CN103928622B - A kind of organic electroluminescence device - Google Patents
A kind of organic electroluminescence device Download PDFInfo
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- CN103928622B CN103928622B CN201310015389.2A CN201310015389A CN103928622B CN 103928622 B CN103928622 B CN 103928622B CN 201310015389 A CN201310015389 A CN 201310015389A CN 103928622 B CN103928622 B CN 103928622B
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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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
The present invention provides a kind of organic electroluminescence device and preparation method thereof, described organic electroluminescence device includes the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, the material of described hole injection layer is the oxide mixture with zinc oxide of rhenium, possibly together with polyfluortetraethylene of binding element in hole injection layer, described hole injection layer has Nanostructure Network, and the aperture of described Nanostructure Network is 100nm～150nm.The hole transmission layer of the organic electroluminescence device of the present invention is mixed with by the oxide of rhenium, azo material, zinc oxide and politef, polyfluortetraethylene of binding element can improve the caking property between hole injection layer and adjacent layer, azo substance decomposition makes hole injection layer form Nanostructure Network, the photoelectric transformation efficiency of hole transport speed and device can be improved, preparation method is simple, has a extensive future.
Description
Technical field
The present invention relates to field of organic electroluminescence, particularly to a kind of organic electroluminescence device and preparation method thereof.
Background technology
1987, C.W.Tang and the VanSlyke of EastmanKodak company of the U.S. reported the breakthrough in organic electroluminescent research, utilized ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, under 10V, brightness reaches 1000cd/m2, its luminous efficiency is 1.51lm/W, and the life-span was more than 100 hours.
The principle of luminosity of OLED is based under the effect of extra electric field, 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, meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton migrates under electric field action, transfers energy to luminescent material, excite electronics from ground state transition to excited state, excited energy passes through Radiation-induced deactivation, produces photon, discharges luminous energy.
In traditional luminescent device, the material of hole injection layer is generally metal-oxide (such as molybdenum oxide), but now the material range of choice of hole injection layer is narrow, meanwhile, metal-oxide absorptance in visible-range is higher, sunlight is caused to lose, and metal-oxide is inorganic matter, relatively big with the organic material nature difference of hole transmission layer, both compatibilitys on the interface of contact are poor, preparation process easily occurs defect, causes hole loss and device light emitting efficiency to lower.
Summary of the invention
For solving the problems referred to above, it is desirable to provide a kind of organic electroluminescence device and preparation method thereof.The hole transmission layer of described organic electroluminescence device adopts the oxide of rhenium, azo material and zinc oxide are mixed with, and add the polyfluortetraethylene of binding element (PTFE) caking property to improve between hole injection layer and adjacent layer, wherein, the oxide work function of rhenium is relatively low, the energy level between hole injection layer with luminescent layer is made to differ less, it is beneficial to hole to inject, and azo substance decomposition makes hole injection layer form Nanostructure Network, hole transport passage can be increased, improve hole transport speed, simultaneous oxidation zinc can effectively stop that electronics traverses to anode generation electronics cancellation, thus improving the luminous efficiency of device.
First aspect, the present invention provides a kind of organic electroluminescence device, including the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, the material of described hole injection layer is the oxide mixture with zinc oxide (ZnO) of rhenium, possibly together with polyfluortetraethylene of binding element (PTFE) in hole injection layer, described hole injection layer has Nanostructure Network, and the aperture of described Nanostructure Network is 100nm～150nm；The oxide of described rhenium is rhenium dioxide (ReO2), rhenium heptoxide (Re2O7), rhenium sesquioxide (Re2O3) or oxidation two rhenium (Re2O)。
Hole injection layer in described organic electroluminescence device is by the oxide of rhenium, azo material, zinc oxide (ZnO) and politef (PTFE) doping prepare, polyfluortetraethylene of binding element (PTFE) can improve the caking property between hole injection layer and adjacent layer, and azo material is decomposed, simultaneously the oxide of rhenium and zinc oxide (ZnO) precipitate out, make hole injection layer form inside and there is Nanostructure Network, hole transport passage can be increased, improve hole transport speed, and the oxide work function of rhenium is relatively low, differ less with the energy level between luminescent layer, it is beneficial to hole to inject, zinc oxide can effectively stop that electronics traverses to anode generation electronics cancellation, thus improving the luminous efficiency of device.
Preferably, the oxide of described rhenium is (10～60) with the weight ratio of zinc oxide (ZnO): (0.5～10).
Described zinc oxide (ZnO) is commercially available zinc oxide (ZnO), it is preferable that the particle diameter of described zinc oxide (ZnO) is 20～200nm.
Preferably, described zinc oxide (ZnO) is (0.5～10) with the weight ratio of politef (PTFE): (0.5～5).Politef (PTFE) is as binding agent, in order to improve the caking property between hole injection layer and adjacent layer, politef (PTFE) is conventional binding agent, generally existing in the form of an emulsion, weight ratio herein is the weight ratio obtained after the quality of the politef (PTFE) being scaled in emulsion according to the mass fraction of emulsion.
Preferably, the thickness of described hole injection layer is 20～100nm.
Preferably, described conductive anode substrate is the glass with anode functional layer, for indium tin oxide glass (ITO), aluminum zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).It is highly preferred that described conductive anode substrate is indium tin oxide glass (ITO).Anode substrate is buy on market, and anode function layer thickness is 80～200nm.
Preferably, the material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) amino] phenyl] hexamethylene (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamines (TCTA) or N, N '-(1-naphthyl)-N; N '-diphenyl-4,4 '-benzidine (NPB)."-three (carbazole-9-base) triphenylamine (TCTA) it is highly preferred that described hole transmission layer is 4,4 ', 4.
Preferably, the thickness of described hole transmission layer is 40～60nm.It is highly preferred that the thickness of described hole transmission layer is 40nm.
Preferably, the material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl pyridine-9-vinyl in Lip river of a specified duration)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyls)-1,1 '-biphenyl (BCzVBi) or oxine aluminum (Alq3).It is highly preferred that the material of described luminescent layer is 4,4 '-bis-(9-ethyl-3-carbazole vinyls)-1,1 '-biphenyl (BCzVBi).
Preferably, the thickness of described luminescent layer is 5～40nm.It is highly preferred that the thickness of described luminescent layer is 30nm.
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazoles (TAZ) or N-aryl benzimidazole (TPBI).It is highly preferred that the material of described electron transfer layer is 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, the thickness of described electron transfer layer is 40～80nm.It is highly preferred that the thickness of described electron transfer layer is 45nm.
Preferably, the material of described electron injecting layer is cesium carbonate (Cs2CO3), cesium fluoride (CsF), nitrine caesium (CsN3) or lithium fluoride (LiF).
It is highly preferred that the material of described electron injecting layer is lithium fluoride (LiF).
Preferably, the thickness of described electron injecting layer is 0.5～10nm.It is highly preferred that the thickness of described electron injecting layer is 0.7nm.
Preferably, the material of described negative electrode is silver (Ag), aluminum (Al), platinum (Pt) or gold (Au).
It is highly preferred that the material of described negative electrode is silver (Ag).
Preferably, the thickness of described negative electrode is 60～300nm.It is highly preferred that the thickness of described negative electrode is 100nm.
Second aspect, the preparation method that the present invention provides a kind of organic electroluminescence device, including following operating procedure:
After conductive anode substrate cleaning, in conductive anode substrate, hole injection layer is prepared in spin coating, concrete preparation method is: the oxide of rhenium, azo material, zinc oxide (ZnO) and politef (PTFE) are added mix homogeneously in solvent, obtain mixture, mixture described in spin coating in conductive anode substrate, at 50～200 DEG C, dry 10～30min, obtains hole injection layer；Described hole injection layer has Nanostructure Network, and the aperture of described Nanostructure Network is 100nm～150nm；
Described azo material is azo-bis-isobutyrate hydrochloride (AIBA), azo two isobutyl imidazoline hydrochloride (AIBI) or azo isobutyl cyano group Methanamide (V30), and the oxide of described rhenium is rhenium dioxide (ReO2), rhenium heptoxide (Re2O7), rhenium sesquioxide (Re2O3) or oxidation two rhenium (Re2O)；
Then on hole injection layer, evaporation prepares hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device.
Described zinc oxide (ZnO) is commercially available zinc oxide (ZnO), it is preferable that the particle diameter of described zinc oxide (ZnO) is 20～200nm.
Described azo-initiator is the water-soluble azo class initiator with low decomposition temperature, for azo-bis-isobutyrate hydrochloride (AIBA), azo two isobutyl imidazoline hydrochloride (AIBI) or azo isobutyl cyano group Methanamide (V30).
Preferably, described solvent is water, ethanol or isopropanol.
Preferably, in described mixture, the oxide of rhenium: azo-initiator: zinc oxide (ZnO): the weight ratio of solvent is (10～60): (2～20): (0.5～10): 100.
Preferably, in described mixture, the weight ratio of described politef (PTFE) and solvent is (0.5～5): 100.Politef (PTFE) is as binding agent, in order to improve the caking property between hole injection layer and adjacent layer, politef (PTFE) is conventional binding agent, generally existing in the form of an emulsion, weight ratio herein is the weight ratio obtained after the quality of the politef (PTFE) being scaled in emulsion according to the mass fraction of emulsion.
Preferably, rotating speed during described spin coating is 500～6000rpm, and the time is 5～30s.
In the preparation method of hole injection layer, by the oxide of rhenium, azo material, zinc oxide (ZnO) and politef (PTFE) add spin coating after mix homogeneously in solvent, then dry, polyfluortetraethylene of binding element (PTFE) can improve the caking property between hole injection layer and adjacent layer, in dry run, azo material is decomposed, simultaneously the oxide of rhenium and zinc oxide (ZnO) precipitate out, form the internal hole transmission layer with Nanostructure Network, hole transport passage can be increased, improve hole transport speed, and the oxide work function of rhenium is relatively low, differ less with the energy level between luminescent layer, it is beneficial to hole to inject, zinc oxide can effectively stop that electronics traverses to anode generation electronics cancellation, thus improving the luminous efficiency of device.
Preferably, the thickness of described hole injection layer is 20～100nm.
Preferably, described conductive anode substrate is the glass with anode functional layer, for indium tin oxide glass (ITO), aluminum zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).It is highly preferred that described conductive anode substrate is indium tin oxide glass (ITO).Anode substrate is buy on market, and anode function layer thickness is 80～200nm.
Described cleaning is liquid detergent and each ultrasonic 15min of deionized water successively, removes the organic pollution of conductive anode substrate surface.
Preferably, the material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) amino] phenyl] hexamethylene (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamines (TCTA) or N, N '-(1-naphthyl)-N; N '-diphenyl-4,4 '-benzidine (NPB)."-three (carbazole-9-base) triphenylamine (TCTA) it is highly preferred that described hole transmission layer is 4,4 ', 4.
Preferably, the thickness of described hole transmission layer is 40～60nm.It is highly preferred that the thickness of described hole transmission layer is 40nm.
Preferably, described evaporation is prepared hole transmission layer and is adopted vacuum evaporation, and pressure during evaporation is 2 × 10-5Pa～2 × 10-3Pa, evaporation rate is 0.1～1nm/s.
Preferably, the material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl pyridine-9-vinyl in Lip river of a specified duration)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyls)-1,1 '-biphenyl (BCzVBi) or oxine aluminum (Alq3).It is highly preferred that the material of described luminescent layer is 4,4 '-bis-(9-ethyl-3-carbazole vinyls)-1,1 '-biphenyl (BCzVBi).
Preferably, the thickness of described luminescent layer is 5～40nm.It is highly preferred that the thickness of described luminescent layer is 30nm.
Preferably, described evaporation is prepared luminescent layer and is adopted vacuum evaporation, and pressure during evaporation is 2 × 10-5Pa～2 × 10-3Pa, evaporation rate is 0.1～1nm/s.
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazoles (TAZ) or N-aryl benzimidazole (TPBI).It is highly preferred that the material of described electron transfer layer is 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, the thickness of described electron transfer layer is 40～80nm.It is highly preferred that the thickness of described electron transfer layer is 45nm.
Preferably, described evaporation is prepared electron transfer layer and is adopted vacuum evaporation, and pressure during evaporation is 2 × 10-5Pa～2 × 10-3Pa, evaporation rate is 0.1～1nm/s.
Preferably, the material of described electron injecting layer is cesium carbonate (Cs2CO3), cesium fluoride (CsF), nitrine caesium (CsN3) or lithium fluoride (LiF).
It is highly preferred that the material of described electron injecting layer is lithium fluoride (LiF).
Preferably, the thickness of described electron injecting layer is 0.5～10nm.It is highly preferred that the thickness of described electron injecting layer is 0.7nm.
Preferably, described evaporation is prepared electron injecting layer and is adopted vacuum evaporation, and pressure during evaporation is 2 × 10-5Pa～2 × 10-3Pa, evaporation rate is 0.1～1nm/s.
Preferably, the material of described negative electrode is silver (Ag), aluminum (Al), platinum (Pt) or gold (Au).
It is highly preferred that the material of described negative electrode is silver (Ag).
Preferably, the thickness of described negative electrode is 60～300nm.It is highly preferred that the thickness of described negative electrode is 100nm.
Preferably, described evaporation is prepared negative electrode and is adopted vacuum evaporation, and pressure during evaporation is 2 × 10-5Pa～2 × 10-3Pa, evaporation rate is 1～10nm/s.
The hole transmission layer of organic electroluminescence device provided by the invention adopts the oxide of rhenium, azo material, zinc oxide and politef (PTFE) are mixed with, wherein, the oxide work function of rhenium is relatively low, at below-5.8eV, the injection in hole is favourable, and the HOMO energy level of luminescent layer is generally-5.5eV～-6.2eV, energy level between hole injection layer with luminescent layer differs less, interface potential barrier is low, energy loss is little, it is also beneficial to hole inject, the work function of simultaneous oxidation zinc is higher, differ bigger with the lumo energy of electron transfer layer, electron transport ability is weak, can effectively stop that electronics traverses to anode generation electronics cancellation, reduce the recombination probability of both hole and electron.In addition, politef (PTFE) is as binding agent, the caking property between hole injection layer and adjacent layer can be improved, azo material is decomposed in preparation process, hole injection layer is made to form Nanostructure Network, hole transport passage can being increased, improving hole transport speed, thus improving the luminous efficiency of device.
The present invention provides a kind of organic electroluminescence device and preparation method thereof, has the advantages that
(1) present invention prepares hole injection layer by the oxide of rhenium, azo material, zinc oxide and politef (PTFE) doping, the oxide work function of rhenium is relatively low, differ less with the energy level between luminescent layer, hole is conducive to inject, simultaneous oxidation zinc is as barrier layer, can effectively stop that electronics traverses to anode generation electronics cancellation, reduce the recombination probability of both hole and electron, improve photoelectric transformation efficiency.
(2) politef (PTFE) can improve the caking property between hole injection layer and adjacent layer, azo material is decomposed in preparation process, hole injection layer is made to form Nanostructure Network, hole transport passage can be increased, improve the luminous efficiency of hole transport speed and device.
(3) oxide ester mp of rhenium is relatively low, when it is as the material of hole injection layer, adopts the method for evaporation to prepare more difficult control, and the preparation method of the present invention is spin coating, and simple to operate controlled, properties of product are stable.
Accompanying drawing explanation
Fig. 1 is the structure chart of organic electroluminescence device prepared by the present invention, including the conductive anode substrate 1 stacked gradually, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6 and negative electrode 7.
Fig. 2 is the organic electroluminescence device of embodiment one preparation and the brightness-luminous efficiency change curve of comparative device in testing example, distinguishes homologous thread 1 and curve 2.
Detailed description of the invention
The following stated 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 making some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment one
A kind of organic electroluminescence device, preparation method comprises the following steps:
(1) 2 × 2cm will be first of a size of2Ito glass clean 15min with liquid detergent and deionized water ultrasonic cleaning successively, remove the organic pollution on surface, the ITO layer thickness of ito glass is 180nm；
On ito glass, hole injection layer is prepared in spin coating, and concrete operations are: according to Re2O7: AIBA: ZnO: politef (PTFE): the weight ratio of water is 30: 15: 1: 2: 100, by Re2O7, AIBA, ZnO, politef (PTFE) be added to the water mix homogeneously, obtain mixture, the particle diameter of ZnO is 50nm, and politef (PTFE) is E.I.Du Pont Company's product, and model is TE3885；With mixture described in the speed spin coating of 4000rpm on ito glass, spin-coating time is 10s, and then dry 25min at 100 DEG C, obtains hole injection layer, and thickness is 80nm；
(2) on hole injection layer, evaporation prepares hole transmission layer TCTA, luminescent layer BCzVBi, electron transfer layer TAZ, electron injecting layer LiF and negative electrode Ag successively, and evaporation condition and each layer thickness are as follows:
Pressure during evaporation hole transmission layer is 5 × 10-4Pa, evaporation rate is 0.2nm/s, and thickness is 40nm；
Pressure during evaporation luminescent layer is 5 × 10-4Pa, evaporation rate is 0.2nm/s, and thickness is 30nm；
Pressure during evaporation electron transfer layer is 5 × 10-4Pa, evaporation rate is 0.3nm/s, and thickness is 45nm；
Pressure during evaporation electron injecting layer is 5 × 10-4Pa, evaporation rate is 0.3nm/s, and thickness is 0.7nm；
Pressure during evaporation cathode is 5 × 10-4Pa, evaporation rate is 5nm/s, and thickness is 100nm, obtains organic electroluminescence device.
Wherein, after preparing hole injection layer, observing the three-dimensional displaing micro tissue topography of this layer with the scanning electron microscope equipment that model is CX-200TM, it can be observed that hole injection layer has Nanostructure Network, the aperture of Nanostructure Network is 100nm～120nm.
Organic electroluminescence device prepared by the present embodiment is bottom emitting organic electroluminescence device, including the conductive anode substrate 1 stacked gradually, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6 and negative electrode 7, structure is shown in Fig. 1, particularly as follows: ITO/ (Re2O7: ZnO)/TCTA/BCzVBi/TAZ/LiF/Ag.
The another preparation organic electroluminescence device for contrasting, is called for short comparative device, and for bottom emitting organic electroluminescence device, its structure is particularly as follows: ITO/V2O5/ TCTA/BCzVBi/TAZ/LiF/Ag, it is corresponding in turn to conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, ITO is anode, thickness is 180nm, directly buy the ito glass with ITO layer, the thickness of hole injection layer is 80nm, and pressure during evaporation preparation is 5 × 10-4Pa, evaporation rate is 0.3nm/s, and all the other each layer thicknesses and preparation method are consistent with the equivalent layer of the present embodiment organic electroluminescence device.Contrast is it can be seen that the present embodiment adopts Re2O7, AIBA, ZnO and politef (PTFE) doping prepare hole injection layer, the hole injection rate of this layer can be improved, and politef (PTFE) can improve the caking property between hole injection layer and adjacent layer, after the azo substance decomposition such as AIBA, hole injection layer exists Nanostructure Network, more hole transport passage can be provided, be beneficial to the luminous efficiency improving hole speed and device.
Embodiment two
A kind of organic electroluminescence device, preparation method comprises the following steps:
(1) 2 × 2cm will be first of a size of2AZO glass clean 15min with liquid detergent and deionized water ultrasonic cleaning successively, remove the organic pollution on surface, the AZO layer thickness of AZO glass is 80nm；
Preparing hole injection layer in AZO spin-on-glass, concrete operations are: according to ReO2: AIBI: ZnO: politef (PTFE): the weight ratio of ethanol is 10: 2: 0.5: 0.5: 100, by ReO2, AIBI, ZnO and politef (PTFE) add mix homogeneously in ethanol, obtain mixture, the particle diameter of ZnO is 20nm, and politef (PTFE) is E.I.Du Pont Company's product, and model is TE3885；With mixture described in the speed spin coating of 500rpm on AZO glass, spin-coating time is 5s, and then dry 10min at 200 DEG C, obtains hole injection layer, and thickness is 100nm；
(2) on hole injection layer, evaporation prepares hole transmission layer NPB, luminescent layer ADN, electron transfer layer Bphen, electron injecting layer Cs successively2CO3With negative electrode Al, evaporation condition and each layer thickness are as follows:
Pressure during evaporation hole transmission layer is 2 × 10-5Pa, evaporation rate is 0.1nm/s, and thickness is 60nm；
Pressure during evaporation luminescent layer is 2 × 10-5Pa, evaporation rate is 0.1nm/s, and thickness is 5nm；
Pressure during evaporation electron transfer layer is 2 × 10-5Pa, evaporation rate is 0.1nm/s, and thickness is 75nm；
Pressure during evaporation electron injecting layer is 2 × 10-5Pa, evaporation rate is 0.1nm/s, and thickness is 5nm；
Pressure during evaporation cathode is 2 × 10-5Pa, evaporation rate is 10nm/s, and thickness is 300nm, obtains organic electroluminescence device.
Wherein, after preparing hole injection layer, observing the three-dimensional displaing micro tissue topography of this layer with the scanning electron microscope equipment that model is CX-200TM, it can be observed that hole injection layer has Nanostructure Network, the aperture of Nanostructure Network is 120nm～130nm.
Organic electroluminescence device prepared by the present embodiment is top radiation organic EL part, including the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, particularly as follows: AZO/ (ReO2: ZnO)/NPB/ADN/Bphen/Cs2CO3/Al。
Embodiment three
A kind of organic electroluminescence device, preparation method comprises the following steps:
(1) 2 × 2cm will be first of a size of2IZO glass clean 15min with liquid detergent and deionized water ultrasonic cleaning successively, remove the organic pollution on surface, the IZO layer thickness of IZO glass is 100nm；
Preparing hole injection layer in IZO spin-on-glass, concrete operations are: according to Re2O3: V30: ZnO: politef (PTFE): the weight ratio of isopropanol is 60: 20: 10: 5: 100, by Re2O3, V30, ZnO and politef (PTFE) add mix homogeneously in isopropanol, obtain mixture, ZnO particle diameter is 200nm, and politef (PTFE) is E.I.Du Pont Company's product, and model is TE3885；
With mixture described in the speed spin coating of 6000rpm on IZO glass, spin-coating time is 30s, and then dry 30min at 50 DEG C, obtains hole injection layer, and thickness is 20nm；
(2) on hole injection layer, evaporation prepares hole transmission layer TAPC, luminescent layer Alq successively3, electron transfer layer TPBi, electron injecting layer CsN3With negative electrode Pt, evaporation condition and each layer thickness are as follows:
Pressure during evaporation hole transmission layer is 2 × 10-3Pa, evaporation rate is 1nm/s, and thickness is 45nm；
Pressure during evaporation luminescent layer is 2 × 10-3Pa, evaporation rate is 1nm/s, and thickness is 40nm；
Pressure during evaporation electron transfer layer is 2 × 10-3Pa, evaporation rate is 1nm/s, and thickness is 60nm；
Pressure during evaporation electron injecting layer is 2 × 10-3Pa, evaporation rate is 1nm/s, and thickness is 10nm；
Pressure during evaporation cathode is 2 × 10-3Pa, evaporation rate is 1nm/s, and thickness is 60nm, obtains organic electroluminescence device.
Wherein, after preparing hole injection layer, observing the three-dimensional displaing micro tissue topography of this layer with the scanning electron microscope equipment that model is CX-200TM, it can be observed that hole injection layer has Nanostructure Network, the aperture of Nanostructure Network is 125nm～140nm.
Organic electroluminescence device prepared by the present embodiment is top radiation organic EL part, including the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, particularly as follows: IZO/ (Re2O3: ZnO)/TAPC/Alq3/TPBi/CsN3/Pt。
Embodiment four
A kind of organic electroluminescence device, preparation method comprises the following steps:
(1) 2 × 2cm will be first of a size of2IZO glass clean 15min with liquid detergent and deionized water ultrasonic cleaning successively, remove the organic pollution on surface, the IZO layer thickness of IZO glass is 200nm；
Preparing hole injection layer in IZO spin-on-glass, concrete operations are: according to Re2O: AIBA: ZnO: politef (PTFE): the weight ratio of water is 20: 10: 5: 2.5: 100, by Re2O, AIBA, ZnO and politef (PTFE) are added to the water mix homogeneously, obtain mixture, and ZnO particle diameter is 100nm, and politef (PTFE) is E.I.Du Pont Company's product, and model is TE3885；
With mixture described in the speed spin coating of 2000rpm on IZO glass, spin-coating time is 15s, and then dry 20min at 150 DEG C, obtains hole injection layer, and thickness is 40nm；
(2) on hole injection layer, evaporation prepares hole transmission layer NPB, luminescent layer DCJTB, electron transfer layer TPBi, electron injecting layer CsF and negative electrode Au successively, and evaporation condition and each layer thickness are as follows:
Pressure during evaporation hole transmission layer is 8 × 10-5Pa, evaporation rate is 0.3nm/s, and thickness is 60nm；
Pressure during evaporation luminescent layer is 8 × 10-5Pa, evaporation rate is 0.3nm/s, and thickness is 8nm；
Pressure during evaporation electron transfer layer is 8 × 10-5Pa, evaporation rate is 0.5nm/s, and thickness is 35nm；
Pressure during evaporation electron injecting layer is 8 × 10-5Pa, evaporation rate is 0.5nm/s, and thickness is 0.5nm；
Pressure during evaporation cathode is 8 × 10-5Pa, evaporation rate is 3nm/s, and thickness is 120nm, obtains organic electroluminescence device.
Wherein, after preparing hole injection layer, observing the three-dimensional displaing micro tissue topography of this layer with the scanning electron microscope equipment that model is CX-200TM, it can be observed that hole injection layer has Nanostructure Network, the aperture of Nanostructure Network is 120nm～150nm.
Organic electroluminescence device prepared by the present embodiment is top radiation organic EL part, including the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, particularly as follows: IZO/ (Re2O:ZnO)/NPB/DCJTB/TPBi/CsF/Au.
Testing example
Adopt current-voltage tester (Keithly company of the U.S., model: 2400) and electroluminescent spectrum tester (photoresearch company of the U.S., model: PR650) test the luminous efficiency of organic electroluminescence device with brightness flop curve, maximum lumen efficiency can be obtained by change curve, to investigate the luminous efficiency of device, test object includes organic electroluminescence device and the comparative device of embodiment one～tetra-preparation.Fig. 2 is the brightness-luminous efficiency change curve of the organic electroluminescence device and the comparative device that comprise doping hole injection layer of embodiment one preparation, homologous thread 1 and curve 2 respectively.The organic electroluminescence device of embodiment one～tetra-preparation and the maximum lumen efficiency data of comparative device are in Table 1.
The organic electroluminescence device of table 1 present invention and the maximum lumen efficiency data table of comparative device
From Fig. 2 and table 1, at different brightnesses, the luminous efficiency of the organic electroluminescence device of embodiment one preparation is all high than the luminous efficiency of comparative device, and the speed that the luminous efficiency of comparative device declines along with the increase of brightness is very fast；The maximum lumen efficiency of the organic electroluminescence device of embodiment one～tetra-preparation is 8.98～11.45m/W, and comparative device is only 8.551m/W, and device light emitting efficiency and stability that namely prepared by the present invention are higher than comparative device.The present invention oxide by rhenium is described, azo material and Zinc oxide doped prepare hole injection layer, the oxide work function of rhenium is relatively low, differ less with the energy level between luminescent layer, hole is conducive to inject, simultaneous oxidation zinc can effectively stop that electronics traverses to anode generation electronics cancellation, reduce the recombination probability of both hole and electron, and politef (PTFE) can improve the caking property between hole injection layer and adjacent layer, azo material is decomposed in preparation process, hole injection layer is made to form Nanostructure Network, hole transport passage can be increased, improve the luminous efficiency of hole transport speed and 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 making some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (5)
1. an organic electroluminescence device, it is characterized in that, including the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, the material of described hole injection layer is the oxide mixture with zinc oxide of rhenium, possibly together with polyfluortetraethylene of binding element in hole injection layer, described hole injection layer has Nanostructure Network, and the aperture of described Nanostructure Network is 100nm～150nm；The oxide of described rhenium is rhenium dioxide, rhenium heptoxide, rhenium sesquioxide or oxidation two rheniums.
2. organic electroluminescence device as claimed in claim 1, it is characterised in that the oxide of described rhenium and the weight ratio of zinc oxide are (10～60): (0.5～10).
3. organic electroluminescence device as claimed in claim 1, it is characterised in that the particle diameter of described zinc oxide is 20～200nm.
4. organic electroluminescence device as claimed in claim 1, it is characterised in that the weight ratio of described zinc oxide and politef is (0.5～10): (0.5～5).
5. organic electroluminescence device as claimed in claim 1, it is characterised in that the thickness of described hole injection layer is 20～100nm.
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| CN1922928A (en) * | 2004-03-05 | 2007-02-28 | 出光兴产株式会社 | Organic electroluminescent element and organic el display device |
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| JP2006114928A (en) * | 2005-12-09 | 2006-04-27 | Idemitsu Kosan Co Ltd | N-type inorganic semiconductor, n-type inorganic semiconductor thin film and method of manufacturing the same |
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