CN104078601B - Organic electroluminescence device and preparation method thereof - Google Patents
Organic electroluminescence device and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of organic electroluminescence device and preparation method thereof, this organic electroluminescence device is layer structure, this layer structure stacks gradually as anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, is provided with alternately laminated mixing barrier layer and inorganic barrier layer on described cathode layer surface.The organic electroluminescence device of the present invention; use the Organic substance of doping phthalocyanine thing and fluoride as mixing barrier layer; make film layer heat stability high; flatness is good; be conducive to inorganic matter film forming in the above, external water, the erosion to organic electroluminescence device of the oxygen isoreactivity material can be efficiently reduced, thus the organic functional material and electrode to organic electroluminescence device defines and be effectively protected; meet the requirement of the sealing of encapsulation, the life-span of OLED can be significantly increased.
Description
Technical field
The present invention relates to field of optoelectronic devices, particularly relate to a kind of organic electroluminescence device.The invention still further relates to the preparation method of this organic electroluminescence device.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is the luminescent layer making one layer of tens nanometer thickness on ito glass with luminous organic material, and luminescent layer is arranged over the metal electrode of one layer of low work function.When on electrode added with voltage, luminescent layer just produces light radiation.
OLED have active illuminating, luminous efficiency high, low in energy consumption and light, thin, without advantages such as visual angle restrictions, be considered to be most likely at the device of new generation occupying dominance on the illumination in future and display device market by insider.As a brand-new illumination and Display Technique, the OLED technology ten years in the past develops swift and violent, achieves huge achievement.More and more illuminate due to the whole world and show that producer puts into research and development one after another, greatly having promoted the industrialization process of OLED so that the growth rate of OLED industry is surprising, had arrived at the eve of scale of mass production at present.
Flexible product is the development trend of organic electroluminescence device, but generally there is at present life-span short problem, and therefore the quality of encapsulation technology directly affects the life-span of device.Present invention is primarily targeted at a kind of organic electroluminescence device of offer and preparation method thereof, this encapsulation technology technique is simple, and water oxygen resistant ability (WVTR) is strong, increases significantly the life-span of flexible OLED devices.
Summary of the invention
It is an object of the invention to solve the problem and shortage that above-mentioned prior art exists, a kind of organic electroluminescence device and preparation method thereof is provided, this organic electroluminescence device uses the Organic substance of doping phthalocyanine thing and fluoride as mixing barrier layer, make film layer heat stability high, flatness is good, be conducive to inorganic matter film forming in the above, external water, the erosion to organic electroluminescence device of the oxygen isoreactivity material can be efficiently reduced.
The technical scheme that the present invention is directed to above-mentioned technical problem and propose is: a kind of organic electroluminescence devices, this organic electroluminescence device is layer structure, and this layer structure stacks gradually as anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；It is provided with alternately laminated mixing barrier layer and inorganic barrier layer on described cathode layer surface；Wherein,
The material on described mixing barrier layer is phthalein cyanogen thing, Organic substance, fluoride and the mixture of oxide composition；Described phthalein cyanogen thing is the one in CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, described Organic substance is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen, 8-hydroxyquinoline aluminum, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, described fluoride is LiF, CeF2、MgF2、AlF3、CaF2Or BaF2In one, described oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2In one；
The material of described inorganic barrier layer is TiO2、MgO、SiO2、ZrO2, ZnO or Al2O3In one；
Described phthalocyanine thing accounts for the 40～60mol% of described mixing barrier layer, described fluoride accounts for the 10～30mol% of described mixing barrier layer, described oxide accounts for the 10～20mol% of described mixing barrier layer, and described Organic substance accounts for the molar percentage on described mixing barrier layer and is not more than 40%.
The thickness on described mixing barrier layer is 100nm～200nm.
The thickness of described inorganic barrier layer is 50nm～100nm.
Described mixing barrier layer and the alternately laminated number of plies of inorganic barrier layer are 4～6 layers.
The material of described hole injection layer is MoO3The doping mixing material of composition it is doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen according to the doping content of 30wt%；
The material of described hole transmission layer is for using 4,4', 4''-tri-(carbazole-9-base) triphenylamine；
The material of described luminescent layer is that three (2-phenylpyridine) conjunction iridium is doped to, according to the doping content of 5wt%, the doping mixing material that 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) forms；
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline；
The material of described electron injecting layer is CsN3The mixing material of composition in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 30wt%；
The material of described cathode layer is ZnS, Ag and the ZnS using the method for vacuum evaporation to stack gradually.
Present invention additionally comprises the preparation method utilizing above-mentioned organic electroluminescence devices, comprise the steps:
A (), on the anode conductive layer of the anode conducting substrate cleaned up, uses the method for vacuum evaporation to stack gradually and prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；
B (), on described cathode layer, first, uses the method preparation mixing barrier layer of vacuum evaporation；Then the method for magnetron sputtering is used to prepare inorganic barrier layer on described mixing barrier layer；Subsequently, barrier layer and inorganic barrier layer are mixed the most alternately laminated preparation several times；Wherein,
The material on described mixing barrier layer is phthalein cyanogen thing, Organic substance, fluoride and the mixture of oxide composition；Phthalein cyanogen thing is the one in CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, described Organic substance is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen, 8-hydroxyquinoline aluminum, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, described fluoride is LiF, CeF2、MgF2、AlF3、CaF2、BaF2In one, described oxide is MoO3、V2O5、WO3、Cs2O、Ni2O、MnO2In one；
The material of described inorganic barrier layer is TiO2、MgO、SiO2、ZrO2, ZnO or Al2O3In one；
Described phthalocyanine thing accounts for the 40～60mol% of described mixing barrier layer, described fluoride accounts for the 10～30mol% of described mixing barrier layer, described oxide accounts for the 10～20mol% of described mixing barrier layer, and described Organic substance accounts for the molar percentage on described mixing barrier layer and is not more than 40%.
The thickness of described inorganic barrier layer is 100nm～200nm；The thickness on described mixing barrier layer is 50nm～100nm.
In described step (a), time prepared by described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer vacuum evaporation, vacuum is 1 × 10-5Pa, evaporation rate is
In described step (b), described mixing barrier layer and inorganic barrier layer alternate frequency are 4～6 times.
In described step (a), time prepared by described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer vacuum evaporation, vacuum is 1 × 10-5Pa；The evaporation rate of described hole injection layer, hole transmission layer and electron transfer layer isDescribed luminescent layer and electron injecting layer evaporation rate areDescribed cathode layer evaporation rate is
Compared with prior art, organic electroluminescence devices of the present invention and preparation method thereof, there is advantages below: the organic electroluminescence device of the present invention, use the Organic substance of doping phthalocyanine thing and fluoride as mixing barrier layer, make film layer heat stability high, flatness is good, be conducive to inorganic matter film forming in the above, external water can be efficiently reduced, the erosion to organic electroluminescence device of the oxygen isoreactivity material, thus the organic functional material and electrode to organic electroluminescence device defines and is effectively protected, meet the requirement of the sealing of encapsulation, the life-span of OLED can be significantly increased.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic electroluminescence device of the present invention.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is given elaboration further.
The organic electroluminescence device of the present invention is layer structure, as it is shown in figure 1, this layer structure stack gradually anode conducting substrate 101, hole injection layer 102, hole transmission layer 103, luminescent layer 104, electron transfer layer 105, electron injecting layer 106, cathode layer 107, mixing barrier layer 108, inorganic barrier layer 109.
In organic electroluminescence device, if be provided with the alternately laminated mixing barrier layer of dried layer and inorganic barrier layer on above-mentioned cathode layer surface.Mixing barrier layer and the alternately laminated number of plies of inorganic barrier layer are 4～6 layers.
The material on mixing barrier layer is phthalein cyanogen thing, Organic substance, fluoride and the mixture of oxide composition；Phthalein cyanogen thing is the one in CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and Organic substance is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen, 8-hydroxyquinoline aluminum, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, fluoride is LiF, CeF2、MgF2、AlF3、CaF2Or BaF2In one, oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2In one；
The material of inorganic barrier layer is TiO2、MgO、SiO2、ZrO2, ZnO or Al2O3In one；
Phthalocyanine thing accounts for the 40～60mol% of mixing barrier layer, and fluoride accounts for the 10～30mol% of mixing barrier layer, and oxide accounts for the 10～20mol% of described mixing barrier layer, and Organic substance accounts for the molar percentage on mixing barrier layer and is not more than 40%.
The thickness on mixing barrier layer is 100nm～200nm, and the thickness of inorganic barrier layer is 50nm～100nm.
In organic electroluminescence device, the material of anode conducting substrate 101 includes anode conductive layer and substrate, its substrate can be glass substrate or organic film substrate, the material of anode conductive layer can be conductive oxide, as, tin indium oxide (ITO), Al-Doped ZnO (AZO), indium-doped zinc oxide (IZO) or fluorine doped zinc oxide (FTO), these conductive oxides are produced on the glass substrate, are called for short ito glass, AZO glass, IZO glass, FTO glass.Anode conducting substrate can be made by oneself, it is also possible to city available from.In actual applications, other suitable materials can be selected as required as anode conducting substrate 101.In actual applications, the anode pattern of required organic electroluminescence device can be prepared on anode conducting substrate 101.Anode conducting substrate 101 is prior art, does not repeats them here.
In organic electroluminescence device, material and the thickness of other functional layers are as follows:
The material of hole injection layer is MoO3The doping mixing material of composition it is doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen according to the doping content of 30wt%；Thickness 10nm；
The material of hole transmission layer is for using 4,4', 4''-tri-(carbazole-9-base) triphenylamine；Thickness 30nm
The material of luminescent layer is that three (2-phenylpyridine) conjunction iridium is doped to, according to the doping content of 5wt%, the doping mixing material that 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) forms；Thickness 20nm；
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline；Thickness 10nm；
The material of electron injecting layer is CsN3The mixing material of composition in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 30wt%；Thickness 20nm.
The material of cathode layer uses ZnS, Ag and the ZnS stacked gradually, and thickness is 30nm.
Preparation method to above-mentioned organic electroluminescence device, comprises the steps:
A (), on the anode conductive layer of the anode conducting substrate cleaned up, uses the method for vacuum evaporation to stack gradually and prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；
Time prepared by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer vacuum evaporation, vacuum is 1 × 10-5Pa；The evaporation rate of hole injection layer, hole transmission layer and electron transfer layer isLuminescent layer and electron injecting layer evaporation rate areCathode layer evaporation rate is
B (), on cathode layer, first, uses the method preparation mixing barrier layer of vacuum evaporation；Then the method for magnetron sputtering is used to prepare inorganic barrier layer on mixing barrier layer；Subsequently, the most alternately laminated mixing barrier layer prepared several times and inorganic barrier layer；Mixing barrier layer and inorganic barrier layer alternate frequency are 4～6 times.
During vacuum evaporation preparation mixing barrier layer, the vacuum of vacuum evaporation is 1 × 10-5Pa～1 × 10-3Pa, the evaporation rate of vacuum evaporation isWhen magnetron sputtering prepares inorganic barrier layer, vacuum is 1 × 10-5Pa～1 × 10-3Pa。
Wherein, the material on mixing barrier layer is phthalein cyanogen thing, Organic substance, fluoride and the mixture of oxide composition；Phthalein cyanogen thing is the one in CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, and Organic substance is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen, 8-hydroxyquinoline aluminum, 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, fluoride is LiF, CeF2、MgF2、AlF3、CaF2、BaF2In one, oxide is MoO3、V2O5、WO3、Cs2O、Ni2O、MnO2In one；
The material of inorganic barrier layer is TiO2、MgO、SiO2、ZrO2, ZnO or Al2O3In one；
Phthalocyanine thing accounts for the 40～60mol% of mixing barrier layer, and fluoride accounts for the 10～30mol% of mixing barrier layer, and oxide accounts for the 10～20mol% of mixing barrier layer, and Organic substance accounts for the molar percentage on mixing barrier layer and is not more than 40%.
The thickness on mixing barrier layer is 100nm～200nm, and the thickness of inorganic barrier layer is 50nm～100nm.
It is specifically described with embodiment 1～the organic electroluminescence device of 6 couples of present invention and preparation process thereof below:
Embodiment 1
Organic electroluminescence device in the present embodiment is layer structure, and this layer structure is followed successively by:
Anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, mixing barrier layer, inorganic barrier layer.
The most specifically it is followed successively by: ito glass substrate, MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, CuPc-TAPC-LiF-MoO3Layer, TiO2Layer.(brace "/" represents that layer structure, whippletree "-" represent mutually doping.)
Above-mentioned organic electroluminescence device uses following steps to prepare:
A) pre-treatment of ito glass substrate: acetone cleaning → ethanol purge → deionized water cleaning → ethanol purge, described cleaning is all carried out with ultrasonic washing unit, and washing is cleaned 5 minutes every time, then dries up with nitrogen, more stand-by with stove-drying；Also need to carry out surface activation process 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；
B) preparation of hole injection layer: by MoO3Being doped in NPB as hole-injecting material, the concentration of doping is 30wt%, and thickness is 10nm, and vacuum is 1 × 10-5Pa, evaporation rate is
C) preparation of hole transmission layer: using 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) is as hole mobile material, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 30nm；
D) luminescent layer: use 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) is as material of main part, and guest materials uses three (2-phenylpyridine) to close iridium (Ir (ppy)3), doping content 5%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
E) preparation of electron transfer layer: being deposited with a layer 4 on luminescent layer, 7-diphenyl-1,10-phenanthroline (Bphen) is as electron transfer layer, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 10nm；
F) preparation of electron injecting layer: with Bphen electron injecting layer material of main part, as by CsN3Mix in Bphen, doping content 30wt%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
G) preparation of cathode layer: negative electrode uses ZnS/Ag/ZnS, and thickness is 100nm, vacuum 1 × 10-5Pa, evaporation rate
H) making on barrier layer is mixed: use the mode of vacuum evaporation to prepare one layer of mixing barrier layer on cathode layer, mixing barrier layer is that four kinds of material doping steam work altogether, and one is CuPc(CuPc), another kind is Organic substance TAPC, the third is LiF, and the 4th kind is MoO3, wherein, CuPc proportion be 50mol%, LiF proportion be 30mol%, MoO3Proportion is 16mol%, and Organic substance TAPC proportion is 4mol%.The vacuum 1 × 10 on mixing barrier layer-5Pa, evaporation rateThickness 200nm；
I) making of inorganic barrier layer: use the method for magnetron sputtering to be fabricated to TiO2Film, the background vacuum 1 × 10 of inorganic barrier layer-5Pa, thickness 100nm.During preparation, the flow being passed through Ar is 10sccm, CH4Flow 20sccm；
J) above-mentioned steps h) and i) 6 times it are alternately repeated.
Embodiment 2
Organic electroluminescence device in the present embodiment is layer structure, and this layer structure is followed successively by:
Anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, mixing barrier layer, inorganic barrier layer.
The most specifically it is followed successively by: ito glass substrate, MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS layer, ZnPc-NPB-CeF2-V2O5Layer, MgO layer.(brace "/" represents that layer structure, whippletree "-" represent mutually doping.)
Above-mentioned organic electroluminescence device uses following steps to prepare:
A) pre-treatment of ito glass substrate: acetone cleaning → ethanol purge → deionized water cleaning → ethanol purge, described cleaning is all carried out with ultrasonic washing unit, and washing is cleaned 5 minutes every time, then dries up with nitrogen, more stand-by with stove-drying；Also need to carry out surface activation process 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；
B) preparation of hole injection layer: by MoO3Being doped in NPB as hole-injecting material, the concentration of doping is 30wt%, and thickness is 10nm, and vacuum is 1 × 10-5Pa, evaporation rate is
C) preparation of hole transmission layer: using 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) is as hole mobile material, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 30nm；
D) luminescent layer: use 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) is as material of main part, and guest materials uses three (2-phenylpyridine) to close iridium (Ir (ppy)3), doping content 5%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
E) preparation of electron transfer layer: being deposited with a layer 4 on luminescent layer, 7-diphenyl-1,10-phenanthroline (Bphen) is as electron transfer layer, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 10nm；
F) preparation of electron injecting layer: with Bphen electron injecting layer material of main part, as by CsN3Mix in Bphen, doping content 30wt%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
G) preparation of cathode layer: negative electrode uses ZnS/Ag/ZnS, and thickness is 100nm, vacuum 1 × 10-5Pa, evaporation rate
H) mixing the making on barrier layer: use the mode of vacuum evaporation to prepare one layer of mixing barrier layer on cathode layer, mixing barrier layer is that four kinds of material doping steam work altogether, and one is ZnPc(Phthalocyanine Zinc), another kind is NPB, and the third is CeF2, the 4th kind is V2O5, ZnPc proportion be 40mol%, NPB proportion be 35mol%, CeF2Proportion is 15mol%, V2O5Proportion is 10mol%, the vacuum 5 × 10 on mixing barrier layer-5Pa, evaporation rateThickness 150nm；
I) making of inorganic barrier layer: use the method for magnetron sputtering to be fabricated to MgO membrane, the background vacuum 1 × 10 of inorganic barrier layer-5Pa, thickness 50nm.During preparation, the flow being passed through Ar is 5sccm, CH4Flow 15sccm；
J) above-mentioned steps h) and i) 5 times it are alternately repeated.
Embodiment 3
Organic electroluminescence device in the present embodiment is layer structure, and this layer structure is followed successively by:
Anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, mixing barrier layer, inorganic barrier layer.
The most specifically it is followed successively by: ito glass substrate, MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, FePc-Alq3-MgF2-WO3Layer, SiO2Layer.(brace "/" represents that layer structure, whippletree "-" represent mutually doping.)
Above-mentioned organic electroluminescence device uses following steps to prepare:
A) pre-treatment of ito glass substrate: acetone cleaning → ethanol purge → deionized water cleaning → ethanol purge, described cleaning is all carried out with ultrasonic washing unit, and washing is cleaned 5 minutes every time, then dries up with nitrogen, more stand-by with stove-drying；Also need to carry out surface activation process 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；
B) preparation of hole injection layer: by MoO3Being doped in NPB as hole-injecting material, the concentration of doping is 30wt%, and thickness is 10nm, and vacuum is 1 × 10-5Pa, evaporation rate is
C) preparation of hole transmission layer: using 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) is as hole mobile material, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 30nm；
D) luminescent layer: use 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) is as material of main part, and guest materials uses three (2-phenylpyridine) to close iridium (Ir (ppy)3), doping content 5%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
E) preparation of electron transfer layer: being deposited with a layer 4 on luminescent layer, 7-diphenyl-1,10-phenanthroline (Bphen) is as electron transfer layer, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 10nm；
F) preparation of electron injecting layer: with Bphen electron injecting layer material of main part, as by CsN3Mix in Bphen, doping content 30wt%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
G) preparation of cathode layer: negative electrode uses ZnS/Ag/ZnS, and thickness is 100nm, vacuum 1 × 10-5Pa, evaporation rate
H) mixing the making on barrier layer: use the mode of vacuum evaporation to prepare one layer of mixing barrier layer on cathode layer, mixing barrier layer is that four kinds of material doping steam work altogether, and one is FePc(FePC), another kind is Alq3, the third is MgF2, the 4th kind is WO3, FePc proportion is 60mol%, Alq3Proportion is 10mol%MgF2Proportion is 10mol%, WO3Proportion is 20mol%, vacuum 1 × 10-5Pa, evaporation rateThickness 200nm；
I) making of inorganic barrier layer: use the method for magnetron sputtering to be fabricated to SiO2Film, the background vacuum 1 × 10 of inorganic barrier layer-5Pa, thickness 70nm.During preparation, the flow being passed through Ar is 7sccm, CH4Flow 10sccm；
J) above-mentioned steps h) and i) 6 times it are alternately repeated.
Embodiment 4
Organic electroluminescence device in the present embodiment is layer structure, and this layer structure is followed successively by:
Anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, mixing barrier layer, inorganic barrier layer.
The most specifically it is followed successively by: ito glass substrate, MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, CoPc-m-MTDATA-AlF3-Cs2O layer, ZrO2Layer.(brace "/" represents that layer structure, whippletree "-" represent mutually doping.)
Above-mentioned organic electroluminescence device uses following steps to prepare:
A) pre-treatment of ito glass substrate: acetone cleaning → ethanol purge → deionized water cleaning → ethanol purge, described cleaning is all carried out with ultrasonic washing unit, and washing is cleaned 5 minutes every time, then dries up with nitrogen, more stand-by with stove-drying；Also need to carry out surface activation process 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；
B) preparation of hole injection layer: by MoO3Being doped in NPB as hole-injecting material, the concentration of doping is 30wt%, and thickness is 10nm, and vacuum is 1 × 10-5Pa, evaporation rate is
C) preparation of hole transmission layer: using 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) is as hole mobile material, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 30nm；
D) luminescent layer: use 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) is as material of main part, and guest materials uses three (2-phenylpyridine) to close iridium (Ir (ppy)3), doping content 5%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
E) preparation of electron transfer layer: being deposited with a layer 4 on luminescent layer, 7-diphenyl-1,10-phenanthroline (Bphen) is as electron transfer layer, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 10nm；
F) preparation of electron injecting layer: with Bphen electron injecting layer material of main part, as by CsN3Mix in Bphen, doping content 30wt%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
G) preparation of cathode layer: negative electrode uses ZnS/Ag/ZnS, and thickness is 100nm, vacuum 1 × 10-5Pa, evaporation rate
H) mixing the making on barrier layer: use the mode of vacuum evaporation to prepare one layer of mixing barrier layer on cathode layer, mixing barrier layer is that four kinds of material doping steam work altogether, and one is CoPc(Cobalt Phthalocyanine), another kind is m-MTDATA, and the third is AlF3, the 4th kind is Cs2O, CoPc proportion be 50mol%, m-MTDATA proportion be 15mol%, AlF3Proportion is 20mol%, Cs2O proportion is 15mol%, the vacuum 5 × 10 on mixing barrier layer-5Pa, evaporation rateThickness 150nm；
I) making of inorganic barrier layer: use the method for magnetron sputtering to be fabricated to ZrO2Film, the background vacuum 5 × 10 of inorganic barrier layer-5Pa, thickness 100nm, during preparation, be passed through Ar flow 10sccm, CH4Flow 20sccm；
J) above-mentioned steps h) and i) 4 times it are alternately repeated.
Embodiment 5
Organic electroluminescence device in the present embodiment is layer structure, and this layer structure is followed successively by:
Anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, mixing barrier layer, inorganic barrier layer.
The most specifically it is followed successively by: ito glass substrate, MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, MnPc-BCP-CaF2-Ni2O layer, ZnO layer.(brace "/" represents that layer structure, whippletree "-" represent mutually doping.)
Above-mentioned organic electroluminescence device uses following steps to prepare:
A) pre-treatment of ito glass substrate: acetone cleaning → ethanol purge → deionized water cleaning → ethanol purge, described cleaning is all carried out with ultrasonic washing unit, and washing is cleaned 5 minutes every time, then dries up with nitrogen, more stand-by with stove-drying；Also need to carry out surface activation process 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；
B) preparation of hole injection layer: by MoO3Being doped in NPB as hole-injecting material, the concentration of doping is 30wt%, and thickness is 10nm, and vacuum is 1 × 10-5Pa, evaporation rate is
C) preparation of hole transmission layer: using 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) is as hole mobile material, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 30nm；
D) luminescent layer: use 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) is as material of main part, and guest materials uses three (2-phenylpyridine) to close iridium (Ir (ppy)3), doping content 5%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
E) preparation of electron transfer layer: being deposited with a layer 4 on luminescent layer, 7-diphenyl-1,10-phenanthroline (Bphen) is as electron transfer layer, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 10nm；
F) preparation of electron injecting layer: with Bphen electron injecting layer material of main part, as by CsN3Mix in Bphen, doping content 30wt%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
G) preparation of cathode layer: negative electrode uses ZnS/Ag/ZnS, and thickness is 100nm, vacuum 1 × 10-5Pa, evaporation rate
H) mixing the making on barrier layer: use the mode of vacuum evaporation to prepare one layer of mixing barrier layer on cathode layer, mixing barrier layer is that four kinds of material doping steam work altogether, and one is MnPc(manganese phthalocyanine), another kind is BCP, and the third is CaF2, the 4th kind is Ni2O, MnPc proportion be 55mol%, BCP proportion be 15mol%CaF2Proportion is 15mol%, Ni2O proportion is 15mol%, the thickness 150nm on mixing barrier layer, vacuum 5 × 10-5Pa, evaporation rate
I) making of inorganic barrier layer: use the method for magnetron sputtering to be fabricated to ZnO film, the background vacuum 5 × 10 of inorganic barrier layer-5Pa, thickness 80nm.During preparation, the flow being passed through Ar is 5sccm, CH4Flow 20sccm；
J) above-mentioned steps h) and i) 6 times it are alternately repeated.
Embodiment 6
Organic electroluminescence device in the present embodiment is layer structure, and this layer structure is followed successively by:
Anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, mixing barrier layer, inorganic barrier layer.
The most specifically it is followed successively by: ito glass substrate, MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, NiPc-TPBi-BaF2-MnO2Layer, Al2O3Layer.(brace "/" represents that layer structure, whippletree "-" represent mutually doping.)
Above-mentioned organic electroluminescence device uses following steps to prepare:
A) pre-treatment of ito glass substrate: acetone cleaning → ethanol purge → deionized water cleaning → ethanol purge, described cleaning is all carried out with ultrasonic washing unit, and washing is cleaned 5 minutes every time, then dries up with nitrogen, more stand-by with stove-drying；Also need to carry out surface activation process 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；
B) preparation of hole injection layer: by MoO3Being doped in NPB as hole-injecting material, the concentration of doping is 30wt%, and thickness is 10nm, and vacuum is 1 × 10-5Pa, evaporation rate is
C) preparation of hole transmission layer: using 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) is as hole mobile material, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 30nm；
D) luminescent layer: use 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) is as material of main part, and guest materials uses three (2-phenylpyridine) to close iridium (Ir (ppy)3), doping content 5%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
E) preparation of electron transfer layer: being deposited with a layer 4 on luminescent layer, 7-diphenyl-1,10-phenanthroline (Bphen) is as electron transfer layer, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 10nm；
F) preparation of electron injecting layer: with Bphen electron injecting layer material of main part, as by CsN3Mix in Bphen, doping content 30wt%, vacuum 1 × 10-5Pa, evaporation rateEvaporation thickness 20nm；
G) preparation of cathode layer: negative electrode uses ZnS/Ag/ZnS, and thickness is 100nm, vacuum 1 × 10-5Pa, evaporation rate
H) mixing the making on barrier layer: use the mode of vacuum evaporation to prepare one layer of mixing barrier layer on cathode layer, mixing barrier layer is that four kinds of material doping steam work altogether, and one is NiPc(Nickel Phthalocyanine), another kind is TPBi, and the third is BaF2, the 4th kind is MnO2, NiPc proportion be 60mol%, TPBi proportion be 19mol%, BaF2Proportion is 16mol%, MnO2Proportion is 15mol%, the vacuum 1 × 10 on mixing barrier layer-3Pa, evaporation rateThickness 150nm；
I) making of inorganic barrier layer: use the method for magnetron sputtering to be fabricated to Al2O3Film, the background vacuum 1 × 10 of inorganic barrier layer-3Pa, thickness 70nm.During preparation, it is passed through the flow 13sccm that flow is 7sccm, CH4 of Ar；
J) above-mentioned steps h) and i) 6 times it are alternately repeated.
Performance test
The organic electroluminescence device of above example 1～6 couples of present invention being carried out water oxygen resistant ability (WVTR) and absorbance test, can see from table 1 below, its water oxygen resistant ability reaches 10-4g/m2The performance of/more than day, it OLED luminescent device made, the life-span also reached average more than 4800 hours.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| WVTR(g/m2/day) | 6.0E-4 | 6.3E-4 | 6.7E-4 | 7.2E-4 | 7.5E-4 | 8.2E-4 |
| Light transmittance | 63% | 64% | 65% | 67% | 68% | 69% |
| Life-span (hour) | 4945 | 4910 | 4883 | 4845 | 4820 | 4800 |
As can be seen here, the organic electroluminescence device of the present invention and the preparation method of this organic electroluminescence device, there is advantages below:
1. the organic electroluminescence device of the present invention; use the Organic substance of doping phthalocyanine thing and fluoride as mixing barrier layer; make film layer heat stability high; flatness is good; be conducive to inorganic matter film forming in the above, external water, the erosion to organic electroluminescence device of the oxygen isoreactivity material can be efficiently reduced, thus the organic functional material and electrode to organic electroluminescence device defines and be effectively protected; meet the requirement of the sealing of encapsulation, the life-span of OLED can be significantly increased.Its water oxygen resistant ability has reached 10-4g/m2/ day, it OLED luminescent device made, the life-span also reached average more than 4800 hours, and encapsulating face light transmittance reaches more than 63%.
2. prepared by the preparation method preparation technology of the organic electroluminescence device of present invention large area simple, easy, and this technology is particularly well-suited to the application of flexible OLED devices, solves the encapsulation problem that flexible OLED faces, and promotes the development of flexible OLED product.
Foregoing; it is only presently preferred embodiments of the present invention; it is not intended to limit embodiment of the present invention; those of ordinary skill in the art are according to the central scope of the present invention and spirit; corresponding flexible or amendment can be carried out very easily, therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.
Claims (10)
1. an organic electroluminescence device, this organic electroluminescence device is layer structure, and this layer structure stacks gradually as anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；It is characterized in that, be provided with alternately laminated mixing barrier layer and inorganic barrier layer on described cathode layer surface；Wherein,
The material on described mixing barrier layer is phthalocyanine thing, Organic substance, fluoride and the mixture of oxide composition；Described phthalocyanine thing is the one in CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, described Organic substance is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen, 8-hydroxyquinoline aluminum, 4,4'; 4 "-three (N-3-methylphenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, described fluoride is LiF, CeF2、MgF2、AlF3、CaF2Or BaF2In one, described oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2In one；
The material of described inorganic barrier layer is TiO2、MgO、SiO2、ZrO2, ZnO or Al2O3In one；
Described phthalocyanine thing accounts for the 40～60mol% of described mixing barrier layer, described fluoride accounts for the 10～30mol% of described mixing barrier layer, described oxide accounts for the 10～20mol% of described mixing barrier layer, and described Organic substance accounts for the molar percentage on described mixing barrier layer and is not more than 40%.
Organic electroluminescence device the most according to claim 1, it is characterised in that the thickness on described mixing barrier layer is 100nm～200nm.
Organic electroluminescence device the most according to claim 1, it is characterised in that the thickness of described inorganic barrier layer is 50nm～100nm.
Organic electroluminescence device the most according to claim 1, it is characterised in that: described mixing barrier layer and the alternately laminated number of plies of inorganic barrier layer are 4～6 layers.
Organic electroluminescence device the most according to claim 1, it is characterised in that:
The material of described hole injection layer is MoO3The doping mixing material of composition it is doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen according to the doping content of 30wt%；
The material of described hole transmission layer is employing 4,4', 4 " and-three (carbazole-9-base) triphenylamine；
The material of described luminescent layer is that three (2-phenylpyridine) conjunction iridium is doped to, according to the doping content of 5wt%, the doping mixing material that 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) forms；
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline；
The material of described electron injecting layer is CsN3The mixing material of composition in 4,7-diphenyl-1,10-phenanthroline is mixed according to the doping content of 30wt%；
The material of described cathode layer is ZnS, Ag and the ZnS using the method for vacuum evaporation to stack gradually.
6. a preparation method for organic electroluminescence device, comprises the steps:
A (), on the anode conductive layer of the anode conducting substrate cleaned up, uses the method for vacuum evaporation to stack gradually and prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；
B (), on described cathode layer, first, uses the method preparation mixing barrier layer of vacuum evaporation；Then the method for magnetron sputtering is used to prepare inorganic barrier layer on described mixing barrier layer；Subsequently, the most alternately laminated mixing barrier layer and inorganic barrier layer several times；Wherein,
The material on described mixing barrier layer is phthalocyanine thing, Organic substance, fluoride and the mixture of oxide composition；Phthalocyanine thing is the one in CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine or Nickel Phthalocyanine, described Organic substance is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamidogen, 8-hydroxyquinoline aluminum, 4,4'; 4 "-three (N-3-methylphenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, described fluoride is LiF, CeF2、MgF2、AlF3、CaF2Or BaF2In one, described oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2In one；
The material of described inorganic barrier layer is TiO2、MgO、SiO2、ZrO2, ZnO or Al2O3In one；
Described phthalocyanine thing accounts for the 40～60mol% of described mixing barrier layer, described fluoride accounts for the 10～30mol% of described mixing barrier layer, described oxide accounts for the 10～20mol% of described mixing barrier layer, and described Organic substance accounts for the molar percentage on described mixing barrier layer and is not more than 40%.
Preparation method the most according to claim 6, it is characterised in that the thickness on described mixing barrier layer is 100nm～200nm；The thickness of described inorganic barrier layer is 50nm～100nm.
Preparation method the most according to claim 6, it is characterized in that, in described step (a), time prepared by described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer vacuum evaporation, vacuum is 1 × 10-5Pa；The evaporation rate of described hole injection layer, hole transmission layer and electron transfer layer isDescribed luminescent layer and electron injecting layer evaporation rate areDescribed cathode layer evaporation rate is
Preparation method the most according to claim 6, it is characterised in that in described step (b), described mixing barrier layer and inorganic barrier layer alternate frequency are 4～6 times.
Preparation method the most according to claim 6, it is characterised in that in described step (b), during described vacuum evaporation preparation mixing barrier layer, the vacuum of vacuum evaporation is 1 × 10-5Pa～1 × 10-3Pa, the evaporation rate of vacuum evaporation isWhen described magnetron sputtering prepares inorganic barrier layer, vacuum is 1 × 10-5Pa～1 × 10-3Pa。
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