CN103904251A - Organic electroluminescent device and preparing method thereof - Google Patents
Organic electroluminescent device and preparing method thereof Download PDFInfo
- Publication number
- CN103904251A CN103904251A CN201210572615.2A CN201210572615A CN103904251A CN 103904251 A CN103904251 A CN 103904251A CN 201210572615 A CN201210572615 A CN 201210572615A CN 103904251 A CN103904251 A CN 103904251A
- Authority
- CN
- China
- Prior art keywords
- layer
- oxygen compound
- barrier layer
- organic
- diphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic electroluminescent device comprising an anode substrate, a hole injection layer, a hole transporting layer, a light-emitting layer, an electron transporting layer, an electron injection layer, a cathode layer, an organic blocking layer and a tellurium-oxide compound layer which are stacked successively. According to the organic electroluminescent device, the organic blocking layer and the tellurium-oxide compound layer are arranged on the cathode layer, and a water and oxygen blocking layer is formed by the organic blocking layer and the tellurium-oxide compound layer, so the advantage of good water and oxygen prevention function can be realized, and the layered water and oxygen blocking layer can be used to effectively prevent the gradual permeation of water and oxygen, so the advantage of better water and oxygen blocking effect can be realized. The waterproof performance of the organic electroluminescent device can reach 10-4g/m2*day, the advantage of good packaging effect can be realized, and the service life can reach more than 5300 hours. Moreover, the invention further relates to a preparing method of the organic electroluminescent device.
Description
Technical field
The present invention relates to electroluminescence field, relate in particular to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is on ito glass, to prepare the luminous organic material of one deck tens nanometer thickness as luminescent layer, and luminescent layer top is provided with the metal electrode of one deck low work function.In the time being added with voltage on electrode, luminescent layer just produces light radiation.
OLED device 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 on 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.
But electroluminescent organic material is invaded responsive especially to oxygen and steam.Because oxygen is quencher, can make luminous quantum efficiency significantly decline, 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, and its stability is declined greatly, thereby causes OLED component failure, reduces the life-span of OLED device.Thereby; effectively suppress degeneration and the inefficacy of OLED device in long-term work process; so that its steady operation reaches enough life-spans; the barrier of encapsulating material has been proposed to high requirement, and the encapsulation technology that plays seal protection effect just becomes to solve a break-through point of OLED problem device lifetime.
Encapsulation technology is the interlayer by forming compact structure, and the core component in encapsulation region is realized to physical protection.But traditional short defect of encapsulation technology ubiquity life-span, waterproof oxygen weak effect, has limited the further application of OLED device.
Summary of the invention
Based on this, be necessary to provide good organic electroluminescence device of a kind of waterproof oxygen 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, organic barrier layer and the tellurium oxygen compound layer that are cascading, wherein, the material on described organic barrier layer is CuPc, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, oxine-aluminium, 4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine or 4,7-diphenyl-1,10-Phen; Described tellurium oxygen compound layer comprises oxide and be entrained in the tellurides in described oxide, and described tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, described oxide is MgO, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the doping mass concentration of described tellurides in described tellurium oxygen compound layer is 10～30%.
In an embodiment, the quantity on described organic barrier layer is 4～6 layers therein, and the quantity of described tellurium oxygen compound layer is identical with the quantity on described organic barrier layer, and described organic barrier layer and described tellurium oxygen compound layer are arranged alternately.
In an embodiment, the thickness on described organic barrier layer is 200～300nm therein.
In an embodiment, the thickness of described tellurium oxygen compound layer is 100～200nm therein.
In an embodiment, the material of described hole injection layer is MoO therein
3doping content according to 25wt% is doped into N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the doping composite material forming in 4 '-diamines;
The material of described hole transmission layer for adopt 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines;
The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material forming in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) 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
3mix 4,7-diphenyl-1 according to the doping content of 25wt%, the composite material forming in 10-phenanthroline.
A preparation method for organic electroluminescence device, comprises the steps:
On the anode layer of anode substrate, stack gradually vacuum evaporation and prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer;
Adopt the mode of vacuum evaporation on described cathode layer, to prepare organic barrier layer, the material on described organic barrier layer is CuPc, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, oxine-aluminium, 4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine or 4,7-diphenyl-1,10-Phen;
Adopt the mode of magnetron sputtering on described organic barrier layer, to prepare tellurium oxygen compound layer, described tellurium oxygen compound layer comprises oxide and is entrained in the tellurides in described oxide, and described tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, described oxide is MgO, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the doping mass concentration of described tellurides in described tellurium oxygen compound layer is 10～30%.
Therein in an embodiment, described preparation method also comprises the step that repeats to prepare described organic barrier layer and described tellurium oxygen compound layer, makes altogether 4～6 layers of described organic barrier layer and is mixed with described the described tellurium oxygen compound layer that machine barrier layer is arranged alternately and quantity is identical.
In an embodiment, prepare in the process of described organic barrier layer therein, evaporation rate is
the thickness on the described organic barrier layer making is 200～300nm.
In an embodiment, the thickness of described tellurium oxygen compound layer is 100～200nm therein.
In an embodiment, the material of described hole injection layer is MoO therein
3doping content according to 25wt% is doped into N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the doping composite material forming in 4 '-diamines;
The material of described hole transmission layer for adopt 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines;
The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material forming in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) 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
3mix 4,7-diphenyl-1 according to the doping content of 25wt%, the composite material forming in 10-phenanthroline.
Above-mentioned organic electroluminescence device is provided with organic barrier layer and tellurium oxygen compound layer on cathode layer, organic barrier layer and tellurium oxygen compound layer form water oxygen barrier layers, there is good anti-oxygen water-proof function, the water oxygen barrier layers of layering setting 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.
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 the anode conducting effect that are cascading), hole injection layer 120(injected hole, being conducive to hole is 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 are compound in this layer, then energy is transferred to light emitting molecule luminous), electron transfer layer 150(transmission electronic, be conducive to electric transmission in luminescent material), electron injecting layer 160(injects electronics, being conducive to electronics is 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., 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.
The functional layers such as 120130140150160 hole injection layers 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
3doping content according to 25wt% is mixed N, N '-diphenyl-N, and N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, obtain in 4 '-diamines (NPB); Hole transmission layer 130 can be 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA); Electron transfer layer 150 can be 4,7-diphenyl-1,10-phenanthroline (Bphen); Electron injecting layer 160 can be mixed in Bphen and obtain according to the doping content of 25wt% by CsN3.In addition, in other embodiments, this organic electroluminescence device 100 can also not 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, as the material of main part of luminescent layer 140 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), wherein, the doping content 5wt% of guest materials in material of main part.
Cathode layer 170 can adopt the preparation of non-transparent metals material, 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 organic barrier layer 182 and the tellurium oxygen compound layer 184 that are cascading.The material on organic barrier layer 182 is CuPc (CuPc), N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), oxine-aluminium (Alq3), 4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (m-MTDATA) or 4; 7-diphenyl-1,10-Phen (BCP).The thickness on organic barrier layer 182 is 200～300nm.Tellurium oxygen compound layer 184 comprises oxide and be entrained in the tellurides in oxide, and wherein, tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, oxide is MgO, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the doping mass concentration of tellurides in tellurium oxygen compound layer 184 is 10～30%.The thickness of tellurium oxygen compound layer 184 is 100～200nm.
Organic barrier layer 182 is identical with the quantity of tellurium oxygen compound layer 184, can be 1 layer or multilayer, preferably 4～6 layers, be also water oxygen barrier layers 180 can by the tellurium oxygen compound layer on 182 and 4～6 layers, organic barrier layer of 4～6 layers 184 alternately folded establishing form.
Above-mentioned organic electroluminescence device 100 is provided with organic barrier layer 182 and tellurium oxygen compound layer 184 on cathode layer 170, organic barrier layer 182 and tellurium oxygen compound layer 184 form water oxygen barrier layers 180, there is good anti-oxygen water-proof function, the water oxygen barrier layers 180 of layering setting 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 also provides a kind of preparation method of organic electroluminescence device, as shown in Figure 2, comprises the steps:
Step S110 stacks gradually vacuum evaporation and prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer on the anode layer of anode substrate.
Before preparing hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, preferred, also comprise the step that antianode substrate cleans, especially ito glass substrate.The step of this cleaning is included in antianode substrate in supersonic cleaning machine and uses successively acetone, ethanol, deionized water and ethanol to clean, and washs 5 minutes at every turn, then dries up with nitrogen, after oven dry.
Step S120, adopts the mode of vacuum evaporation on cathode layer, to prepare organic barrier layer.The material on organic barrier layer is CuPc, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, oxine-aluminium, 4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines or 4; 7-diphenyl-1,10-Phen.
Preferably, in the process of the organic barrier layer of preparation of present embodiment, evaporation rate is
the thickness on the organic barrier layer making is 200～300nm.
Step S130, adopts the mode of magnetron sputtering on organic barrier layer, to prepare tellurium oxygen compound layer.Tellurium oxygen compound layer comprises oxide and be entrained in the tellurides in oxide, and wherein, tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, oxide is MgO, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the doping mass concentration of tellurides in tellurium oxygen compound layer 144 is 10～30%.
Preferably, the thickness of the tellurium oxygen compound layer of preparation is 100～200nm in the present embodiment.
Organic barrier layer and tellurium oxygen compound layer form water oxygen barrier layers, in the time that needs are prepared multilayer water oxygen barrier layers, can prepare first after tellurium oxygen compound layer repeating step S120 and step S130 for several times again.
In the preparation method of above-mentioned organic electroluminescence device, the preparation of described cathode layer also comprises: after electron injecting layer evaporation, first surperficial evaporation one deck ZnS layer at electron injecting layer, subsequently at ZnS layer surface evaporation one deck Ag layer, finally at the surface of Ag layer again evaporation one deck ZnS layer, make cathode layer after complete.
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: MgO(30wt%), wherein, in equivalent layer, ": " represents doping, the former doping mass percent in whole layer of percentage data representation in parantheses, "/" represents stacked, concrete preparation process is as follows:
A) ito glass substrate pre-treatment: use successively acetone, ethanol, deionized water, ethanol to clean in supersonic cleaning machine, wash 5 minutes at every turn, then dry up stove-drying with nitrogen; Again the ito glass substrate after cleaning is carried out to 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.
B) preparation of organic function layer:
Hole injection layer: by MoO
3be doped in NPB as hole-injecting material, doping content 30wt% adopts the mode of vacuum evaporation to prepare the hole injection layer that thickness is 10nm, vacuum degree 3 × 10 in preparation process on ito glass substrate
-5pa, evaporation rate
Hole transmission layer: employing 4,4 ', 4 " and tri-(carbazole-9-yl) triphenylamine (TCTA), as hole mobile material, adopts the mode of vacuum evaporation on hole injection layer, to 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-yl) 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 the mode of vacuum evaporation evaporation a layer thickness be 10nm on luminescent layer 4,7-diphenyl-1,10-phenanthroline (Bphen) is as electron transfer layer, wherein, vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
The preparation of electron injecting layer: by CsN
3mix in Bphen as electron injection material, doping content 30wt%, the electron injecting layer that the mode evaporation a layer thickness that adopts vacuum evaporation on electron transfer layer is 20nm, wherein, vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
C) preparation of cathode layer: adopt the mode of vacuum evaporation on electron injecting layer, evaporate a layer thickness be the Al of 100nm as cathode layer, wherein, vacuum degree 3 × 10 in preparation process
-5pa, evaporation rate
D) preparation on organic barrier layer: adopt CuPc that the mode of vacuum evaporation prepares a layer thickness 300nm on cathode layer as organic barrier layer, wherein, vacuum degree 1 × 10 in preparation process
-5pa, evaporation rate
E) preparation of tellurium oxygen compound layer: tellurium oxygen compound layer is made up of two kinds of materials, one is Sb
2te
3, another kind is MgO, adopts the mode of magnetron sputtering on organic barrier layer, to prepare the tellurium oxygen compound layer of thickness 200nm, wherein, in sputter procedure, base vacuum degree is 1 × 10
-5pa, Sb
2te
3doping content in whole tellurium oxygen compound layer is 30wt%.
Alternately repeating 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:Al
2o
3(10wt%), wherein, in equivalent layer, ": " represents doping, the former doping mass percent in whole layer of percentage data representation in parantheses, and "/" represents stacked, concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation on organic barrier layer: adopt NPB that the mode of vacuum evaporation prepares a layer thickness 250nm on cathode layer as organic barrier layer, wherein, vacuum degree 5 × 10 in preparation process
-5pa, evaporation rate
E) preparation of tellurium oxygen compound layer: tellurium oxygen compound layer is made up of two kinds of materials, one is Bi
2te, another kind is Al
2o
3, adopt the mode of magnetron sputtering on organic barrier layer, to prepare the tellurium oxygen compound layer of thickness 100nm, wherein, in sputter procedure, base vacuum degree is 1 × 10
-5pa, Bi
2the doping content of Te in whole tellurium oxygen compound layer is 10wt%.
Alternately repeating 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:TiO
2(20wt%), wherein, in equivalent layer, ": " represents doping, the former doping mass percent in whole layer of percentage data representation in parantheses, and "/" represents stacked, concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation on organic barrier layer: adopt Alq3 that the mode of vacuum evaporation prepares a layer thickness 200nm on cathode layer as organic barrier layer, wherein, vacuum degree 5 × 10 in preparation process
-5pa, evaporation rate
E) preparation of tellurium oxygen compound layer: tellurium oxygen compound layer is made up of two kinds of materials, one is CdTe, another kind is TiO
2, adopt the mode of magnetron sputtering on organic barrier layer, to prepare the tellurium oxygen compound layer of thickness 160nm, wherein, in sputter procedure, base vacuum degree is 1 × 10
-5pa, the doping content of CdTe in whole tellurium oxygen compound layer is 20wt%.
Alternately repeating 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: ZrO
2(20wt%), wherein, in equivalent layer, ": " represents doping, the former doping mass percent in whole layer of percentage data representation in parantheses, and "/" represents stacked, concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation on organic barrier layer: adopt m-MTDATA that the mode of vacuum evaporation prepares a layer thickness 250nm on cathode layer as organic barrier layer, wherein, vacuum degree 5 × 10 in preparation process
-5pa, evaporation rate
E) preparation of tellurium oxygen compound layer: tellurium oxygen compound layer is made up of two kinds of materials, one is In
2te
3, another kind is ZrO
2, adopt the mode of magnetron sputtering on organic barrier layer, to prepare the tellurium oxygen compound layer of thickness 150nm, wherein, in sputter procedure, base vacuum degree is 5 × 10
-5pa, In
2te
3doping content in whole tellurium oxygen compound layer is 20wt%.
Alternately repeating 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:HfO
2(20wt%), wherein, in equivalent layer, ": " represents doping, the former doping mass percent in whole layer of percentage data representation in parantheses, and "/" represents stacked, concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation on organic barrier layer: adopt BCP that the mode of vacuum evaporation prepares a layer thickness 250nm on cathode layer as organic barrier layer, wherein, vacuum degree 5 × 10 in preparation process
-5pa, evaporation rate
E) preparation of tellurium oxygen compound layer: tellurium oxygen compound layer is made up of two kinds of materials, one is SnTe, another kind is HfO
2, adopt the mode of magnetron sputtering on organic barrier layer, to prepare the tellurium oxygen compound layer of thickness 150nm, wherein, in sputter procedure, base vacuum degree is 5 × 10
-5pa, the doping content of SnTe in whole tellurium oxygen compound layer is 20wt%.
Alternately repeating 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:Ta
2o
5(20wt%), wherein, in equivalent layer, ": " represents doping, the former doping mass percent in whole layer of percentage data representation in parantheses, and "/" represents stacked, concrete preparation process is as follows:
A), b), c) with embodiment 1;
D) preparation on organic barrier layer: adopt CuPc that the mode of vacuum evaporation prepares a layer thickness 250nm on cathode layer as organic barrier layer, wherein, vacuum degree 1 × 10 in preparation process
-3pa, evaporation rate
E) preparation of tellurium oxygen compound layer: tellurium oxygen compound layer is made up of two kinds of materials, one is PbTe, another kind is Ta
2o
5, adopt the mode of magnetron sputtering on organic barrier layer, to prepare the tellurium oxygen compound layer of thickness 120nm, wherein, in sputter procedure, base vacuum degree is 1 × 10
-3pa, the doping content of PbTe in whole tellurium oxygen compound layer is 20wt%.
Alternately repeating step d) and e) 4 times.
Table 1 is the waterproof oxygen performance detection data of the various embodiments described above:
Table 1
The ability that can be found out the organic electroluminescence device waterproof that adopts present embodiment structure by table 1 data is strong, and device lifetime is longer.
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, 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, organic barrier layer and the tellurium oxygen compound layer that are cascading, wherein, the material on described organic barrier layer is CuPc, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, oxine-aluminium, 4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine or 4; 7-diphenyl-1,10-Phen; Described tellurium oxygen compound layer comprises oxide and be entrained in the tellurides in described oxide, and described tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, described oxide is MgO, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the doping mass concentration of described tellurides in described tellurium oxygen compound layer is 10～30%.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, the quantity on described organic barrier layer is 4～6 layers, and the quantity of described tellurium oxygen compound layer is identical with the quantity on described organic barrier layer, and described organic barrier layer and described tellurium oxygen compound layer are arranged alternately.
3. organic electroluminescence device as claimed in claim 1 or 2, is characterized in that, the thickness on described organic barrier layer is 200～300nm.
4. organic electroluminescence device as claimed in claim 1 or 2, is characterized in that, the thickness of described tellurium oxygen compound layer is 100～200nm.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described hole injection layer is MoO
3doping content according to 25wt% is doped into N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the doping composite material forming in 4 '-diamines;
The material of described hole transmission layer for adopt 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines;
The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material forming in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) 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
3mix 4,7-diphenyl-1 according to the doping content of 25wt%, the composite material forming in 10-phenanthroline.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
On the anode layer of anode substrate, stack gradually vacuum evaporation and prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer;
Adopt the mode of vacuum evaporation on described cathode layer, to prepare organic barrier layer, the material on described organic barrier layer is CuPc, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, oxine-aluminium, 4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine or 4,7-diphenyl-1,10-Phen;
Adopt the mode of magnetron sputtering on described organic barrier layer, to prepare tellurium oxygen compound layer, described tellurium oxygen compound layer comprises oxide and is entrained in the tellurides in described oxide, and described tellurides is Sb
2te
3, Bi
2te, CdTe, In
2te
3, SnTe or PbTe, described oxide is MgO, Al
2o
3, TiO
2, ZrO
2, HfO
2or Ta
2o
5, the doping mass concentration of described tellurides in described tellurium oxygen compound layer is 10～30%.
7. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, also comprise the step that repeats to prepare described organic barrier layer and described tellurium oxygen compound layer, make altogether 4～6 layers of described organic barrier layer and be mixed with described the described tellurium oxygen compound layer that machine barrier layer is arranged alternately and quantity is identical.
8. the preparation method of the organic electroluminescence device as described in claim 6 or 7, is characterized in that, prepares in the process of described organic barrier layer, and evaporation rate is
the thickness on the described organic barrier layer making is 200～300nm.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thickness of described tellurium oxygen compound layer is 100～200nm.
10. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the material of described hole injection layer is MoO
3doping content according to 25wt% is doped into N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the doping composite material forming in 4 '-diamines;
The material of described hole transmission layer for adopt 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines;
The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are doped into the doping composite material forming in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) 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
3mix 4,7-diphenyl-1 according to the doping content of 25wt%, the composite material forming in 10-phenanthroline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210572615.2A CN103904251B (en) | 2012-12-25 | 2012-12-25 | A kind of organic electroluminescence device and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210572615.2A CN103904251B (en) | 2012-12-25 | 2012-12-25 | A kind of organic electroluminescence device and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103904251A true CN103904251A (en) | 2014-07-02 |
| CN103904251B CN103904251B (en) | 2016-04-13 |
Family
ID=50995484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210572615.2A Active CN103904251B (en) | 2012-12-25 | 2012-12-25 | A kind of organic electroluminescence device and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103904251B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005339687A (en) * | 2004-05-27 | 2005-12-08 | Tdk Corp | Optical recording medium |
| US20070295390A1 (en) * | 2006-05-05 | 2007-12-27 | Nanosolar, Inc. | Individually encapsulated solar cells and solar cell strings having a substantially inorganic protective layer |
| US20080180022A1 (en) * | 2007-01-30 | 2008-07-31 | Samsung Sdi Co., Ltd. | Organic light emitting display and method for manufacturing the same |
| CN101359722A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Encapsulation method for top radiation organic EL part |
| CN100539788C (en) * | 2003-08-05 | 2009-09-09 | 不伦瑞克工业大学 | Hydrophobic, linear or two-dimensional polycyclic aromatics layer are as the purposes of barrier layer or encapsulation and the electric components that includes organic polymer that is made of this class layer |
| CN102057750A (en) * | 2008-04-09 | 2011-05-11 | 新加坡科技研究局 | Multilayer film for encapsulating oxygen and/or moisture sensitive electronic devices |
| WO2011103341A1 (en) * | 2010-02-18 | 2011-08-25 | Alliance For Sustainable Energy, Llc | Moisture barrier |
| CN102458840A (en) * | 2009-04-24 | 2012-05-16 | 德莎欧洲公司 | Transparent barrier laminates |
| CN102723442A (en) * | 2011-03-30 | 2012-10-10 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN102751442A (en) * | 2011-04-19 | 2012-10-24 | 海洋王照明科技股份有限公司 | Organic electroluminescence device and manufacture method of organic electroluminescence device |
-
2012
- 2012-12-25 CN CN201210572615.2A patent/CN103904251B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100539788C (en) * | 2003-08-05 | 2009-09-09 | 不伦瑞克工业大学 | Hydrophobic, linear or two-dimensional polycyclic aromatics layer are as the purposes of barrier layer or encapsulation and the electric components that includes organic polymer that is made of this class layer |
| JP2005339687A (en) * | 2004-05-27 | 2005-12-08 | Tdk Corp | Optical recording medium |
| US20070295390A1 (en) * | 2006-05-05 | 2007-12-27 | Nanosolar, Inc. | Individually encapsulated solar cells and solar cell strings having a substantially inorganic protective layer |
| US20080180022A1 (en) * | 2007-01-30 | 2008-07-31 | Samsung Sdi Co., Ltd. | Organic light emitting display and method for manufacturing the same |
| CN102057750A (en) * | 2008-04-09 | 2011-05-11 | 新加坡科技研究局 | Multilayer film for encapsulating oxygen and/or moisture sensitive electronic devices |
| CN101359722A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Encapsulation method for top radiation organic EL part |
| CN102458840A (en) * | 2009-04-24 | 2012-05-16 | 德莎欧洲公司 | Transparent barrier laminates |
| WO2011103341A1 (en) * | 2010-02-18 | 2011-08-25 | Alliance For Sustainable Energy, Llc | Moisture barrier |
| CN102723442A (en) * | 2011-03-30 | 2012-10-10 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN102751442A (en) * | 2011-04-19 | 2012-10-24 | 海洋王照明科技股份有限公司 | Organic electroluminescence device and manufacture method of organic electroluminescence device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103904251B (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103904246A (en) | Organic electroluminescent device and preparing method thereof | |
| CN104576954A (en) | Organic electroluminescent component and manufacturing method thereof | |
| CN103904244B (en) | A kind of organic electroluminescence device and preparation method thereof | |
| CN104183718A (en) | Organic light emission diode and preparation method thereof | |
| CN103904251B (en) | A kind of organic electroluminescence device and preparation method | |
| CN103904241B (en) | Organic electroluminescence device and preparation method | |
| CN104638126A (en) | Organic light-emitting device and preparation method thereof | |
| CN104103768A (en) | Organic light-emitting display and manufacturing method thereof | |
| CN104103764A (en) | Organic light-emitting display and manufacturing method thereof | |
| CN104078601B (en) | Organic electroluminescence device and preparation method thereof | |
| CN104218166A (en) | Organic light-emitting device and preparation method thereof | |
| CN104078599B (en) | Organic electroluminescence device and preparation method thereof | |
| CN103904240A (en) | Organic light-emitting device and preparation method | |
| CN103904250A (en) | Organic electroluminescent device and preparing method thereof | |
| CN103904235B (en) | Organic electroluminescence device and preparation method thereof | |
| CN103904232A (en) | Organic light-emitting device and preparation method | |
| CN103904242A (en) | Organic electroluminescent device and preparing method thereof | |
| CN104518095A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104103763A (en) | Organic light-emitting display and manufacturing method thereof | |
| CN104518131A (en) | Organic electroluminescent device and preparation method | |
| CN103904237A (en) | Transparent organic light-emitting device and preparation method | |
| CN104103767A (en) | Organic light-emitting display and preparation method thereof | |
| CN104103773A (en) | Organic light-emitting display and manufacturing method thereof | |
| CN103904236A (en) | Organic light-emitting device and preparation method | |
| CN104103772A (en) | Organic light-emitting display and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |