CN104051662A - Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof - Google Patents
Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof Download PDFInfo
- Publication number
- CN104051662A CN104051662A CN201310078234.3A CN201310078234A CN104051662A CN 104051662 A CN104051662 A CN 104051662A CN 201310078234 A CN201310078234 A CN 201310078234A CN 104051662 A CN104051662 A CN 104051662A
- Authority
- CN
- China
- Prior art keywords
- layer
- evaporation
- type doped
- composite anode
- phthalocyanine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- 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 manufacturing method thereof. The composite anode comprises a glass base, a doped metal oxide layer, a conductive metal simple substance layer and a p-type doped layer which are sequentially laminated, wherein the doped metal oxide layer mainly improves light emitting efficiency of the device, the conductive metal simple substance layer mainly improves conductivity of the anode, and the material of the p-type doped layer is mixed materials of a metal oxide and a phthalocyanines compound, the p-type doped layer improves conductivity and hole injection capability of the anode. The invention further discloses an organic electroluminescent device comprising the composite anode and a manufacturing method of the organic electroluminescent device, and the composite anode of the organic electroluminescent device facilitates light scattering and improves hole injection capability and light emitting efficiency.
Description
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of composite anode and preparation method thereof and organic electroluminescence device and preparation method thereof.
Background technology
1987, the C.W.Tang of 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, between interface, have the specific refractivity between poor (as glass and the ITO(tin indium oxide) of refractive index, glass refraction is that 1.5, ITO is 1.8, 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 substrate of glass stacking gradually, blended metal oxide layer, conducting metal simple substance layer and p-type doped layer, 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, and described composite anode is made up of the substrate of glass stacking gradually, blended metal oxide layer, conducting metal simple substance layer and p-type doped layer; Described blended metal oxide layer material is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in one and the composite material that forms of magnesium oxide (MgO) ratio that is 1:0.1～0.3 according to mass ratio, described p-type doped layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in the composite material that forms of a kind of and phthalocyanine-like compound ratio that is 1:0.05～0.4 according to mass ratio, described phthalocyanine-like compound is the one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc) and phthalocyanine vanadium (VPc).
Preferably, the thickness of described blended metal oxide layer is 2～30nm.
Preferably, described conducting metal simple substance layer material is the one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), and described conducting metal simple substance layer thickness is 2～20nm.
Preferably, the thickness of described p-type doped layer is 2～30nm.
Preferably, described substrate of glass is commercially available simple glass.
Second aspect, the invention provides a kind of preparation method of composite anode, comprises the following steps:
The substrate of glass of required size is provided, dry after cleaning;
On substrate of glass exiting surface, adopt the method for vacuum evaporation to prepare successively described blended metal oxide layer, conducting metal simple substance layer and p-type doped layer, obtain described composite anode; Wherein, described blended metal oxide layer material is MoO
3, WO
3and V
2o
5the composite material that forms of a kind of and the MgO ratio that is 1:0.1～0.3 according to mass ratio, described blended metal oxide layer and conducting metal simple substance layer evaporation condition are: evaporation pressure is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 1～10nm/s; Described p-type doped layer material is MoO
3, WO
3and V
2o
5the composite material that forms of a kind of and phthalocyanine-like compound ratio that is 1:0.05～0.4 according to mass ratio, described phthalocyanine-like compound is the one in CuPc, Phthalocyanine Zinc and phthalocyanine vanadium, the evaporation pressure of described p-type doped layer is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 0.1～1nm/s.
Preferably, the thickness of described blended metal oxide layer is 2～30nm.
Preferably, described conducting metal simple substance layer material is the one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), and described conducting metal simple substance layer thickness is 2～20nm.
Preferably, the thickness of described p-type doped layer is 2～30nm.
Preferably, described substrate of glass is commercially available simple glass.
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.
Composite anode of the present invention is made up of the substrate of glass stacking gradually, blended metal oxide layer, conducting metal simple substance layer and p-type doped layer; Wherein, blended metal oxide layer is mainly the light extraction efficiency that improves device; Conducting metal simple substance layer material is conducting metal simple substance, can improve the conductivity of anode; P-type doped layer utilizes metal oxide to mix with phthalocyanine-like compound as hole-injecting material, can improve the hole injectability of anode.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise the composite anode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described composite anode is made up of the substrate of glass stacking gradually, blended metal oxide layer, conducting metal simple substance layer and p-type doped layer; Described blended metal oxide layer material is MoO
3, WO
3and V
2o
5in the composite material that forms of a kind of and the MgO ratio that is 1:0.1～0.3 according to mass ratio, described p-type doped layer is MoO
3, WO
3and V
2o
5in the composite material that forms of a kind of and phthalocyanine-like compound ratio that is 1:0.05～0.4 according to mass ratio, described phthalocyanine-like compound is the one in CuPc, ZnPc and VPc.
Preferably, the thickness of described blended metal oxide layer is 2～30nm.
Preferably, described conducting metal simple substance layer material is the one in Ag, Al, Pt and Au, and described conducting metal simple substance layer thickness is 2～20nm.
Preferably, the thickness of described p-type doped layer is 2～30nm.
Preferably, described hole transmission layer material is 1,1-, bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), described hole transmission layer material thickness is 20～60nm, more preferably, described hole transmission layer material is 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, and more preferably, described luminescent layer material is BCzVBi, and 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 vacuum evaporation to prepare successively described blended metal oxide layer, conducting metal simple substance layer and p-type doped layer, obtain described composite anode; Wherein, described blended metal oxide layer material is MoO
3, WO
3and V
2o
5the composite material that forms of a kind of and the MgO ratio that is 1:0.1～0.3 according to mass ratio, described blended metal oxide layer and conducting metal simple substance layer evaporation condition are: evaporation pressure is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 1～10nm/s; Described p-type doped layer material is MoO
3, WO
3and V
2o
5the composite material that forms of a kind of and phthalocyanine-like compound ratio that is 1:0.05～0.4 according to mass ratio, described phthalocyanine-like compound is the one in CuPc, Phthalocyanine Zinc and phthalocyanine vanadium, the evaporation pressure of described p-type doped layer is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 0.1～1nm/s;
On p-type doped layer, evaporation is prepared 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 blended metal oxide layer is 2～30nm.
Preferably, described conducting metal simple substance layer material is the one in Ag, Al, Pt and Au, and described conducting metal simple substance layer thickness is 2～20nm.
Preferably, the thickness of described p-type doped layer is 2～30nm.
Preferably, described substrate of glass is commercially available simple glass.
Preferably, described hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer evaporation coating method are: evaporation pressure is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 0.1～1nm/s.
Preferably, the evaporation condition of described negative electrode is: evaporation pressure is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 1～10nm/s.
Preferably, described in the substrate of glass of required size is provided, concrete operations are: substrate of glass is carried out to photoetching treatment, be then cut into needed size.
Preferably, 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 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 NPB, and thickness is 45nm.
Preferably, described luminescent layer material is DCJTB, ADN, BCzVBi or Alq
3, thickness is 5～40nm, and more preferably, described luminescent layer material is BCzVBi, and thickness is preferably 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 substrate of glass stacking gradually, blended metal oxide layer, conducting metal simple substance layer and p-type doped layer, wherein, blended metal oxide layer adulterates with metal oxide and the magnesium oxide of refractive index high (2.0～2.3), because the refractive index of organic layer is generally 1.7, light arrives blended metal oxide layer from organic layer can not produce total reflection, therefore high refractive index metal oxide can extract the light of organic layer inside, MgO particle diameter is larger simultaneously, can effectively improve scattering of light effect, improve light extraction efficiency, conducting metal simple substance layer material is conducting metal simple substance, can improve the conductivity of anode, p-type doped layer utilizes metal oxide to mix with phthalocyanine-like compound, can improve the hole injectability of device, and phthalocyanine-like compound is crystallinity organic material, very easily crystallization forms regular orderly structure, make light in organic crystal, carry out effective scattering, improve light extraction 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 substrate of glass stacking gradually, blended metal oxide layer, conducting metal simple substance layer and p-type doped layer, has improved electric conductivity and the hole injectability of anode;
(2) preparation method of composite anode provided by the invention, technique is simple, and cost is low;
(3) composite anode provided by the invention can be applicable 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;
Current density and the luminous efficiency graph of a relation of Fig. 2 organic electroluminescence device that to be the embodiment of the present invention 5 provide with comparative example.
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 adopt the method for vacuum evaporation on substrate of glass exiting surface, to prepare blended metal oxide layer, blended metal oxide layer material is MoO
3the composite material forming with the MgO ratio that is 1:0.2 according to mass ratio (is expressed as MoO
3: MgO), blended metal oxide layer thickness is 10nm, evaporation pressure is 2 × 10
-4pa, evaporation speed is 1nm/s; Then on blended metal oxide layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Ag, and thickness is 5nm, and evaporation pressure is 2 × 10
-4pa, evaporation speed is 1nm/s; Finally on conducting metal simple substance layer, evaporation is prepared p-type doped layer, and p-type doped layer material is MoO
3the composite material forming with the CuPc ratio that is 1:0.2 according to mass ratio (is expressed as MoO
3: CuPc), p-type doped layer thickness is 15nm, evaporation pressure is 2 × 10
-4pa, evaporation speed is 0.1nm/s.
Embodiment 2
A preparation method for composite anode, comprises following operating procedure:
(1) first substrate of glass is carried out to photoetching treatment, be then cut into 2 × 2cm
2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first adopt the method for vacuum evaporation on substrate of glass exiting surface, to prepare blended metal oxide layer, blended metal oxide layer material is WO
3(be expressed as WO with MgO is 1:0.1 according to mass ratio
3: MgO), blended metal oxide layer thickness is 20nm, evaporation pressure is 3 × 10
-3pa, evaporation speed is 6nm/s; Then on blended metal oxide layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Al, and thickness is 20nm, and evaporation pressure is 3 × 10
-3pa, evaporation speed is 6nm/s; Finally on conducting metal simple substance layer, evaporation is prepared p-type doped layer, and p-type doped layer material is V
2o
5the composite material forming with the ZnPc ratio that is 1:0.4 according to mass ratio (is expressed as V
2o
5: ZnPc), p-type doped layer thickness is 2nm, evaporation pressure is 3 × 10
-3pa, evaporation speed is 0.5nm/s.
Embodiment 3
A preparation method for composite anode, comprises following operating procedure:
(1) first substrate of glass is carried out to photoetching treatment, be then cut into 2 × 2cm
2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry;
(2) first adopt the method for vacuum evaporation on substrate of glass exiting surface, to prepare blended metal oxide layer, blended metal oxide layer material is V
2o
5the composite material forming with the MgO ratio that is 1:0.3 according to mass ratio (is expressed as V
2o
5: MgO), blended metal oxide layer thickness is 2nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 10nm/s; Then on blended metal oxide layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Pt, and thickness is 2nm, and evaporation pressure is 1 × 10
-3pa, evaporation speed is 10nm/s; Finally on conducting metal simple substance layer, evaporation is prepared p-type doped layer, and p-type doped layer material is MoO
3the composite material forming with the VPc ratio that is 1:0.05 according to mass ratio (is expressed as MoO
3: VPc), p-type doped layer thickness is 55nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 1nm/s.
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 adopt the method for vacuum evaporation on substrate of glass exiting surface, to prepare blended metal oxide layer, blended metal oxide layer material is MoO
3the composite material forming with the MgO ratio that is 1:0.2 according to mass ratio (is expressed as MoO
3: MgO), blended metal oxide layer thickness is 15nm, evaporation pressure is 5 × 10
-4pa, evaporation speed is 5nm/s; Then on blended metal oxide layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Au, and thickness is 12nm, and evaporation pressure is 5 × 10
-4pa, evaporation speed is 5nm/s; Finally on conducting metal simple substance layer, evaporation is prepared p-type doped layer, and p-type doped layer material is WO
3the composite material forming with the CuPc ratio that is 1:0.25 according to mass ratio (is expressed as WO
3: CuPc), p-type doped layer thickness is 25nm, evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.4nm/s.
Embodiment 5
A kind of organic electroluminescence device, the composite anode stacking gradually, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described composite anode is composite anode prepared by the embodiment of the present invention 1.
In concrete preparation process, on composite anode, evaporation is prepared hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device, wherein,
Hole transmission layer material is NPB, and the pressure adopting when evaporation is 2 × 10
-4pa, evaporation speed is 0.1nm/s, evaporation thickness is 45nm;
Luminescent layer material is BCzVBi, and 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 transmission layer 2, luminescent layer 3, electron transfer layer 4, electron injecting layer 5 and the negative electrode 6 that stack gradually, composite anode 1 comprises the substrate of glass 11, blended metal oxide layer 12, conducting metal simple substance layer 13 and the p-type doped layer 14 that stack gradually.Concrete structure is expressed as:
Substrate of glass/MoO
3: MgO/Ag/MoO
3: CuPc/NPB/BCzVBi/TPBI/LiF/Ag.
Embodiment 6
A kind of organic electroluminescence device, the composite anode stacking gradually, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described composite anode is composite anode prepared by the embodiment of the present invention 2.
In concrete preparation process, on composite anode, evaporation is prepared hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device, wherein,
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 Alq
3, 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 transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, composite anode comprises the substrate of glass, blended metal oxide layer, conducting metal simple substance layer and the p-type doped layer that stack gradually.Concrete structure is expressed as:
Substrate of glass/WO
3: MgO/Al/V
2o
5: ZnPc/TCTA/Alq
3/ TPBI/Cs
2cO
3/ Pt.
Embodiment 7
A kind of organic electroluminescence device, the composite anode stacking gradually, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described composite anode is composite anode prepared by the embodiment of the present invention 3.
In concrete preparation process, on composite anode, evaporation is prepared hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device, wherein,
Hole transmission layer material is NPB, and the pressure adopting when evaporation is 1 × 10
-3pa, evaporation speed is 1nm/s, evaporation thickness is 60nm;
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 transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, composite anode comprises the substrate of glass, blended metal oxide layer, conducting metal simple substance layer and the p-type doped layer that stack gradually.Concrete structure is expressed as:
Substrate of glass/V
2o
5: MgO/Pt/MoO
3: VPc/NPB/DCJTB/Bphen/CsF/Au.
Embodiment 8
A kind of organic electroluminescence device, the composite anode stacking gradually, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described composite anode is composite anode prepared by the embodiment of the present invention 4.
In concrete preparation process, on composite anode, evaporation is prepared hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains organic electroluminescence device, wherein,
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 transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, composite anode comprises the substrate of glass, blended metal oxide layer, conducting metal simple substance layer and the p-type doped layer that stack gradually.Concrete structure is expressed as:
Substrate of glass/MoO
3: MgO/Au/WO
3: CuPc/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 (ITO) glass, and thickness is 120nm, and hole injection layer material is MoO
3, thickness is 30nm.The concrete structure of comparative example's organic electroluminescence device is: substrate of glass/ITO/MoO
3/ NPB/BCzVBi/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 luminous efficiency with current density change curve, to investigate the luminous efficiency of device, tested object is embodiment 5 and comparative example's organic electroluminescence device.Test result as shown in Figure 2.Fig. 2 is the embodiment of the present invention 5 and the luminous efficiency of comparative example's organic electroluminescence device and the graph of a relation of current density.
As can be seen from Figure 2, under different current densities, all large than comparative example of the luminous efficiency of embodiment 5, the luminous efficiency of embodiment 5 maximums is 8.7lm/W, and that comparative example is only 4.4lm/W, and the luminous efficiency of comparative example along with the increase of current density fast-descending, this explanation, composite anode prepared by the present invention has improved the light extraction efficiency of device, effectively improve scattering of light effect, improve the conductivity of anode, and phthalocyanine-like compound is crystallinity organic material, very easily crystallization forms regular orderly structure, make light in organic crystal, carry out effective scattering, improve light extraction efficiency.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a composite anode, is characterized in that, described composite anode is made up of the substrate of glass stacking gradually, blended metal oxide layer, conducting metal simple substance layer and p-type doped layer; Described blended metal oxide layer material is the composite material that the ratio that is 1:0.1～0.3 according to mass ratio of a kind of and magnesium oxide in molybdenum trioxide, tungstic acid and vanadic oxide forms, described p-type doped layer material is the composite material that the ratio that is 1:0.05～0.4 according to mass ratio of a kind of and phthalocyanine-like compound in molybdenum trioxide, tungstic acid and vanadic oxide forms, and described phthalocyanine-like compound is the one in CuPc, Phthalocyanine Zinc and phthalocyanine vanadium.
2. composite anode as claimed in claim 1, is characterized in that, the thickness of described blended metal oxide layer is 2～30nm.
3. composite anode as claimed in claim 1, is characterized in that, described conducting metal simple substance layer material is the one in silver, aluminium, platinum and gold, and the thickness of described conducting metal simple substance layer is 2～20nm.
4. composite anode as claimed in claim 1, is characterized in that, the thickness of described p-type doped layer is 2～30nm.
5. a preparation method for composite anode, is characterized in that, comprises following operating procedure:
The substrate of glass of required size is provided, dry after cleaning;
On substrate of glass exiting surface, adopt the method for vacuum evaporation to prepare successively described blended metal oxide layer, conducting metal simple substance layer and p-type doped layer, obtain described composite anode; Wherein, described blended metal oxide layer material is the composite material that the ratio that is 1:0.1～0.3 according to mass ratio of a kind of and magnesium oxide in molybdenum trioxide, tungstic acid and vanadic oxide forms, and described blended metal oxide layer and conducting metal simple substance layer evaporation condition are: evaporation pressure is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 1～10nm/s; Described p-type doped layer material is the composite material that the ratio that is 1:0.05～0.4 according to mass ratio of a kind of and phthalocyanine-like compound in molybdenum trioxide, tungstic acid and vanadic oxide forms, described phthalocyanine-like compound is the one in CuPc, Phthalocyanine Zinc and phthalocyanine vanadium, and the evaporation pressure of described p-type doped layer is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 0.1～1nm/s.
6. the preparation method of composite anode as claimed in claim 5, is characterized in that, the thickness of described blended metal oxide layer is 2～30nm.
7. the preparation method of composite anode as claimed in claim 5, is characterized in that, described conducting metal simple substance layer material is the one in silver, aluminium, platinum and gold, and described metal simple-substance layer thickness is 2～20nm.
8. the preparation method of composite anode as claimed in claim 5, is characterized in that, the thickness of described p-type doped layer is 2～30nm.
9. an organic electroluminescence device, it is characterized in that, comprise the composite anode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described composite anode is made up of the substrate of glass stacking gradually, blended metal oxide layer, conducting metal simple substance layer and p-type doped layer; Described blended metal oxide layer material is the composite material that the ratio that is 1:0.1～0.3 according to mass ratio of a kind of and magnesium oxide in molybdenum trioxide, tungstic acid and vanadic oxide forms, described p-type doped layer material is the composite material that the ratio that is 1:0.05～0.4 according to mass ratio of a kind of and phthalocyanine-like compound in molybdenum trioxide, tungstic acid and vanadic oxide forms, and described phthalocyanine-like compound is the one in CuPc, Phthalocyanine Zinc and phthalocyanine vanadium.
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 vacuum evaporation to prepare successively described blended metal oxide layer, conducting metal simple substance layer and p-type doped layer, obtain described composite anode; Wherein, described blended metal oxide layer material is the composite material that the ratio that is 1:0.1～0.3 according to mass ratio of a kind of and magnesium oxide in molybdenum trioxide, tungstic acid and vanadic oxide forms, and described blended metal oxide layer and conducting metal simple substance layer evaporation condition are: evaporation pressure is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 1～10nm/s; Described p-type doped layer material is the composite material that the ratio that is 1:0.05～0.4 according to mass ratio of a kind of and phthalocyanine-like compound in molybdenum trioxide, tungstic acid and vanadic oxide forms, described phthalocyanine-like compound is the one in CuPc, Phthalocyanine Zinc and phthalocyanine vanadium, and the evaporation pressure of described p-type doped layer is 2 × 10
-4～3 × 10
-3pa, evaporation speed is 0.1～1nm/s;
On p-type doped layer, evaporation is prepared hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, finally obtains described organic electroluminescence device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310078234.3A CN104051662A (en) | 2013-03-12 | 2013-03-12 | Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310078234.3A CN104051662A (en) | 2013-03-12 | 2013-03-12 | Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104051662A true CN104051662A (en) | 2014-09-17 |
Family
ID=51504261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310078234.3A Pending CN104051662A (en) | 2013-03-12 | 2013-03-12 | Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104051662A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108281563A (en) * | 2017-01-05 | 2018-07-13 | 昆山工研院新型平板显示技术中心有限公司 | A kind of electrode and apply its organic electroluminescence device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711439A (en) * | 2007-05-31 | 2010-05-19 | 伊斯曼柯达公司 | Electroluminescent device having improved light output |
| CN102005540A (en) * | 2010-10-12 | 2011-04-06 | 西安文景光电科技有限公司 | Organic electroluminescent device taking metal and P-type disc-shaped compound as composite anode |
| CN102169966A (en) * | 2011-04-28 | 2011-08-31 | 中国科学院长春应用化学研究所 | Organic light emitting diode |
| CN102468444A (en) * | 2010-11-16 | 2012-05-23 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| WO2012141875A1 (en) * | 2011-04-12 | 2012-10-18 | Arkema Inc. | Internal optical extraction layer for oled devices |
-
2013
- 2013-03-12 CN CN201310078234.3A patent/CN104051662A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101711439A (en) * | 2007-05-31 | 2010-05-19 | 伊斯曼柯达公司 | Electroluminescent device having improved light output |
| CN102005540A (en) * | 2010-10-12 | 2011-04-06 | 西安文景光电科技有限公司 | Organic electroluminescent device taking metal and P-type disc-shaped compound as composite anode |
| CN102468444A (en) * | 2010-11-16 | 2012-05-23 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| WO2012141875A1 (en) * | 2011-04-12 | 2012-10-18 | Arkema Inc. | Internal optical extraction layer for oled devices |
| CN102169966A (en) * | 2011-04-28 | 2011-08-31 | 中国科学院长春应用化学研究所 | Organic light emitting diode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108281563A (en) * | 2017-01-05 | 2018-07-13 | 昆山工研院新型平板显示技术中心有限公司 | A kind of electrode and apply its organic electroluminescence device |
| CN108281563B (en) * | 2017-01-05 | 2019-11-12 | 昆山工研院新型平板显示技术中心有限公司 | A kind of electrode and the organic electroluminescence device using it |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103579526A (en) | Organic electroluminescence device and manufacturing method thereof | |
| CN103456895A (en) | Organic electroluminescence device and manufacturing method thereof | |
| CN104124370A (en) | Organic light-emitting device and preparation method thereof | |
| CN104124368A (en) | Organic light-emitting device and preparation method thereof | |
| CN104037344A (en) | Stacked organic light emitting device and preparation method thereof | |
| CN104124352A (en) | Organic light-emitting device and preparation method thereof | |
| CN104124342A (en) | Organic light-emitting device and preparation method thereof | |
| CN104124338A (en) | Organic light-emitting device and preparation method thereof | |
| CN104124354A (en) | Organic light-emitting device and preparation method thereof | |
| CN104051662A (en) | Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof | |
| CN104124396A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104051641A (en) | Laminated organic electroluminescent device and manufacturing method thereof | |
| CN104051642A (en) | Laminated organic electroluminescent device and manufacturing method thereof | |
| CN104124362A (en) | Organic light-emitting device and preparation method thereof | |
| CN103682128A (en) | Organic light-emitting device and preparation method thereof | |
| CN103972408A (en) | Organic light-emitting device and method for manufacturing same | |
| CN104124381A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104037327A (en) | Stacked organic light emitting device and preparation method | |
| CN104051665A (en) | Composite anode and a manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof | |
| CN103579511A (en) | Inverted top-emitting organic electroluminescence device and manufacturing method thereof | |
| CN104124358A (en) | Organic light-emitting device and preparation method thereof | |
| CN104124372A (en) | Organic light-emitting device and preparation method thereof | |
| CN104518140A (en) | Organic electroluminescent device and preparation method thereof | |
| CN104051660A (en) | Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof | |
| CN104051643A (en) | Laminated organic electroluminescent device and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140917 |