CN103904246A - Organic electroluminescent device and preparing method thereof - Google Patents
Organic electroluminescent device and preparing method thereof Download PDFInfo
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- CN103904246A CN103904246A CN201210572588.9A CN201210572588A CN103904246A CN 103904246 A CN103904246 A CN 103904246A CN 201210572588 A CN201210572588 A CN 201210572588A CN 103904246 A CN103904246 A CN 103904246A
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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Abstract
The invention discloses an organic electroluminescent device and a preparing method thereof. The organic electroluminescent device comprises an anode substrate, a hole injection layer, a hole transporting layer, a light-emitting layer, an electron transporting layer, an electron injection layer and a cathode layer which are stacked successively. At least one organic blocking layer and a layer of inorganic blocking layer are evaporated and deposited alternately on the cathode layer. The material of the organic blocking layer is metal phthalocyanine compound. The material of the inorganic blocking layer is a mixture consisting of oxide doped with 10-40 wt% of fluoride. According to the organic electroluminescent device of the invention, the cheap organic blocking layer and the inorganic blocking layer are evaporated and deposited alternately for packaging on the basis of an existing organic electroluminescent device, so the film layer water and oxygen prevention capability can be improved, and the erosion of external active matters, such as the water, the oxygen, etc., on the organic electroluminescent device can be effectively reduced, so that the device organic function material and the electrode can be effectively protected. According to the organic electroluminescent device of the invention, advantages of simple preparation process and easy large-area preparation can be realized.
Description
Technical field
The present invention relates to field of electronic devices, particularly include organic electroluminescence devices and preparation method thereof.
Background technology
Organic electroluminescence device (Organic Light-Emitting Diode, OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is to make luminescent layer at the luminous organic material of indium tin oxide (Indium TinOxides, ITO) making one deck tens nanometer thickness on glass, and there is the metal electrode of one deck low work function luminescent layer top.Its luminescence mechanism and process are to inject respectively electronics and hole from yin, yang the two poles of the earth, and transmit in organic layer in the electronics and the hole that are injected into, and compound in luminescent layer, thereby stimulated luminescence layer molecule produces singlet exciton, singlet exciton attenuation and luminous.
OLED device have active illuminating, luminous efficiency high, low in energy consumption, light, thin, without advantages such as angle limitations, thought to be most likely at by insider the device of new generation that occupies dominance on following illumination and display device market.As a brand-new illumination and Display Technique, the ten years development in the past of OLED technology is swift and violent, has obtained huge achievement.Throw light on because the whole world is increasing and show that producer drops into research and development one after another, having promoted greatly the industrialization process of OLED, making the growth rate of OLED industry surprising, having arrived the eve of scale of mass production at present.
But, due to outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device, cause the decline of organic functional material inefficacy and electrode performance, so short defect of organic electroluminescence device ubiquity life-span at present, if make organic electroluminescence device reach enough useful life, the most key effectively encapsulates device exactly, and therefore the quality of encapsulation directly affects the life-span of device.
Summary of the invention
Based on this, be necessary to provide a kind of waterproof, organic electroluminescence device that oxygen ability is strong and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually, on described cathode layer, replace at least organic barrier layer of one deck and one deck inorganic barrier layer of evaporation; The material on described organic barrier layer is metal phthalocyanine compound, and the material of described inorganic barrier layer is the mixture of the oxide composition of doping 10-40wt% fluoride.
Utilize coordination and the metal-complexing in the 4th cycle of phthalocyanine to form metal phthalocyanine compound, the metal phthalocyanine compound forming has good photoelectric effect.Oxide is the oxide that is pellucidity, owing to being transparent, so adopt transparent oxide can not exert an influence to the transmission of light as the material of inorganic obstacle; Fluoride has the performance of waterproof, oil-stain-preventing, can be used as waterproof material, and the 10-40wt% fluoride that adulterates in transparent oxide not only can guarantee higher light transmittance, can also improve the waterproof oxygen ability of encapsulating structure.
In some embodiment, described organic barrier layer and inorganic barrier layer are 4-6 layer therein.
In some embodiment, the thickness on every layer of described organic barrier layer is 100nm-200nm therein, and the thickness of every layer of described inorganic barrier layer is 50～100nm.
In some embodiment, described metal phthalocyanine compound is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine therein.
In some embodiment, described oxide is TiO therein
2, MgO, SiO
2, ZrO
2, ZnO or Al
2o
3, described fluoride is AlF
3, HfF
4, ZrF
4, CeF
2, YF
3or MgF
2.
In an embodiment, described metal phthalocyanine compound is Phthalocyanine Zinc therein, and the material of described inorganic barrier layer is doping 10wt%HfF
4the mixture of MgO composition.
In an embodiment, described cathode layer is sandwich structure therein, and two outer field materials are ZnS, and the material in intermediate layer is Ag, and each described outer field thickness is 30nm, and the thickness in described intermediate layer is 10nm.
In an embodiment, the material of described hole injection layer is doping 30wt% MoO therein
3n, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, the thickness of described hole injection layer is 10nm; The material of described hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine, the thickness of described hole transmission layer is 30nm; The material of described luminescent layer is that doping 5wt% tri-(2-phenylpyridine) closes 1,3 of iridium, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, the thickness 20nm of described luminescent layer; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, and the thickness of described electron transfer layer is 10nm; The material of described electron injecting layer is doping 30wt%CsN
34,7-diphenyl-1,10-phenanthroline, the thickness of described electron injecting layer is 20nm.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
(1), stack gradually vacuum evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer on the anode layer surface of anode substrate;
(2), the organic barrier layer of vacuum evaporation on described cathode layer; Wherein, the material on described organic barrier layer is metal phthalocyanine compound;
(3), sample, fluoride and oxide that step (2) is made together put into magnetron sputtering apparatus, on described organic barrier layer, magnetron sputtering is prepared inorganic barrier layer; Wherein, the material of described inorganic barrier layer is the mixture of the oxide composition of doping 10-40wt% fluoride;
(4), repeatedly replace repeating step (2) and step (3);
After above-mentioned processing step finishes, obtain organic electroluminescence device.
In an embodiment, in the described vacuum evaporation of step (2), vacuum degree is 1 × 10 therein
-5pa-1 × 10
-3pa, evaporation rate is
In an embodiment, in the described magnetron sputtering of step (3), vacuum degree is 1 × 10 therein
-5pa-1 × 10
-3pa, also comprises when magnetron sputtering and passes into the argon gas that flow is 5～10sccm.
Organic electroluminescence device of the present invention adopts organic barrier layer and inorganic barrier layer to replace evaporation and encapsulates on existing organic electroluminescence device basis.Organic barrier layer adopts the metal phthalocyanine compound with good electron-transporting and luminescent properties; and inorganic layer adopts the transparent oxide material of doped fluoride; improve rete waterproof oxygen ability; effectively reduce outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device, thereby device organic functional material and electrode have been formed to effective protection.
The front cover light transmittance of organic electroluminescence device of the present invention reaches more than 77%, and moisture-vapor transmission (WaterVapor Transmission Rate is called for short WVTR) reaches 10
-4g/m
2day, life-span (the T70@1000cd/m of organic electroluminescence device of the present invention
2) reached more than 4800 hours.
Organic electroluminescence device of the present invention adopts cheap encapsulating material to encapsulate, preparation technology is simple, easily large area preparation, the flexible OLED device that the OLED device that is applicable to prepare take substrate of glass and plastics or metal are prepared as substrate, is specially adapted to the application of flexible OLED device.
Accompanying drawing explanation
Fig. 1 is the organic electroluminescence device structural representation of an embodiment of the present invention;
Reference numeral: 10, anode substrate, 20, functional layer, 201, hole injection layer, 202, hole transmission layer, 203, luminescent layer, 204, electron transfer layer, 205, electron injecting layer, 30, cathode layer 40, organic barrier layer, 50, inorganic barrier layer.
Embodiment
As shown in Figure 1, be organic electroluminescence device of the present invention, comprising:
(1) anode substrate 10;
(2) functional layer 20, be positioned between anode substrate 10 (comprise substrate and play the anode layer of anode conducting effect) and cathode layer 30 (power supply electronics is provided for device), comprise the hole injection layer 201 (injected holes that stack gradually, being conducive to hole is injected into transferring material from anode), hole transmission layer 202 (transporting holes, be conducive to hole transport in luminescent material), (electronics and hole are compound in this layer for luminescent layer 203, then energy is transferred to light emitting molecule luminous), electron transfer layer 204 (transmission electronics, be conducive to electric transmission in luminescent material), (inject electronics with electron injecting layer 205, being conducive to electronics is injected into transferring material from anode), described hole injection layer 201 is positioned on described anode substrate 10,
(3) cathode layer 30;
(4) organic barrier layer 40, evaporation is on described cathode layer 30; Organic barrier layer 40 is metal phthalocyanine compound CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and organic barrier layer 40 is 4-6 layer, and every layer thickness is 100nm-200nm;
(5) inorganic barrier layer 50, evaporation is on described organic barrier layer 40; Inorganic barrier layer 50 is the mixture of the oxide composition of doping 10-40wt% fluoride, and described oxide is TiO
2, MgO, SiO
2, ZrO
2, ZnO or Al
2o
3, described fluoride is AlF
3, HfF
4, ZrF
4, CeF
2, YF
3or MgF
2; Inorganic barrier layer 50 is 4-6 layer, and every layer thickness is 50～100nm.
When organic barrier layer and inorganic barrier layer exceed when two-layer, described organic barrier layer 40 and alternately evaporation of inorganic barrier layer 50.
The preparation method of organic electroluminescence device of the present invention, comprises the steps:
S1, stack gradually vacuum evaporation functional layer 20 (comprising hole injection layer 201, hole transmission layer 202, luminescent layer 203, electron transfer layer 204, electron injecting layer 205) and cathode layer 30 on the anode layer surface of anode substrate 10;
S2, on described cathode layer 30 the organic barrier layer 40 of vacuum evaporation; Wherein, the material on described organic barrier layer 40 is metal phthalocyanine compound; In described vacuum evaporation, vacuum degree is 1 × 10
-5pa-1 × 10
-3pa, evaporation rate
S3, sample, fluoride and oxide that step (2) is made are together put into magnetron sputtering apparatus, and on described organic barrier layer 40, magnetron sputtering is prepared inorganic barrier layer 50; Wherein, the material of described inorganic barrier layer 50 is the mixture of the oxide composition of doping 10-40wt% fluoride; In described magnetron sputtering, vacuum degree is 1 × 10
-5pa-1 × 10
-3pa, also comprises when magnetron sputtering and passes into the argon gas that flow is 5～10sccm;
S4, repeatedly alternately repeating step (2) and step (3);
After above-mentioned processing step finishes, obtain organic electroluminescence device.
In the preparation method of above-mentioned organic electroluminescence device, the preparation of described cathode layer 30 also comprises: after electron injecting layer 205 evaporations, first surperficial evaporation one deck ZnS layer at electron injecting layer 205, subsequently at ZnS layer surface evaporation one deck Ag layer, finally again at Ag layer surface evaporation one deck ZnS layer, make cathode layer 30 after complete.
The substrate of above-mentioned anode substrate 10 is generally glass, the anode layer on it, and namely conductive layer, the material of anode layer is generally ITO, IZO, AZO, FTO etc., preferably ITO; Be prepared with ITO, IZO, AZO, FTO layer at glass surface, be called for short ito glass, IZO glass, AZO glass, FTO glass.
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1 organic electroluminescence device
Comprise:
(1) anode substrate;
(2) functional layer, between anode substrate and cathode layer, comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually, and described hole injection layer is positioned on described anode substrate;
(3) cathode layer;
(4) organic barrier layer, evaporation is on described cathode layer; Organic barrier layer is CuPc (CuPc), and organic barrier layer is 6 layers, and every layer thickness is 150nm;
(5) inorganic barrier layer, evaporation is on described organic barrier layer; Inorganic barrier layer is doping 40wt% AlF
3tiO
2the mixture of composition; Inorganic barrier layer is 6 layers, and every layer thickness is 100nm.
Described organic barrier layer and inorganic barrier layer replace evaporation.
The organic electroluminescence device of the present embodiment is prepared and obtained by following steps:
(1), prepare anode substrate (ito glass substrate);
First ito glass substrate is cleaned in supersonic wave cleaning machine with acetone, ethanol, deionized water, ethanol successively, individual event washing is cleaned 5 minutes, then dries up with nitrogen, and stove-drying is stand-by; Ito glass substrate after cleaning is also needed to carry out surface activation process, 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) prepare functional layer (be followed successively by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, wherein hole injection layer is positioned on anode substrate)
A hole injection layer
Vacuum evaporation hole injection layer on ito glass substrate, the material of described hole injection layer is the MoO of doping 30wt%
3n, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), vacuum degree is 1 × 10
-5pa, evaporation rate is
the thickness of hole injection layer is 10nm;
B hole transmission layer
At the surface vacuum evaporation hole transmission layer of hole injection layer, the material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), vacuum degree is 1 × 10
-5pa, evaporation rate is
evaporation thickness is 30nm;
C luminescent layer
At the surface vacuum evaporation luminescent layer of hole transmission layer, the material of main part of described luminescent layer 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), doping content 5wt%, vacuum degree is 1 × 10
-5pa, evaporation rate is
evaporation thickness is 20nm;
D electron transfer layer
At surface vacuum evaporation one deck 4 of luminescent layer, 7-diphenyl-1,10-phenanthroline (Bphen), vacuum degree is 1 × 10
-5pa, evaporation rate is
evaporation thickness is 10nm;
E electron injecting layer
At the surface vacuum evaporation electron injecting layer of electron transfer layer, the material of electron injecting layer is doping 30wt% CsN
3bphen, vacuum degree is 1 × 10
-5pa, evaporation rate is
evaporation thickness is 20nm;
(3) prepare cathode layer
At the surperficial evaporation transparent cathode layer ZnS/Ag/ZnS of electron injecting layer, described cathode layer is sandwich structure, and two outer field materials are ZnS, and the material in intermediate layer is Ag, and each described outer field thickness is 30nm, and the thickness in described intermediate layer is 10nm.Vacuum degree is 1 × 10
-5pa, evaporation rate is
(4), prepare organic barrier layer
On the organic barrier layer of surface vacuum evaporation of cathode layer, the material on organic barrier layer is CuPc (CuPc), and vacuum degree is 1 × 10
-5pa, evaporation rate is
the thickness on organic barrier layer is 150nm;
(5), prepare inorganic barrier layer
Prepare inorganic barrier layer at organic barrier layer surface magnetron sputtering, the material of described inorganic barrier layer is doping 40wt%AlF
3tiO
2the mixture of composition, vacuum degree is 1 × 10
-5pa, passes into Ar, and flow is 10sccm, and the thickness of inorganic barrier layer is 100nm;
(6), alternately repeating step (4) and step (5) 6 times, to obtain final product.
Embodiment 2 organic electroluminescence devices
Comprise:
(1) anode substrate; With embodiment 1;
(2) functional layer; With embodiment 1;
(3) cathode layer; With embodiment 1;
(4) organic barrier layer, evaporation is on described cathode layer; Organic barrier layer is ZnPc (Phthalocyanine Zinc), and organic barrier layer is 5 layers, and every layer thickness is 100nm;
(5) inorganic barrier layer, evaporation is on described organic barrier layer; Inorganic barrier layer is doping 10wt%HfF
4the mixture of MgO composition; Inorganic barrier layer is 5 layers, and every layer thickness is 50nm.
Described organic barrier layer and inorganic barrier layer replace evaporation.
The organic electroluminescence device of the present embodiment is prepared and obtained by following steps:
(1), prepare anode substrate (ito glass substrate)
With embodiment 1 step (1).
(2) prepare functional layer
With embodiment 1 step (2).
(3) prepare cathode layer
With embodiment 1 step (3).
(4), prepare organic barrier layer
On the organic barrier layer of surface vacuum evaporation of cathode layer, the material on organic barrier layer is ZnPc (Phthalocyanine Zinc), vacuum degree 1 × 10
-5pa, evaporation rate is
the thickness on organic barrier layer is 100nm;
(5), prepare inorganic barrier layer
Prepare inorganic barrier layer at organic barrier layer surface magnetron sputtering, the material of described inorganic barrier layer is doping 10wt%HfF
4the mixture of MgO composition, vacuum degree is 5 × 10
-5pa, passes into Ar, and flow is 5sccm, and the thickness of inorganic barrier layer is 50nm;
(6), alternately repeating step (4) and step (5) 5 times, to obtain final product.
Embodiment 3 organic electroluminescence devices
Comprise:
(1) anode substrate; With embodiment 1;
(2) functional layer; With embodiment 1;
(3) cathode layer; With embodiment 1;
(4) organic barrier layer, evaporation is on described cathode layer; Organic barrier layer is FePc (FePC), and organic barrier layer is 5 layers, and every layer thickness is 100nm;
(5) inorganic barrier layer, evaporation is on described organic barrier layer; Inorganic barrier layer is doping 30wt%ZrF
4siO
2the mixture of composition; Inorganic barrier layer is 5 layers, and every layer thickness is 65nm.
Described organic barrier layer and inorganic barrier layer replace evaporation.
The organic electroluminescence device of the present embodiment is prepared and obtained by following steps:
(1), prepare anode substrate (ito glass substrate)
With embodiment 1 step (1).
(2) prepare functional layer
With embodiment 1 step (2).
(3) prepare cathode layer
With embodiment 1 step (3).
(4), prepare organic barrier layer
On the organic barrier layer of surface vacuum evaporation of cathode layer, the material on organic barrier layer is FePc (FePC), vacuum degree 5 × 10
-5pa, evaporation rate is
the thickness on organic barrier layer is 100nm;
(5), prepare inorganic barrier layer
Prepare inorganic barrier layer at organic barrier layer surface magnetron sputtering, the material of described inorganic barrier layer is doping 30wt%ZrF
4siO
2the mixture of composition, vacuum degree is 5 × 10
-5pa, passes into Ar, and flow is 8sccm, and the thickness of inorganic barrier layer is 65nm;
(6), alternately repeating step (4) and step (5) 5 times, to obtain final product.
Embodiment 4 organic electroluminescence devices
Comprise:
(1) anode substrate; With embodiment 1;
(2) functional layer; With embodiment 1;
(3) cathode layer; With embodiment 1;
(4) organic barrier layer, evaporation is on described cathode layer; Organic barrier layer is CoPc (Cobalt Phthalocyanine), and organic barrier layer is 5 layers, and every layer thickness is 200nm;
(5) inorganic barrier layer, evaporation is on described organic barrier layer; Inorganic barrier layer is doping 30wt%CeF
2zrO
2the mixture of composition; Inorganic barrier layer is 5 layers, and every layer thickness is 70nm.
Described organic barrier layer and inorganic barrier layer replace evaporation.
The organic electroluminescence device of the present embodiment is prepared and obtained by following steps:
(1), prepare anode substrate (ito glass substrate)
With embodiment 1 step (1).
(2) prepare functional layer
With embodiment 1 step (2).
(3) prepare cathode layer
With embodiment 1 step (3).
(4), prepare organic barrier layer
On the organic barrier layer of surface vacuum evaporation of cathode layer, the material on organic barrier layer is CoPc (Cobalt Phthalocyanine), vacuum degree 5 × 10
-5pa, evaporation rate is
the thickness on organic barrier layer is 200nm;
(5), prepare inorganic barrier layer
Prepare inorganic barrier layer at organic barrier layer surface magnetron sputtering, the material of described inorganic barrier layer is doping 30wt% CeF
2zrO
2the mixture of composition, vacuum degree is 5 × 10
-5pa, passes into Ar, and flow is 6sccm, and the thickness of inorganic barrier layer is 70nm;
(6), alternately repeating step (4) and step (5) 5 times, to obtain final product.
Embodiment 5 organic electroluminescence devices
Comprise:
(1) anode substrate; With embodiment 1;
(2) functional layer; With embodiment 1;
(3) cathode layer; With embodiment 1;
(4) organic barrier layer, evaporation is on described cathode layer; Organic barrier layer is MnPc (manganese phthalocyanine), and organic barrier layer is 5 layers, and every layer thickness is 150nm;
(5) inorganic barrier layer, evaporation is on described organic barrier layer; Inorganic barrier layer is the mixture of the ZnO composition of doping 20wt%YF3; Inorganic barrier layer is 5 layers, and every layer thickness is 50nm.
Described organic barrier layer and inorganic barrier layer replace evaporation.
The organic electroluminescence device of the present embodiment is prepared and obtained by following steps:
(1), prepare anode substrate (ito glass substrate)
With embodiment 1 step (1).
(2) prepare functional layer
With embodiment 1 step (2).
(3) prepare cathode layer
With embodiment 1 step (3).
(4), prepare organic barrier layer
On the organic barrier layer of surface vacuum evaporation of cathode layer, the material on organic barrier layer is MnPc (manganese phthalocyanine), and vacuum degree is 5 × 10
-5pa, evaporation rate is
the thickness on organic barrier layer is 150nm;
(5), prepare inorganic barrier layer
Prepare inorganic barrier layer at organic barrier layer surface magnetron sputtering, the material of described inorganic barrier layer is doping 20wt%YF
3the mixture of ZnO composition, vacuum degree is 5 × 10
-5pa, passes into Ar, and flow is 5sccm, and the thickness of inorganic barrier layer is 50nm;
(6), alternately repeating step (4) and step (5) 5 times, to obtain final product.
Embodiment 6 organic electroluminescence devices
Comprise:
(1) anode substrate; With embodiment 1;
(2) functional layer; With embodiment 1;
(3) cathode layer; With embodiment 1;
(4) organic barrier layer, evaporation is on described cathode layer; Organic barrier layer is NiPc (Nickel Phthalocyanine), and organic barrier layer is 4 layers, and every layer thickness is 150nm;
(5) inorganic barrier layer, evaporation is on described organic barrier layer; Inorganic barrier layer is doping 30wt%MgF
2al
2o
3the mixture of composition; Inorganic barrier layer is 4 layers, and every layer thickness is 70nm.
Described organic barrier layer and inorganic barrier layer replace evaporation.
The organic electroluminescence device of the present embodiment is prepared and obtained by following steps:
(1), prepare anode substrate (ito glass substrate)
With embodiment 1 step (1).
(2) prepare functional layer
With embodiment 1 step (2).
(3) prepare cathode layer
With embodiment 1 step (3).
(4), prepare organic barrier layer
On the organic barrier layer of surface vacuum evaporation of cathode layer, the material on organic barrier layer is NiPc (Nickel Phthalocyanine), and vacuum degree is 1 × 10
-3pa, evaporation rate is
the thickness on organic barrier layer is 150nm;
(5), prepare inorganic barrier layer
Prepare inorganic barrier layer at organic barrier layer surface magnetron sputtering, the material of described inorganic barrier layer is doping 30wt%MgF
2al
2o
3the mixture of composition, vacuum degree is 1 × 10
-3pa, passes into Ar, and flow is 6sccm, and the thickness of inorganic barrier layer is 70nm;
(6), alternately repeating step (4) and step (5) 4 times, to obtain final product.
The organic electroluminescence device of embodiment 1-6 has been carried out to the test of moisture-vapor transmission (WVTR), useful life and transmitance, result is as shown in table 1:
The test result of table 1 embodiment 1-6
As can be seen from Table 1, the moisture-vapor transmission of the organic electroluminescence device of the present embodiment 1-6 (WVTR) is minimum reaches 5.2 × 10
-4g/m
2day, meets the instructions for use of flexible organic electroluminescent device completely, and light transmittance reaches more than 77%, reaches useful life more than 4800 hours.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an organic electroluminescence device, comprise the anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually, it is characterized in that, on described cathode layer, replace at least organic barrier layer of one deck and one deck inorganic barrier layer of evaporation; The material on described organic barrier layer is metal phthalocyanine compound, and the material of described inorganic barrier layer is the mixture of the oxide composition of doping 10-40wt% fluoride.
2. organic electroluminescence device according to claim 1, is characterized in that, described organic barrier layer and inorganic barrier layer are 4-6 layer, and the thickness on every layer of described organic barrier layer is 100～200nm, and the thickness of every layer of described inorganic barrier layer is 50～100nm.
3. organic electroluminescence device according to claim 1 and 2, is characterized in that, described metal phthalocyanine compound is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine.
4. organic electroluminescence device according to claim 1 and 2, is characterized in that, described oxide is TiO
2, MgO, SiO
2, ZrO
2, ZnO or Al
2o
3, described fluoride is AlF
3, HfF
4, ZrF
4, CeF
2, YF
3or MgF
2.
5. organic electroluminescence device according to claim 1, is characterized in that, described metal phthalocyanine compound is Phthalocyanine Zinc, and the material of described inorganic barrier layer is doping 10wt%HfF
4the mixture of MgO composition.
6. organic electroluminescence device according to claim 1, is characterized in that, described cathode layer is sandwich structure, and two outer field materials are ZnS, and the material in intermediate layer is Ag, and each described outer field thickness is 30nm, and the thickness in described intermediate layer is 10nm.
7. organic electroluminescence device according to claim 1, is characterized in that, the material of described hole injection layer is doping 30wt%MoO
3n, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, the thickness of described hole injection layer is 10nm; The material of described hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine, the thickness of described hole transmission layer is 30nm; The material of described luminescent layer is that doping 5wt% tri-(2-phenylpyridine) closes 1,3 of iridium, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, the thickness 20nm of described luminescent layer; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, and the thickness of described electron transfer layer is 10nm; The material of described electron injecting layer is doping 30wt%CsN
34,7-diphenyl-1,10-phenanthroline, the thickness of described electron injecting layer is 20nm.
8. a preparation method for the arbitrary described organic electroluminescence device of claim 1-7, is characterized in that, comprises the following steps:
(1), stack gradually vacuum evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer on the anode layer surface of anode substrate;
(2), the organic barrier layer of vacuum evaporation on described cathode layer; Wherein, the material on described organic barrier layer is metal phthalocyanine compound;
(3), sample, fluoride and oxide that step (2) is made together put into magnetron sputtering apparatus, on described organic barrier layer, magnetron sputtering is prepared inorganic barrier layer; Wherein, the material of described inorganic barrier layer is the mixture of the oxide composition of doping 10-40wt% fluoride;
(4), repeatedly replace repeating step (2) and step (3);
After above-mentioned processing step finishes, obtain organic electroluminescence device.
9. the preparation method of organic electroluminescence device according to claim 8, is characterized in that, in the described vacuum evaporation of step (2), vacuum degree is 1 × 10
-5pa-1 × 10
-3pa, evaporation rate is
10. the preparation method of organic electroluminescence device according to claim 8, is characterized in that, in the described magnetron sputtering of step (3), vacuum degree is 1 × 10
-5pa-1 × 10
-3pa, also comprises when magnetron sputtering and passes into the argon gas that flow is 5～10sccm.
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