CN104124365A - Organic light-emitting device and preparation method thereof - Google Patents

Organic light-emitting device and preparation method thereof Download PDF

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Publication number
CN104124365A
CN104124365A CN201310143951.XA CN201310143951A CN104124365A CN 104124365 A CN104124365 A CN 104124365A CN 201310143951 A CN201310143951 A CN 201310143951A CN 104124365 A CN104124365 A CN 104124365A
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layer
electron
glass
silicon compound
bis
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周明杰
黄辉
张振华
王平
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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 CN201310143951.XA priority Critical patent/CN104124365A/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
    • H10K50/82—Cathodes
    • H10K50/826—Multilayers, e.g. opaque multilayers
    • 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
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • 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
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/856—Arrangements for extracting light from the devices comprising reflective means

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides an organic light-emitting device and a preparation method thereof. According to the organic light-emitting device, a first metal layer, a silicon compound doping layer, and a second metal layer are successively laminated to form a cathode. Therefore, the electron injection capability and stability of the device are improved and the light can reach the conductive anode glass substrate effectively, thereby improving the luminous efficiency of the device. The preparation method is simple and is easy to control and operation; and the raw material is easy to access.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of taking organic material as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, has application prospect very widely in fields such as demonstration, illuminations.
The structure of organic electroluminescence device is sandwich structure, accompanies one or more layers organic film between negative electrode and conductive anode.Containing in the device of sandwich construction, inner side, the two poles of the earth mainly comprises luminescent layer, implanted layer and transport layer.Organic electroluminescence device is carrier injection type luminescent device, add after operating voltage at anode and negative electrode, hole is from anode, electronics is injected into respectively the organic material layer of device work from negative electrode, it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode.
In traditional luminescent device, general is all using the metal of low work function or alloy as negative electrode, in this structure, the metallochemistry character of low work function is active, in air, be easy to oxidation, make the less stable of device, and the electronic injection ability of negative electrode is not good, cause device luminous efficiency, to go out optical property lower.
Summary of the invention
In order to address the above problem, the present invention aims to provide a kind of organic electroluminescence device compared with high light-emitting efficiency and preparation method thereof that has.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described negative electrode comprises the first metal layer, silicon compound doped layer and the second metal level that stack gradually, the material of described the first metal layer is magnesium, strontium, one in calcium and ytterbium, the material of described silicon compound doped layer is the first composite material that silicon compound and the electron transport material ratio that is 0.5:1～1:1 according to mass ratio forms, described silicon compound is silicon monoxide, one in silicon dioxide and sodium metasilicate, described electron transport material is 4, 7-diphenyl-1, 10-phenanthroline, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene, 2-(4-tert-butyl benzene)-5-(4-xenyl)-1, 3, 4-oxazole and 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] in one, the material of described the second metal level is the second composite material of a kind of ratio formation that is 20:1～5:1 according to mass ratio in a kind of and silver, aluminium, platinum and the gold in magnesium, strontium, calcium and ytterbium.
Preferably, conductive anode substrate of glass is the one in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).
Preferably, the material of hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in one.More preferably, the material of hole injection layer is MoO 3.
Preferably, the thickness of hole injection layer is 20～80nm.More preferably, the thickness of hole injection layer is 40nm.
Preferably, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the one in 4'-diamines (NPB).More preferably, the material of hole transmission layer is TCTA.
Preferably, the thickness of hole transmission layer is 20～60nm.More preferably, the thickness of hole transmission layer is 50nm.
Preferably, the material of luminescent layer 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-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in one.More preferably, the material of luminescent layer is Alq 3.
Preferably, the thickness of luminescent layer is 5～40nm.More preferably, the thickness of luminescent layer is 20nm.
The material of electron transfer layer is to have higher electron mobility, the effectively organic molecule material of conduction electron.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, the one in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of electron transfer layer is TAZ.
Preferably, the thickness of electron transfer layer is 40～200nm.More preferably, the thickness of electron transfer layer is 200nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) in one.More preferably, the material of the second electron injecting layer is LiF.
Preferably, the thickness of electron injecting layer is 0.5～10nm.More preferably, the thickness of electron injecting layer is 0.7nm.
Negative electrode is arranged on electron injecting layer.Negative electrode comprises the first metal layer, silicon compound doped layer and the second metal level that stack gradually.
The material of the first metal layer is the metal of work function-2.0eV～-3.5eV, is selected from the one in magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb).
On electron injecting layer, prepare the first metal layer that one deck is made up of low workfunction metal, low workfunction metal can reduce the injection barrier of electronics, effectively improves the injection efficiency of electronics.
Preferably, the thickness of the first metal layer is 1～5nm.
The material of silicon compound doped layer is the first composite material that silicon compound and the electron transport material ratio that is 0.5:1～1:1 according to mass ratio forms.
Silicon compound particle is larger, be microspheroidal, rete is formed and arrange orderly micro-sphere structure, reach lenticular effect, change the incidence angle of scattered light, carry out again rescattering, improve front lighting intensity, and easy crystallization electron transport material can improve the transmission rate of electronics, after crystallization, make segment marshalling, make film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, thereby can not be coupled with the free electron of metal level, the loss of avoiding parallel free electron to produce with vertical photon coupling, improve photon utilance.
Silicon compound is silicon monoxide (SiO), silicon dioxide (SiO 2) and sodium metasilicate (Na 2siO 3) in one.
Electron transport material is the organic material for the easy crystallization of transmission electronic, and its glass transition temperature is 50～100 ° of C.
Electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 2-(4-tert-butyl benzene)-5-(4-xenyl)-1,3,4-oxazole and 2,2'-(1,3-phenyl) one in two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles].
Preferably, the thickness of silicon compound doped layer is 10～50nm.
The material of the second metal level is the second composite material of a kind of ratio formation that is 20:1～5:1 according to mass ratio in one and silver (Ag), aluminium (Al), platinum (Pt) and the gold (Au) in magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb).
Magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb) are the low workfunction metal of work function-2.0eV～-3.5eV.Silver (Ag), aluminium (Al), platinum (Pt) and gold (Au) are the high-work-function metal of work function-4.0eV～-5.5eV.The composite material that low workfunction metal and high-work-function metal are mixed to form, low workfunction metal can reduce potential barrier, improve electron injection efficiency, high-work-function metal improves device stability, make light reflect at cathode terminal simultaneously, light reflects back into the bottom outgoing of device, has effectively improved the luminous efficiency of device.
Preferably, the thickness of the second metal level is 100～300nm.
Preferably, the thickness of negative electrode is 111～350nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
Clean conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively, and the condition of described thermal resistance evaporation is pressure 5 × 10 -5～2 × 10 -3pa, the evaporation speed of described hole injection layer and electron injecting layer is 1～10nm/s, the evaporation speed of described hole transmission layer, luminescent layer and electron transfer layer is 0.1～1nm/s;
On described electron injecting layer, thermal resistance evaporation prepares that the first metal layer, electron beam evaporation plating are prepared silicon compound doped layer, thermal resistance evaporation is prepared the second metal level, obtains negative electrode successively, wherein, the material of described the first metal layer is magnesium, strontium, one in calcium and ytterbium, the material of described silicon compound doped layer is the first composite material that silicon compound and the electron transport material ratio that is 0.5:1～1:1 according to mass ratio forms, described silicon compound is silicon monoxide, one in silicon dioxide and sodium metasilicate, described electron transport material is 4, 7-diphenyl-1, 10-phenanthroline, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene, 2-(4-tert-butyl benzene)-5-(4-xenyl)-1, 3, 4-oxazole and 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] in one, the material of described the second metal level is the second composite material of a kind of ratio formation that is 20:1～5:1 according to mass ratio in a kind of and silver, aluminium, platinum and the gold in magnesium, strontium, calcium and ytterbium, and described thermal resistance evaporation condition is pressure 5 × 10 -5～2 × 10 -3pa, speed 1～10nm/s, described electron beam evaporation plating condition is energy density 10～100W/cm 2,
After above step completes, obtain described organic electroluminescence device.
Preferably, conductive anode substrate of glass is the one in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).
Preferably, conductive anode substrate of glass is carried out to photoetching treatment, be then cut into needed size.
By the cleaning to conductive anode substrate of glass, remove surperficial organic pollution.
Particularly, the clean operation of conductive anode substrate of glass is: conductive anode substrate of glass is used to liquid detergent, the each ultrasonic cleaning 15min of deionized water successively, remove surperficial organic pollution, obtain clean conductive anode substrate of glass.
By the method for thermal resistance evaporation, in clean conductive anode substrate of glass, evaporation arranges hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively.Wherein, the condition of thermal resistance evaporation is pressure 5 × 10 -5～2 × 10 -3pa, the evaporation speed of hole injection layer and electron injecting layer is 1～10nm/s, the evaporation speed of hole transmission layer, luminescent layer and electron transfer layer is 0.1～1nm/s.
Preferably, the material of hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in one.More preferably, the material of hole injection layer is MoO 3.
Preferably, the thickness of hole injection layer is 20～80nm.More preferably, the thickness of hole injection layer is 40nm.
Preferably, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the one in 4'-diamines (NPB).More preferably, the material of hole transmission layer is TCTA.
Preferably, the thickness of hole transmission layer is 20～60nm.More preferably, the thickness of hole transmission layer is 50nm.
Preferably, the material of luminescent layer 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-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in one.More preferably, the material of luminescent layer is Alq 3.
Preferably, the thickness of luminescent layer is 5～40nm.More preferably, the thickness of luminescent layer is 20nm.
The material of electron transfer layer is to have higher electron mobility, the effectively organic molecule material of conduction electron.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, the one in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of electron transfer layer is TAZ.
Preferably, the thickness of electron transfer layer is 40～200nm.More preferably, the thickness of electron transfer layer is 200nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) in one.More preferably, the material of the second electron injecting layer is LiF.
Preferably, the thickness of electron injecting layer is 0.5～10nm.More preferably, the thickness of electron injecting layer is 0.7nm.
Negative electrode is arranged on electron injecting layer by evaporation.Negative electrode comprises the first metal layer, silicon compound doped layer and the second metal level that stack gradually.
The first metal layer is arranged on electron injecting layer by the method for thermal resistance evaporation.
The material of the first metal layer is the metal of work function-2.0eV～-3.5eV, is selected from the one in magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb).
On electron injecting layer, prepare the first metal layer that one deck is made up of low workfunction metal, low workfunction metal can reduce the injection barrier of electronics, effectively improves the injection efficiency of electronics.
Preferably, the thickness of the first metal layer is 1～5nm.
Silicon compound doped layer is arranged on the first metal layer by the method for electron beam evaporation plating.
The material of silicon compound doped layer is the first composite material that silicon compound and the electron transport material ratio that is 0.5:1～1:1 according to mass ratio forms.
Silicon compound particle is larger, be microspheroidal, rete is formed and arrange orderly micro-sphere structure, reach lenticular effect, change the incidence angle of scattered light, carry out again rescattering, improve front lighting intensity, and easy crystallization electron transport material can improve the transmission rate of electronics, after crystallization, make segment marshalling, make film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, thereby can not be coupled with the free electron of metal level, the loss of avoiding parallel free electron to produce with vertical photon coupling, improve photon utilance.
Silicon compound is silicon monoxide (SiO), silicon dioxide (SiO 2) and sodium metasilicate (Na 2siO 3) in one.
Electron transport material is the organic material for the easy crystallization of transmission electronic, and its glass transition temperature is 50～100 ° of C.
Electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 2-(4-tert-butyl benzene)-5-(4-xenyl)-1,3,4-oxazole and 2,2'-(1,3-phenyl) one in two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles].
Preferably, the thickness of silicon compound doped layer is 10～50nm.
The second metal level is arranged on silicon compound doped layer by the method for thermal resistance evaporation.
The material of the second metal level is the second composite material of a kind of ratio formation that is 20:1～5:1 according to mass ratio in one and silver (Ag), aluminium (Al), platinum (Pt) and the gold (Au) in magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb).
Magnesium (Mg), strontium (Sr), calcium (Ca) and ytterbium (Yb) are the low workfunction metal of work function-2.0eV～-3.5eV.Silver (Ag), aluminium (Al), platinum (Pt) and gold (Au) are the high-work-function metal of work function-4.0eV～-5.5eV.The composite material that low workfunction metal and high-work-function metal are mixed to form, low workfunction metal can reduce potential barrier, improve electron injection efficiency, high-work-function metal improves device stability, make light reflect at cathode terminal simultaneously, light reflects back into the bottom outgoing of device, has effectively improved the luminous efficiency of device.
Preferably, the thickness of the second metal level is 100～300nm.
Preferably, the thickness of negative electrode is 111～350nm.
The present invention has following beneficial effect:
(1) organic electroluminescence device that prepared by the present invention adopts the first metal layer, silicon compound doped layer and the second metal level that stack gradually as negative electrode, electronic injection ability, the stability of device are improved, and make luminous energy more effectively arrive at conductive anode substrate of glass, thereby improve the luminous efficiency of device.
(2) the first metal layer adopts low workfunction metal to improve the injection efficiency of electronics; Silicon compound doped layer is made up of the electron transport material of silicon compound and easily crystallization, can reach lenticular effect, the incidence angle of the light that change scattering is come, light is carried out to scattering, make film surface form wave structure, make the light scattering of Vertical Launch, improve photon utilance; The second metal level is the composite material that low workfunction metal and high-work-function metal are mixed to form, and improves the reflection of light at cathode terminal, has effectively improved the luminous efficiency of device.
(3) preparation method of the present invention is simple, be easy to control and operation, and raw material easily obtains.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art 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 structure chart of the organic electroluminescence device that provides of the embodiment of the present invention 1;
Fig. 2 is the current density of organic electroluminescence device and the graph of a relation of current efficiency that the organic electroluminescence device that provides of the embodiment of the present invention 1 and comparative example provide.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Be below specific embodiment and comparative example part, wherein, "/" represents stacked, and ": " represents the mass ratio of the former with the latter.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by ito glass liquid detergent, the each ultrasonic cleaning 15min of deionized water for substrate, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 8 × 10 -5under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, the material of hole injection layer is MoO 3, thickness is 40nm; The material of hole transmission layer is TCTA, and thickness is 50nm; The material of luminescent layer is Alq3, and thickness is 20nm; The material of electron transfer layer is TAZ, and thickness is 200nm; The material of electron injecting layer is LiF, and thickness is 0.7nm.
Wherein, MoO 3with the evaporation speed of LiF be 3nm/s, the evaporation speed of TCTA, Alq3 and TAZ is 0.2nm/s;
(3) be 8 × 10 at pressure -5under the condition of Pa, on electron injecting layer, prepare negative electrode, first prepare the first metal layer with the speed thermal resistance evaporation of 3nm/s, then taking energy density as 50W/cm 2electron beam evaporation plating prepare silicon compound doped layer, finally prepare the second metal level with the speed thermal resistance evaporation of 3nm/s, obtain negative electrode.
Particularly, in the present embodiment, the material of the first metal layer is Mg, and thickness is 2nm; The material of silicon compound doped layer is SiO 2be the composite material of 0.6:1 formation with Bphen according to mass ratio, thickness is 25nm; The material of the second metal level is that Mg and Ag are the composite material that 10:1 forms according to mass ratio, and thickness is 150nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ITO/MoO 3/ TCTA/Alq3/TAZ/LiF/Mg/SiO 2: Bphen(0.6:1)/Mg:Ag(10:1).
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises that the conductive anode substrate of glass 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and the negative electrode 70(that stack gradually comprise the first metal layer 701, silicon compound doped layer 702, the second metal level 703).
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by AZO liquid detergent, the each ultrasonic cleaning 15min of deionized water for substrate of glass, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 2 × 10 -3under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, the material of hole injection layer is WO 3, thickness is 80nm; The material of hole transmission layer is TCTA, and thickness is 60nm; The material of luminescent layer is ADN, and thickness is 5nm; The material of electron transfer layer is Bphen, and thickness is 200nm; The material of electron injecting layer is CsF, and thickness is 10nm.
Wherein, WO 3with the evaporation speed of CsF be 10nm/s, the evaporation speed of TCTA, ADN and Bphen is 0.1nm/s;
(3) be 2 × 10 at pressure -3under the condition of Pa, on electron injecting layer, prepare negative electrode, first prepare the first metal layer with the speed thermal resistance evaporation of 10nm/s, then taking energy density as 10W/cm 2electron beam evaporation plating prepare silicon compound doped layer, finally prepare the second metal level with the speed thermal resistance evaporation of 10nm/s, obtain negative electrode.
Particularly, in the present embodiment, the material of the first metal layer is Sr, and thickness is 1nm; The material of silicon compound doped layer is that SiO and BCP are the composite material that 1:1 forms according to mass ratio, and thickness is 10nm; The material of the second metal level is that Ca and Al are the composite material that 5:1 forms according to mass ratio, and thickness is 100nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: AZO/WO 3/ TCTA/ADN/Bphen/CsF/Sr/SiO:BCP(1:1)/Ca:Al(5:1).
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by IZO liquid detergent, the each ultrasonic cleaning 15min of deionized water for substrate of glass, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 × 10 -5under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, the material of hole injection layer is V 2o 5, thickness is 20nm; The material of hole transmission layer is TAPC, and thickness is 30nm; The material of luminescent layer is BCzVBi, and thickness is 40nm; The material of electron transfer layer is TAZ, and thickness is 60nm; The material of electron injecting layer is Cs 2cO 3, thickness is 0.5nm.
Wherein, V 2o 5and Cs 2cO 3evaporation speed be 1nm/s, the evaporation speed of TAPC, BCzVBi and TAZ is 1nm/s;
(3) be 5 × 10 at pressure -5under the condition of Pa, on electron injecting layer, prepare negative electrode, first prepare the first metal layer with the speed thermal resistance evaporation of 1nm/s, then taking energy density as 100W/cm 2electron beam evaporation plating prepare silicon compound doped layer, finally prepare the second metal level with the speed thermal resistance evaporation of 1nm/s, obtain negative electrode.
Particularly, in the present embodiment, the material of the first metal layer is Ca, and thickness is 5nm; The material of silicon compound doped layer is Na 2siO 3be the composite material of 0.5:1 formation with PBD according to mass ratio, thickness is 50nm; The material of the second metal level is that Yb and Pt are the composite material that 20:1 forms according to mass ratio, and thickness is 300nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO/V 2o 5/ TAPC/BCzVBi/TAZ/Cs 2cO 3/ Ca/Na 2siO 3: PBD(0.5:1)/Yb:Pt(20:1).
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by IZO liquid detergent, the each ultrasonic cleaning 15min of deionized water for substrate of glass, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 × 10 -4under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass;
Particularly, in the present embodiment, the material of hole injection layer is MoO 3, thickness is 30nm; The material of hole transmission layer is NPB, and thickness is 20nm; The material of luminescent layer is DCJTB, and thickness is 5nm; The material of electron transfer layer is TPBi, and thickness is 40nm; The material of electron injecting layer is CsN 3, thickness is 1nm.
Wherein, MoO 3and CsN 3evaporation speed be 5nm/s, the evaporation speed of NPB, DCJTB and TPBi is 0.2nm/s;
(3) be 5 × 10 at pressure -4under the condition of Pa, on electron injecting layer, prepare negative electrode, first prepare the first metal layer with the speed thermal resistance evaporation of 5nm/s, then taking energy density as 30W/cm 2electron beam evaporation plating prepare silicon compound doped layer, finally prepare the second metal level with the speed thermal resistance evaporation of 5nm/s, obtain negative electrode.
Particularly, in the present embodiment, the material of the first metal layer is Yb, and thickness is 2nm; The material of silicon compound doped layer is SiO 2be the composite material of 0.6:1 formation with OXD-7 according to mass ratio, thickness is 15nm; The material of the second metal level is that Sr and Au are the composite material that 10:1 forms according to mass ratio, and thickness is 200nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO/MoO 3/ NPB/DCJTB/TPBi/CsN 3/ Yb/SiO 2: OXD-7(0.6:1)/Sr:Au(10:1).
Comparative example
A preparation method for organic electroluminescence device, comprises the following steps:
(1) by ito glass liquid detergent, the each ultrasonic cleaning 15min of deionized water for substrate, obtain clean conductive anode substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 8 × 10 -5under the condition of Pa, thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively in clean conductive anode substrate of glass, thermal resistance evaporation negative electrode on electron injecting layer.
Particularly, in the present embodiment, the material of hole injection layer is MoO 3, thickness is 40nm; The material of hole transmission layer is TCTA, and thickness is 50nm; The material of luminescent layer is Alq3, and thickness is 20nm; The material of electron transfer layer is TAZ, and thickness is 200nm; The material of electron injecting layer is LiF, and thickness is 0.7nm; The material of negative electrode is Ag, and thickness is 150.
Wherein, MoO 3, LiF and Ag evaporation speed be 3nm/s, the evaporation speed of TCTA, Alq3 and TAZ is 0.2nm/s;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ITO/MoO 3/ TCTA/Alq3/TAZ/LiF/Ag.
Utilize the Keithley2400 test electric property of Keithley company of the U.S., colorimeter (Japanese Konica Minolta company, model: CS-100A) test brightness and colourity, fiber spectrometer (marine optics company of the U.S., model: USB4000) testing electroluminescent spectrum.
Fig. 2 is the organic electroluminescence device of embodiment 1 and the current density of the organic electroluminescence device of comparative example and the graph of a relation of current efficiency.Wherein, curve 1 is the current density of organic electroluminescence device and the graph of a relation of current efficiency of embodiment 1; The current density of organic electroluminescence device and the graph of a relation of current efficiency that curve 2 provides for comparative example.
As can see from Figure 2, under different current densities, all large than comparative example of the current efficiency of embodiment 1, the maximum current efficiency of embodiment 1 is 7.86cd/A, and that comparative example is only 5.96cd/A, this explanation, negative electrode can reduce the injection barrier of electronics, and the incidence angle of the light that change scattering is come, carries out scattering to light, make film surface form wave structure, improve photon utilance.Improve the reflection of light at cathode terminal simultaneously, make light reflect back into the bottom outgoing of device, effectively improved the luminous efficiency of device.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (6)

1. an organic electroluminescence device, it is characterized in that, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described negative electrode comprises the first metal layer, silicon compound doped layer and the second metal level that stack gradually, the material of described the first metal layer is magnesium, strontium, one in calcium and ytterbium, the material of described silicon compound doped layer is the first composite material that silicon compound and the electron transport material ratio that is 0.5:1～1:1 according to mass ratio forms, described silicon compound is silicon monoxide, one in silicon dioxide and sodium metasilicate, described electron transport material is 4, 7-diphenyl-1, 10-phenanthroline, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene, 2-(4-tert-butyl benzene)-5-(4-xenyl)-1, 3, 4-oxazole and 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] in one, the material of described the second metal level is the second composite material of a kind of ratio formation that is 20:1～5:1 according to mass ratio in a kind of and silver, aluminium, platinum and the gold in magnesium, strontium, calcium and ytterbium.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described conductive anode substrate of glass is the one in indium tin oxide glass, aluminium zinc oxide glass and indium-zinc oxide glass.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described hole injection layer is the one in molybdenum trioxide, tungstic acid and vanadic oxide; The material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the one in 4'-diamines; The material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis-(betanaphthyl) anthracene, 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1, the one in 1 '-biphenyl and oxine aluminium; The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2, the one in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material of electron injecting layer is the one in cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
4. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Clean conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively, and the condition of described thermal resistance evaporation is pressure 5 × 10 -5～2 × 10 -3pa, the evaporation speed of described hole injection layer and electron injecting layer is 1～10nm/s, the evaporation speed of described hole transmission layer, luminescent layer and electron transfer layer is 0.1～1nm/s;
On described electron injecting layer, thermal resistance evaporation prepares that the first metal layer, electron beam evaporation plating are prepared silicon compound doped layer, thermal resistance evaporation is prepared the second metal level, obtains negative electrode successively, wherein, the material of described the first metal layer is magnesium, strontium, one in calcium and ytterbium, the material of described silicon compound doped layer is the first composite material that silicon compound and the electron transport material ratio that is 0.5:1～1:1 according to mass ratio forms, described silicon compound is silicon monoxide, one in silicon dioxide and sodium metasilicate, described electron transport material is 4, 7-diphenyl-1, 10-phenanthroline, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene, 2-(4-tert-butyl benzene)-5-(4-xenyl)-1, 3, 4-oxazole and 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] in one, the material of described the second metal level is the second composite material of a kind of ratio formation that is 20:1～5:1 according to mass ratio in a kind of and silver, aluminium, platinum and the gold in magnesium, strontium, calcium and ytterbium, and described thermal resistance evaporation condition is pressure 5 × 10 -5～2 × 10 -3pa, speed 1～10nm/s, described electron beam evaporation plating condition is energy density 10～100W/cm 2,
After above step completes, obtain described organic electroluminescence device.
5. the preparation method of organic electroluminescence device as claimed in claim 4, is characterized in that, described conductive anode substrate of glass is the one in indium tin oxide glass, aluminium zinc oxide glass and indium-zinc oxide glass.
6. the preparation method of organic electroluminescence device as claimed in claim 4, is characterized in that, the material of described hole injection layer is the one in molybdenum trioxide, tungstic acid and vanadic oxide; The material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the one in 4'-diamines; The material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis-(betanaphthyl) anthracene, 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1, the one in 1 '-biphenyl and oxine aluminium; The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2, the one in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material of electron injecting layer is the one in cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
CN201310143951.XA 2013-04-24 2013-04-24 Organic light-emitting device and preparation method thereof Pending CN104124365A (en)

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Application publication date: 20141029