CN103972403A - Organic light-emitting device and production method thereof - Google Patents

Organic light-emitting device and production method thereof Download PDF

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CN103972403A
CN103972403A CN201310038856.3A CN201310038856A CN103972403A CN 103972403 A CN103972403 A CN 103972403A CN 201310038856 A CN201310038856 A CN 201310038856A CN 103972403 A CN103972403 A CN 103972403A
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metal
layer
evaporation
function
metal oxide
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周明杰
王平
黄辉
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
    • H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
    • 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
    • H10K50/16—Electron transporting layers
    • 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]
    • H10K50/17—Carrier injection layers
    • 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]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • 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

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

Abstract

The invention provides an organic light-emitting device. The organic light-emitting device comprises an anode, a hole injection layer, a first hole transport layer, a first light-emitting layer, a first electron transport layer, a charge generation layer, a second hole transport layer, a second light-emitting layer, a second electron transport layer, an electron injection layer and a cathode which are laminated sequentially. The charge generation layer comprises a first metal doped layer laminated on the surface of the first electron transport layer, a second metal doped layer formed on the surface of the first metal doped layer and a bipolar metal oxide layer formed on the surface of the second metal doped layer, the first metal doped layer is made of materials including metal oxides and cesium salt doped in the metal oxides, the metal oxides are selected from at least one of tantalum pentoxide, niobium pentoxide and vanadium dioxide, and the cesium salt is selected from at least one of cesium carbonate, cesium chloride and cesium azide. The organic light-emitting device is high in light emitting efficiency. The invention further provides a production method of the organic light-emitting device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
The principle of luminosity of organic electroluminescence device 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.Yet the luminous efficiency of organic electroluminescence device is lower at present.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode stacking gradually, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises the first metal-doped layer that is laminated in described the first electron transfer layer surface, be formed at the second metal-doped layer on described the first metal-doped layer surface and be formed at the surperficial bipolarity metal oxide layer of described the second metal-doped layer, the material of described the first metal-doped layer comprises metal oxide and is entrained in the cesium salt in described metal oxide, described metal oxide is selected from tantalum pentoxide, at least one in niobium pentaoxide or vanadium dioxide, described cesium salt is selected from cesium carbonate, cesium chloride, at least one in cesium fluoride or nitrine caesium, wherein, the mass ratio of described cesium salt and described metal oxide is 1:20～2:5, the material of described the second metal-doped layer comprises low-function function metal and is entrained in the high power function metal in described low-function function metal, wherein said low-function function metal is power function at the metal of-2.0eV ~-4.0eV, described high power function metal is power function at the metal of-4.0eV ~-6.0eV, wherein, the mass ratio of described low-function function metal and described high power function metal is 1:9～3:7, the material of described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide.
In an embodiment, the thickness of described low workfunction metal layer is 1nm ~ 20nm therein, and the thickness of described doped metallic oxide layer is 10nm ~ 30nm, and the thickness of described high-work-function metal layer is 1nm ~ 20nm.
In an embodiment, the material of described low-function function metal is selected from least one in calcium, ytterbium, magnesium or barium therein, and the material of described high power function metal is selected from least one in silver, aluminium, platinum or gold.
Therein in an embodiment, the material of described the first luminescent layer and described the second luminescent layer is selected from 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--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
Therein in an embodiment, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N; N '-diphenyl-4, at least one in 4 '-benzidine.
In an embodiment, the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1 therein, 10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
A preparation method for organic electroluminescence device, comprises the following steps:
At anode surface successively evaporation, prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
At described the first electron transfer layer surface evaporation, prepare the first metal-doped layer, the material of described the first metal-doped layer comprises metal oxide and is entrained in the cesium salt in described metal oxide, described metal oxide is selected from least one in tantalum pentoxide, niobium pentaoxide or vanadium dioxide, described cesium salt is selected from least one in cesium carbonate, cesium chloride, cesium fluoride or nitrine caesium, wherein, the mass ratio of described cesium salt and described metal oxide is 1:20～2:5, and evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, described metal oxide and described cesium salt evaporate respectively in two evaporation boats, and the evaporation speed of described metal oxide is 1nm/s ~ 10nm/s, and the evaporation speed of described cesium salt is 1nm/s ~ 10nm/s;
At the surperficial evaporation of described the first metal-doped layer, prepare the second metal-doped layer, the material of described the second metal-doped layer comprises low-function function metal and is entrained in the high power function metal in described low-function function metal, wherein said low-function function metal is power function at the metal of-2.0eV ~-4.0eV, described high power function metal is power function at the metal of-4.0eV ~-6.0eV, wherein, the mass ratio of described low-function function metal and described high power function metal is 1:9～3:7, and evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, described low-function function metal and described high power function metal evaporate respectively in two evaporation boats, the evaporation speed of described low-function function metal is 1nm/s ~ 10nm/s, and the evaporation speed of described high power function metal is 1nm/s ~ 10nm/s;
At the surperficial evaporation of described the second metal-doped layer, prepare bipolarity metal oxide layer, the material of described bipolarity metal oxide is selected from least one in molybdenum trioxide, tungstic acid or vanadic oxide, and evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s; And
On bipolarity metal oxide layer surface successively evaporation, form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode.
Therein in an embodiment, the material of described the first luminescent layer and described the second luminescent layer is selected from 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--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
In an embodiment, the thickness of described the first metal-doped layer is 5nm ~ 20nm therein, and the thickness of described the second metal-doped layer is 2nm ~ 20nm, and the thickness of described bipolarity metal oxide layer is 0.5nm ~ 5nm.
In an embodiment, the material of described low-function function metal is selected from least one in calcium, ytterbium, magnesium or barium therein, and the material of described high power function metal is selected from least one in silver, aluminium, platinum or gold.
Above-mentioned organic electroluminescence device and preparation method thereof, charge generation layer is by low the first metal-doped layer, the second metal-doped layer and bipolarity metal oxide layer form, the first metal-doped layer comprises that high-index material can prevent the total reflection of light, form mineral crystal light is carried out to scattering, improve the light extraction efficiency of light, doping cesium salt forms the transmission rate that n doping improves electronics, the second metal-doped layer comprises high power function metal and end power function metal, the material of low workfunction metal layer has higher work function (work function absolute value is less), be conducive to reduce the injection barrier (electronics injects by lumo energy) between lumo energy and charge generation layer, improve the injection efficiency of electronics, and high-work-function metal layer can reduce the potential barrier (hole is injected by HOMO energy level) between charge generation layer and organic material HOMO energy level, improved the injection efficiency in hole, bipolarity metal oxide layer can be used as resilient coating, making to form tunnelling between organic layer and charge generation layer injects, reduce energy loss, the charge generation layer of this structure can effectively improve the luminous efficiency of organic electroluminescence device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's the flow chart of the organic electroluminescence device of an execution mode;
Fig. 3 is brightness and the luminous efficiency graph of a relation of the organic electroluminescence device of embodiment 1 preparation.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises anode 10, hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34, the first electron transfer layer 36, charge generation layer 40, the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and the negative electrode 70 stacking gradually.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Hole injection layer 20 is formed at anode 10 surfaces.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably WO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The material of the first hole transmission layer 32 is selected from 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 '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably TAPC.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 25nm.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The material of the first luminescent layer 34 is selected from 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) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 34.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of the first electron transfer layer 36 is 40nm ~ 200nm, is preferably 60nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.Described charge generation layer 40 comprise be laminated in the first electron transfer layer 36 surfaces the first metal-doped layer 42, be formed at the second metal-doped layer 44 on the first metal-doped layer 42 surface and be formed at the bipolarity metal oxide layer on the second metal-doped layer 44 surface.
The material of the first metal-doped layer 42 comprises metal oxide and is entrained in the cesium salt in described metal oxide, described metal oxide is selected from refractive index and is more than or equal to more than 2.0 metal oxides, preferably, described metal oxide is selected from least one in tantalum pentoxide, niobium pentaoxide or vanadium dioxide, described cesium salt is selected from least one in cesium carbonate, cesium chloride, cesium fluoride or nitrine caesium, wherein, the mass ratio of described cesium salt and described metal oxide is 1:20～2:5.The thickness of the first metal-doped layer 42 is 5nm ~ 20nm.
The second metal-doped layer 44 is formed at the first metal-doped layer 42 surface.The material of the second metal-doped layer 44 comprises low-function function metal and is entrained in the high power function metal in described low-function function metal, wherein said low-function function metal is power function at the metal of-2.0eV ~-4.0eV, described high power function metal is power function at the metal of-4.0eV ~-6.0eV, wherein, the mass ratio of described low-function function metal and described high power function metal is 1:9～3:7.Preferably, the material of described low-function function metal is selected from least one in calcium (Ca), ytterbium (Yb), magnesium (Mg) or barium (Ba), and the material of described high power function metal is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).The thickness of the second metal-doped layer 44 is 2nm ~ 20nm.
Bipolarity metal oxide layer 46 is formed at the surface of the second metal-doped layer 44.The material of bipolarity metal oxide 46 is selected from least one in molybdenum trioxide, tungstic acid or vanadic oxide.The thickness of bipolarity metal oxide layer 46 is 0.5nm ~ 5nm.
The second hole transmission layer 52 is formed at the surface of bipolarity metal oxide layer 46.The material of the second hole transmission layer 52 is selected from 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 '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably TAPC.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 25nm.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 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) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 60nm.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 is selected from cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) at least one, be preferably CsN 3.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 2.5nm.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is by the first metal-doped layer 42, the second metal-doped layer 44 and bipolarity metal oxide layer 46 form, the material of the first metal-doped layer 42 comprises that high-index material can prevent the total reflection of light, form mineral crystal light is carried out to scattering, improve the light extraction efficiency of light, doping cesium salt forms the transmission rate that n doping improves electronics, the second metal-doped layer 44 comprises high power function metal and end power function metal, the material of low workfunction metal layer has higher work function (work function absolute value is less), be conducive to reduce the injection barrier (electronics injects by lumo energy) between lumo energy and charge generation layer, improve the injection efficiency of electronics, and high-work-function metal layer can reduce the potential barrier (hole is injected by HOMO energy level) between charge generation layer and organic material HOMO energy level, improved the injection efficiency in hole, and bipolarity metal oxide layer 46 can be used as resilient coating, making to form tunnelling between organic layer and charge generation layer injects, reduce energy loss, the charge generation layer 40 of this structure can effectively improve the luminous efficiency of organic electroluminescence device.
Be appreciated that in this organic electroluminescence device 100 and also other functional layers can be set as required.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an embodiment, it comprises the following steps:
Step S110, at anode surface successively evaporation, prepare hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34 and the first electron transfer layer 36.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
In present embodiment, before anode 10 surfaces form hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning of isopropyl acetone 15min, to remove the organic pollution on anode 10 surfaces.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably WO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The first hole transmission layer 32 is prepared by evaporation.The material of the first hole transmission layer 32 is selected from 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 '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably TAPC.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 25nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The first luminescent layer 34 is prepared by evaporation.The material of the first luminescent layer 34 is selected from 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) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 34.The first electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of the first electron transfer layer 36 is 40nm ~ 200nm, is preferably 60nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Step S120, at the surperficial evaporation of the first electron transfer layer 36, prepare low workfunction metal layer 42.
The material of the first metal-doped layer 42 comprises metal oxide and is entrained in the cesium salt in described metal oxide, described metal oxide is selected from refractive index and is more than or equal to more than 2.0 metal oxides, preferably, described metal oxide is selected from least one in tantalum pentoxide, niobium pentaoxide or vanadium dioxide, described cesium salt is selected from least one in cesium carbonate, cesium chloride, cesium fluoride or nitrine caesium, wherein, the mass ratio of described cesium salt and described metal oxide is 1:20～2:5.The thickness of the first metal-doped layer 42 is 5nm ~ 20nm.
Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, described metal oxide and described cesium salt are put into respectively two different boats and are carried out evaporation, and the evaporation speed of metal oxide is 1nm/s～10nm/s, and the evaporation speed of described cesium salt is 1nm/s ~ 10nm/s.
Step S130, at the first metal-doped layer 42 surperficial evaporation, prepare the second metal-doped layer 44.
The second metal-doped layer 44 is formed at the first metal-doped layer 42 surface.The material of the second metal-doped layer 44 comprises low-function function metal and is entrained in the high power function metal in described low-function function metal, wherein said low-function function metal is power function at the metal of-2.0eV ~-4.0eV, described high power function metal is power function at the metal of-4.0eV ~-6.0eV, wherein, the mass ratio of described low-function function metal and described high power function metal is 1:9～3:7.Preferably, the material of described low-function function metal is selected from least one in calcium (Ca), ytterbium (Yb), magnesium (Mg) or barium (Ba), and the material of described high power function metal is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).The thickness of the second metal-doped layer 44 is 2nm ~ 20nm.
Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, high power function metal and low-function function metal evaporate respectively in two evaporation boats, and the evaporation speed of high power function metal is 1nm/s ~ 10nm/s, and the evaporation speed of low-function function metal is 1nm/s ~ 10nm/s.
Step S140, at the second metal-doped layer 44 surperficial evaporation, prepare bipolarity metal oxide layer 46.
Bipolarity metal oxide layer 46 is formed at the surface of the second metal-doped layer 44.The material of bipolarity metal oxide 46 is selected from least one in molybdenum trioxide, tungstic acid or vanadic oxide.The thickness of bipolarity metal oxide layer 46 is 0.5nm ~ 5nm.。
Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
Step S150, on bipolarity metal oxide 46 surfaces successively evaporation, prepare the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and negative electrode 70.
The second hole transmission layer 52 is formed at the surface of high-work-function metal layer 46.The material of the second hole transmission layer 52 is selected from 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 '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably TAPC.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 25nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 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) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 60nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 is selected from cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) at least one, be preferably CsN 3.The thickness of electron injecting layer 60 is 0.5nm～10nm, is preferably 2.5nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.Evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device preparation method, technique is simple, and the luminous efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method of organic electroluminescence device provided by the invention is elaborated.
The preparation used of the embodiment of the present invention and comparative example and tester are: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 test electric property of U.S. Keithley company, CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
Structure prepared by the present embodiment is: ito glass/WO 3/ TAPC/BCzVBi/Bphen/Ta 2o 5: Cs 2cO 3/ Ca:Ag/MoO 3/ TAPC/BCzVBi/Bphen/CsN 3the organic electroluminescence device of/Ag.
First ITO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Evaporation hole injection layer, material is WO 3, thickness is 40nm; Evaporation the first hole transmission layer, material is TAPC, thickness is 25nm; Evaporation the first luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the first electron transfer layer, material is Bphen, thickness is 30nm; Prepare charge generation layer: by the first metal-doped layer, the second metal-doped layer and bipolarity metal oxide layer, formed.The material of the metal-doped layer of evaporation first comprises Ta 2o 5and Cs 2cO 3, wherein, Cs 2cO 3with Ta 2o 5mass ratio be 1:20, evaporation is 8 * 10 at vacuum pressure -4under Pa, carry out Ta 2o 5and Cs 2cO 3put into respectively two boat evaporations, Ta 2o 5evaporation evaporation speed be 3nm/s, Cs 2cO 3evaporation speed be 5nm/s, the thickness of the first metal-doped layer is 10nm; The metal-doped layer of evaporation second, material comprises Ca and is entrained in the Ag in Ca, the mass ratio 1:5 of Ag and Ca, evaporation is 8 * 10 at vacuum pressure -4under Pa, carry out, Ca and Ag put into respectively two boat evaporations, and the evaporation evaporation speed of Ca is 5nm/s, and the evaporation speed of Ag is 2nm/s, and the second metal-doped layer thickness is 15nm; Evaporation bipolarity metal oxide layer, material is MoO 3, thickness is 1nm; Evaporation is 8 * 10 at vacuum pressure -4under Pa, carry out MoO 3evaporation speed be 2nm/s, evaporation the second hole transmission layer, material is TAPC, thickness is 25nm; Evaporation the second luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the second electron transfer layer, material is Bphen, thickness is 30nm; Evaporation electron injecting layer, material is CsN 3, thickness is 2.5nm; Evaporation negative electrode, material is Ag, thickness is 150nm.Finally obtain needed electroluminescent device.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ito glass/WO 3/ TAPC/BCzVBi/Bphen/Ta 2o5:Cs 2cO 3/ Ca:Ag/MoO 3/ TAPC/BCzVBi/Bphen/CsN 3the organic electroluminescence device of/Ag (curve 1) is ito glass/MoO with structure prepared by comparative example 3/ TCTA/BCzVBi/TAZ/CsN 3the brightness of the organic electroluminescence device of/Ag (curve 2) and the relation of luminous efficiency.In the organic electroluminescence device that in organic electroluminescence device prepared by comparative example, each layer thickness is prepared with embodiment 1, each layer thickness is identical.
As seen from Figure 3, under different brightness, the luminous efficiency of embodiment 1 is large than comparative example all, the maximum lumen efficiency of the organic electroluminescence device of embodiment 1 preparation is 10.9lm/W, and the luminous efficiency of organic electroluminescence device prepared by comparative example is only 8.4lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer is by the first metal-doped layer, the second metal-doped layer and bipolarity metal oxide layer form, the metal-doped layer of high index of refraction can form mineral crystal, light is carried out to scattering, improve the injection efficiency of electronics and the transmission rate in hole, and high-work-function metal layer can improve the injection efficiency in hole, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
The luminous efficiency of the organic electroluminescence device that below prepared by each embodiment is all similar with embodiment 1, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/V 2o 5/ NPB/ADN/TAZ/Nb 2o 5: CsF/Yb:Al/WO 3/ TCTA/ADN/TAZ/CsN 3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is V 2o 5, thickness is 80nm; Evaporation is prepared the first hole transmission layer, and material is NPB, and thickness is 60nm; Evaporation is prepared the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is TAZ, and thickness is 200nm; Evaporation is prepared charge generation layer: the first metal-doped layer, the second metal-doped layer and bipolarity metal oxide layer, consist of.The material of the metal-doped layer of evaporation first comprises Nb 2o 5and CsF, wherein, CsF and Nb 2o 5mass ratio be 1:20, evaporation is 5 * 10 at vacuum pressure -3under Pa, carry out Nb 2o 5put into respectively two boat evaporations, Nb with CsF 2o 5evaporation evaporation speed be 1nm/s, the evaporation speed of CsF is 1nm/s, the thickness of the first metal-doped layer is 5nm; The metal-doped layer of evaporation second, material comprises Yb and is entrained in the Al in Yb, the mass ratio 3:10 of Al and Yb, evaporation is 5 * 10 at vacuum pressure -3under Pa, carry out, Yb and Al put into respectively two boat evaporations, and the evaporation evaporation speed of Al is 10nm/s, and the evaporation speed of Yb is 10nm/s, and the second metal-doped layer thickness is 2nm; Evaporation bipolarity metal oxide layer, material is WO 3, thickness is 5nm; Evaporation is 5 * 10 at vacuum pressure -3under Pa, carry out WO 3evaporation speed be 1nm/s; Then evaporation the second hole transmission layer, material is TCTA, thickness is 20nm; Evaporation is prepared the second luminescent layer, and material is ADN, and thickness is 7nm; Evaporation is prepared the second electron transfer layer, and material is TAZ, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is CsN 3, thickness is 0.5nm; Evaporation is prepared negative electrode, and material is Pt, and thickness is 60nm, finally obtains needed electroluminescent device.
Embodiment 3
Structure prepared by the present embodiment is IZO/MoO 3/ TAPC/Alq 3/ Bphen/VO 2: CsN 3/ Mg:Pt/V 2o 5/ NPB/Alq 3the organic electroluminescence device of/TPBi/CsF/Al.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is MoO 3, thickness is 20nm; Evaporation is prepared the first hole transmission layer, and material is TAPC, and thickness is 30nm; Evaporation is prepared the first luminescent layer, and material is Alq 3, thickness is 40nm; Evaporation is prepared the first electron transfer layer, and material is Bphen, and thickness is 200nm; Evaporation is prepared charge generation layer: the first metal-doped layer, the second metal-doped layer and bipolarity metal oxide layer, consist of.The material of the metal-doped layer of evaporation first comprises VO 2and CsN 3, wherein, CsN 3with VO 2mass ratio be 2:5, evaporation is 2 * 10 at vacuum pressure -4under Pa, carry out VO 2and CsN 3put into respectively two boat evaporations, VO 2evaporation evaporation speed be 10nm/s, CsN 3evaporation speed be 10nm/s, the thickness of the first metal-doped layer is 20nm; The metal-doped layer of evaporation second, material comprises Mg and is entrained in the Pt in Mg, the mass ratio 1:10 of Pt and Mg, evaporation is 2 * 10 at vacuum pressure -4under Pa, carry out, Mg and Pt put into respectively two boat evaporations, and the evaporation evaporation speed of Pt is 1nm/s, and the evaporation speed of Mg is 1nm/s, and the second metal-doped layer thickness is 20nm; Evaporation bipolarity metal oxide layer, material is V 2o 5, thickness is 0.5nm; Evaporation is 2 * 10 at vacuum pressure -4under Pa, carry out V 2o 5evaporation speed be 10nm/s; Evaporation is prepared the second hole transmission layer, and material is NPB, and thickness is 60nm; Evaporation is prepared the second luminescent layer, and material is Alq3, and thickness is 30nm; Evaporation is prepared the second electron transfer layer, and material is TPBi, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is CsF, and thickness is 10nm; Evaporation is prepared negative electrode, and material is Al, and thickness is 300nm, finally obtains needed electroluminescent device.
Embodiment 4
Structure prepared by the present embodiment is IZO/MoO 3/ TCTA/DCJTB/Bphen/Ta 2o 5: CsCl/Ba:Au/MoO 3/ TAPC/DCJTB/Bphen/Cs 2cO 3the organic electroluminescence device of/Au.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is MoO 3, thickness is 30nm; Evaporation is prepared the first hole transmission layer, and material is TCTA, and thickness is 50nm; Evaporation is prepared the first luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation is prepared charge generation layer: the first metal-doped layer, the second metal-doped layer and bipolarity metal oxide layer, consist of.The material of the metal-doped layer of evaporation first comprises Ta 2o 5and CsCl, wherein, CsCl and Ta 2o 5mass ratio be 1:4, evaporation is 5 * 10 at vacuum pressure -4under Pa, carry out Ta 2o 5put into respectively two boat evaporations, Ta with CsCl 2o 5evaporation evaporation speed be 6nm/s, the evaporation speed of CsCl is 4nm/s, the thickness of the first metal-doped layer is 7nm; The metal-doped layer of evaporation second, material comprises Ba and is entrained in the Au in Ba, the mass ratio 9:50 of Au and Ba, evaporation is 5 * 10 at vacuum pressure -4under Pa, carry out, Ba and Au put into respectively two boat evaporations, and the evaporation evaporation speed of Au is 5nm/s, and the evaporation speed of Ba is 2nm/s, and the second metal-doped layer thickness is 10nm; Evaporation bipolarity metal oxide layer, material is MoO 3, thickness is 2.5nm; Evaporation is 5 * 10 at vacuum pressure -4under Pa, carry out MoO 3evaporation speed be 3nm/s; Evaporation is prepared the second hole transmission layer, and material is TAPC, and thickness is 50nm; Evaporation is prepared the second luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, and thickness is 100nm; Evaporation is prepared electron injecting layer, and material is Cs 2cO 3, thickness is 2nm; Evaporation is prepared negative electrode, and material is Au, and thickness is 180nm, finally obtains needed electroluminescent device.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, it is characterized in that, comprise the anode stacking gradually, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises the first metal-doped layer that is laminated in described the first electron transfer layer surface, be formed at the second metal-doped layer on described the first metal-doped layer surface and be formed at the surperficial bipolarity metal oxide layer of described the second metal-doped layer, the material of described the first metal-doped layer comprises metal oxide and is entrained in the cesium salt in described metal oxide, described metal oxide is selected from tantalum pentoxide, at least one in niobium pentaoxide or vanadium dioxide, described cesium salt is selected from cesium carbonate, cesium chloride, at least one in cesium fluoride or nitrine caesium, wherein, the mass ratio of described cesium salt and described metal oxide is 1:20～2:5, the material of described the second metal-doped layer comprises low-function function metal and is entrained in the high power function metal in described low-function function metal, wherein said low-function function metal is power function at the metal of-2.0eV ~-4.0eV, described high power function metal is power function at the metal of-4.0eV ~-6.0eV, wherein, the mass ratio of described low-function function metal and described high power function metal is 1:9～3:7, the material of described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide.
2. organic electroluminescence device according to claim 1, it is characterized in that, the thickness of described the first metal-doped layer is 5nm ~ 20nm, and the thickness of described the second metal-doped layer is 2nm ~ 20nm, and the thickness of described bipolarity metal oxide layer is 0.5nm ~ 5nm.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described low-function function metal is selected from least one in calcium, ytterbium, magnesium or barium, and the material of described high power function metal is selected from least one in silver, aluminium, platinum or gold.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first luminescent layer and described the second luminescent layer is selected from 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--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
5. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
6. organic electroluminescence device according to claim 1, is characterized in that, the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
At anode surface successively evaporation, prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
At described the first electron transfer layer surface evaporation, prepare the first metal-doped layer, the material of described the first metal-doped layer comprises metal oxide and is entrained in the cesium salt in described metal oxide, described metal oxide is selected from least one in tantalum pentoxide, niobium pentaoxide or vanadium dioxide, described cesium salt is selected from least one in cesium carbonate, cesium chloride, cesium fluoride or nitrine caesium, wherein, the mass ratio of described cesium salt and described metal oxide is 1:20～2:5, and evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, described metal oxide and described cesium salt evaporate respectively in two evaporation boats, and the evaporation speed of described metal oxide is 1nm/s ~ 10nm/s, and the evaporation speed of described cesium salt is 1nm/s ~ 10nm/s;
At the surperficial evaporation of described the first metal-doped layer, prepare the second metal-doped layer, the material of described the second metal-doped layer comprises low-function function metal and is entrained in the high power function metal in described low-function function metal, wherein said low-function function metal is power function at the metal of-2.0eV ~-4.0eV, described high power function metal is power function at the metal of-4.0eV ~-6.0eV, wherein, the mass ratio of described low-function function metal and described high power function metal is 1:9～3:7, and evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, described low-function function metal and described high power function metal evaporate respectively in two evaporation boats, the evaporation speed of described low-function function metal is 1nm/s ~ 10nm/s, and the evaporation speed of described high power function metal is 1nm/s ~ 10nm/s;
At the surperficial evaporation of described the second metal-doped layer, prepare bipolarity metal oxide layer, the material of described bipolarity metal oxide is selected from least one in molybdenum trioxide, tungstic acid or vanadic oxide, and evaporation is 5 * 10 at vacuum pressure -3~ 2 * 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s; And
On bipolarity metal oxide layer surface successively evaporation, form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode.
8. the preparation method of organic electroluminescence device according to claim 7, it is characterized in that: the material of described the first luminescent layer and described the second luminescent layer is selected from 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--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
9. the preparation method of organic electroluminescence device according to claim 7, it is characterized in that: the thickness of described the first metal-doped layer is 5nm ~ 20nm, the thickness of described the second metal-doped layer is 2nm ~ 20nm, and the thickness of described bipolarity metal oxide layer is 0.5nm ~ 5nm.
10. the preparation method of organic electroluminescence device according to claim 7, it is characterized in that: the material of described low-function function metal is selected from least one in calcium, ytterbium, magnesium or barium, and the material of described high power function metal is selected from least one in silver, aluminium, platinum or gold.
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Application publication date: 20140806