CN103904241B - Organic electroluminescence device and preparation method - Google Patents
Organic electroluminescence device and preparation method Download PDFInfo
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- CN103904241B CN103904241B CN201210572062.0A CN201210572062A CN103904241B CN 103904241 B CN103904241 B CN 103904241B CN 201210572062 A CN201210572062 A CN 201210572062A CN 103904241 B CN103904241 B CN 103904241B
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Abstract
The present invention relates to a kind of organic electroluminescence device, comprises the anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, inorganic barrier layer and the doping tellurium compound layer that are cascading.This above-mentioned organic electroluminescence device is provided with inorganic barrier layer and doping tellurium compound layer on cathode layer, inorganic barrier layer and doping tellurium compound layer form water oxygen barrier layers, there is good oxygen water-proof function, the water oxygen barrier layers that layering is arranged can permeate by effectively anti-sealing oxygen gradually, the better effects if of block water oxygen.The water resistance of above-mentioned organic electroluminescence device can reach 10
-4g/m
2my god, packaging effect is good, and the life-span can reach more than 5300 hours.In addition, the invention still further relates to a kind of preparation method of organic electroluminescence device.
Description
Technical field
The present invention relates to electroluminescence field, particularly relate 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 be on ito glass, prepare one deck tens nanometer thickness luminous organic material as luminescent layer, be provided with the metal electrode of one deck low work function above luminescent layer.When electrode being added with voltage, luminescent layer just produces light radiation.
OLED have active illuminating, luminous efficiency high, low in energy consumption, light, thin, without advantages such as angle limitations, be considered to have broad application prospects in 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, achieves huge achievement.
But electroluminescent organic material invades responsive especially to oxygen and steam.Because oxygen is quencher, luminous quantum efficiency can be made significantly to decline, and oxygen also can make its transmittability decline to the oxidation of hole transmission layer.The impact of steam is more apparent, and its main failure mode is the hydrolysis of organic compound, its stability is declined greatly, thus causes OLED to lose efficacy, and reduces the life-span of OLED.Thus; the degeneration of effective suppression OLED in long-term work process and inefficacy; with the life-span making its steady operation reach enough; high requirement is proposed to the barrier of encapsulating material, and the encapsulation technology playing seal protection effect just becomes the break-through point solving OLED life problems.
Encapsulation technology is the interlayer by forming compact structure, realizes physical protection to the core component in encapsulation region.But the defect that traditional encapsulation technology ubiquity life-span is short, water oxygen resistant weak effect, limits the further application of OLED.
Summary of the invention
Based on this, be necessary to provide good organic electroluminescence device of a kind of water oxygen resistant effect 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, cathode layer, inorganic barrier layer and the doping tellurium compound layer that are cascading, wherein, the material of described inorganic barrier layer is CuPc, N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, oxine-aluminium, 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine or 4,7-diphenyl-1,10-Phens; Described doping tellurium compound layer comprises tellurides and is entrained in the nitride in described tellurides, and described tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, described nitride is Si
3n
4, AlN, BN, HfN, TaN or TiN, the doping mass concentration of described nitride in described doping tellurium compound layer is 10 ~ 40%.
Wherein in an embodiment, the quantity of described inorganic barrier layer is 4 ~ 6 layers, and the quantity of described doping tellurium compound layer is identical with the quantity of described inorganic barrier layer, and described inorganic barrier layer and described doping tellurium compound layer are arranged alternately.
Wherein in an embodiment, the thickness of described inorganic barrier layer is 200 ~ 300nm.
Wherein in an embodiment, the thickness of described doping tellurium compound layer is 100 ~ 200nm.
Wherein in an embodiment, the material of described hole injection layer is MoO
3n is doped into, the doping composite material formed in N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines according to the doping content of 25wt%;
The material of described hole transmission layer is employing 4,4 ', 4 "-three (carbazole-9-base) triphenylamine;
The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material formed in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene according to the doping content of 5wt%;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline;
The material of described electron injecting layer is CsN
3the composite material formed in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 25wt%.
A preparation method for organic electroluminescence device, comprises the steps:
The anode layer of anode substrate stacks gradually vacuum evaporation and prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer;
The mode of vacuum evaporation is adopted to prepare inorganic barrier layer on described cathode layer, the material of described inorganic barrier layer is CuPc, N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, oxine-aluminium, 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine or 4,7-diphenyl-1,10-Phens;
Adopt the mode of magnetron sputtering on described inorganic barrier layer, prepare doping tellurium compound layer, described doping tellurium compound layer comprises tellurides and is entrained in the nitride in described tellurides, and described tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, described nitride is Si
3n
4, AlN, BN, HfN, TaN or TiN, the doping mass concentration of described nitride in described doping tellurium compound layer is 10 ~ 40%.
Wherein in an embodiment, described preparation method also comprises the step repeating to prepare described inorganic barrier layer and described doping tellurium compound layer, altogether obtained 4 ~ 6 layers of described inorganic barrier layer and being arranged alternately and the identical described doping tellurium compound layer of quantity with described inorganic barrier layer of mixing.
Wherein in an embodiment, prepare in described inorganic barrier layer process, evaporation rate is
the thickness of obtained described inorganic barrier layer is 200 ~ 300nm.
Wherein in an embodiment, the thickness of described doping tellurium compound layer is 100 ~ 200nm.
Wherein in an embodiment, the material of described hole injection layer is MoO
3n is doped into, the doping composite material formed in N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines according to the doping content of 25wt%;
The material of described hole transmission layer is employing 4,4 ', 4 "-three (carbazole-9-base) triphenylamine;
The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material formed in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene according to the doping content of 5wt%;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline;
The material of described electron injecting layer is CsN
3the composite material formed in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 25wt%.
Above-mentioned organic electroluminescence device is provided with inorganic barrier layer and doping tellurium compound layer on cathode layer, inorganic barrier layer and doping tellurium compound layer form water oxygen barrier layers, there is good oxygen water-proof function, the water oxygen barrier layers that layering is arranged can permeate by effectively anti-sealing oxygen gradually, the better effects if of block water oxygen.The water resistance of above-mentioned organic electroluminescence device can reach 10
-4g/m
2my god, packaging effect is good, and the life-span can reach more than 6700 hours.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the preparation flow schematic diagram of the organic electroluminescence device of an execution mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments organic electroluminescence device and preparation method thereof is described in further detail below.
As shown in Figure 1, the organic electroluminescence device 100 of one execution mode comprises the anode substrate 110(substrate and anode conducting effect that are cascading), hole injection layer 120(injected hole, be conducive to hole to be injected into transferring material from anode), hole transmission layer 130(transporting holes, be conducive to hole transport in luminescent material), luminescent layer 140(electronics and hole compound in this layer, then energy trasfer is luminous to light emitting molecule), electron transfer layer 150(transmission electronic, be conducive to electric transmission in luminescent material), electron injecting layer 160(injects electronics, be conducive to electronics to be injected into transferring material from anode), cathode layer 170(power supply provides electronics for device) and the material layer of water oxygen barrier layers 180(block water oxygen).
The substrate of anode substrate 110 is generally glass, the anode layer on it, and namely the material of conductive layer is generally ITO, IZO, AZO, FTO etc., preferred ITO; There is ITO, IZO, AZO, FTO layer in glass surface preparation, be called for short ito glass, IZO glass, AZO glass, FTO glass.
The functional layers such as hole injection layer 120, hole transmission layer 130, electron transfer layer 150, electron injecting layer 160 adopt conventional material preparation.As hole injection layer 120 can pass through MoO
3mix N according to the doping content of 25wt%, obtain in N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB); Hole transmission layer 130 can be 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA); Electron transfer layer 150 can be 4,7-diphenyl-1,10-phenanthroline (Bphen); Electron injecting layer 160 can be mixed in Bphen according to the doping content of 25wt% by CsN3 and obtain.In addition, in other embodiments, this organic electroluminescence device 100 can not also comprise hole injection layer 120, hole transmission layer 130, electron transfer layer 150 and electron injecting layer 160 or only include above-mentioned wherein a kind of, two or three functional layer.
Luminescent layer 140 can adopt conventional material preparation, material of main part as luminescent layer 140 adopts 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), guest materials adopts three (2-phenylpyridines) to close iridium (Ir (ppy)
3), wherein, the doping content 5wt% of guest materials in material of main part.
Cathode layer 170 can adopt non-transparent metals material to prepare, and as aluminium, nickel or gold etc., can also adopt the transparent material preparation with dielectric layer/metal level/dielectric layer structure, as ITO/Ag/ITO, ZnS/Ag/ZnS etc.In the present embodiment, the preferred aluminium of the material of cathode layer 170.
Water oxygen barrier layers 180 comprises the inorganic barrier layer 182 and doping tellurium compound layer 184 that stack gradually.The material of inorganic barrier layer 182 is CuPc (CuPc), N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), oxine-aluminium (Alq3), 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA) or 4; 7-diphenyl-1,10-Phen (BCP).The thickness of inorganic barrier layer 182 is 200 ~ 300nm.Doping tellurium compound layer comprises tellurides and nitride, and tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, nitride is Si
3n
4, AlN, BN, HfN, TaN or TiN, the doping mass concentration of nitride in doping tellurium compound layer is 10 ~ 40%.The thickness of doping tellurium compound layer 184 is 100 ~ 200nm.
Inorganic barrier layer 182 is identical with the quantity of doping tellurium compound layer 184, can be 1 layer or multilayer, preferably 4 ~ 6 layers, and also namely water oxygen barrier layers 180 alternately can be folded to establish with the doping tellurium compound layer 184 of 4 ~ 6 layers by the inorganic barrier layer 182 of 4 ~ 6 layers and forms.
Above-mentioned organic electroluminescence device 100 is provided with inorganic barrier layer 182 and doping tellurium compound layer 184 on cathode layer 170, inorganic barrier layer 182 and doping tellurium compound layer 184 form water oxygen barrier layers 180, there is good oxygen water-proof function, the water oxygen barrier layers 180 that layering is arranged can permeate by effectively anti-sealing oxygen gradually, the better effects if of block water oxygen.The water resistance of above-mentioned organic electroluminescence device 100 can reach 10
-4g/m
2my god, packaging effect is good, and the life-span can reach more than 6500 hours.
In addition, present embodiment additionally provides a kind of preparation method of organic electroluminescence device, as shown in Figure 2, comprises the steps:
Step S210, the anode layer of anode substrate stacks gradually vacuum evaporation and prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.
Before preparing hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, preferably, the step that antianode substrate carries out cleaning also is comprised, especially ito glass substrate.The step of this cleaning is included in antianode substrate in supersonic cleaning machine and uses acetone, ethanol, deionized water and ethanol purge successively, and each washing 5 minutes, then dries up with nitrogen, after oven dry.
Step S220, adopts the mode of vacuum evaporation to prepare inorganic barrier layer on cathode layer.The material of inorganic barrier layer is CuPc, N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, oxine-aluminium, 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamines or 4; 7-diphenyl-1,10-Phen.
Preferably, prepare in inorganic barrier layer process in present embodiment, evaporation rate is
the thickness of obtained inorganic barrier layer is 200 ~ 300nm.
Step 170S230, adopts the mode of magnetron sputtering on inorganic barrier layer, prepare doping tellurium compound layer.Doping tellurium compound layer comprises tellurides and nitride, and tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, nitride is Si
3n
4, AlN, BN, HfN, TaN or TiN, the doping mass concentration of nitride in doping tellurium compound layer is 10 ~ 40%.
Preferably, the thickness of the doping tellurium compound layer prepared in the present embodiment is 100 ~ 200nm.
Inorganic barrier layer and doping tellurium compound layer form water oxygen barrier layers, when multilayer water oxygen barrier layers prepared by needs, can repeat step S120 and step S170 more for several times after having prepared doping tellurium compound layer first.
In the preparation method of above-mentioned organic electroluminescence device, the preparation of described cathode layer also comprises: after electron injecting layer evaporation, first at surperficial evaporation one deck ZnS layer of electron injecting layer, subsequently at ZnS layer surface evaporation one deck Ag layer, finally at Ag layer surface evaporation one deck ZnS layer again, complete rear obtained cathode layer.
Above-mentioned preparation method's principle is simple, low for equipment requirements, can wide popularization and application.
It is below embodiment part
Embodiment 1:
The structure of the organic electroluminescence device of the present embodiment is: ito glass substrate/MoO
3: NPB(30wt%)/TCTA/Ir (ppy)
3: TPBI(5wt%)/Bphen/CsN
3: Bphen(30wt%)/Al cathode layer/CuPc/Sb
2te
3: Si
3n
4(40wt%), wherein, in equivalent layer, ": " represents doping, and in parantheses, percent data represents the former doping mass percent in whole layer, and "/" represents stacked, and concrete preparation process is as follows:
A) ito glass substrate pre-treatment: use acetone, ethanol, deionized water, ethanol purge successively in supersonic cleaning machine, each washing 5 minutes, then dries up with nitrogen, stove-drying; Again surface activation process is carried out to the ito glass substrate 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.
B) preparation of organic function layer:
Hole injection layer: by MoO
3be doped into as hole-injecting material in NPB, doping content 30wt%, ito glass substrate adopts the mode of vacuum evaporation prepare hole injection layer that thickness is 10nm, vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
Hole transmission layer: adopt 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), as hole mobile material, adopts the mode of vacuum evaporation on hole injection layer, evaporate the hole transmission layer of thickness 30nm, wherein, vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
Luminescent layer: material of main part adopts 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), guest materials adopts three (2-phenylpyridines) to close iridium (Ir (ppy)
3), the doping content 5wt% of guest materials in material of main part, adopts the mode of vacuum evaporation on hole transmission layer, to evaporate the luminescent layer that thickness is 20nm, wherein vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
The preparation of electron transfer layer: adopt mode evaporation a layer thickness on luminescent layer of vacuum evaporation be 4,7-diphenyl-1, the 10-phenanthrolines (Bphen) of 10nm as electron transfer layer, wherein, vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
The preparation of electron injecting layer: by CsN
3mix as electron injection material in Bphen, doping content 30wt%, the mode evaporation a layer thickness adopting vacuum evaporation is on the electron transport layer the electron injecting layer of 20nm, wherein, and vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
C) preparation of cathode layer: adopt the mode of vacuum evaporation evaporate on electron injecting layer a layer thickness be the Al of 100nm as cathode layer, wherein, vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
D) preparation of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare the CuPc of a layer thickness 300nm as inorganic barrier layer on cathode layer, wherein, vacuum degree 1 × 10 in preparation process
-5pa, evaporation rate
E) preparation of doping tellurium compound layer: doping tellurium compound layer is made up of two kinds of materials, and one is Sb
2te
3, another kind is Si
3n
4, adopt the mode of magnetron sputtering on inorganic barrier layer, prepare the doping tellurium compound layer of thickness 200nm, wherein, in sputter procedure, background vacuum is 1 × 10
-5pa, Si
3n
4doping content in whole doping tellurium compound layer is 30wt%.
Alternately repeat step d) and e) 6 times.
Embodiment 2:
The structure of the organic electroluminescence device of the present embodiment is: ito glass substrate/MoO
3: NPB(30wt%)/TCTA/Ir (ppy)
3: TPBI(5wt%)/Bphen/CsN
3: Bphen(30wt%)/Al cathode layer/NPB/Bi
2te:AlN(10wt%), wherein, in equivalent layer, ": " represents doping, and in parantheses, percent data represents the former doping mass percent in whole layer, and "/" represents stacked, and concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare the NPB of a layer thickness 250nm as inorganic barrier layer on cathode layer, wherein, vacuum degree 5 × 10 in preparation process
-5pa, evaporation rate
E) preparation of doping tellurium compound layer: doping tellurium compound layer is made up of two kinds of materials, and one is Bi
2te, another kind is AlN, and adopt the mode of magnetron sputtering on inorganic barrier layer, prepare the doping tellurium compound layer of thickness 100nm, wherein, in sputter procedure, background vacuum is 1 × 10
-5pa, the AlN doping content in whole doping tellurium compound layer is 10wt%.
Alternately repeat step d) and e) 6 times.
Embodiment 3:
The structure of the organic electroluminescence device of the present embodiment is: ito glass substrate/MoO
3: NPB(30wt%)/TCTA/Ir (ppy)
3: TPBI(5wt%)/Bphen/CsN
3: Bphen(30wt%)/Al cathode layer/Alq3/CdTe:BN(30wt%), wherein, in equivalent layer, ": " represents doping, and in parantheses, percent data represents the former doping mass percent in whole layer, and "/" represents stacked, and concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare the Alq3 of a layer thickness 200nm as inorganic barrier layer on cathode layer, wherein, vacuum degree 5 × 10 in preparation process
-5pa, evaporation rate
E) preparation of doping tellurium compound layer: doping tellurium compound layer is made up of two kinds of materials, one is CdTe, and another kind is BN, adopts the mode of magnetron sputtering on inorganic barrier layer, prepare the doping tellurium compound layer of thickness 150nm, wherein, in sputter procedure, background vacuum is 1 × 10
-5pa, the BN doping content in whole doping tellurium compound layer is 30wt%.
Alternately repeat step d) and e) 6 times.
Embodiment 4:
The structure of the organic electroluminescence device of the present embodiment is: ito glass substrate/MoO
3: NPB(30wt%)/TCTA/Ir (ppy)
3: TPBI(5wt%)/Bphen/CsN
3: Bphen(30wt%)/Al cathode layer/m-MTDATA/In
2te
3: HfN(20wt%), wherein, in equivalent layer, ": " represents doping, and in parantheses, percent data represents the former doping mass percent in whole layer, and "/" represents stacked, and concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare the m-MTDATA of a layer thickness 250nm as inorganic barrier layer on cathode layer, wherein, vacuum degree 5 × 10 in preparation process
-5pa, evaporation rate
E) preparation of doping tellurium compound layer: doping tellurium compound layer is made up of two kinds of materials, and one is In
2te
3, another kind is HfN, and adopt the mode of magnetron sputtering on inorganic barrier layer, prepare the doping tellurium compound layer of thickness 150nm, wherein, in sputter procedure, background vacuum is 5 × 10
-5pa, the HfN doping content in whole doping tellurium compound layer is 20wt%.
Alternately repeat step d) and e) 5 times.
Embodiment 5:
The structure of the organic electroluminescence device of the present embodiment is: ito glass substrate/MoO
3: NPB(30wt%)/TCTA/Ir (ppy)
3: TPBI(5wt%)/Bphen/CsN
3: Bphen(30wt%)/Al cathode layer/BCP/SnTe:TaN(25wt%), wherein, in equivalent layer, ": " represents doping, and in parantheses, percent data represents the former doping mass percent in whole layer, and "/" represents stacked, and concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare the BCP of a layer thickness 250nm as inorganic barrier layer on cathode layer, wherein, vacuum degree 5 × 10 in preparation process
-5pa, evaporation rate
E) preparation of doping tellurium compound layer: doping tellurium compound layer is made up of two kinds of materials, one is SnTe, and another kind is TaN, adopts the mode of magnetron sputtering on inorganic barrier layer, prepare the doping tellurium compound layer of thickness 120nm, wherein, in sputter procedure, background vacuum is 5 × 10
-5pa, the TaN doping content in whole doping tellurium compound layer is 20wt%.
Alternately repeat step d) and e) 5 times.
Embodiment 6:
The structure of the organic electroluminescence device of the present embodiment is: ito glass substrate/MoO
3: NPB(30wt%)/TCTA/Ir (ppy)
3: TPBI(5wt%)/Bphen/CsN
3: Bphen(30wt%)/Al cathode layer/CuPc/PbTe:TiN(20wt%), wherein, in equivalent layer, ": " represents doping, and in parantheses, percent data represents the former doping mass percent in whole layer, and "/" represents stacked, and concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation of inorganic barrier layer: adopt the mode of vacuum evaporation to prepare the CuPc of a layer thickness 250nm as inorganic barrier layer on cathode layer, wherein, vacuum degree 1 × 10 in preparation process
-3pa, evaporation rate
E) preparation of doping tellurium compound layer: doping tellurium compound layer is made up of two kinds of materials, one is PbTe, and another kind is TiN, adopts the mode of magnetron sputtering on inorganic barrier layer, prepare the doping tellurium compound layer of thickness 110nm, wherein, in sputter procedure, background vacuum is 1 × 10
-3pa, the TiN doping content in whole doping tellurium compound layer is 20wt%.
Alternately repeat step d) and e) 4 times.
Table 1 is the water oxygen resistant performance detection data of the various embodiments described above:
Table 1
Can be found out that by table 1 data the ability of the organic electroluminescence device waterproof adopting present embodiment structure is strong, device lifetime is longer.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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, it is characterized in that, comprise the anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, inorganic barrier layer and the doping tellurium compound layer that are cascading, wherein, the material of described inorganic barrier layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine-aluminium, 4,4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine or 4; 7-diphenyl-1,10-Phen; Described doping tellurium compound layer comprises tellurides and is entrained in the nitride in described tellurides, and described tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, described nitride is Si
3n
4, AlN, BN, HfN, TaN or TiN, the doping mass concentration of described nitride in described doping tellurium compound layer is 10 ~ 40%.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, the quantity of described inorganic barrier layer is 4 ~ 6 layers, and the quantity of described doping tellurium compound layer is identical with the quantity of described inorganic barrier layer, and described inorganic barrier layer and described doping tellurium compound layer are arranged alternately.
3. organic electroluminescence device as claimed in claim 1 or 2, it is characterized in that, the thickness of every layer of described inorganic barrier layer is 200 ~ 300nm.
4. organic electroluminescence device as claimed in claim 1 or 2, it is characterized in that, the thickness of every layer of described doping tellurium compound layer is 100 ~ 200nm.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole injection layer is MoO
3n is doped into, the doping composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines according to the doping content of 25wt%;
The material of described hole transmission layer is employing 4,4', 4 "-three (carbazole-9-base) triphenylamine;
The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material formed in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene according to the doping content of 5wt%;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline;
The material of described electron injecting layer is CsN
3the composite material formed in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 25wt%.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
The anode layer of anode substrate stacks gradually vacuum evaporation and prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer;
The mode of vacuum evaporation is adopted to prepare inorganic barrier layer on described cathode layer, the material of described inorganic barrier layer is CuPc, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine-aluminium, 4,4'; 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine or 4,7-diphenyl-1,10-Phens;
Adopt the mode of magnetron sputtering on described inorganic barrier layer, prepare doping tellurium compound layer, described doping tellurium compound layer comprises tellurides and is entrained in the nitride in described tellurides, and described tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
2, SnTe or PbTe, described nitride is Si
3n
4, AlN, BN, HfN, TaN or TiN, the doping mass concentration of described nitride in described doping tellurium compound layer is 10 ~ 40%.
7. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, also comprise the step repeating to prepare described inorganic barrier layer and described doping tellurium compound layer, altogether obtained 4 ~ 6 layers of described inorganic barrier layer and being arranged alternately with described inorganic barrier layer and the identical described doping tellurium compound layer of quantity.
8. the preparation method of organic electroluminescence device as claimed in claims 6 or 7, it is characterized in that, prepare in described inorganic barrier layer process, evaporation rate is
the thickness of every layer of obtained described inorganic barrier layer is 200 ~ 300nm.
9. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, the thickness of every layer of described doping tellurium compound layer is 100 ~ 200nm.
10. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, the material of described hole injection layer is MoO
3n is doped into, the doping composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines according to the doping content of 25wt%;
The material of described hole transmission layer is 4,4', 4 " and-three (carbazole-9-base) triphenylamine;
The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material formed in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene according to the doping content of 5wt%;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline;
The material of described electron injecting layer is CsN
3the composite material formed in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 25wt%.
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