascading.
Compared with prior art, the present invention has following beneficial effect:
1, organic electroluminescence device provided by the invention refers to the encapsulated layer comprising inorganic barrier layer and inorganic barrier layer arranged on cathode surface; Adulterate in the material of inorganic barrier layer chlorine, the compactness of rete can be improved, and hydrate can be formed by the steam entered with the external world, steam is stoped to enter in device, in inorganic barrier layer, the oxygen ion vacancy of oxide inside can catch oxygen simultaneously, and therefore inorganic barrier layer has good oxygen and the obstructing capacity of steam; Organic substance in inorganic barrier layer has adhesive and pliability, the while of can improving inorganic barrier layer adhering, effectively can also reduce the stress between rete; Therefore, the encapsulated layer be made up of inorganic barrier layer and inorganic barrier layer has very high barrier property, effectively can reduce outside oxygen, steam isoreactivity material to the erosion of the organic compound in organic electroluminescence device and electrode, effectively can also reduce the stress between rete simultaneously, thus effective protection can be formed to device;
2, the encapsulated layer of organic electroluminescence device provided by the invention can to rigid basement (substrate of glass, metallic substrates) and flexible substrates (plastic-substrates), especially flexible substrates is encapsulated, this is because the organic substance in thin layer has pliability, what can realize flexible device can tortuosity, thus effective protection can be formed to flexible device, for flexible display technologies brings breakthrough progress;
3, the encapsulated layer of organic electroluminescence device provided by the invention comprises multiple encapsulation unit be made up of inorganic barrier layer and inorganic barrier layer, add the average length of the pin hole of inorganic matter in inorganic barrier layer, organic substance cycloalkanyl boron in inorganic barrier layer has also more effectively filled up the pin hole of inorganic matter in inorganic barrier layer, because this reducing the impact of pin hole for encapsulation, make encapsulated layer be provided with very high compactness, more effectively improve the barrier of encapsulated layer;
4, the water resistance (WVTR) of the encapsulated layer of organic electroluminescence device provided by the invention reaches 4.16 × 10 -6g/m 2about day, the life-span of device reaches more than 11500 hours (T70@1000cd/m 2);
5, the encapsulating material of preparation method's employing of organic electroluminescence device provided by the invention is cheap, and preparation technology is simple, easy large area preparation;
6, the technique for atomic layer deposition that the preparation method of organic electroluminescence device provided by the invention adopts accurately can control thickness and the composition of film, avoid the pollution of harmful substance simultaneously, there are good step coverage and large area thickness evenness, level and smooth, continuous and fine and close film can be provided.
Accompanying drawing explanation
Fig. 1 is the organic electroluminescence device schematic diagram in embodiment 1;
Fig. 2 is the structural representation of the encapsulated layer of Fig. 1.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with accompanying drawing and preferred embodiment, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not used in restriction the present invention.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1:
Fig. 1 is the organic electroluminescence device schematic diagram in embodiment 1; As shown in Figure 1, this organic electroluminescence device comprise be cascading from lower to upper ito glass substrate (10), organic luminescence function layer (20), negative electrode (30) and encapsulated layer (40); Wherein organic electroluminescent functional layer (20) comprises the hole injection layer (21), hole transmission layer (22), luminescent layer (23), electron transfer layer (24) and the electron injecting layer (25) that are cascading from lower to upper.Fig. 2 is the structural representation of the encapsulated layer of Fig. 1; As shown in Figure 2, encapsulated layer (40) is included in the inorganic barrier layer (41) and inorganic barrier layer (42) that negative electrode (30) is cascading on the surface; More specifically, first at negative electrode (30) deposited on silicon inorganic barrier layer (41), again at the surface deposition inorganic barrier layer (42) of inorganic barrier layer (41), inorganic barrier layer (41) and inorganic barrier layer (42) form an encapsulation unit, repeat above-mentioned thin film deposition steps 6 times, obtain the encapsulated layer (40) being repeated to be formed by 6 encapsulation units.
A preparation method for organic electroluminescence device, comprises the steps:
(1) pre-treatment of ito glass substrate (10): first by ito glass successively with acetone cleaning, ethanol purge, washed with de-ionized water and ethanol purge, all clean with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, dry up with nitrogen, stove-drying is stand-by; Then surface activation process is carried out to the ito glass after cleaning, to increase the oxygen content of conductive surface layer, improve the work function of conductive layer surface; The thickness of ito glass substrate is 100nm;
(2) preparation of organic luminescence function layer (20): adopt on the method for vacuum evaporation ito glass substrate surface after treatment and prepare organic luminescence function layer, organic luminescence function layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that are cascading;
Hole injection layer (21), material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) and be entrained in N, N'-diphenyl-N, molybdenum trioxide (MoO in N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) 3), molybdenum trioxide (MoO 3) doping mass fraction be 30%, thickness is 10nm, and the vacuum degree of the vacuum evaporation of employing is 3 × 10 -5pa, evaporation rate is
Hole transmission layer (22), material is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), and thickness is 30nm, and the vacuum degree of the vacuum evaporation of employing is 3 × 10 -5pa, evaporation rate is
Luminescent layer (23), material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium [Ir (ppy) 3], the doping mass fraction of guest materials is 5%, and thickness is 20nm, and the vacuum degree of the vacuum evaporation of employing is 3 × 10 -5pa, evaporation rate is
Electron transfer layer (24), material is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 10nm, and the vacuum degree of the vacuum evaporation of employing is 3 × 10 -5pa, evaporation rate is
Electron injecting layer (25), the cesium azide (CsN that material is 4,7-diphenyl-1,10-phenanthroline (Bphen) and is entrained in 4,7-diphenyl-1,10-phenanthroline (Bphen) 3), cesium azide (CsN 3) doping mass fraction be 30%, thickness is 20nm, and the vacuum degree of the vacuum evaporation of employing is 3 × 10 -5pa, evaporation rate is
(3) preparation of negative electrode (30): adopt the method for vacuum evaporation to prepare negative electrode on the surface at organic luminescence function layer, material is aluminium (Al), and thickness is 100nm, and the vacuum degree of the vacuum evaporation of employing is 3 × 10 -5pa, evaporation rate is
(4) preparation of encapsulated layer (40):
A) preparation of inorganic barrier layer (41): adopt atomic layer deposition method (ALD) to prepare inorganic barrier layer on cathode surface, operating pressure is 10Pa, and depositing temperature is 40 DEG C; Material is the titanium oxide (TiO of chlorine doping 2: Cl), the presoma adopted in the process of deposition inorganic barrier layer is four (dichloromethyl amido) titanium [Ti (N (CH 2cl) 2) 4] and steam, four (dichloromethyl amido) titanium [Ti (N (CH 2cl) 2) 4] injection length be 0.5s, the injection length of steam is 30ms, between the two interval 7s nitrogen injection (N 2), four (dichloromethyl amido) titanium [Ti (N (CH 2cl) 2) 4], steam and nitrogen (N 2) flow be 20sccm, the thickness of inorganic barrier layer is 20nm;
B) preparation of inorganic barrier layer (42): adopt the method for magnetron sputtering to prepare inorganic barrier layer on the surface of inorganic barrier layer, material is three (3-cyclo-dodecyl propyl group) boron, and structural formula is as P 1shown in: the thickness of inorganic barrier layer is 300nm; The vacuum degree of the magnetron sputtering adopted is 1 × 10 -5pa, accelerating voltage is 300V, and magnetic field is 50G, and power density is 1W/cm 2;
Alternately repeat step a) in step (4) and step b) 6 times, obtain organic electroluminescence device.
The water resistance (WVTR) of the organic electroluminescence device that the present embodiment obtains is 4.11 × 10 -6g/m 2day, the life-span is 11590 hours.
Ca film electrical testing method is adopted to test the vapor permeability of the present embodiment organic electroluminescence device, concrete grammar is: deposit calcium film on the glass substrate, then on calcium film, prepare the encapsulated layer of the present embodiment, by glass substrate and encapsulated layer, calcium film is sealed, then vapor permeability (WVTR is calculated by the electrical parameter of test Ca film, g/m2day), formula is: WVTR = &delta; 2 M [ H 2 O ] M [ Ca ] ( 1 - R i R ) h i 24 h t ; Wherein, δ is the density of Ca, and M represents molal weight, Ri and hi is respectively resistance and the thickness initial value of the front Ca of test, and t is the testing time, R and h is respectively resistance and the thickness of the rear Ca of test; R and Ri adopts Keithley 2400 to test, h and hi adopts step instrument test.Test organic electroluminescence device brightness decay of the present invention to original intensity (original intensity is 1000cd/m2) 70% time used by digital sourcemeter 2400 and luminance meter CS-100A, obtain the life value of organic electroluminescence device.
Embodiment 2:
A preparation method for organic electroluminescence device, comprises the steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of encapsulated layer:
A) preparation of inorganic barrier layer: adopt atomic layer deposition method (ALD) to prepare inorganic barrier layer on cathode surface, operating pressure is 50Pa, and depositing temperature is 60 DEG C; Material is the zirconia (ZrO of chlorine doping 2: Cl), the presoma adopted in the process of deposition inorganic barrier layer is four (dichloromethyl amido) zirconium [Zr (N (CH 2cl) 2) 4] and steam, four (dichloromethyl amido) zirconium [Zr (N (CH 2cl) 2) 4] injection length be 1s, the injection length of steam is 40ms, between the two interval 10s nitrogen injection (N 2), four (dichloromethyl amido) zirconium [Zr (N (CH 2cl) 2) 4], steam and nitrogen (N 2) flow be 20sccm, the thickness of inorganic barrier layer is 19nm;
B) preparation of inorganic barrier layer: adopt the method for magnetron sputtering to prepare inorganic barrier layer on the surface of inorganic barrier layer, material is three (11-(3-methylcycloheptyl) undecyl) boron, structural formula is as P 2shown in: the thickness of inorganic barrier layer is 250nm; The vacuum degree of the magnetron sputtering adopted is 1 × 10 -5pa, accelerating voltage is 800V, and magnetic field is 200G, and power density is 40W/cm 2;
Alternately repeat step a) in step (4) and step b) 6 times, obtain organic electroluminescence device.
The water resistance (WVTR) of the organic electroluminescence device that the present embodiment obtains is 4.14 × 10 -6g/m 2day, the life-span is 11567 hours.
Embodiment 3:
A preparation method for organic electroluminescence device, comprises the steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of encapsulated layer:
A) preparation of inorganic barrier layer: adopt atomic layer deposition method (ALD) to prepare inorganic barrier layer on cathode surface, operating pressure is 40Pa, and depositing temperature is 55 DEG C; Material is the hafnium oxide (HfO of chlorine doping 2: Cl), the presoma adopted in the process of deposition inorganic barrier layer is four (dichloromethyl amido) hafnium [Hf (N (CH 2cl) 2) 4] and steam, four (dichloromethyl amido) hafnium [Hf (N (CH 2cl) 2) 4] injection length be 0.2s, the injection length of steam is 20ms, between the two interval 5s nitrogen injection (N 2), four (dichloromethyl amido) hafnium [Hf (N (CH 2cl) 2) 4], steam and nitrogen (N 2) flow be 10sccm, the thickness of inorganic barrier layer is 15nm;
B) preparation of inorganic barrier layer: adopt the method for magnetron sputtering to prepare inorganic barrier layer on the surface of inorganic barrier layer, material is three (2-cyclopentyl ethyl) boron, and structural formula is as P 3shown in: the thickness of inorganic barrier layer is 200nm; The vacuum degree of the magnetron sputtering adopted is 1 × 10 -4pa, accelerating voltage is 500V, and magnetic field is 150G, and power density is 20W/cm 2;
Alternately repeat step a) in step (4) and step b) 6 times, obtain organic electroluminescence device.
The water resistance (WVTR) of the organic electroluminescence device that the present embodiment obtains is 4.15 × 10 -6g/m 2day, the life-span is 11550 hours.
Embodiment 4:
A preparation method for organic electroluminescence device, comprises the steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of encapsulated layer:
A) preparation of inorganic barrier layer: adopt atomic layer deposition method (ALD) to prepare inorganic barrier layer on cathode surface, operating pressure is 35Pa, and depositing temperature is 45 DEG C; Material is the titanium oxide (TiO of chlorine doping 2: Cl), the presoma adopted in the process of deposition inorganic barrier layer is four (dichloromethyl amido) titanium [Ti (N (CH 2cl) 2) 4] and steam, four (dichloromethyl amido) titanium [Ti (N (CH 2cl) 2) 4] injection length be 0.3s, the injection length of steam is 30ms, between the two interval 5s nitrogen injection (N 2), four (dichloromethyl amido) titanium [Ti (N (CH 2cl) 2) 4], steam and nitrogen (N 2) flow be 10sccm, the thickness of inorganic barrier layer is 17nm;
B) preparation of inorganic barrier layer: adopt the method for magnetron sputtering to prepare inorganic barrier layer on the surface of inorganic barrier layer, material is three (6-(2,3,4,5,6,7,8,9,10,11,12,13,14,15-14 n-hexyl) cyclopentadecane base n-hexane base) boron, structural formula is as shown in P4: the thickness of inorganic barrier layer is 250nm; The vacuum degree of the magnetron sputtering adopted is 1 × 10 -4pa, accelerating voltage is 600V, and magnetic field is 180G, and power density is 30W/cm 2;
Alternately repeat step a) in step (4) and step b) 5 times, obtain organic electroluminescence device.
The water resistance (WVTR) of the organic electroluminescence device that the present embodiment obtains is 4.16 × 10 -6g/m 2day, the life-span is 11541 hours.
Embodiment 5:
A preparation method for organic electroluminescence device, comprises the steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of encapsulated layer:
A) preparation of inorganic barrier layer: adopt atomic layer deposition method (ALD) to prepare inorganic barrier layer on cathode surface, operating pressure is 50Pa, and depositing temperature is 40 DEG C; Material is the zirconia (ZrO of chlorine doping 2: Cl), the presoma adopted in the process of deposition inorganic barrier layer is four (dichloromethyl amido) zirconium [Zr (N (CH 2cl) 2) 4] and steam, four (dichloromethyl amido) zirconium [Zr (N (CH 2cl) 2) 4] injection length be 0.4s, the injection length of steam is 25ms, between the two interval 10s nitrogen injection (N 2), four (dichloromethyl amido) zirconium [Zr (N (CH 2cl) 2) 4], steam and nitrogen (N 2) flow be 15sccm, the thickness of inorganic barrier layer is 20nm;
B) preparation of inorganic barrier layer: adopt the method for magnetron sputtering to prepare inorganic barrier layer on the surface of inorganic barrier layer, material is three (5-(3,4,5,6,7,8-Hexaethyl ring octyl group) n-pentyl) boron, structural formula is as P 5shown in: the thickness of inorganic barrier layer is 220nm; The vacuum degree of the magnetron sputtering adopted is 1 × 10 -4pa, accelerating voltage is 700V, and magnetic field is 150G, and power density is 35W/cm 2;
Alternately repeat step a) in step (4) and step b) 5 times, obtain organic electroluminescence device.
The water resistance (WVTR) of the organic electroluminescence device that the present embodiment obtains is 4.17 × 10 -6g/m 2day, the life-span is 11524 hours.
Embodiment 6:
A preparation method for organic electroluminescence device, comprises the steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of encapsulated layer:
A) preparation of inorganic barrier layer: adopt atomic layer deposition method (ALD) to prepare inorganic barrier layer on cathode surface, operating pressure is 25Pa, and depositing temperature is 50 DEG C; Material is the hafnium oxide (HfO of chlorine doping 2: Cl), the presoma adopted in the process of deposition inorganic barrier layer is four (dichloromethyl amido) hafnium [Hf (N (CH 2cl) 2) 4] and steam, four (dichloromethyl amido) hafnium [Hf (N (CH 2cl) 2) 4] injection length be 0.6s, the injection length of steam is 20ms, between the two interval 8s nitrogen injection (N 2), four (dichloromethyl amido) hafnium [Hf (N (CH 2cl) 2) 4], steam and nitrogen (N 2) flow be 11sccm, the thickness of inorganic barrier layer is 15nm;
B) preparation of inorganic barrier layer: adopt the method for magnetron sputtering to prepare inorganic barrier layer on the surface of inorganic barrier layer, material is three (5-ring octyl group n-pentyl) boron, and structural formula is as P 6shown in: the thickness of inorganic barrier layer is 210nm; The vacuum degree of the magnetron sputtering adopted is 1 × 10 -3pa, accelerating voltage is 500V, and magnetic field is 100G, and power density is 20W/cm 2;
Alternately repeat step a) in step (4) and step b) 4 times, obtain organic electroluminescence device.
The water resistance (WVTR) of the organic electroluminescence device that the present embodiment obtains is 4.20 × 10 -6g/m 2day, the life-span is 11500 hours.
Effect example
For the beneficial effect of valid certificates organic electroluminescence device of the present invention and preparation method thereof, measure the water resistance of organic electroluminescence device prepared by embodiment 1 ~ 6 and be all 1000cd/m at starting brightness 2under useful life.
The water resistance of the organic electroluminescence device in table 1. embodiment 1 ~ 6 and useful life information slip
Table 1 be organic electroluminescence device in embodiment 1 ~ 6 water resistance and useful life information slip.As can be seen from Table 1, the water resistance (WVTR) of organic electroluminescence device provided by the invention reaches 4.16 × 10 -6g/m 2about day, the life-span all reaches more than 11500 hours (T70@1000cd/m 2: namely starting brightness is 1000cd/m 2brightness decay is to 70% time used); illustrate that organic electroluminescence device provided by the invention is by arranging encapsulated layer; effectively reduce outside oxygen, steam isoreactivity material to the erosion of the organic compound in organic electroluminescence device and electrode; thus effective protection is defined to device, improve the life-span of device.
Encapsulation rete compactness is most important, can select suitable process conditions according to device detection result.Certainly, the above is only individual example of the present invention, all according to the structure described in the present patent application the scope of the claims, principle and similar change, all should be contained in the scope of the present patent application patent.

Claims (10)

1. an organic electroluminescence device, the organic luminescence function layer, negative electrode and the encapsulated layer that comprise anode conducting substrate and be cascading on the surface of described anode conducting substrate, it is characterized in that, described encapsulated layer is included in inorganic barrier layer and inorganic barrier layer that the surface of described negative electrode is cascading; The material of described inorganic barrier layer is titanium oxide, the zirconia of chlorine doping or the hafnium oxide of chlorine doping that chlorine adulterates; The material of described inorganic barrier layer is cycloalkanyl boron, and the structural formula of described cycloalkanyl boron is as shown in P: wherein R 1to be identical or different carbon number be 1 ~ 6 straight chained alkyl, branched alkyl or cycloalkyl, l is the integer of 1 ~ 10, and m is the integer of 5 ~ 15, and n is the integer of 0 ~ m-1.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described inorganic barrier layer is 15nm ~ 20nm; The thickness of described inorganic barrier layer is 200nm ~ 300nm.
3. organic electroluminescence device according to claim 1, is characterized in that, described inorganic barrier layer and described inorganic barrier layer form an encapsulation unit, and described encapsulated layer is laminated by 4 ~ 6 described encapsulation units.
4. organic electroluminescence device according to claim 1, is characterized in that, described anode conducting substrate is electro-conductive glass substrate, conducting metal substrate or conductive plastics substrate.
5. organic electroluminescence device according to claim 4, is characterized in that, the material of described electro-conductive glass substrate is indium tin oxide, aluminium zinc oxide or indium-zinc oxide;
The material of described conductive plastics substrate is PETG, polysulfones ether, polyethylene naphthalate or polyimides.
6. organic electroluminescence device according to claim 1, is characterized in that, described organic luminescence function layer comprises luminescent layer, and comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
(1) anode pattern first preparing organic electroluminescence device on the surface of the conductive substrates of cleaning forms anode conducting substrate, then adopts the method for vacuum evaporation to stack gradually on the surface of described anode conducting substrate and prepares organic luminescence function layer and negative electrode;
(2) on the surface of described negative electrode, prepare encapsulated layer, described encapsulated layer is included in inorganic barrier layer and inorganic barrier layer that the surface of described negative electrode is cascading, and preparation method is as follows:
A) preparation of inorganic barrier layer: adopt atomic layer deposition method to prepare inorganic barrier layer on the surface of described negative electrode, the operating pressure of described ald is 10Pa ~ 50Pa, and temperature is 40 DEG C ~ 60 DEG C; The material of described inorganic barrier layer is titanium oxide, the zirconia of chlorine doping or the hafnium oxide of chlorine doping that chlorine adulterates; The presoma adopted in the process of described deposition inorganic barrier layer is a kind of amido thing in four (dichloromethyl amido) titanium, four (dichloromethyl amido) zirconiums or four (dichloromethyl amido) hafnium and steam; The injection length of described amido thing is 0.2s ~ 1s, and the injection length of described steam is 20ms ~ 40ms, injects described amido thing and to inject between described steam interval 5s ~ 10s nitrogen injection as Purge gas; The flow of described amido thing, described steam and described nitrogen is 10sccm ~ 20sccm;
B) preparation of inorganic barrier layer: adopt the method for magnetron sputtering to prepare inorganic barrier layer on the surface of described inorganic barrier layer, the vacuum degree of described magnetron sputtering is 1 × 10 -5pa ~ 1 × 10 -3pa, accelerating voltage is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2; The material of described inorganic barrier layer is cycloalkanyl boron, and the structural formula of described cycloalkanyl boron is as shown in P: wherein R 1to be identical or different carbon number be 1 ~ 6 straight chained alkyl, branched alkyl or cycloalkyl, l is the integer of 1 ~ 10, and m is the integer of 5 ~ 15, and n is the integer of 0 ~ m-1.
8. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, the thickness of described inorganic barrier layer is 15nm ~ 20nm; The thickness of described inorganic barrier layer is 200nm ~ 300nm.
9. the preparation method of organic electroluminescence device according to claim 7, it is characterized in that, described inorganic barrier layer and described inorganic barrier layer form an encapsulation unit, repeat step (2) 4 ~ 6 times by step (a) and (b) sequence alternate successively, prepare the encapsulated layer being repeated to be formed by 4 ~ 6 described encapsulation units.
10. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, described anode conducting substrate is electro-conductive glass substrate, conducting metal substrate or conductive plastics substrate.
CN201310561328.6A 2013-11-12 2013-11-12 Organic light-emitting device and preparation method thereof Pending CN104638117A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106257705A (en) * 2015-06-22 2016-12-28 东京毅力科创株式会社 Lamination diaphragm seal forming method and formation device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106257705A (en) * 2015-06-22 2016-12-28 东京毅力科创株式会社 Lamination diaphragm seal forming method and formation device
JP2017010749A (en) * 2015-06-22 2017-01-12 東京エレクトロン株式会社 Method and device for forming laminated sealing film
CN106257705B (en) * 2015-06-22 2019-06-11 东京毅力科创株式会社 Lamination seals film forming method and forms device

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