CN104638174A - 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
CN104638174A
CN104638174A CN201310561620.8A CN201310561620A CN104638174A CN 104638174 A CN104638174 A CN 104638174A CN 201310561620 A CN201310561620 A CN 201310561620A CN 104638174 A CN104638174 A CN 104638174A
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layer
barrier layer
inorganic barrier
deposition method
organic electroluminescence
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周明杰
钟铁涛
王平
黄辉
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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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Priority to CN201310561620.8A priority Critical patent/CN104638174A/en
Publication of CN104638174A publication Critical patent/CN104638174A/en
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to an organic light emitting device and a manufacturing method thereof. The organic light emitting device is of stratified structure. 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, a barrier layer is arranged on the cathode layer and is composed of an organic barrier layer and an inorganic barrier layer which are stacked alternatively. The organic barrier layer is made of hydrogenated carbon and nitrogen compound, and the inorganic barrier layer is made of mixture formed of oxyacid salt, carbide and sulfide. The organic barrier layer and the inorganic barrier layer are alternatively stacked, 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 barrier layer and the inorganic barrier layer 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 tin indium oxide (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.
OLED have active illuminating, luminous efficiency high, low in energy consumption, light, thin, without advantages such as angle limitations, thought by insider to be most likely at the device of new generation following illumination and display device market occupying dominance.As a brand-new illumination and Display Technique, the ten years development in the past of OLED technology is swift and violent, achieves huge achievement.More and more throw light on due to the whole world and show producer and drop into research and development one after another, promoted the industrialization process of OLED greatly.
Flexible product is the development trend of organic electroluminescence device, but the current ubiquity life-span is short, and the quality of encapsulation directly affects the life-span of device.For reaching the object of encapsulation, organic electroluminescence device sets up the barrier layer with passivation protection.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.But in the manufacturing process making flexible organic light emitting apparatus (being also called bendable organic light emitting apparatus), 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 on the barrier layer of flexible organic light emitting apparatus 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, this layer structure comprises successively: anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, 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; Wherein:
The material of described inorganic barrier layer is rete hydrogenated carbon nitrogen compound;
The material of described inorganic barrier layer is the mixture be made up of oxygen hydrochlorate, carbide and sulfide; Described oxygen hydrochlorate is MgAl 2o 4, Bi 2ti 4o 11, CrNiO 4, CoCr 2o 4, Fe 2luO 4or Y 3al 5o 12; Described carbide is SiC, WC, TaC, BC, TiC or HfC; Described sulfide is CdS, PbS, FeS 2, CuS, ZnS or NiS; Described carbide in the weight percent content of described oxygen hydrochlorate be 10 ~ 30wt%; Described sulfide in the weight percent content of described oxygen hydrochlorate be 10 ~ 30wt%.
Further, described rete hydrogenated carbon nitrogen compound uses methane and nitrogen as raw material and obtained by plasma reinforced chemical vapour deposition method.
Further, the number of plies on described barrier layer is four, five or six.
Further, the thickness of described inorganic barrier layer is 400nm ~ 600nm; The thickness of described inorganic barrier layer is 100nm ~ 200nm.
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 (can be abbreviated as NPB) adulterates mutually, wherein, MoO 3be 0.3:1 ~ 0.4:1 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 (can be abbreviated as TCTA);
The material of described luminescent layer is for close iridium (can be abbreviated as Ir (ppy) 3) and 1 by three (2-phenylpyridines), 3, the mixture that 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (can be abbreviated as TPBI) 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 ~ 0.08:1;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (can be abbreviated as Bphen);
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 0.3:1 ~ 0.4:1 with the percentage by weight of 4,7-diphenyl-1,10-phenanthroline;
The material of described cathode layer is metallic aluminium (Al).
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 () is on described cathode layer, plasma reinforced chemical vapour deposition method is first adopted to prepare inorganic barrier layer, then on described inorganic barrier layer, adopt magnetically controlled sputter method to prepare inorganic barrier layer, thus be combined into barrier layer by described inorganic barrier layer and 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 rete hydrogenated carbon nitrogen compound, and described rete hydrogenated carbon nitrogen compound uses methane and nitrogen as raw material and obtained by described plasma reinforced chemical vapour deposition method;
The material of described inorganic barrier layer is the mixture be made up of oxygen hydrochlorate, carbide and sulfide; Described oxygen hydrochlorate is MgAl 2o 4, Bi 2ti 4o 11, CrNiO 4, CoCr 2o 4, Fe 2luO 4or Y 3al 5o 12; Described carbide is SiC, WC, TaC, BC, TiC or HfC; Described sulfide is CdS, PbS, FeS 2, CuS, ZnS or NiS; Described carbide in the weight percent content of described oxygen hydrochlorate be 10 ~ 30wt%; Described sulfide in the weight percent content of described oxygen hydrochlorate be 10 ~ 30wt%.
Further, in described step (a), when adopting vacuum deposition method to prepare described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, vacuum degree is 3 × 10 -5pa ~ 3 × 10 -3pa, evaporation rate is coating film thickness is 10nm ~ 30nm; When adopting vacuum deposition method to prepare described cathode layer, vacuum degree is 3 × 10 -5pa ~ 3 × 10 -3pa, evaporation rate is coating film thickness is 100nm ~ 150nm.
Further, in described step (b), when adopting plasma reinforced chemical vapour deposition method to prepare described inorganic barrier layer, the flow of described methane is 5 ~ 15sccm, the flow of described nitrogen is 5 ~ 15sccm, and operating pressure is 10Pa ~ 80Pa, and radio-frequency power is 0.1W/cm 2~ 0.5W/cm 2, coating film thickness is 400nm ~ 600nm.
Further, in described step (b), when adopting magnetically controlled sputter method to prepare described inorganic barrier layer, vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, coating film thickness is 100nm ~ 200nm.
Further, in described step (b), the number of plies on described barrier layer is four, five or six.
Barrier layer of the present invention is 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 is poor and inorganic barrier layer flexibility is poor and produce.
In addition, inorganic barrier layer of the present invention contains rete hydrogenated carbon nitrogen compound (CNx:H), this rete hydrogenated carbon nitrogen compound (CNx:H) has some premium properties following: first, inorganic barrier layer causes increasing relative to the chemical bond force of inorganic barrier layer due to the nitrogen-atoms that there is hydrogenated carbon nitrogen compound, thus causes the adhesiveness on barrier layer of the present invention to increase; The second, during the diaphragm of rete hydrogenated carbon nitrogen compound (CNx:H) as organic electroluminescence device, there is excellent flexibility and stress.The stress characteristics of rete hydrogenated carbon nitrogen compound (CNx:H) (x) can be controlled by the nitrogen quantity be incorporated in rete, to meet the requirement of different ambient stress; 3rd, rete hydrogenated carbon nitrogen compound (CNx:H) has the compactness of film, therefore, has very high screening ability to moisture and oxygen.The rete hydrogenated carbon nitrogen compound (CNx:H) of inorganic barrier layer of the present invention forms laminar structure, can improve the shielding to moisture and oxygen further; 4th, the rete hydrogenated carbon nitrogen compound (CNx:H) of inorganic barrier layer of the present invention is that using plasma strengthens chemical vapour deposition (CVD) preparation.Plasma enhanced chemical vapor deposition contributes to rete hydrogenated carbon nitrogen compound and form film in difform substrate, thus is conducive to the flexibility of rete hydrogenated carbon nitrogen compound.In addition, the method can at room temperature use, and therefore can have the application of wide region.In sum, rete hydrogenated carbon nitrogen compound (CNx:H) of the present invention effectively improves the water proofing property of inorganic barrier layer, corrosion resistance and stress durability.
The inorganic barrier layer that the present invention is alternately stacked and inorganic barrier layer, compactness is high, and water oxygen resistant ability is strong.And the preparation method of inorganic barrier layer of the present invention and inorganic barrier layer 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.
Embodiment 1
As shown in Figure 1, the organic electroluminescence device of the present embodiment is layer structure, and 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 alternately stacked inorganic barrier layer 108 and inorganic barrier layer 109.Described inorganic barrier layer 108 and described inorganic barrier layer 109 are combined into described barrier layer, described alternately stacked number of times is repeatedly, described barrier layer is multilayer, 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/CNx:H/MgAl 2o 4: SiC:CdS, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate; ITO is the material of anode conducting substrate 101; MoO 3: NPB is the material of hole injection layer 102, wherein MoO 3be 0.3:1 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 0.3:1 with the doping weight ratio of Bphen; Al is the material of cathode layer 107; CNx:H is the material of inorganic barrier layer 108; MgAl 2o 4: SiC:CdS is the material of inorganic barrier layer, wherein MgAl 2o 4, SiC and CdS doping weight ratio be 100:20:15.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
The pre-treatment of step (one) anode conducting substrate 101: using ito glass as anode conducting substrate 101, first anode conducting substrate 101 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; Anode conducting substrate 101 after cleaning also needs the process carrying out surface active, and to increase the oxygen content of anode conducting substrate 101, improve the work function of conductive layer surface, the thickness of gained anode conducting substrate 101 is 100nm.
The preparation of step (two) hole injection layer 102: on anode conducting substrate 101 prepared by above-mentioned steps (), 30wt%MoO 3penetrate in NPB, adopt vacuum deposition method the MoO of abovementioned dopant 3be the luminescent layer 102 that 10nm is thick with NPB evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (three) hole transmission layer 103: on hole injection layer 102 prepared by above-mentioned steps (two), use TCTA as the material of hole transmission layer 103, adopt vacuum deposition method to be the hole transmission layer 103 that 30nm is thick TCTA evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (four) luminescent layer 104: on hole transmission layer 103 prepared by above-mentioned steps (three), 5wt% (Ir (ppy) 3) penetrate in TPBI, adopt vacuum deposition method the (Ir (ppy) of abovementioned dopant 3) with TPBI evaporation be the luminescent layer 104 that 20nm is thick, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (five) electron transfer layer 105: on luminescent layer 104 prepared by above-mentioned steps (four), use Bphen as the material of electron transfer layer 105, adopt vacuum deposition method to be the electron transfer layer 105 that 10nm is thick Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (six) electron injecting layer 106: on electron transfer layer 105 prepared by above-mentioned steps (five), 30wt%CsN 3penetrate in Bphen, adopt vacuum deposition method the CsN of abovementioned dopant 3be the electron injecting layer 106 that 20nm is thick with Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (seven) cathode layer 107: on electron injecting layer 106 prepared by above-mentioned steps (six), use Al as the material of cathode layer 107, adopt vacuum deposition method to be the cathode layer 107 that 100nm is thick Al evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (eight) inorganic barrier layer 108: on cathode layer 107 prepared by above-mentioned steps (seven), adopts plasma reinforced chemical vapour deposition method to prepare rete hydrogenated carbon nitrogen compound CNx:H, thus obtains inorganic barrier layer 108.The technological parameter of plasma reinforced chemical vapour deposition method is set to: working gas is the CH of 10sccm 4with the N of 8sccm 2, operating pressure is 50Pa, and radio-frequency power is 0.2W/cm 2, thickness of coating is 600nm.
The preparation of step (nine) inorganic barrier layer 109: on inorganic barrier layer 108 prepared by above-mentioned steps (eight), by MgAl 2o 4, SiC with CdS phase adulterates, SiC accounts for MgAl 2o 4ratio be that 20wt%, CdS account for MgAl 2o 4ratio be 15wt%, adopt magnetically controlled sputter method doping MgAl 2o 4, SiC and CdS be prepared as the thick inorganic barrier layer of 170nm 109.The technological parameter of magnetically controlled sputter method is set to: 1 × 10 -5the vacuum degree of Pa.
Step (ten) alternately repeats above-mentioned steps (eight) and (nine) totally 5 times.
Embodiment 2
As shown in Figure 2, the organic electroluminescence device of the present embodiment is layer structure, and 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 alternately stacked inorganic barrier layer 208 and inorganic barrier layer 209.Described inorganic barrier layer 208 and described inorganic barrier layer 209 are combined into described barrier layer, described alternately stacked number of times is repeatedly, described barrier layer is multilayer, described inorganic barrier layer 208 and described inorganic barrier layer 209 are also multilayer, it should be noted that: Fig. 2 only draws alternately stacked one deck inorganic barrier layer 208 and one deck inorganic barrier layer 209, all the other alternately stacked inorganic barrier layer 208 and inorganic barrier layer 209 make omission in order to the succinct of drawing.
The structural formula of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/CNx:H/Bi 2ti 4o 11: WC:PbS, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate; ITO is the material of anode conducting substrate 201; MoO 3: NPB is the material of hole injection layer 202, wherein MoO 3be 0.3:1 with the doping weight ratio of NPB; TCTA is the material of hole transmission layer 203; TPBI:Ir (ppy) 3for the material of luminescent layer 204, wherein TPBI and Ir (ppy) 3doping weight ratio be 1:0.05; Bphen is the material of electron transfer layer 205; CsN 3: Bphen is the material of electron injecting layer 206, wherein CsN 3be 0.3:1 with the doping weight ratio of Bphen; Al is the material of cathode layer 207; CNx:H is the material of inorganic barrier layer 208; Bi 2ti 4o 11: WC:PbS is the material of inorganic barrier layer, wherein Bi 2ti 4o 11, WC and PbS doping weight ratio be 100:30:10.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
The pre-treatment of step (one) anode conducting substrate 201: using ito glass as anode conducting substrate 201, first anode conducting substrate 201 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; Anode conducting substrate 201 after cleaning also needs the process carrying out surface active, and to increase the oxygen content of anode conducting substrate 201, improve the work function of conductive layer surface, the thickness of gained anode conducting substrate 201 is 100nm.
The preparation of step (two) hole injection layer 202: on anode conducting substrate 201 prepared by above-mentioned steps (), 30wt%MoO 3be incorporated in NPB, adopt vacuum deposition method the MoO of abovementioned dopant 3be the luminescent layer 202 that 10nm is thick with NPB evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (three) hole transmission layer 203: on hole injection layer 202 prepared by above-mentioned steps (two), use TCTA as the material of hole transmission layer 203, adopt vacuum deposition method to be the hole transmission layer 203 that 30nm is thick TCTA evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (four) luminescent layer 204: on hole transmission layer 203 prepared by above-mentioned steps (three), 5wt% (Ir (ppy) 3) be incorporated in TPBI, adopt vacuum deposition method the (Ir (ppy) of abovementioned dopant 3) with TPBI evaporation be the luminescent layer 204 that 20nm is thick, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (five) electron transfer layer 205: on luminescent layer 204 prepared by above-mentioned steps (four), use Bphen as the material of electron transfer layer 205, adopt vacuum deposition method to be the electron transfer layer 205 that 10nm is thick Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (six) electron injecting layer 206: on electron transfer layer 205 prepared by above-mentioned steps (five), 30wt%CsN 3be incorporated in Bphen, adopt vacuum deposition method the CsN of abovementioned dopant 3be the electron injecting layer 206 that 20nm is thick with Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (seven) cathode layer 207: on electron injecting layer 206 prepared by above-mentioned steps (six), use Al as the material of cathode layer 207, adopt vacuum deposition method to be the cathode layer 207 that 100nm is thick Al evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (eight) inorganic barrier layer 208: on cathode layer 207 prepared by above-mentioned steps (seven), adopts plasma reinforced chemical vapour deposition method to prepare rete hydrogenated carbon nitrogen compound CNx:H, thus obtains inorganic barrier layer 208.The technological parameter of plasma reinforced chemical vapour deposition method is set to: working gas is the CH of 12sccm 4with the N of 10sccm 2, operating pressure is 20Pa, and radio-frequency power is 0.3W/cm 2, thickness of coating is 550nm.
The preparation of step (nine) inorganic barrier layer 209: on inorganic barrier layer 208 prepared by above-mentioned steps (eight), by Bi 2ti 4o 11, WC with PbS phase adulterates, WC accounts for Bi 2ti 4o 11ratio be that 30wt%, PbS account for Bi 2ti 4o 11ratio be 10wt%, adopt magnetically controlled sputter method doping Bi 2ti 4o 11, WC and PbS be prepared as the thick inorganic barrier layer of 200nm 209.The technological parameter of magnetically controlled sputter method is set to: 1 × 10 -5the vacuum degree of Pa.
Step (ten) alternately repeats above-mentioned steps (eight) and (nine) totally 4 times.
Embodiment 3
As shown in Figure 3, the organic electroluminescence device of the present embodiment is layer structure, and 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 alternately stacked inorganic barrier layer 308 and inorganic barrier layer 309.Described inorganic barrier layer 308 and described inorganic barrier layer 309 are combined into described barrier layer, described alternately stacked number of times is repeatedly, described barrier layer is multilayer, described inorganic barrier layer 308 and described inorganic barrier layer 309 are also multilayer, it should be noted that: Fig. 3 only draws alternately stacked one deck inorganic barrier layer 308 and one deck inorganic barrier layer 309, all the other alternately stacked inorganic barrier layer 308 and inorganic barrier layer 309 make omission in order to the succinct of drawing.
The structural formula of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/CNx:H/CrNiO 4: TaC:FeS 2, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate; ITO is the material of anode conducting substrate 301; MoO 3: NPB is the material of hole injection layer 302, wherein MoO 3be 0.4:1 with the doping weight ratio of NPB; TCTA is the material of hole transmission layer 303; TPBI:Ir (ppy) 3for the material of luminescent layer 304, wherein TPBI and Ir (ppy) 3doping weight ratio be 1:0.08; Bphen is the material of electron transfer layer 305; CsN 3: Bphen is the material of electron injecting layer 306, wherein CsN 3be 0.4:1 with the doping weight ratio of Bphen; Al is the material of cathode layer 307; CNx:H is the material of inorganic barrier layer 308; CrNiO 4: TaC:FeS 2for the material of inorganic barrier layer, wherein CrNiO 4, TaC and FeS 2doping weight ratio be 100:10:30.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
The pre-treatment of step (one) anode conducting substrate 301: using ito glass as anode conducting substrate 301, first anode conducting substrate 301 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; Anode conducting substrate 301 after cleaning also needs the process carrying out surface active, and to increase the oxygen content of anode conducting substrate 301, improve the work function of conductive layer surface, the thickness of gained anode conducting substrate 101 is 100nm.
The preparation of step (two) hole injection layer 302: on anode conducting substrate 301 prepared by above-mentioned steps (), 40wt%MoO 3be incorporated in NPB, adopt vacuum deposition method the MoO of abovementioned dopant 3be the luminescent layer 302 that 10nm is thick with NPB evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -4the vacuum degree of Pa, evaporation rate.
The preparation of step (three) hole transmission layer 303: on hole injection layer 302 prepared by above-mentioned steps (two), use TCTA as the material of hole transmission layer 303, adopt vacuum deposition method to be the hole transmission layer 303 that 30nm is thick TCTA evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -4the vacuum degree of Pa, evaporation rate.
The preparation of step (four) luminescent layer 304: on hole transmission layer 303 prepared by above-mentioned steps (three), 8wt% (Ir (ppy) 3) be incorporated in TPBI, adopt vacuum deposition method the (Ir (ppy) of abovementioned dopant 3) with TPBI evaporation be the luminescent layer 304 that 20nm is thick, the technological parameter of vacuum deposition method is set to: 3 × 10 -4the vacuum degree of Pa, evaporation rate.
The preparation of step (five) electron transfer layer 305: on luminescent layer 304 prepared by above-mentioned steps (four), use Bphen as the material of electron transfer layer 305, adopt vacuum deposition method to be the electron transfer layer 305 that 10nm is thick Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -4the vacuum degree of Pa, evaporation rate.
The preparation of step (six) electron injecting layer 306: on electron transfer layer 105 prepared by above-mentioned steps (five), 40wt%CsN 3be incorporated in Bphen, adopt vacuum deposition method the CsN of abovementioned dopant 3be the electron injecting layer 306 that 20nm is thick with Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -4the vacuum degree of Pa, evaporation rate.
The preparation of step (seven) cathode layer 307: on electron injecting layer 306 prepared by above-mentioned steps (six), use Al as the material of cathode layer 307, adopt vacuum deposition method to be the cathode layer 307 that 150nm is thick Al evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -4the vacuum degree of Pa, evaporation rate.
The preparation of step (eight) inorganic barrier layer 308: on cathode layer 307 prepared by above-mentioned steps (seven), adopts plasma reinforced chemical vapour deposition method to prepare rete hydrogenated carbon nitrogen compound CNx:H, thus obtains inorganic barrier layer 308.The technological parameter of plasma reinforced chemical vapour deposition method is set to: working gas is the CH of 8sccm 4with the N of 10sccm 2, operating pressure is 60Pa, and radio-frequency power is 0.4W/cm 2, thickness of coating is 450nm.
The preparation of step (nine) inorganic barrier layer 309: on inorganic barrier layer 308 prepared by above-mentioned steps (eight), by CrNiO 4, TaC and FeS 2adulterate mutually, TaC accounts for CrNiO 4ratio be 10wt%, FeS 2account for CrNiO 4ratio be 30wt%, adopt magnetically controlled sputter method doping CrNiO 4, TaC and FeS 2be prepared as the thick inorganic barrier layer of 100nm 309.The technological parameter of magnetically controlled sputter method is set to: 1 × 10 -5the vacuum degree of Pa.
Step (ten) alternately repeats above-mentioned steps (eight) and (nine) totally 3 times.
Embodiment 4
As shown in Figure 4, the organic electroluminescence device of the present embodiment is layer structure, and 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 alternately stacked inorganic barrier layer 408 and inorganic barrier layer 409.Described inorganic barrier layer 408 and described inorganic barrier layer 409 are combined into described barrier layer, described alternately stacked number of times is repeatedly, described barrier layer is multilayer, described inorganic barrier layer 408 and described inorganic barrier layer 409 are also multilayer, it should be noted that: Fig. 4 only draws alternately stacked one deck inorganic barrier layer 408 and one deck inorganic barrier layer 409, all the other alternately stacked inorganic barrier layer 408 and inorganic barrier layer 409 make omission in order to the succinct of drawing.
The structural formula of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/CNx:H/CoCr 2o 4: BC:CuS, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate; ITO is the material of anode conducting substrate 401; MoO 3: NPB is the material of hole injection layer 402, wherein MoO 3be 0.35:1 with the doping weight ratio of NPB; TCTA is the material of hole transmission layer 403; TPBI:Ir (ppy) 3for the material of luminescent layer 404, wherein TPBI and Ir (ppy) 3doping weight ratio be 1:0.07; Bphen is the material of electron transfer layer 405; CsN 3: Bphen is the material of electron injecting layer 406, wherein CsN 3be 0.35:1 with the doping weight ratio of Bphen; Al is the material of cathode layer 407; CNx:H is the material of inorganic barrier layer 408; CoCr 2o 4: BC:CuS is the material of inorganic barrier layer, wherein CoCr 2o 4, BC and CuS doping weight ratio be 100:20:20.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
The pre-treatment of step (one) anode conducting substrate 401: using ito glass as anode conducting substrate 401, first anode conducting substrate 401 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; Anode conducting substrate 401 after cleaning also needs the process carrying out surface active, and to increase the oxygen content of anode conducting substrate 401, improve the work function of conductive layer surface, the thickness of gained anode conducting substrate 401 is 100nm.
The preparation of step (two) hole injection layer 402: on anode conducting substrate 401 prepared by above-mentioned steps (), 35wt%MoO 3be incorporated in NPB, adopt vacuum deposition method the MoO of abovementioned dopant 3be the luminescent layer 402 that 10nm is thick with NPB evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -3the vacuum degree of Pa, evaporation rate.
The preparation of step (three) hole transmission layer 403: on hole injection layer 402 prepared by above-mentioned steps (two), use TCTA as the material of hole transmission layer 403, adopt vacuum deposition method to be the hole transmission layer 403 that 30nm is thick TCTA evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -3the vacuum degree of Pa, evaporation rate.
The preparation of step (four) luminescent layer 404: on hole transmission layer 403 prepared by above-mentioned steps (three), 7wt% (Ir (ppy) 3) be incorporated in TPBI, adopt vacuum deposition method the (Ir (ppy) of abovementioned dopant 3) with TPBI evaporation be the luminescent layer 404 that 20nm is thick, the technological parameter of vacuum deposition method is set to: 3 × 10 -3the vacuum degree of Pa, evaporation rate.
The preparation of step (five) electron transfer layer 405: on luminescent layer 404 prepared by above-mentioned steps (four), use Bphen as the material of electron transfer layer 405, adopt vacuum deposition method to be the electron transfer layer 405 that 10nm is thick Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -3the vacuum degree of Pa, evaporation rate.
The preparation of step (six) electron injecting layer 406: on electron transfer layer 405 prepared by above-mentioned steps (five), 35wt%CsN 3be incorporated in Bphen, adopt vacuum deposition method the CsN of abovementioned dopant 3be the electron injecting layer 406 that 20nm is thick with Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -3the vacuum degree of Pa, evaporation rate.
The preparation of step (seven) cathode layer 407: on electron injecting layer 406 prepared by above-mentioned steps (six), use Al as the material of cathode layer 407, adopt vacuum deposition method to be the cathode layer 407 that 120nm is thick Al evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -3the vacuum degree of Pa, evaporation rate.
The preparation of step (eight) inorganic barrier layer 408: on cathode layer 407 prepared by above-mentioned steps (seven), adopts plasma reinforced chemical vapour deposition method to prepare rete hydrogenated carbon nitrogen compound CNx:H, thus obtains inorganic barrier layer 408.The technological parameter of plasma reinforced chemical vapour deposition method is set to: working gas is the CH of 15sccm 4with the N of 15sccm 2, operating pressure is 80Pa, and radio-frequency power is 0.5W/cm 2, thickness of coating is 500nm.
The preparation of step (nine) inorganic barrier layer 409: on inorganic barrier layer 408 prepared by above-mentioned steps (eight), by CoCr 2o 4, BC with CuS phase adulterates, BC accounts for CoCr 2o 4ratio be that 20wt%, CuS account for CoCr 2o 4ratio be 20wt%, adopt magnetically controlled sputter method doping CoCr 2o 4, BC and CuS be prepared as the thick inorganic barrier layer of 170nm 409.The technological parameter of magnetically controlled sputter method is set to: 1 × 10 -5the vacuum degree of Pa.
Step (ten) alternately repeats above-mentioned steps (eight) and (nine) totally 3 times.
Embodiment 5
As shown in Figure 5, the organic electroluminescence device of the present embodiment is layer structure, and 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 alternately stacked inorganic barrier layer 508 and inorganic barrier layer 509.Described inorganic barrier layer 508 and described inorganic barrier layer 509 are combined into described barrier layer, described alternately stacked number of times is repeatedly, described barrier layer is multilayer, described inorganic barrier layer 508 and described inorganic barrier layer 509 are also multilayer, it should be noted that: Fig. 5 only draws alternately stacked one deck inorganic barrier layer 508 and one deck inorganic barrier layer 509, all the other alternately stacked inorganic barrier layer 508 and inorganic barrier layer 509 make omission in order to the succinct of drawing.
The structural formula of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/CNx:H/Fe 2luO 4: TIC:ZnS, wherein: brace "/" represents layer structure, colon ": " represent and mutually adulterate; ITO is the material of anode conducting substrate 501; MoO 3: NPB is the material of hole injection layer 502, wherein MoO 3be 0.3:1 with the doping weight ratio of NPB; TCTA is the material of hole transmission layer 503; TPBI:Ir (ppy) 3for the material of luminescent layer 504, wherein TPBI and Ir (ppy) 3doping weight ratio be 1:0.05; Bphen is the material of electron transfer layer 505; CsN 3: Bphen is the material of electron injecting layer 506, wherein CsN 3be 0.3:1 with the doping weight ratio of Bphen; Al is the material of cathode layer 507; CNx:H is the material of inorganic barrier layer 508; Fe 2luO 4: TIC:ZnS is the material of inorganic barrier layer, wherein Fe 2luO 4, TIC and ZnS doping weight ratio be 100:20:18.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
The pre-treatment of step (one) anode conducting substrate 501: using ito glass as anode conducting substrate 501, first anode conducting substrate 501 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; Anode conducting substrate 501 after cleaning also needs the process carrying out surface active, and to increase the oxygen content of anode conducting substrate 501, improve the work function of conductive layer surface, the thickness of gained anode conducting substrate 501 is 100nm.
The preparation of step (two) hole injection layer 502: on anode conducting substrate 101 prepared by above-mentioned steps (), 30wt%MoO 3be incorporated in NPB, adopt vacuum deposition method the MoO of abovementioned dopant 3be the luminescent layer 502 that 10nm is thick with NPB evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (three) hole transmission layer 503: on hole injection layer 502 prepared by above-mentioned steps (two), use TCTA as the material of hole transmission layer 503, adopt vacuum deposition method to be the hole transmission layer 503 that 30nm is thick TCTA evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (four) luminescent layer 504: on hole transmission layer 503 prepared by above-mentioned steps (three), 5wt% (Ir (ppy) 3) be incorporated in TPBI, adopt vacuum deposition method the (Ir (ppy) of abovementioned dopant 3) with TPBI evaporation be the luminescent layer 504 that 20nm is thick, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (five) electron transfer layer 505: on luminescent layer 504 prepared by above-mentioned steps (four), use Bphen as the material of electron transfer layer 505, adopt vacuum deposition method to be the electron transfer layer 505 that 10nm is thick Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (six) electron injecting layer 506: on electron transfer layer 105 prepared by above-mentioned steps (five), 30wt%CsN 3be incorporated in Bphen, adopt vacuum deposition method the CsN of abovementioned dopant 3be the electron injecting layer 506 that 20nm is thick with Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (seven) cathode layer 507: on electron injecting layer 506 prepared by above-mentioned steps (six), use Al as the material of cathode layer 507, adopt vacuum deposition method to be the cathode layer 507 that 100nm is thick Al evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (eight) inorganic barrier layer 508: on cathode layer 507 prepared by above-mentioned steps (seven), adopts plasma reinforced chemical vapour deposition method to prepare rete hydrogenated carbon nitrogen compound CNx:H, thus obtains inorganic barrier layer 508.The technological parameter of plasma reinforced chemical vapour deposition method is set to: working gas is the CH of 5sccm 4with the N of 5sccm 2, operating pressure is 10Pa, and radio-frequency power is 0.1W/cm 2, thickness of coating is 450nm.
The preparation of step (nine) inorganic barrier layer 509: on inorganic barrier layer 508 prepared by above-mentioned steps (eight), by Fe 2luO 4, TIC with ZnS phase adulterates, TIC accounts for Fe 2luO 4ratio be that 20wt%, ZnS account for Fe 2luO 4ratio be 18wt%, adopt magnetically controlled sputter method doping Fe 2luO 4, TIC and ZnS be prepared as the thick inorganic barrier layer of 160nm 509.The technological parameter of magnetically controlled sputter method is set to: 5 × 10 -5the vacuum degree of Pa.
Step (ten) alternately repeats above-mentioned steps (eight) and (nine) totally 3 times.
Embodiment 6
As shown in Figure 6, the organic electroluminescence device of the present embodiment is layer structure, and 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 alternately stacked inorganic barrier layer 608 and inorganic barrier layer 609.Described inorganic barrier layer 608 and described inorganic barrier layer 609 are combined into described barrier layer, described alternately stacked number of times is repeatedly, described barrier layer is multilayer, described inorganic barrier layer 608 and described inorganic barrier layer 609 are also multilayer, it should be noted that: Fig. 6 only draws alternately stacked one deck inorganic barrier layer 608 and one deck inorganic barrier layer 609, all the other alternately stacked inorganic barrier layer 608 and inorganic barrier layer 609 make omission in order to the succinct of drawing.
The structural formula of described organic electroluminescence device is ITO/MoO 3: NPB/TCTA/TPBI:Ir (ppy) 3/ Bphen/CsN 3: Bphen/Al/CNx:H/Y 3al 5o 12: HFc:NiS, wherein: brace "/" represents layer structure, colon ": " expression is adulterated mutually; ITO is the material of anode conducting substrate 601; MoO 3: NPB is the material of hole injection layer 602, wherein MoO 3be 0.3:1 with the doping weight ratio of NPB; TCTA is the material of hole transmission layer 603; TPBI:Ir (ppy) 3for the material of luminescent layer 604, wherein TPBI and Ir (ppy) 3doping weight ratio be 1:0.05; Bphen is the material of electron transfer layer 605; CsN 3: Bphen is the material of electron injecting layer 606, wherein CsN 3be 0.3:1 with the doping weight ratio of Bphen; Al is the material of cathode layer 607; CNx:H is the material of inorganic barrier layer 608; Y 3al 5o 12: Hfc:NiS is the material of inorganic barrier layer, wherein Y 3al 5o 12, HFc and NiS doping weight ratio be 100:20:12.
Above-mentioned organic electroluminescence device is prepared according to the following steps:
The pre-treatment of step (one) anode conducting substrate 101: using ito glass as anode conducting substrate 601, first anode conducting substrate 601 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; Anode conducting substrate 601 after cleaning also needs the process carrying out surface active, and to increase the oxygen content of anode conducting substrate 601, improve the work function of conductive layer surface, the thickness of gained anode conducting substrate 601 is 100nm.
The preparation of step (two) hole injection layer 602: on anode conducting substrate 601 prepared by above-mentioned steps (), 30wt%MoO 3be incorporated in NPB, adopt vacuum deposition method the MoO of abovementioned dopant 3be the luminescent layer 602 that 10nm is thick with NPB evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (three) hole transmission layer 603: on hole injection layer 102 prepared by above-mentioned steps (two), use TCTA as the material of hole transmission layer 603, adopt vacuum deposition method to be the hole transmission layer 603 that 30nm is thick TCTA evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (four) luminescent layer 604: on hole transmission layer 603 prepared by above-mentioned steps (three), 5wt% (Ir (ppy) 3) be incorporated in TPBI, adopt vacuum deposition method the (Ir (ppy) of abovementioned dopant 3) with TPBI evaporation be the luminescent layer 604 that 20nm is thick, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (five) electron transfer layer 605: on luminescent layer 604 prepared by above-mentioned steps (four), use Bphen as the material of electron transfer layer 605, adopt vacuum deposition method to be the electron transfer layer 605 that 10nm is thick Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (six) electron injecting layer 606: on electron transfer layer 105 prepared by above-mentioned steps (five), 30wt%CsN 3be incorporated in Bphen, adopt vacuum deposition method the CsN of abovementioned dopant 3be the electron injecting layer 606 that 600nm is thick with Bphen evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (seven) cathode layer 607: on electron injecting layer 606 prepared by above-mentioned steps (six), use Al as the material of cathode layer 607, adopt vacuum deposition method to be the cathode layer 607 that 100nm is thick Al evaporation, the technological parameter of vacuum deposition method is set to: 3 × 10 -5the vacuum degree of Pa, evaporation rate.
The preparation of step (eight) inorganic barrier layer 608: on cathode layer 607 prepared by above-mentioned steps (seven), adopts plasma reinforced chemical vapour deposition method to prepare rete hydrogenated carbon nitrogen compound CNx:H, thus obtains inorganic barrier layer 608.The technological parameter of plasma reinforced chemical vapour deposition method is set to: working gas is the CH of 5sccm 4with the N of 10sccm 2, operating pressure is 25Pa, and radio-frequency power is 0.2W/cm 2, thickness of coating is 400nm.
The preparation of step (nine) inorganic barrier layer 609: on inorganic barrier layer 608 prepared by above-mentioned steps (eight), by Y 3al 5o 12, HFc with NiS phase adulterates, HFc accounts for Y 3al 5o 12ratio be that 20wt%, NiS account for Y 3al 5o 12ratio be 12wt%, adopt magnetically controlled sputter method doping Y 3al 5o 12, Hfc and NiS be prepared as the thick inorganic barrier layer of 150nm 609.The technological parameter of magnetically controlled sputter method is set to: 1 × 10 -3the vacuum degree of Pa.
Step (ten) alternately repeats above-mentioned steps (eight) and (nine) 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 7.00 × 10 -6g/m 2/ more than day, the OLED made by it, the life-span reaches average more than 14556 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, this layer structure comprises successively: 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, 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; Wherein:
The material of described inorganic barrier layer is rete hydrogenated carbon nitrogen compound;
The material of described inorganic barrier layer is the mixture be made up of oxygen hydrochlorate, carbide and sulfide; Described oxygen hydrochlorate is MgAl 2o 4, Bi 2ti 4o 11, CrNiO 4, CoCr 2o 4, Fe 2luO 4or Y 3al 5o 12; Described carbide is SiC, WC, TaC, BC, TiC or HfC; Described sulfide is CdS, PbS, FeS 2, CuS, ZnS or NiS; Described carbide in the weight percent content of described oxygen hydrochlorate be 10 ~ 30wt%; Described sulfide in the weight percent content of described oxygen hydrochlorate be 10 ~ 30wt%.
2. organic electroluminescence device according to claim 1, is characterized in that, described rete hydrogenated carbon nitrogen compound uses methane and nitrogen as raw material and obtained by plasma reinforced chemical vapour deposition method.
3. organic electroluminescence device according to claim 1, is characterized in that, the number of plies on described barrier layer is four, five or six.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described inorganic barrier layer is 400nm ~ 600nm; The thickness of described inorganic barrier layer is 100nm ~ 200nm.
5. 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 0.3:1 ~ 0.4:1 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 ~ 0.08:1;
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 0.3:1 ~ 0.4:1 with the percentage by weight of 4,7-diphenyl-1,10-phenanthroline;
The material of described cathode layer is metallic aluminium.
6. 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 () is on described cathode layer, plasma reinforced chemical vapour deposition method is first adopted to prepare inorganic barrier layer, then on described inorganic barrier layer, adopt magnetically controlled sputter method to prepare inorganic barrier layer, thus be combined into barrier layer by described inorganic barrier layer and 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 rete hydrogenated carbon nitrogen compound, and described rete hydrogenated carbon nitrogen compound uses methane and nitrogen as raw material and obtained by described plasma reinforced chemical vapour deposition method;
The material of described inorganic barrier layer is the mixture be made up of oxygen hydrochlorate, carbide and sulfide; Described oxygen hydrochlorate is MgAl 2o 4, Bi 2ti 4o 11, CrNiO 4, CoCr 2o 4, Fe 2luO 4or Y 3al 5o 12; Described carbide is SiC, WC, TaC, BC, TiC or HfC; Described sulfide is CdS, PbS, FeS 2, CuS, ZnS or NiS; Described carbide in the weight percent content of described oxygen hydrochlorate be 10 ~ 30wt%; Described sulfide in the weight percent content of described oxygen hydrochlorate be 10 ~ 30wt%.
7. preparation method according to claim 6, is characterized in that, in described step (a), when adopting vacuum deposition method to prepare described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, vacuum degree is 3 × 10 -5pa ~ 3 × 10 -3pa, evaporation rate is 0.1/s ~ 0.2/s, and coating film thickness is 10nm ~ 30nm; When adopting vacuum deposition method to prepare described cathode layer, vacuum degree is 3 × 10 -5pa ~ 3 × 10 -3pa, evaporation rate is 0.5 ~ 5/s, and coating film thickness is 100nm ~ 150nm.
8. preparation method according to claim 6, it is characterized in that, in described step (b), when adopting plasma reinforced chemical vapour deposition method to prepare described inorganic barrier layer, the flow of described methane is 5 ~ 15sccm, the flow of described nitrogen is 5 ~ 15sccm, and operating pressure is 10Pa ~ 80Pa, and radio-frequency power is 0.1W/cm 2~ 0.5W/cm 2, coating film thickness is 400nm ~ 600nm.
9. preparation method according to claim 6, is characterized in that, in described step (b), when adopting magnetically controlled sputter method to prepare described inorganic barrier layer, vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, coating film thickness is 100nm ~ 200nm.
10. preparation method according to claim 6, is characterized in that, in described step (b), the number of plies on described barrier layer is four, five or six.
CN201310561620.8A 2013-11-12 2013-11-12 Organic light emitting device and manufacturing method thereof Pending CN104638174A (en)

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