CN104051657A - Composite anode and preparation method thereof, and organic light-emitting device and preparation method thereof - Google Patents

Composite anode and preparation method thereof, and organic light-emitting device and preparation method thereof Download PDF

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Publication number
CN104051657A
CN104051657A CN201310077741.5A CN201310077741A CN104051657A CN 104051657 A CN104051657 A CN 104051657A CN 201310077741 A CN201310077741 A CN 201310077741A CN 104051657 A CN104051657 A CN 104051657A
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Prior art keywords
rhenium
layer
spin coating
composite anode
cesium
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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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Priority to CN201310077741.5A priority Critical patent/CN104051657A/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
    • H10K50/805—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 thereof. The composite anode is composed of a glass substrate, a cesium salt layer, an intermediate layer and a rhenium oxide layer. The cesium salt layer can be prepared by using the spin coating method and is made of metallic compounds with the large grain size, so that the light scattering can be enhanced. The intermediate layer is made of mixing materials with the poly (3,4-ethylene dioxythiohene) and the poly (styrene sulfonate), so that the conductivity of the anode; and the preparation is carried out by using the spin coating mode. The rhenium oxide layer is prepared by using the spin coating way, thereby simplifying the preparation method of the device; and the highest occupied molecular orbital of the rhenium oxide has the low energy level, so that the cavity injection can be enhanced and the luminous efficiency of the device can be improved. In addition, the invention also discloses an organic light-emitting device containing the composite anode and a preparation method thereof.

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 composite anode and preparation method thereof and organic electroluminescence device and preparation method thereof.
Background technology
1987, the C.W.Tang of Eastman Kodak company of the U.S. 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 in 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 entirety 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 made up of the oxide skin(coating) of the substrate of glass stacking gradually, cesium salt layer, intermediate layer and rhenium, this composite anode can be applicable to polymer solar battery and organic electroluminescence device, while being applied to organic electroluminescence device, be conducive to the injection in device hole, improve 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, described composite anode is made up of the oxide skin(coating) of the substrate of glass stacking gradually, cesium salt layer, intermediate layer and rhenium, and the material of described cesium salt layer is cesium fluoride (CsF), cesium chloride (CsCl) and cesium carbonate (Cs 2cO 3) in one, described intermediate layer for poly-(3,4-dioxoethyl thiophene) (PEDOT) and poly-(p styrene sulfonic acid) be (PSS) composite material of 2:1～6:1 formation in mass ratio, the material of the oxide skin(coating) of described rhenium is (ReO 2), rhenium heptoxide (Re 2o 7), rhenium sesquioxide (Re 2o 3) and oxidation two rhenium (Re 2o) one in.
Preferably, the thickness of described cesium salt layer is 5～20nm.
Preferably, the thickness in described intermediate layer is 5～20nm.
Preferably, the thickness of the oxide skin(coating) of described rhenium is 5～20nm.
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;
On substrate of glass exiting surface, adopt the method for spin coating to prepare the oxide skin(coating) of described cesium salt layer, intermediate layer and rhenium, obtain described composite anode; First, by CsF, CsCl and Cs 2cO 3in one and solvent, form the cesiated salt solution that cesium salt mass fraction is 1%～40%, then on substrate of glass exiting surface, described in spin coating, cesiated salt solution obtains described cesium salt layer, and described spin coating rotating speed is 500～6000rpm, time is 5～60s, spin coating post-drying; PEDOT and PSS are mixed to form to composite material for 2:1～6:1 in mass ratio, after adding water, form PEDOT mass fraction and be 1%～5% the aqueous solution, on cesium salt layer, the spin coating aqueous solution obtains intermediate layer, and spin coating rotating speed is 500～8000rpm, time is 5～60s, spin coating post-drying; By the oxide of rhenium and solvent, the oxide solution of the rhenium that the oxide mass mark that forms rhenium is 10%～50%, the oxide of described rhenium is ReO 2, Re 2o 7, Re 2o 3and Re 2one in O; On intermediate layer, the oxide solution of spin coating rhenium obtains the oxide skin(coating) of rhenium, and spin coating rotating speed is 500～8000rpm, and the time is 5～60s, spin coating post-drying.
Preferably, the thickness of described cesium salt layer is 5～20nm.
Preferably, the thickness in described intermediate layer is 5～20nm.
Preferably, the thickness of the oxide skin(coating) of described rhenium is 5～20nm.
Preferably, described substrate of glass is commercially available simple glass.
Preferably, described solvent is water, ethanol or isopropyl alcohol.
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, substrate of glass is used successively liquid detergent by being operating as that described cleaning is dried afterwards, deionized water, and acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry.
Preferably, after spin coating, at 100～200 DEG C, dry 15～60min.
Composite anode of the present invention is made up of the oxide skin(coating) of the substrate of glass stacking gradually, cesium salt layer, intermediate layer and rhenium, cesium salt layer of the present invention can adopt the method preparation of spin coating, cesium salt layer material is metallic compound simultaneously, and particle diameter is larger, can strengthen scattering of light; The composite material that intermediate layer forms for poly-(3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid), conductivity is higher, can improve the conductivity of anode, can adopt the method preparation of spin coating simultaneously; The oxide skin(coating) of described rhenium can adopt the method preparation of spin coating, simplified the preparation method of device, and oxide HOMO highest occupied molecular orbital (HOMO) energy level of rhenium is lower, can strengthen the injection in hole, improves the luminous efficiency of device.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise and stack gradually composite anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described composite anode is made up of the oxide skin(coating) of the substrate of glass stacking gradually, cesium salt layer, intermediate layer and rhenium, and the material of described cesium salt layer is CsF, CsCl and Cs 2cO 3in one, described intermediate layer is the composite material that PEDOT and PSS form for 2:1～6:1 in mass ratio, the material of the oxide skin(coating) of described rhenium is ReO 2, Re 2o 7, Re 2o 3and Re 2one in O.
Preferably, the thickness of described cesium salt layer is 5～20nm.
Preferably, the thickness in described intermediate layer is 5～20nm.
Preferably, the thickness of the oxide skin(coating) of described rhenium is 5～20nm.
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 50nm.
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 NPB, and thickness is 45nm.
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, more preferably, described luminescent layer material is Alq 3, thickness is preferably 30nm.
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;
On substrate of glass exiting surface, adopt the method for spin coating to prepare the oxide skin(coating) of described cesium salt layer, intermediate layer and rhenium, obtain described composite anode; First, by CsF, CsCl and Cs 2cO 3in one and solvent, form the cesiated salt solution that cesium salt mass fraction is 1%～40%, then on substrate of glass exiting surface, described in spin coating, cesiated salt solution obtains described cesium salt layer, and described spin coating rotating speed is 500～6000rpm, time is 5～60s, after spin coating, is drying; PEDOT and PSS are mixed to form to composite material for 2:1～6:1 in mass ratio, after adding water, form PEDOT mass fraction and be 1%～5% the aqueous solution, on cesium salt layer, the spin coating aqueous solution obtains intermediate layer, and spin coating rotating speed is 500～8000rpm, time is 5～60s, spin coating post-drying; By the oxide of rhenium and solvent, the oxide solution of the rhenium that the oxide mass mark that forms rhenium is 10%～50%, the oxide of described rhenium is ReO 2, Re 2o 7, Re 2o 3and Re 2one in O; On intermediate layer, the oxide solution of spin coating rhenium obtains the oxide skin(coating) of rhenium, and spin coating rotating speed is 500～8000rpm, and the time is 5～60s, spin coating post-drying;
On the oxide skin(coating) of rhenium, evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, finally obtains described organic electroluminescence device.
Preferably, the thickness of described cesium salt layer is 5～20nm.
Preferably, the thickness in described intermediate layer is 5～20nm.
Preferably, the thickness of the oxide skin(coating) of described rhenium is 5～20nm.
Preferably, described substrate of glass is commercially available simple glass.
Preferably, described solvent is water, ethanol or isopropyl alcohol.
Preferably, after spin coating, at 100～200 DEG C, dry 15～60min.
Preferably, the evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 2 × 10 -4pa～3 × 10 -3pa, evaporation speed is 1～10nm/s.
Preferably, described hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer evaporation condition are: evaporation pressure is 2 × 10 -4pa～3 × 10 -3pa, evaporation speed is 0.1～1nm/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, substrate of glass is used successively liquid detergent by being operating as that described cleaning is dried afterwards, deionized water, and acetone, ethanol, the 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 50nm.
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 45nm.
Preferably, described luminescent layer material is DCJTB, ADN, BCzVBi or Alq 3, thickness is 5～40nm, more preferably, described luminescent layer material is Alq 3, thickness is 30nm.
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 made up of the oxide skin(coating) of the substrate of glass stacking gradually, cesium salt layer, intermediate layer and rhenium, cesium salt layer of the present invention can adopt the method preparation of spin coating, cesium salt layer material is metallic compound simultaneously, and particle diameter is larger, can strengthen scattering of light; The composite material that intermediate layer forms for poly-(3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid), conductivity is higher, can improve the conductivity of anode, can adopt the method preparation of spin coating simultaneously; The oxide skin(coating) of described rhenium can adopt the method preparation of spin coating, simplified the preparation method of device, and the oxide HOMO energy level of rhenium is lower, can strengthen the injection in hole, improves luminous efficiency.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) composite anode provided by the invention is made up of the oxide skin(coating) of the substrate of glass stacking gradually, cesium salt layer, intermediate layer and rhenium, 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 to, in organic electroluminescence device and organic solar batteries, while being applied to organic electroluminescence device, be conducive to scattering of light, can improve the luminous efficiency of device.
Brief description of the drawings
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 skill in the art, 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 voltage and the brightness relationship figure 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, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first CsF and water are mixed, form the CsF aqueous solution that CsF mass fraction is 20%, the spin coating CsF aqueous solution on substrate of glass exiting surface, spin speed is 4000rpm, time is 15s, after spin coating, at 200 DEG C, heats 15min, obtains the cesium salt layer that thickness is 10nm after cooling; Then by PEDOT and PSS by weight mixing (being expressed as PEDOT:PSS) for 3:1, add water and form the aqueous solution that PEDOT mass fraction is 2%, spin coating PEDOT and the PSS aqueous solution on cesium salt layer, spin coating rotating speed is 6000rpm, time is 20s, after spin coating, at 100 DEG C, heat 30min, obtain the intermediate layer that thickness is 15nm after cooling; By Re 2o 7mix with water, form Re 2o 7mass fraction is 25% Re 2o 7the aqueous solution, spin coating Re on intermediate layer 2o 7the aqueous solution, spin coating rotating speed is 4000rpm, the time is 10s, after spin coating, at 150 DEG C, heats 30min, obtains the oxide skin(coating) that thickness is the rhenium of 10nm after cooling.
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, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first CsCl and ethanol are mixed, form the CsCl ethanolic solution that CsCl mass fraction is 1%, the ethanolic solution of spin coating CsCl on substrate of glass exiting surface, spin speed is 6000rpm, time is 5s, after spin coating, at 200 DEG C, heats 15min, obtains the cesium salt layer that thickness is 5nm after cooling; Then by PEDOT and PSS by weight mixing for 6:1, add water and form in the aqueous solution that PEDOT mass fraction is 5%, spin coating PEDOT and the PSS aqueous solution on cesium salt layer, spin coating rotating speed is 8000rpm, time is 60s, after spin coating, at 100 DEG C, heat 60min, obtain the intermediate layer that thickness is 20nm after cooling; By ReO 2be mixed to form ReO with ethanol 2mass fraction is 25% ReO 2ethanolic solution, spin coating ReO on intermediate layer 2ethanolic solution, spin coating rotating speed is 500rpm, the time is 5s, after spin coating, at 200 DEG C, heats 60min, obtains the oxide skin(coating) that thickness is the rhenium of 20nm after cooling.
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, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first by Cs 2cO 3mix with isopropyl alcohol, form Cs 2cO 3mass fraction is 40% Cs 2cO 3aqueous isopropanol, spin coating Cs on substrate of glass exiting surface 2cO 3aqueous isopropanol, spin speed is 500rpm, the time is 60s, after spin coating, at 100 DEG C, heats 60min, obtains the cesium salt layer that thickness is 20nm after cooling; Then by PEDOT and PSS by weight mixing for 2:1, after adding water, form PEDOT mass fraction and be 1% the aqueous solution, spin coating PEDOT and the PSS aqueous solution on cesium salt layer, spin coating rotating speed is 500rpm, time is 5s, after spin coating, at 100 DEG C, heat 15min, obtain the intermediate layer that thickness is 5nm after cooling; By Re 2o 3mix with isopropyl alcohol, form Re 2o 3mass fraction is 10% Re 2o 3aqueous isopropanol, spin coating Re on intermediate layer 2o 3aqueous isopropanol, spin coating rotating speed is 8000rpm, the time is 60s, after spin coating, at 100 DEG C, heats 15min, obtains the oxide skin(coating) that thickness is the rhenium of 5nm after cooling;
Embodiment 4
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, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first CsF and water are mixed, form the Cs that CsF mass fraction is 25% 2cO 3the aqueous solution, the aqueous solution of spin coating CsF on substrate of glass exiting surface, spin speed is 200rpm, the time is 10s, after spin coating, at 200 DEG C, heats 20min, obtains the cesium salt layer that thickness is 12nm after cooling; Then by PEDOT and PSS by weight mixing for 3:1, after adding water, form PEDOT mass fraction and be 1.5% the aqueous solution, spin coating PEDOT and the PSS aqueous solution on cesium salt layer, spin coating rotating speed is 2500rpm, time is 15s, after spin coating, at 150 DEG C, heat 30min, obtain the intermediate layer that thickness is 15nm after cooling; By Re 2o and isopropyl alcohol mix, and form Re 2o mass fraction is 30% Re 2o aqueous isopropanol, spin coating Re on intermediate layer 2the aqueous isopropanol of O, spin coating rotating speed is 3000rpm, the time is 20s, after spin coating, at 200 DEG C, heats 20min, obtains the oxide skin(coating) that thickness is the rhenium of 15nm after cooling;
Embodiment 5
A kind of organic electroluminescence device, the composite anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, composite anode is anode prepared by the embodiment of the present invention 1.
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 when evaporation is 2 × 10 -4pa, evaporation speed is 1nm/s, evaporation thickness is 50nm;
Hole transmission layer material is TAPC, and the pressure adopting when evaporation is 2 × 10 -4pa, evaporation speed is 0.1nm/s, evaporation thickness is 45nm;
Luminescent layer material is Alq 3, the pressure adopting when evaporation is 2 × 10 -4pa, evaporation speed is 0.1nm/s, evaporation thickness is 30nm;
The material of electron transfer layer is TPBI, and the pressure adopting when 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 when 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 when 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 the oxide skin(coating) 14 of the substrate of glass 11, cesium salt layer 12, intermediate layer 13 and the rhenium that stack gradually.Concrete structure is expressed as:
Substrate of glass/CsF-PEDOT:PSS-Re 2o 7/ MoO 3/ NPB/Alq 3/ TPBI/LiF/Ag.
Embodiment 6
A kind of organic electroluminescence device, the composite anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, composite anode is anode prepared by the embodiment of the present invention 2.
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 when evaporation is 3 × 10 -3pa, evaporation speed is 6nm/s, evaporation thickness is 20nm;
Hole transmission layer material is TCTA, and the pressure adopting when evaporation is 3 × 10 -3pa, evaporation speed is 0.6nm/s, evaporation thickness is 60nm;
Luminescent layer material is BCzVBi, and the pressure adopting when 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 when 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 when 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 when 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 the oxide skin(coating) of the substrate of glass, cesium salt layer, intermediate layer and the rhenium that stack gradually.Concrete structure is expressed as:
Substrate of glass/CsCl-PEDOT:PSS-ReO 2/ V 2o 5/ TCTA/BCzVBi/TPBI/Cs 2cO 3/ Pt.
Embodiment 7
A kind of organic electroluminescence device, the composite anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, composite anode is anode prepared by the embodiment of the present invention 3.
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 when evaporation is 1 × 10 -3pa, evaporation speed is 10nm/s, evaporation thickness is 80nm;
Hole transmission layer material is NPB, and the pressure adopting when evaporation is 1 × 10 -3pa, evaporation speed is 1nm/s, evaporation thickness is 55nm;
Luminescent layer material is DCJTB, and the pressure adopting when evaporation is 1 × 10 -3pa, evaporation speed is 1nm/s, evaporation thickness is 5nm;
The material of electron transfer layer is Bphen, and the pressure adopting when 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 when 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 when 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 the oxide skin(coating) of the substrate of glass, cesium salt layer, intermediate layer and the rhenium that stack gradually.Concrete structure is expressed as:
Substrate of glass/Cs 2cO 3-PEDOT:PSS-Re 2o 3/ MoO 3/ NPB/DCJTB/Bphen/CsF/Au.
Embodiment 8
A kind of organic electroluminescence device, the composite anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, composite anode is anode prepared by the embodiment of the present invention 4.
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 when evaporation is 5 × 10 -4pa, evaporation speed is 5nm/s, evaporation thickness is 30nm;
Hole transmission layer material is TCTA, and the pressure adopting when evaporation is 5 × 10 -4pa, evaporation speed is 0.4nm/s, evaporation thickness is 60nm;
Luminescent layer material is ADN, and the pressure adopting when evaporation is 5 × 10 -4pa, evaporation speed is 0.4nm/s, evaporation thickness is 8nm;
The material of electron transfer layer is TAZ, and the pressure adopting when 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 when 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 when 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 the oxide skin(coating) of the substrate of glass, cesium salt layer, intermediate layer and the rhenium that stack gradually.Concrete structure is expressed as:
Substrate of glass/CsF-PEDOT:PSS-Re 2o/WO 3/ 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, and the difference of comparative example and embodiment 5 is that the anode in comparative example is indium tin oxide glass (ITO), and thickness is 120nm; The concrete structure of comparative example's organic electroluminescence device is: substrate of glass/ITO/MoO 3/ NPB/Alq 3/ 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 (marine optics Ocean Optics company of the U.S., model: USB4000), current-voltage tester (Keithly company of the U.S., 2400), colorimeter (Japanese Konica Minolta company model:, model: CS-100A) test organic electroluminescence device brightness with change in voltage 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 voltage of comparative example's organic electroluminescence device and the graph of a relation of brightness.
As can be seen from Figure 2, under different voltage, all large than comparative example of the brightness of embodiment 5, in the time of 10V, the brightness of embodiment 5 is 8762cd/m 2, and that comparative example is only 6524cd/m 2, 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, the light extraction efficiency and the brightness that have improved 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, it is characterized in that, described composite anode is made up of the oxide skin(coating) of the substrate of glass stacking gradually, cesium salt layer, intermediate layer and rhenium, the material of described cesium salt layer is the one in cesium fluoride, cesium chloride and cesium carbonate, described kinds of interlayer is poly-(3,4-dioxoethyl thiophene) and gather the composite material that (p styrene sulfonic acid) is 2:1～6:1 formation in mass ratio, the material of the oxide skin(coating) of described rhenium is the one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums.
2. composite anode as claimed in claim 1, is characterized in that, the thickness of described cesium salt layer is 5～20nm.
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 the oxide skin(coating) of described rhenium is 5～20nm.
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;
Adopt the method for spin coating to prepare the oxide skin(coating) of described cesium salt layer, intermediate layer and rhenium in substrate of glass, obtain described composite anode; First, by the one in cesium fluoride, cesium chloride and cesium carbonate and solvent, form the cesiated salt solution that cesium salt mass fraction is 1%～40%, then on substrate of glass exiting surface, described in spin coating, cesiated salt solution obtains described cesium salt layer, described spin coating rotating speed is 500～6000rpm, time is 5～60s, after spin coating, is drying; To gather (3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid) be mixed to form composite material for 2:1～6:1 in mass ratio, after adding water, form poly-(3,4-dioxoethyl thiophene) the mass fraction aqueous solution that is 1%～5%, on cesium salt layer, the spin coating aqueous solution obtains intermediate layer, spin coating rotating speed is 500～8000rpm, and the time is 5～60s, spin coating post-drying; By the oxide of rhenium and solvent, the oxide solution of the rhenium that the oxide mass mark that forms rhenium is 10%～50%, the oxide of described rhenium is the one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums; On intermediate layer, the oxide solution of spin coating rhenium obtains the oxide skin(coating) of rhenium, and spin coating rotating speed is 500～8000rpm, and the time is 5～60s.
6. the preparation method of composite anode as claimed in claim 5, is characterized in that, the thickness of described cesium salt layer is 5～20nm.
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 the oxide skin(coating) of described rhenium is 5～20nm.
9. an organic electroluminescence device, it is characterized in that, comprise the composite anode stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described composite anode is by the substrate of glass stacking gradually, cesium salt layer, the oxide skin(coating) composition of intermediate layer and rhenium, the material of described cesium salt layer is cesium fluoride, one in cesium chloride and cesium carbonate, described intermediate layer is poly-(3, 4-dioxoethyl thiophene) and gather the composite material that (p styrene sulfonic acid) is 2:1～6:1 formation in mass ratio, the material of the oxide skin(coating) of described rhenium is rhenium dioxide, rhenium heptoxide, one in rhenium sesquioxide and oxidation two rheniums.
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;
On substrate of glass exiting surface, adopt the method for spin coating to prepare the oxide skin(coating) of described cesium salt layer, intermediate layer and rhenium, obtain described composite anode; First, by the one in cesium fluoride, cesium chloride and cesium carbonate and solvent, form the cesiated salt solution that cesium salt mass fraction is 1%～40%, then on substrate of glass exiting surface, described in spin coating, cesiated salt solution obtains described cesium salt layer, described spin coating rotating speed is 500～6000rpm, time is 5～60s, spin coating post-drying; To gather (3,4-dioxoethyl thiophene) and poly-(p styrene sulfonic acid) be mixed to form composite material for 2:1～6:1 in mass ratio, after adding water, form poly-(3,4-dioxoethyl thiophene) the mass fraction aqueous solution that is 1%～5%, on cesium salt layer, the spin coating aqueous solution obtains intermediate layer, spin coating rotating speed is 500～8000rpm, and the time is 5～60s, spin coating post-drying; By the oxide of rhenium and solvent, the oxide solution of the rhenium that the oxide mass mark that forms rhenium is 10%～50%, the oxide of described rhenium is the one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums; On intermediate layer, the oxide solution of spin coating rhenium obtains the oxide skin(coating) of rhenium, and spin coating rotating speed is 500～8000rpm, and the time is 5～60s, spin coating post-drying;
On the oxide skin(coating) of rhenium, evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, finally obtains described organic electroluminescence device.
CN201310077741.5A 2013-03-12 2013-03-12 Composite anode and preparation method thereof, and organic light-emitting device and preparation method thereof Pending CN104051657A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1617642A (en) * 2003-11-13 2005-05-18 爱美思公司 Organic electroluminescent devices
US20050170211A1 (en) * 2004-02-02 2005-08-04 Sharp Kabushiki Kaisha Organic electroluminescent element
CN102208461A (en) * 2010-03-30 2011-10-05 海洋王照明科技股份有限公司 Solar cell and preparation method thereof
CN102593372A (en) * 2012-03-21 2012-07-18 吉林大学 Flexible top-emitting organic electroluminescent device having ultra-smooth anode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1617642A (en) * 2003-11-13 2005-05-18 爱美思公司 Organic electroluminescent devices
US20050170211A1 (en) * 2004-02-02 2005-08-04 Sharp Kabushiki Kaisha Organic electroluminescent element
CN102208461A (en) * 2010-03-30 2011-10-05 海洋王照明科技股份有限公司 Solar cell and preparation method thereof
CN102593372A (en) * 2012-03-21 2012-07-18 吉林大学 Flexible top-emitting organic electroluminescent device having ultra-smooth anode

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Application publication date: 20140917