CN104051666A - Composite anode, preparation method of composite anode, organic electroluminescent device and preparation method of organic electroluminescent device - Google Patents

Composite anode, preparation method of composite anode, organic electroluminescent device and preparation method of organic electroluminescent device Download PDF

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Publication number
CN104051666A
CN104051666A CN201310078485.1A CN201310078485A CN104051666A CN 104051666 A CN104051666 A CN 104051666A CN 201310078485 A CN201310078485 A CN 201310078485A CN 104051666 A CN104051666 A CN 104051666A
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layer
poly
polythiophene
composite anode
spin coating
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周明杰
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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    • 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
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Abstract

The invention discloses a composite anode and a preparation method of the composite anode. The composite anode is formed by a glass substrate, a polythiophene layer, a middle layer and a doping layer which are stacked in sequence. The polythiophene high polymer material in the polythiophene layer is easy to crystallize, and the chain segments of the material after crystallization are tidily and orderly arranged, thereby imposing strong scattering effect on light, and helping to improve the light emitting efficiency. The middle layer is a mixed material formed by poly(3,4-ethylenedioxythiophene) and poly(p-styrenesulfonic acid), so that the middle layer is strong in conductivity, suitable for conduction of electrons, and the conductivity of the anode is enhanced. The doping layer can improve the hole injection capability of a device and conductivity of the anode, and the light-emitting efficiency is improved. The invention also discloses the organic electroluminescent device and a preparation method of the organic electroluminescent device.

Description

A kind of composite anode and preparation method thereof and organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of composite anode and preparation method thereof and organic electroluminescence device and preparation method thereof.
Background technology
1987, the C.W.Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in organic electroluminescent research.Utilize ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).Under 10V, brightness reaches 1000cd/m 2, its luminous efficiency is 1.51lm/W, the life-span is greater than 100 hours.
The principle of luminosity of OLED is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.
In traditional luminescent device, the light of device inside only has 18% left and right can be transmitted into outside to go, and other part can consume at device outside with other forms, (as the specific refractivity between glass and ITO, glass refraction is that 1.5, ITO is 1.8 between interface, refractive index poor, light arrives glass from ITO, will there is total reflection), caused the loss of total reflection, thereby it is lower to cause integral body to go out optical property.Therefore, be necessary to improve the luminous efficiency of OLED.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of composite anode and preparation method thereof, described composite anode is comprised of the substrate of glass stacking gradually, polythiophene layer, intermediate layer and doped layer; This composite anode can be applicable to polymer solar battery and organic electroluminescence device, while being applied to organic electroluminescence device, is conducive to improve the injection in device hole, improves conductivity and the luminous efficiency of device simultaneously.The present invention also provides and has comprised organic electroluminescence device of above-mentioned composite anode and preparation method thereof.
First aspect, the invention provides a kind of composite anode, and described composite anode is comprised of the substrate of glass stacking gradually, polythiophene layer, intermediate layer and doped layer; A kind of in poly-3-hexyl thiophene (P3HT), poly-3 methyl thiophene (P3AT) and poly-dodecyl thiophene (P3DDT) of the material of described polythiophene layer; Described intermediate layer is (PSS) (PEDOT) composite material of the ratio formation of 2:1～6:1 with poly-(p styrene sulfonic acid) for poly-(3,4-dioxoethyl thiophene) in mass ratio; Described doped layer is that metal simple-substance and metal oxide are the composite material of the ratio formation of 0.1:1～0.4:1 in mass ratio, and described metal oxide is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in a kind of; Described metal simple-substance is a kind of in silver (Ag), aluminium (Al), platinum (Pt) and golden (Au).
Preferably, the thickness of described polythiophene layer is 40～300nm.
Preferably, the thickness in described intermediate layer is 5～20nm.
Preferably, the thickness of described doped layer is 2～30nm.
Preferably, described substrate of glass is commercially available simple glass.
Second aspect, the invention provides a kind of preparation method of composite anode, comprises the following steps:
The substrate of glass of required size is provided, dry after cleaning;
A kind of in P3HT, P3AT and P3DDT is dissolved into and in organic solvent, obtains the polythiophene solution that concentration is 8～30g/L, in substrate of glass, spin coating polythiophene solution obtains polythiophene layer, spin coating rotating speed is 500～6000rpm, time is 5～30s, after spin coating, at 100～200 ℃, dries 15～60min; By PEDOT and PSS is the ratio mixing of 2:1～6:1 in mass ratio, add that to obtain PEDOT mass fraction after water be 1%～5% the aqueous solution, on polythiophene layer, the spin coating aqueous solution obtains intermediate layer, spin coating rotating speed is 500～8000rpm, time is 5～60s, after spin coating, at 100～200 ℃, dries 15～60min; Finally on intermediate layer, vacuum evaporation metal simple-substance and metal oxide are the composite material of the ratio formation of 0.1:1～0.4:1 in mass ratio, obtain doped layer, and described metal oxide is MoO 3, WO 3and V 2o 5in a kind of; Described metal simple-substance is a kind of in Ag, Al, Pt and Au; Doped layer evaporation pressure is 2 * 10 -4pa～3 * 10 -3pa, evaporation speed is 1～10nm/s.
Preferably, the thickness of described polythiophene layer is 40～300nm.
Preferably, the thickness in described intermediate layer is 5～20nm.
Preferably, the thickness of described doped layer is 2～30nm.
Preferably, described substrate of glass is commercially available simple glass.
Preferably, described organic solvent is a kind of in chlorobenzene, chloroform, toluene and paraxylene.
Preferably, described in the substrate of glass of required size is provided, concrete operations are: substrate of glass is carried out to photoetching treatment, be then cut into needed size.
Preferably, being operating as that described cleaning is dried afterwards used liquid detergent successively by substrate of glass, deionized water, and acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry.
Composite anode of the present invention is comprised of the substrate of glass stacking gradually, polythiophene layer, intermediate layer and doped layer; The easy crystallization of polythiophene class macromolecular material in described polythiophene layer, after crystallization, material segment marshalling, orderly, can have strong scattering process to light, is conducive to improve the light extraction efficiency of device; And the composite material that intermediate layer forms for poly-(3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid), conductivity is strong, is applicable to the conduction of electronics, has strengthened the conductivity of anode; Doped layer is mixed by metal oxide and metal simple-substance, can improve hole injectability and the conductivity of device, has improved the luminous efficiency of device.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described composite anode is comprised of the substrate of glass stacking gradually, polythiophene layer, intermediate layer and doped layer; The material of described polythiophene layer is a kind of in P3HT, P3AT and P3DDT; Described intermediate layer is that PEDOT and PSS are the composite material of the ratio formation of 2:1～6:1 in mass ratio; Described doped layer is that metal simple-substance and metal oxide are the composite material of the ratio formation of 0.1:1～0.4:1 in mass ratio, and described metal oxide is MoO 3, WO 3and V 2o 5in a kind of; Described metal simple-substance is a kind of in Ag, Al, Pt and Au.
Preferably, the thickness of described polythiophene layer is 40～300nm.
Preferably, the thickness in described intermediate layer is 5～20nm.
Preferably, the thickness of described doped layer is 2～30nm.
Preferably, described substrate of glass is commercially available simple glass.
Preferably, described hole injection layer material is molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5), thickness is 20～80nm.More preferably, described hole injection layer material is MoO 3, thickness is 30nm.
Preferably, described hole transmission layer material is 1,1-, bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), described hole transmission layer material thickness is 20～60nm, more preferably, described hole transmission layer material is TAPC, and thickness is 50nm.
Preferably, described luminescent layer material is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) or oxine aluminium (Alq 3), thickness is 5～40nm, and more preferably, described luminescent layer material is DCJTB, and thickness is preferably 10nm.
Preferably, described electron transfer layer material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or N-aryl benzimidazole (TPBI), thickness is 40～80nm, more preferably, described electron transfer layer material is TPBI, and thickness is 45nm.
Preferably, described electron injecting layer material is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) or lithium fluoride (LiF), thickness is 0.5～10nm, and more preferably, described electron injecting layer material is LiF, and thickness is 1nm.
Preferably, described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and thickness is 80～250nm, and more preferably, described negative electrode is Ag, and thickness is 100nm.
Fourth aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises following operating procedure:
The substrate of glass of required size is provided, dry after cleaning;
A kind of in P3HT, P3AT and P3DDT is dissolved into and in organic solvent, obtains the polythiophene solution that concentration is 8～30g/L, in substrate of glass, spin coating polythiophene solution obtains polythiophene layer, spin coating rotating speed is 500～6000rpm, time is 5～30s, after spin coating, at 100～200 ℃, dries 15～60min; By PEDOT and PSS is the ratio mixing of 2:1～6:1 in mass ratio, add that to obtain PEDOT mass fraction after water be 1%～5% the aqueous solution, on polythiophene layer, the spin coating aqueous solution obtains intermediate layer, spin coating rotating speed is 500～8000rpm, time is 5～60s, after spin coating, at 100～200 ℃, dries 15～60min; Finally on intermediate layer, vacuum evaporation metal simple-substance and metal oxide are the composite material of the ratio formation of 0.1:1～0.4:1 in mass ratio, and described metal oxide is MoO 3, WO 3and V 2o 5in a kind of; Described metal simple-substance is a kind of in Ag, Al, Pt and Au; Evaporation pressure is 2 * 10 -4pa～3 * 10 -3pa, evaporation speed is 1～10nm/s;
On doped layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are prepared in vacuum evaporation successively, finally obtain described organic electroluminescence device.
Preferably, the thickness of described polythiophene layer is 40～300nm.
Preferably, the thickness in described intermediate layer is 5～20nm.
Preferably, the thickness of described doped layer is 2～30nm.
Preferably, described substrate of glass is commercially available simple glass.
Preferably, described organic solvent is a kind of in chlorobenzene, chloroform, toluene and paraxylene.
Preferably, described hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer evaporation coating method are: evaporation pressure is 2 * 10 -4～3 * 10 -3pa, evaporation speed is 0.1～1nm/s.
Preferably, the evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 2 * 10 -4～3 * 10 -3pa, evaporation speed is 1～10nm/s.
Preferably, described in the substrate of glass of required size is provided, concrete operations are: substrate of glass is carried out to photoetching treatment, be then cut into needed size.
Preferably, being operating as that described cleaning is dried afterwards used liquid detergent successively by substrate of glass, deionized water, and acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry.
Preferably, described hole injection layer material is MoO 3, WO 3or V 2o 5, thickness is 20～80nm.More preferably, described hole injection layer material is MoO 3, thickness is 30nm.
Preferably, described hole transmission layer material is TAPC, TCTA or NPB, and described hole transmission layer material thickness is 20～60nm, and more preferably, described hole transmission layer material is TAPC, and thickness is 50nm.
Preferably, described luminescent layer material is DCJTB, ADN, BCzVBi or Alq 3, thickness is 5～40nm, and more preferably, described luminescent layer material is DCJTB, and thickness is preferably 10nm.
Preferably, described electron transfer layer material is Bphen, TAZ or TPBI, and thickness is 40～80nm, and more preferably, described electron transfer layer material is TPBI, and thickness is 45nm.
Preferably, described electron injecting layer material is Cs 2cO 3, CsF, CsN 3or LiF, thickness is 0.5～10nm, and more preferably, described electron injecting layer material is LiF, and thickness is 1nm.
Preferably, described negative electrode is Ag, Al, Pt or Au, and thickness is 80～250nm, and more preferably, described negative electrode is Ag, and thickness is 100nm.
Composite anode in organic electroluminescence device of the present invention is comprised of the substrate of glass stacking gradually, polythiophene layer, intermediate layer and doped layer; The easy crystallization of polythiophene class macromolecular material in described polythiophene layer, after crystallization, this material segment marshalling, orderly, can have strong scattering process to light, is conducive to improve the light extraction efficiency of device; And the composite material that intermediate layer forms for poly-(3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid), conductivity is strong, is applicable to the conduction of electronics, has strengthened the conductivity of anode; Doped layer can improve the hole injectability of device and the conductivity of anode, improves the luminous efficiency of device.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) composite anode provided by the invention is comprised of the substrate of glass stacking gradually, polythiophene layer, intermediate layer and doped layer, has improved electric conductivity and the hole injectability of anode;
(2) preparation method of composite anode provided by the invention, technique is simple, and cost is low;
(3) composite anode provided by the invention can be applicable in organic electroluminescence device and organic solar batteries, while being applied to organic electroluminescence device, be conducive to improve device conductivity and hole injectability, effectively improve scattering of light effect simultaneously, improved the luminous efficiency of device.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in execution mode be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of the organic electroluminescence device that provides of the embodiment of the present invention 5;
Fig. 2 is current density and the luminous efficiency graph of a relation of the embodiment of the present invention 5 and comparative example's organic electroluminescence device.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Embodiment 1
A preparation method for composite anode, comprises following operating procedure:
(1) first substrate of glass is carried out to photoetching treatment, be then cut into 2 * 2cm 2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first P3HT is dissolved into and in chlorobenzene, obtains the P3HT solution that concentration is 16g/L, spin coating P3HT solution on substrate of glass exiting surface, spin speed is 4000rpm, the time is 10s, after spin coating, at 100 ℃, heat 40min, obtain the polythiophene layer that thickness is 120nm after cooling; Then by PEDOT and PSS by weight mixing for 5:1, add that to obtain PEDOT mass fraction after water be 3.5% the aqueous solution, on polythiophene layer, spin coating PEDOT and PSS(are expressed as PEDOT:PSS) aqueous solution, spin coating rotating speed is 2000rpm, time is 10s, after spin coating, at 100 ℃, heat 30min, obtain the intermediate layer that thickness is 10nm after cooling; Evaporation Ag and MoO on intermediate layer 3the composite material that is in mass ratio the ratio formation of 0.25:1 (is expressed as MoO 3: Ag), obtain the intermediate layer that thickness is 5nm, evaporation pressure is 2 * 10 -4pa, evaporation speed is 1nm/s.
Embodiment 2
A preparation method for composite anode, comprises following operating procedure:
(1) first substrate of glass is carried out to photoetching treatment, be then cut into 2 * 2cm 2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first P3AT is dissolved into and in chlorobenzene, obtains the P3AT solution that concentration is 8g/L, spin coating P3AT solution on substrate of glass exiting surface, spin speed is 500rpm, the time is 5s, after spin coating, at 200 ℃, heat 30min, obtain the polythiophene layer that thickness is 300nm after cooling; Then by PEDOT and PSS by weight mixing for 2:1, add that to form PEDOT mass fraction after water be 1% the aqueous solution, spin coating PEDOT and the PSS aqueous solution on polythiophene layer, spin coating rotating speed is 8000rpm, time is 60s, after spin coating, at 200 ℃, heat 15min, cooling after, obtain the intermediate layer that thickness is 5nm; Evaporating Al and WO on intermediate layer 3the composite material forming for 0.4:1 in mass ratio (is expressed as WO 3: Al), obtain the doped layer that thickness is 30nm, evaporation pressure is 3 * 10 -3pa, evaporation speed is 6nm/s.
Embodiment 3
A preparation method for composite anode, comprises following operating procedure:
(1) first substrate of glass is carried out to photoetching treatment, be then cut into 2 * 2cm 2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first P3DDT is dissolved into and in chlorobenzene, obtains the P3DDT solution that concentration is 30g/L, spin coating P3DDT solution on substrate of glass exiting surface, spin speed is 6000rpm, the time is 30s, after spin coating, at 200 ℃, heat 15min and dry, obtaining thickness is the polythiophene layer of 40nm; Then by PEDOT and PSS by weight mixing for 6:1, add that to form PEDOT mass fraction after water be 5% the aqueous solution, spin coating PEDOT and the PSS aqueous solution on polythiophene layer, spin coating rotating speed is 500rpm, time is 5s, after spin coating, at 100 ℃, heat 60min, obtain the intermediate layer that thickness is 20nm; Evaporation Pt and V on intermediate layer 2o 5the composite material that is in mass ratio the ratio formation of 0.1:1 (is expressed as V 2o 5: Pt), obtain the doped layer that thickness is 2nm, evaporation pressure is 1 * 10 -3pa, evaporation speed is 10nm/s.
Embodiment 4
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) first substrate of glass is carried out to photoetching treatment, be then cut into 2 * 2cm 2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first P3HT is dissolved into and in chlorobenzene, obtains the P3HT solution that concentration is 20g/L, spin coating P3HT solution on substrate of glass exiting surface, spin speed is 3000rpm, the time is 15s, after spin coating, at 150 ℃, heat 30min, obtain the polythiophene layer that thickness is 200nm after cooling; Then by PEDOT and PSS by weight mixing for 3:1, add after water, form the aqueous solution that PEDOT mass fraction is 2.5%, spin coating PEDOT and the PSS aqueous solution on polythiophene layer, spin coating rotating speed is 3000rpm, and the time is 20s, after spin coating, at 150 ℃, heats 40min, after cooling, obtain the intermediate layer that thickness is 10nm; Evaporation Au and WO on intermediate layer 3the composite material that is in mass ratio the ratio formation of 0.35:1 (is expressed as WO 3: Au), obtain the doped layer that thickness is 20nm, evaporation pressure is 5 * 10 -4pa evaporation speed is 5nm/s.
Embodiment 5
An organic electroluminescence device, comprises the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described composite anode is the anode of the embodiment of the present invention 1 preparation.
In concrete preparation process, on composite anode, evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device, wherein,
Hole injection layer material is MoO 3, the pressure adopting during evaporation is 2 * 10 -4pa, evaporation speed is 1nm/s, evaporation thickness is 30nm;
Hole transmission layer material is TAPC, and the pressure adopting during evaporation is 2 * 10 -4pa, evaporation speed is 0.1nm/s, evaporation thickness is 50nm;
Luminescent layer material is DCJTB, and the pressure adopting during evaporation is 2 * 10 -4pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm;
The material of electron transfer layer is TPBI, and the pressure adopting during evaporation is 2 * 10 -4pa, evaporation speed is 0.1nm/s, evaporation thickness is 45nm;
The material of electron injecting layer is LiF, and the pressure adopting during evaporation is 2 * 10 -4pa, evaporation speed is 0.1nm/s, evaporation thickness is 1nm;
The material of negative electrode is Ag, and the pressure adopting during evaporation is 2 * 10 -4pa, evaporation speed is 1nm/s, evaporation thickness is 100nm.
Fig. 1 is the structural representation of the organic electroluminescence device prepared of the present embodiment, as shown in Figure 1, organic electroluminescence device prepared by the present embodiment, comprise the composite anode 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6 and the negative electrode 7 that stack gradually, composite anode 1 comprises substrate of glass 11, polythiophene layer 12, intermediate layer 13 and the doped layer 14 stacking gradually.Concrete structure is expressed as:
Substrate of glass/P3HT-PEDOT:PSS-MoO 3: Ag/MoO 3/ TAPC/DCJTB/TPBI/LiF/Ag.
Embodiment 6
An organic electroluminescence device, comprises the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described composite anode is the anode of the embodiment of the present invention 2 preparations.
In concrete preparation process, on composite anode, evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device, wherein,
Hole injection layer material is WO 3, the pressure adopting during evaporation is 3 * 10 -3pa, evaporation speed is 6nm/s, evaporation thickness is 20nm;
Hole transmission layer material is TCTA, and the pressure adopting during evaporation is 3 * 10 -3pa, evaporation speed is 0.6nm/s, evaporation thickness is 60nm;
Luminescent layer material is Alq 3, the pressure adopting during evaporation is 3 * 10 -3pa, evaporation speed is 0.5nm/s, evaporation thickness is 40nm;
The material of electron transfer layer is TPBI, and the pressure adopting during evaporation is 3 * 10 -3pa, evaporation speed is 0.5nm/s, evaporation thickness is 75nm;
The material of electron injecting layer is Cs 2cO 3, the pressure adopting during evaporation is 3 * 10 -3pa, evaporation speed is 0.5nm/s, evaporation thickness is 10nm;
The material of negative electrode is Pt, and the pressure adopting during evaporation is 3 * 10 -3pa, evaporation speed is 6nm/s, evaporation thickness is 80nm.
Organic electroluminescence device prepared by the present embodiment, comprise the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, composite anode comprises substrate of glass, polythiophene layer, intermediate layer and the doped layer stacking gradually.Concrete structure is expressed as:
Substrate of glass/P3AT-PEDOT:PSS-WO 3: Al/WO 3/ TCTA/Alq 3/ TPBI/Cs 2cO 3/ Pt.
Embodiment 7
An organic electroluminescence device, comprises the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described composite anode is the anode of the embodiment of the present invention 3 preparations.
In concrete preparation process, on composite anode, evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device, wherein,
Hole injection layer material is MoO 3, the pressure adopting during evaporation is 1 * 10 -3pa, evaporation speed is 10nm/s, evaporation thickness is 20nm;
Hole transmission layer material is NPB, and the pressure adopting during evaporation is 1 * 10 -3pa, evaporation speed is 1nm/s, evaporation thickness is 55nm;
Luminescent layer material is BCzVBi, and the pressure adopting during evaporation is 1 * 10 -3pa, evaporation speed is 1nm/s, evaporation thickness is 30nm;
The material of electron transfer layer is Bphen, and the pressure adopting during evaporation is 1 * 10 -3pa, evaporation speed is 1nm/s, evaporation thickness is 60nm;
The material of electron injecting layer is CsF, and the pressure adopting during evaporation is 1 * 10 -3pa, evaporation speed is 1nm/s, evaporation thickness is 0.5nm;
The material of negative electrode is Au, and the pressure adopting during evaporation is 1 * 10 -3pa, evaporation speed is 10nm/s, evaporation thickness is 100nm.
Organic electroluminescence device prepared by the present embodiment, comprise the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, composite anode comprises substrate of glass, polythiophene layer, intermediate layer and the doped layer stacking gradually.Concrete structure is expressed as:
Substrate of glass/P3DDT-PEDOT:PSS-V 2o 5: Pt/MoO 3/ NPB/BCzVBi/Bphen/CsF/Au.
Embodiment 8
An organic electroluminescence device, comprises the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described composite anode is the anode of the embodiment of the present invention 4 preparations.
In concrete preparation process, on composite anode, evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device, wherein,
Hole injection layer material is V 2o 5, the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 5nm/s, evaporation thickness is 60nm;
Hole transmission layer material is TCTA, and the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 0.4nm/s, evaporation thickness is 60nm;
Luminescent layer material is ADN, and the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 0.4nm/s, evaporation thickness is 5nm;
The material of electron transfer layer is TAZ, and the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 0.4nm/s, evaporation thickness is 35nm;
The material of electron injecting layer is CsN 3, the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 0.4nm/s, evaporation thickness is 2nm;
The material of negative electrode is Al, and the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 5nm/s, evaporation thickness is 250nm.
Organic electroluminescence device prepared by the present embodiment, comprise the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, composite anode comprises substrate of glass, polythiophene layer, intermediate layer and the doped layer stacking gradually.Concrete structure is expressed as:
Substrate of glass/P3HT-PEDOT:PSS-WO 3: Au/V 2o 5/ TCTA/ADN/TAZ/CsN 3/ Al.
Comparative example
For being presented as creativeness of the present invention, the present invention is also provided with comparative example, the difference of comparative example and embodiment 5 is that the anode in comparative example is indium tin oxide glass (ITO), thickness is 120nm, and the concrete structure of comparative example's organic electroluminescence device is: substrate of glass/ITO/MoO 3/ TAPC/DCJTB/TPBI/LiF/Ag, respectively corresponding substrate of glass, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Effect embodiment
Adopt fiber spectrometer (U.S. marine optics Ocean Optics company, model: USB4000), current-voltage tester (U.S. Keithly company, 2400), colorimeter (Japanese Konica Minolta company model:, model: CS-100A) luminous efficiency of test organic electroluminescence device is with current density change curve, to investigate the luminous efficiency of device, tested object is embodiment 5 and comparative example's organic electroluminescence device.Test result as shown in Figure 2.Fig. 2 is the embodiment of the present invention 5 and the luminous efficiency of comparative example's organic electroluminescence device and the graph of a relation of current density.
As can be seen from Figure 2, under different current densities, the luminous efficiency of embodiment 5 is large than comparative example all, and the luminous efficiency of embodiment 5 maximums is 8.1lm/W, and that comparative example is only 3.9lm/W, and the luminous efficiency of comparative example along with the increase of current density fast-descending, this explanation, composite anode prepared by the present invention effectively improves scattering of light effect, has improved the conductivity of anode, and the hole injectability of enhance device, has improved the light extraction efficiency of device.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (10)

1. a composite anode, is characterized in that, described composite anode is comprised of the substrate of glass stacking gradually, polythiophene layer, intermediate layer and doped layer; A kind of in poly-3-hexyl thiophene, poly-3 methyl thiophene and poly-dodecyl thiophene of the material of described polythiophene layer; The composite material that the ratio that described kinds of interlayer is 2:1～6:1 for poly-(3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid) in mass ratio forms; Described doped layer material is the composite material that metal simple-substance and metal oxide form for the ratio of 0.1:1～0.4:1 in mass ratio, and described metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide; Described metal simple-substance is a kind of in silver, aluminium, platinum and gold.
2. composite anode as claimed in claim 1, is characterized in that, the thickness of described polythiophene layer is 40～300nm.
3. composite anode as claimed in claim 1, is characterized in that, the thickness in described intermediate layer is 5～20nm.
4. composite anode as claimed in claim 1, is characterized in that, the thickness of described doped layer is 2～30nm.
5. a preparation method for composite anode, is characterized in that, comprises following operating procedure:
The substrate of glass of required size is provided, dry after cleaning;
A kind of in poly-3-hexyl thiophene, poly-3 methyl thiophene and poly-dodecyl thiophene is dissolved into and in organic solvent, obtains the polythiophene solution that concentration is 8～30g/L, in substrate of glass, spin coating polythiophene solution obtains polythiophene layer, spin coating rotating speed is 500～6000rpm, time is 5～30s, after spin coating, at 100～200 ℃, dries 15～60min; To gather (3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid) be the ratio mixing of 2:1～6:1 in mass ratio, after adding water, gathered (3,4-dioxoethyl thiophene) aqueous solution that mass fraction is 1%～5%, on polythiophene layer, the spin coating aqueous solution obtains intermediate layer, spin coating rotating speed is 500～8000rpm, and the time is 5～60s, after spin coating, at 100～200 ℃, dries 15～60min; Last on intermediate layer vacuum evaporation metal simple-substance and metal oxide be the composite material of the ratio formation of 0.1:1～0.4:1 in mass ratio, obtain doped layer, described metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide; Described metal simple-substance is a kind of in silver, aluminium, platinum and gold; Evaporation pressure is 2 * 10 -4pa～3 * 10 -3pa, evaporation speed is 1～10nm/s.
6. the preparation method of composite anode as claimed in claim 5, is characterized in that, the thickness of described polythiophene layer is 40～300nm.
7. the preparation method of composite anode as claimed in claim 5, is characterized in that, the thickness in described intermediate layer is 5～20nm.
8. the preparation method of composite anode as claimed in claim 5, is characterized in that, the thickness of described doped layer is 2～30nm.
9. an organic electroluminescence device, it is characterized in that, comprise the composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described composite anode is comprised of the substrate of glass stacking gradually, polythiophene layer, intermediate layer and doped layer; A kind of in poly-3-hexyl thiophene, poly-3 methyl thiophene and poly-dodecyl thiophene of the material of described polythiophene layer; The composite material that the ratio that described intermediate layer is 2:1～6:1 for poly-(3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid) in mass ratio forms; Described doped layer is the composite material that metal simple-substance and metal oxide form for the ratio of 0.1:1～0.4:1 in mass ratio, and described metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide; Described metal simple-substance is a kind of in silver, aluminium, platinum and gold.
10. a preparation method for organic electroluminescence device, is characterized in that, comprises following operating procedure:
The substrate of glass of required size is provided, dry after cleaning;
A kind of in poly-3-hexyl thiophene, poly-3 methyl thiophene and poly-dodecyl thiophene is dissolved into and in organic solvent, obtains the polythiophene solution that concentration is 8～30g/L, in substrate of glass, spin coating polythiophene solution obtains polythiophene layer, spin coating rotating speed is 500～6000rpm, time is 5～30s, after spin coating, at 100～200 ℃, dries 15～60min; To gather (3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid) be the ratio mixing of 2:1～6:1 in mass ratio, after adding water, gathered (3,4-dioxoethyl thiophene) aqueous solution that mass fraction is 1%～5%, on polythiophene layer, the spin coating aqueous solution obtains intermediate layer, spin coating rotating speed is 500～8000rpm, and the time is 5～60s, after spin coating, at 100～200 ℃, dries 15～60min; Last on intermediate layer vacuum evaporation metal simple-substance and metal oxide be the composite material of the ratio formation of 0.1:1～0.4:1 in mass ratio, obtain doped layer, described metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide; Described metal simple-substance is a kind of in silver, aluminium, platinum and gold; Doped layer evaporation pressure is 2 * 10 -4pa～3 * 10 -3pa, evaporation speed is 1～10nm/s;
On doped layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are prepared in vacuum evaporation successively, finally obtain described organic electroluminescence device.
CN201310078485.1A 2013-03-12 2013-03-12 Composite anode, preparation method of composite anode, organic electroluminescent device and preparation method of organic electroluminescent device Pending CN104051666A (en)

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CN102005540A (en) * 2010-10-12 2011-04-06 西安文景光电科技有限公司 Organic electroluminescent device taking metal and P-type disc-shaped compound as composite anode
CN202035172U (en) * 2010-12-22 2011-11-09 西安文景光电科技有限公司 Single pixel three primary color mixing organic electroluminescent white light source possessing composite anode
CN102468444A (en) * 2010-11-16 2012-05-23 海洋王照明科技股份有限公司 Organic light-emitting device and preparation method thereof
WO2012141875A1 (en) * 2011-04-12 2012-10-18 Arkema Inc. Internal optical extraction layer for oled devices

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101711439A (en) * 2007-05-31 2010-05-19 伊斯曼柯达公司 Electroluminescent device having improved light output
CN102005540A (en) * 2010-10-12 2011-04-06 西安文景光电科技有限公司 Organic electroluminescent device taking metal and P-type disc-shaped compound as composite anode
CN102468444A (en) * 2010-11-16 2012-05-23 海洋王照明科技股份有限公司 Organic light-emitting device and preparation method thereof
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Application publication date: 20140917