CN104638184A - Organic light emitting device and manufacturing method thereof - Google Patents

Organic light emitting device and manufacturing method thereof Download PDF

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Publication number
CN104638184A
CN104638184A CN201310562053.8A CN201310562053A CN104638184A CN 104638184 A CN104638184 A CN 104638184A CN 201310562053 A CN201310562053 A CN 201310562053A CN 104638184 A CN104638184 A CN 104638184A
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layer
inorganic barrier
barrier layer
organic electroluminescence
electroluminescence device
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周明杰
钟铁涛
王平
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention relates to an organic light emitting device and a manufacturing method thereof. The organic light emitting device is of a stratified structure, and the stratified structure sequentially comprises a conductive anode substrate, a hole injection layer, a hole transmission layer, a light emitting layer, an electronic transmission layer, an electronic injection layer and a cathode layer. Organic barrier layers and inorganic barrier layers are alternatively stacked on the cathode layer. The organic barrier layer is a silicon carbon oxygen compound film, the inorganic barrier layer is made of B203: F, Al2O3: F, Ga2O3: F, In2O3: F or Tl2O3:F. As with the organic barrier layers and the inorganic barrier layers which are alternatively stacked, the organic barrier layer is the silicon carbon nitrogen compound film and the organic light emitting device is high in compactness and good in water oxidation resistance performance. In addition, the manufacturing method of the organic light emitting device has the advantages of low-cost materials, simplicity in process and easy large-area manufacturing and the like.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to field of optoelectronic devices, particularly relate to 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 that the luminous organic material making one deck tens nanometer thickness on ito glass makes luminescent layer, has the metal electrode of one deck low work function above luminescent layer.When electrode being added with voltage, luminescent layer just produces light radiation.
Electroluminescent organic material invades responsive especially to oxygen and steam, on the one hand because oxygen is quencher, the luminous quantum efficiency of OLED can be made significantly to decline, and oxygen also can make the transmittability of OLED decline to the oxidation of OLED; On the other hand, steam is more apparent on the impact of OLED, and its main failure mode makes the Hydrolysis of Organic Chemicals As A Function of Ph to OLED, thus reduces stability and the life-span of OLED.Thus; the degeneration of effective suppression OLED in long-term work process and inefficacy; with the life-span making OLED steady operation reach enough, this proposes high requirement to the barrier of encapsulating material, and the encapsulation technology playing seal protection effect has just become the break-through point solving OLED life problems.
Encapsulation technology is the barrier layer by forming compact structure, realizes physical protection to the core component in encapsulation region.Using inorganic material (such as silicon nitride) as the technology on the barrier layer of organic electroluminescence device quite maturation and being widely used in various display.
Flexible product is the development trend of organic electroluminescence device, but the current ubiquity life-span is short, and the quality of its encapsulation directly affects the life-span of device.But in the manufacturing process making flexible organic electroluminescence devices (being also called bendable organic electroluminescence devices), because the pliability of inorganic material is not good, so that organic light emitting apparatus is after bending, and barrier layer can produce crack.Thus, steam can infiltrate via crack and affect the electrical of thin-film transistor.If using organic material as passivation protection layer, then can have preferably pliability.But comparatively inorganic material is poor for the water-resisting ability of organic material, therefore steam easily infiltrates organic light emitting apparatus and affects that it is electrical.Therefore, how promoting the reliability of flexible organic electroluminescence device real is one of subject under discussion of desiring most ardently solution at present.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, a kind of organic electroluminescence device is provided, this organic electroluminescence device is layer structure, and this layer structure comprises successively: alternately laminated inorganic barrier layer and inorganic barrier layer on anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer and described cathode layer;
Wherein:
The material of described inorganic barrier layer is silicon nitride compound film;
The material of described inorganic barrier layer is B 2o 3: F, Al 2o 3: F, Ga 2o 3: F, In 2o 3: F or Tl 2o 3: F.
Further, described silicon nitride compound film uses hmds, NH 3and O 2also obtained by plasma reinforced chemical vapour deposition method as raw material.
Further, described inorganic barrier layer is that use fluoroform substrate and steam are obtained as raw material and by Atomic layer deposition method, and described fluoroform substrate is B (CH 2f) 3, Al (CH 2f) 3, Ga (CH 2f) 3, In (CH 2f) 3or Tl (CH 2f) 3.
Further, described inorganic barrier layer and the alternately laminated number of plies of described inorganic barrier layer are four, five or six.
Further, the thickness of described inorganic barrier layer is 150nm ~ 200nm; The thickness of described inorganic barrier layer is 15nm ~ 20nm.
Further, the material of described hole injection layer is by MoO 3and the mixture that N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines adulterates mutually, wherein, MoO 3be 0.25:1 with the percentage by weight of N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines;
The material of described hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine;
The material of described luminescent layer is for close iridium and 1 by three (2-phenylpyridines), 3, the mixture that 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene adulterates mutually, wherein, three (2-phenylpyridines) close iridium and 1, the percentage by weight of 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene is 0.05:1;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline;
The material of described electron injecting layer is by CsN 3with the mixture that 4,7-diphenyl-1,10-phenanthroline adulterates mutually, wherein, CsN 3be 0.25:1 with the percentage by weight of 4,7-diphenyl-1,10-phenanthroline;
The material of described cathode layer is metallic aluminium.
The present invention also proposes a kind of preparation method of organic electroluminescence device, and it comprises the following steps:
A () adopts vacuum deposition method to form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer successively on the anode conducting substrate cleaned up;
B (), on described cathode layer, first uses hmds, NH 3and O 2under Ar atmosphere is enclosed, inorganic barrier layer is obtained by plasma reinforced chemical vapour deposition method as raw material; Then on described inorganic barrier layer, use fluoroform substrate and steam as raw material and obtain inorganic barrier layer by Atomic layer deposition method; Finally, alternately laminatedly successively inorganic barrier layer and inorganic barrier layer is prepared; Wherein:
The material of described inorganic barrier layer is silicon nitride compound film;
The material of described inorganic barrier layer is B 2o 3: F, Al 2o 3: F, Ga 2o 3: F, In 2o 3: F or Tl 2o 3: F; Described fluoroform substrate is B (CH 2f) 3, Al (CH 2f) 3, Ga (CH 2f) 3, In (CH 2f) 3or Tl (CH 2f) 3.
Further, in described step (b), when adopting plasma reinforced chemical vapour deposition method to prepare described inorganic barrier layer, described hmds flow 6 ~ 14sccm, described Ar flow is 70 ~ 80sccm, described NH 3flow 2 ~ 18sccm, described O 2flow 2 ~ 18sccm, the thickness of described inorganic barrier layer is 150nm ~ 200nm.
Further, in described step (b), adopt Atomic layer deposition method when preparing described inorganic barrier layer, the N of interval 5 ~ 10s between the two when injecting described fluoroform substrate and described steam 2, the injection length of described fluoroform substrate and described steam is 10 ~ 20ms, and flow is 10 ~ 20sccm, the thickness 15 ~ 20nm of described inorganic barrier layer.
Further, in described step (b), the number of times of described inorganic barrier layer and the alternately laminated preparation of described inorganic barrier layer is four, five or six.
Compared with prior art, organic electroluminescence device of the present invention has following advantage:
First, the inorganic barrier layer of organic electroluminescence device of the present invention is silicon nitride compound (SiOxNy), it has following premium properties: 1, inorganic barrier layer causes increasing relative to the chemical bond force of inorganic barrier layer due to the nitrogen-atoms that there is silicon nitride compound, thus make inorganic barrier layer and inorganic barrier layer caking property by force, and then the adhesiveness on barrier layer of the present invention is caused to increase; 2, inorganic barrier layer does not all have hole, and edge does not have defect, and evenness is high, has the compactness of film, strong to oxygen screening ability.3, when silicon nitride compound film is used as the diaphragm of organic electroluminescence device, can extend water oxygen path, namely extend the path that water penetrates into functional layer from the outside, waterproof ability improves greatly.4, inorganic barrier layer using plasma strengthens chemical vapour deposition (CVD) preparation, and plasma enhanced chemical vapor deposition contributes to rete hydrogenated carbon nitrogen compound in difform substrate, forms film, thus is conducive to the flexibility of film.In addition, plasma enhanced chemical vapor deposition can at room temperature use, and therefore can have the application of wide region.
The second, the inorganic barrier layer rete compactness of organic electroluminescence device of the present invention is good, and edge does not have defect, for lower than 20% non-crystalline substances.And in same layer inorganic barrier layer, choose unlike material and adulterate, can greatly reduce its internal stress.
3rd, in alternately stacked structure between alternately stacked inorganic barrier layer and inorganic barrier layer, make use of the strong flexibility of inorganic barrier layer and the strong water-resisting ability of inorganic barrier layer this alternately stacked complementary structure, thus avoid the problem that the water-resisting ability of inorganic barrier layer in prior art is poor and inorganic barrier layer flexibility is poor and produce.
In sum, the inorganic barrier layer that the present invention stacks gradually and inorganic barrier layer, the material of described inorganic barrier layer is silicon nitride compound film, compactness is high, water oxygen resistant ability is strong, corrosion resistance stress durability is strong, and preparation method of the present invention to have cheaper starting materials, technique simple and be easy to large area and the feature such as prepare.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 1.
Fig. 2 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 2.
Fig. 3 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 3.
Fig. 4 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 4.
Fig. 5 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 5.
Fig. 6 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 6.
Embodiment
Below in conjunction with embodiment, elaboration is further given to organic electroluminescence device of the present invention and preparation method thereof.
Organic electroluminescence device of the present invention is layer structure, anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, it is characterized in that, described cathode layer is also provided with barrier layer, and described barrier layer is made up of alternately laminated inorganic barrier layer and inorganic barrier layer.
The preparation method of above-mentioned organic electroluminescence device, specifically comprises the following steps:
A () adopts vacuum deposition method to form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer successively on the anode conducting substrate cleaned up;
B (), on described cathode layer, first uses hmds (HMDS, structural formula is as follows), NH 3and O 2as raw material and by plasma reinforced chemical vapour deposition method (english abbreviation under Ar atmosphere is enclosed, PECVD) obtained inorganic barrier layer, then uses fluoroform substrate and steam to obtain inorganic barrier layer as raw material and by Atomic layer deposition method on described inorganic barrier layer; Wherein:
Barrier layer obtained on described cathode layer is at least one deck;
The material of described inorganic barrier layer is silicon nitride compound film (its expression formula is SiOxNy);
The material of described inorganic barrier layer is B 2o 3: F, Al 2o 3: F, Ga 2o 3: F, In 2o 3: F or Tl 2o 3: F, wherein, colon ": " expression is adulterated mutually; Described fluoroform substrate is B (CH 2f) 3, Al (CH 2f) 3, Ga (CH 2f) 3, In (CH 2f) 3or Tl (CH 2f) 3, this structural formula is as follows.
Described Atomic layer deposition method be a kind of can by material with the monatomic form membrane method being plated in substrate surface in layer.Described Atomic layer deposition method has depositing homogeneous and the advantage such as deposit thickness is consistent.
In described organic electroluminescence device, anode conducting substrate comprises anode conductive layer and substrate, the material of its anode conductive layer is conductive oxide, comprise tin indium oxide (ITO), Al-Doped ZnO (AZO), mix indium zinc oxide (IZO) or mix any one of fluorine zinc oxide (FTO), the material of its substrate is glass, plastics or metal, the thickness of anode conducting substrate is 100nm, can make by oneself, also can commercially obtain.In actual applications, the material can other being selected as required suitable is as anode conducting substrate.In actual applications, the anode pattern of required organic electroluminescence device can be prepared on anode conducting substrate.Anode conducting substrate is prior art, does not repeat them here.
In organic electroluminescence device, material and the thickness of other functional layers are as follows:
The material of described hole injection layer is by MoO 3be doped into N, the mixture of N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (being abbreviated as NPB), MoO 3the percentage by weight accounting for NPB is 25wt%, vacuum degree 3 × 10 -5pa, evaporation rate thickness is 10nm;
The material of described hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (being abbreviated as TCTA), vacuum degree 3 × 10 -5pa, evaporation rate evaporation thickness 40nm;
The material of described luminescent layer (is abbreviated as Ir (ppy) for three (2-phenylpyridines) are closed iridium 3) be doped into the mixture of 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (being abbreviated as TPBI), Ir (ppy) 3the percentage by weight accounting for TPBI is 5wt%, vacuum degree 3 × 10 -5pa, evaporation rate evaporation thickness 20nm;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (being abbreviated as Bphen), vacuum degree 3 × 10 -5pa, evaporation rate evaporation thickness 30nm;
The material of described electron injecting layer is by CsN 3be doped into the mixture of Bphen, CsN 3the percentage by weight accounting for Bphen is 25wt%, vacuum degree 3 × 10 -5pa, evaporation rate evaporation thickness 20nm;
The material of cathode layer is metallic aluminium (Al), vacuum degree 3 × 10 -5pa, evaporation rate thickness is 100nm.
With embodiment 1 ~ 6, organic electroluminescence device of the present invention and preparation method thereof is illustrated below:
Embodiment 1
As shown in Figure 1, the organic electroluminescence device of the present embodiment is layer structure, every layer is followed successively by: 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, and inorganic barrier layer 108 overlapping successively and inorganic barrier layer 109.Described inorganic barrier layer 108 and described inorganic barrier layer 109 are also multilayer, it should be noted that: Fig. 1 only draws alternately stacked one deck inorganic barrier layer 108 and one deck inorganic barrier layer 109, all the other alternately stacked inorganic barrier layer 108 and inorganic barrier layer 109 make omission in order to the succinct of drawing.
The structure of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/SiOxNy/B 2o 3: F, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate.Being described in detail as follows of the structure of described organic electroluminescence device:
ITO is the material of anode conducting substrate 101;
MoO 3: NPB is the material of hole injection layer 102, wherein MoO 3be 0.25:1 with the doping weight ratio of NPB;
TCTA is the material of hole transmission layer 103;
TPBI:Ir (ppy) 3for the material of luminescent layer 104, wherein TPBI and Ir (ppy) 3doping weight ratio be 1:0.05;
Bphen is the material of electron transfer layer 105;
CsN 3: Bphen is the material of electron injecting layer 106, wherein CsN 3be 0.25:1 with the doping weight ratio of Bphen;
Al is the material of cathode layer 107;
SiOxNy is the material of inorganic barrier layer 108;
B 2o 3: F is the material of inorganic barrier layer 109;
Above-mentioned organic electroluminescence device is prepared according to the following steps:
The pre-treatment of step S1, anode conducting substrate 101:
Using ito glass substrate as anode conducting substrate 101, first ito glass substrate is done following cleaning: acetone cleaning → ethanol purge → washed with de-ionized water → ethanol purge, described cleaning is all cleaned with supersonic wave cleaning machine, every scavenging period is 5 minutes, then dry up with nitrogen, then use stove-drying stand-by; Ito glass substrate after cleaning also needs the process carrying out surface active, and to increase the oxygen content of anode conducting substrate and ito glass substrate, improve the work function of conductive layer surface, the thickness of gained ito glass substrate is 100nm;
The preparation of step S2, hole injection layer 102: the anode conducting substrate 101(ITO glass substrate prepared at above-mentioned steps S1) on, by MoO 3be doped into the mixture of formation after in NPB as hole-injecting material, MoO 3the percentage by weight accounting for NPB is 25wt%; Adopt the method vacuum evaporation of vacuum evaporation to obtain the hole injection layer 102 that thickness is 10nm, the vacuum degree of vacuum evaporation used is 3 × 10 -5pa, evaporation rate is
The preparation of step S3, hole transmission layer 103: on hole injection layer 102 prepared by above-mentioned steps S2, take TCTA as hole mobile material, adopt the method vacuum evaporation of vacuum evaporation to obtain the hole transmission layer 103 that thickness is 40nm, the vacuum degree of vacuum evaporation used is 3 × 10 -5pa, evaporation rate is
The preparation of step S4, luminescent layer 104: on hole transmission layer 103 prepared by above-mentioned steps S3, by Ir (ppy) 3be doped into the mixture of formation after in TPBI as emitting layer material, Ir (ppy) 3the percentage by weight accounting for TPB is 5wt%; Adopt the method vacuum evaporation of vacuum evaporation to obtain the luminescent layer 104 that thickness is 20nm, the vacuum degree of vacuum evaporation used is 3 × 10 -5p, evaporation rate is
The preparation of step S5, electron transfer layer 105: on luminescent layer 104 prepared by above-mentioned steps S4, adopt the Bphen of method evaporation one deck 30nm of vacuum evaporation as electron transfer layer 105, the vacuum degree of vacuum evaporation used is 3 × 10 -5p, evaporation rate is
The preparation of step S6, electron injecting layer 106: on electron transfer layer 105 prepared by above-mentioned steps S5, by CsN 3mix the mixture of formation after in Bphen as electron injecting layer material, CsN 3the percentage by weight accounting for Bphen is 25wt%; Adopt the method vacuum evaporation of vacuum evaporation to obtain the electron injecting layer 106 that thickness is 20nm, the vacuum degree of vacuum evaporation used is 3 × 10 -5pa, evaporation rate is
The preparation of step S7, cathode layer 107: on electron injecting layer 106 prepared by above-mentioned steps S6, using metallic aluminium as cathode material, adopt the method vacuum evaporation of vacuum evaporation to obtain the cathode layer 107 that thickness is 100nm, the vacuum degree of vacuum evaporation used is 3 × 10 -5pa, evaporation rate is
The making of step S8, inorganic barrier layer 108: on cathode layer 107 prepared by above-mentioned steps S7, adopts HMDS(hmds), NH 3and O 2for raw material, prepare the SiOxNy rete of thickness 200nm under Ar atmosphere is enclosed with plasma enhanced chemical vapor deposition method, i.e. described inorganic barrier layer 108, wherein, HMDS flow is 10sccm, Ar flow is 75sccm, NH 3flow is 10sccm, O 2flow is 10sccm;
The making of step S9, inorganic barrier layer 109: on inorganic barrier layer 108 prepared by above-mentioned steps S8, adopt ald to prepare the inorganic barrier layer 109 of thickness 20nm, inorganic barrier layer 109 material is B 2o 3: F, raw material adopts B (CH respectively 2f) 3and steam, B (CH 2f) 3be 15ms with steam injection length, the N of interval 7s between the two 2, fluoroform substrate and steam inject flow and are 15sccm;
Step S10, alternately repeat above-mentioned steps S8 and S9 totally 5 times.
Embodiment 2
As shown in Figure 2, the organic electroluminescence device of the present embodiment is layer structure, every layer is followed successively by: anode conducting substrate 201, hole injection layer 202, hole transmission layer 203, luminescent layer 204, electron transfer layer 205, electron injecting layer 206, cathode layer 207, and inorganic barrier layer 208 overlapping successively and inorganic barrier layer 209.
The structure of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/SiOxNy/Al 2o 3: F, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate.This implements the structure of described organic electroluminescence device and the similar of embodiment 1, and its difference is: Al 2o 3: F is the material of inorganic barrier layer 209.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
Step S1 ~ step S7, with embodiment 1, repeats no more.
Step S8 ~ step S10 is as follows:
The making of step S8, inorganic barrier layer 208: on cathode layer 207 prepared by above-mentioned steps S7, adopts HMDS(hmds), NH 3and O 2for raw material, under Ar atmosphere is enclosed, prepare the SiOxNy rete of thickness 190nm with plasma enhanced chemical vapor deposition method, i.e. described inorganic barrier layer 208; Wherein, HMDS flow is 14sccm, Ar flow is 80sccm, NH 3flow is 18sccm, O 2flow is 18sccm;
The making of step S9, inorganic barrier layer 209: on inorganic barrier layer 208 prepared by above-mentioned steps S8, adopt ald to prepare the inorganic barrier layer 209 of thickness 19nm, inorganic barrier layer 209 material is Al 2o 3: F, raw material adopts Al (CH respectively 2f) 3and steam, Al (CH 2f) 3be 20ms with steam injection length, the N of interval 10s between the two 2, Al (CH 2f) 3inject flow with steam and be 20sccm;
Step S10, alternately repeat above-mentioned steps S8 and S9 totally 4 times.
Embodiment 3
As shown in Figure 3, the organic electroluminescence device of the present embodiment is layer structure, every layer is followed successively by: anode conducting substrate 301, hole injection layer 302, hole transmission layer 303, luminescent layer 304, electron transfer layer 305, electron injecting layer 306, cathode layer 307, and inorganic barrier layer 308 overlapping successively and inorganic barrier layer 309.
The structure of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/SiOxNy/Ga 2o 3: F, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate.This implements the structure of described organic electroluminescence device and the similar of embodiment 1, and its difference is: Ga 2o 3: F is the material of inorganic barrier layer 309.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
Step S1 ~ step S7, with embodiment 1, repeats no more.
Step S8 ~ step S10 is as follows:
The making of step S8, inorganic barrier layer 208: on cathode layer 207 prepared by above-mentioned steps S7, adopts HMDS(hmds), NH 3and O 2for raw material, prepare the SiOxNy rete of thickness 180nm under Ar atmosphere is enclosed with plasma enhanced chemical vapor deposition method, i.e. described inorganic barrier layer 308, wherein, HMDS flow is 12sccm, Ar flow is 76sccm, NH 3flow is 15sccm, O 2flow is 16sccm;
The making of step S9, inorganic barrier layer 209: on inorganic barrier layer 308 prepared by above-mentioned steps S8, adopt ald to prepare the inorganic barrier layer 309 of thickness 18nm, inorganic barrier layer 309 material is Ga 2o 3: F, raw material adopts Ga (CH respectively 2f) 3and steam, Ga (CH 2f) 3be 10ms with steam injection length, the N of interval 5s between the two 2, Ga (CH 2f) 3inject flow with steam and be 10sccm;
Step S10, alternately repeat above-mentioned steps S8 and S9 totally 3 times.
Embodiment 4
As shown in Figure 4, the organic electroluminescence device of the present embodiment is layer structure, every layer is followed successively by: anode conducting substrate 401, hole injection layer 402, hole transmission layer 403, luminescent layer 404, electron transfer layer 405, electron injecting layer 406, cathode layer 407, and inorganic barrier layer 408 overlapping successively and inorganic barrier layer 409.
The structure of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/SiOxNy/In 2o 3: F, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate.This implements the structure of described organic electroluminescence device and the similar of embodiment 1, and its difference is: In 2o 3: F is the material of inorganic barrier layer 409.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
Step S1 ~ step S7, with embodiment 1, repeats no more.
Step S8 ~ step S10 is as follows:
The making of step S8, inorganic barrier layer 408: on cathode layer 407 prepared by above-mentioned steps S7, adopts HMDS(hmds), NH 3and O 2for raw material, prepare the SiOxNy rete of thickness 170nm under Ar atmosphere is enclosed with plasma enhanced chemical vapor deposition method, i.e. described inorganic barrier layer 408, wherein, HMDS flow is 6sccm, Ar flow is 70sccm, NH 3flow is 2sccm, O 2flow is 2sccm;
The making of step S9, inorganic barrier layer 409: on inorganic barrier layer 408 prepared by above-mentioned steps S8, adopt ald to prepare the inorganic barrier layer 409 of thickness 16nm, inorganic barrier layer 409 material is In 2o 3: F, raw material adopts In (CH respectively 2f) 3and steam, In 2o 3: F and steam injection length are 15ms, between the two the N of interval 7s 2, In (CH 2f) 3inject flow with steam and be 17sccm;
Step S10, alternately repeat above-mentioned steps S8 and S9 totally 3 times.
Embodiment 5
As shown in Figure 5, the organic electroluminescence device of the present embodiment is layer structure, every layer is followed successively by: anode conducting substrate 501, hole injection layer 502, hole transmission layer 503, luminescent layer 504, electron transfer layer 505, electron injecting layer 506, cathode layer 507, and inorganic barrier layer 508 overlapping successively and inorganic barrier layer 509.
The structure of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/SiOxNy/Tl 2o 3: F, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate.This implements the structure of described organic electroluminescence device and the similar of embodiment 1, and its difference is: Tl 2o 3: F is the material of inorganic barrier layer 509.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
Step S1 ~ step S7, with embodiment 1, repeats no more.
Step S8 ~ step S10 is as follows:
The making of step S8, inorganic barrier layer 508: on cathode layer 507 prepared by above-mentioned steps S7, adopts HMDS(hmds), NH 3and O 2for raw material, prepare the SiOxNy rete of thickness 150nm under Ar atmosphere is enclosed with plasma enhanced chemical vapor deposition method, i.e. described inorganic barrier layer 508, wherein, HMDS flow is 8sccm, Ar flow is 70sccm, NH 3flow is 5sccm, O 2flow is 5sccm;
The making of step S9, inorganic barrier layer 509: on inorganic barrier layer 508 prepared by above-mentioned steps S8, adopt ald to prepare the inorganic barrier layer 509 of thickness 15nm, inorganic barrier layer 509 material is Tl 2o 3: F, raw material adopts Tl (CH respectively 2f) 3and steam, Tl (CH 2f) 3be 15ms with steam injection length, the N of interval 7s between the two 2, Tl (CH 2f) 3inject flow with steam and be 11sccm;
Step S10, alternately repeat above-mentioned steps S8 and S9 totally 3 times.
Embodiment 6
As shown in Figure 6, the organic electroluminescence device of the present embodiment is layer structure, every layer is followed successively by: anode conducting substrate 601, hole injection layer 602, hole transmission layer 603, luminescent layer 604, electron transfer layer 605, electron injecting layer 606, cathode layer 607, and inorganic barrier layer 608 overlapping successively and inorganic barrier layer 609.
The structure of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/SiOxNy/Tl 2o 3: F, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate.This implements the structure of described organic electroluminescence device and the similar of embodiment 1, and its difference is: Tl 2o 3: F is the material of inorganic barrier layer 609.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
Step S1 ~ step S7, with embodiment 1, repeats no more.
Step S8 ~ step S10 is as follows:
The making of step S8, inorganic barrier layer 608: on cathode layer 607 prepared by above-mentioned steps S7, adopts HMDS(hmds), NH 3and O 2for raw material, prepare the SiOxNy rete of thickness 150nm under Ar atmosphere is enclosed with plasma enhanced chemical vapor deposition method, i.e. described inorganic barrier layer 608, wherein, HMDS flow is 7sccm, Ar flow is 77sccm, NH 3flow is 10sccm, O 2flow is 10sccm;
The making of step S9, inorganic barrier layer 609: on inorganic barrier layer 608 prepared by above-mentioned steps S8, adopt ald to prepare the inorganic barrier layer 609 of thickness 15nm, inorganic barrier layer 609 material is Tl 2o 3: F, raw material adopts Tl (CH respectively 2f) 3and steam, Tl (CH 2f) 3be 10ms with steam injection length, the N of interval 10s between the two 2, Tl (CH 2f) 3inject flow with steam and be 15sccm;
Step S10, alternately repeat above-mentioned steps S8 and S9 totally 3 times.
Carried out Performance Detection to the organic electroluminescence prepared in each embodiment below, test result is as shown in table 1.
Table 1
From table 1, data can be seen, the organic electroluminescence in each embodiment, water oxygen resistant ability reaches 3.12 × 10 -6above, the OLED made by it, the life-span reaches average more than 14000 hours.Inorganic barrier layer of the present invention and inorganic barrier layer effectively improve the water proofing property of organic electroluminescence device, corrosion resistance and stress durability.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection range required by claims.

Claims (10)

1. an organic electroluminescence device, this organic electroluminescence device is layer structure, and this layer structure comprises successively: alternately laminated inorganic barrier layer and inorganic barrier layer on anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer and described cathode layer; It is characterized in that,
The material of described inorganic barrier layer is silicon nitride compound film;
The material of described inorganic barrier layer is B 2o 3: F, Al 2o 3: F, Ga 2o 3: F, In 2o 3: F or Tl 2o 3: F.
2. organic electroluminescence device according to claim 1, is characterized in that, described silicon nitride compound film uses hmds, NH 3and O 2also obtained by plasma reinforced chemical vapour deposition method as raw material.
3. organic electroluminescence device according to claim 1, is characterized in that, described inorganic barrier layer is that use fluoroform substrate and steam are obtained as raw material and by Atomic layer deposition method, and described fluoroform substrate is B (CH 2f) 3, Al (CH 2f) 3, Ga (CH 2f) 3, In (CH 2f) 3or Tl (CH 2f) 3.
4. organic electroluminescence device according to claim 1, is characterized in that, described inorganic barrier layer and the alternately laminated number of plies of described inorganic barrier layer are four, five or six.
5. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described inorganic barrier layer is 150nm ~ 200nm; The thickness of described inorganic barrier layer is 15nm ~ 20nm.
6. organic electroluminescence device according to claim 1, is characterized in that,
The material of described hole injection layer is by MoO 3and the mixture that N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines adulterates mutually, wherein, MoO 3be 0.25:1 with the percentage by weight of N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines;
The material of described hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine;
The material of described luminescent layer is for close iridium and 1 by three (2-phenylpyridines), 3, the mixture that 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene adulterates mutually, wherein, three (2-phenylpyridines) close iridium and 1, the percentage by weight of 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene is 0.05:1;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline;
The material of described electron injecting layer is by CsN 3with the mixture that 4,7-diphenyl-1,10-phenanthroline adulterates mutually, wherein, CsN 3be 0.25:1 with the percentage by weight of 4,7-diphenyl-1,10-phenanthroline;
The material of described cathode layer is metallic aluminium.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
A () adopts vacuum deposition method to form hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer successively on the anode conducting substrate cleaned up;
B (), on described cathode layer, first uses hmds, NH 3and O 2under Ar atmosphere is enclosed, inorganic barrier layer is obtained by plasma reinforced chemical vapour deposition method as raw material; Then on described inorganic barrier layer, use fluoroform substrate and steam as raw material and obtain inorganic barrier layer by Atomic layer deposition method; Finally, alternately laminatedly successively inorganic barrier layer and inorganic barrier layer is prepared; Wherein:
The material of described inorganic barrier layer is silicon nitride compound film;
The material of described inorganic barrier layer is B 2o 3: F, Al 2o 3: F, Ga 2o 3: F, In 2o 3: F or Tl 2o 3: F; Described fluoroform substrate is B (CH 2f) 3, Al (CH 2f) 3, Ga (CH 2f) 3, In (CH 2f) 3or Tl (CH 2f) 3.
8. preparation method according to claim 7, is characterized in that, in described step (b), when adopting plasma reinforced chemical vapour deposition method to prepare described inorganic barrier layer, described hmds flow 6 ~ 14sccm, described Ar flow is 70 ~ 80sccm, described NH 3flow 2 ~ 18sccm, described O 2flow 2 ~ 18sccm, the thickness of described inorganic barrier layer is 150nm ~ 200nm.
9. preparation method according to claim 7, is characterized in that, in described step (b), adopts Atomic layer deposition method when preparing described inorganic barrier layer, the N of interval 5 ~ 10s between the two when injecting described fluoroform substrate and described steam 2, the injection length of described fluoroform substrate and described steam is 10 ~ 20ms, and flow is 10 ~ 20sccm, the thickness 15 ~ 20nm of described inorganic barrier layer.
10. preparation method according to claim 7, is characterized in that, in described step (b), the number of times of described inorganic barrier layer and the alternately laminated preparation of described inorganic barrier layer is four, five or six.
CN201310562053.8A 2013-11-12 2013-11-12 Organic light emitting device and manufacturing method thereof Pending CN104638184A (en)

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