CN103137876B - Organnic electroluminescent device and preparation method thereof - Google Patents
Organnic electroluminescent device and preparation method thereof Download PDFInfo
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Abstract
A kind of Organnic electroluminescent device, comprise the substrate, anode, the first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and the negative electrode that stack gradually, charge generating layers comprises the metal level, molybdenum oxide layer and the layer gold that are sequentially laminated in the first organic electro luminescent layer, and the material of metal level is magnesium, aluminium, neodymium, samarium or ytterbium.This Organnic electroluminescent device is laminated construction, first organic electro luminescent layer and the second organic electro luminescent layer are connected in series by charge generating layers, charge generating layers comprises the metal level be sequentially laminated in the first organic electro luminescent layer, molybdenum oxide layer and layer gold, this structure makes charge generating layers have efficient electric charge and produces character and transferring charge character fast, more multi-hole-electron luminescence pair can be produced, improve the luminous efficiency of Organnic electroluminescent device, its current efficiency can be doubled and redoubled along with the number of serial light emitting cell, Organnic electroluminescent device is made to have drive current little, the character that luminous efficiency is high.
Description
[technical field]
The present invention relates to organic electroluminescence device field, particularly relate to a kind of Organnic electroluminescent device and preparation method thereof.
[background technology]
Organic electroluminescent LED (OrganicLight-EmittingDiode), hereinafter referred to as OLED, there is the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, a kind of Display Technique and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.
Organic electroluminescent LED has a kind of structure of similar sandwich, it is negative electrode and anode up and down respectively, the organic material functional layer of single or multiple lift different materials kind and different structure is clipped between two electrodes, be followed successively by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer.Organic electroluminescence device is carrier injection type luminescent device, after anode and negative electrode add operating voltage, hole is from anode, electronics is injected into the organic material layer of device work respectively from negative electrode, two kinds of charge carriers form hole-electron to luminescence in luminous organic material, and then light sends from electrode side.
The drive current of existing Organnic electroluminescent device is comparatively large, and luminous efficiency is low, and device lifetime is low, the serious application constraining organic electroluminescent LED.
[summary of the invention]
Based on this, be necessary to provide the Organnic electroluminescent device that a kind of drive current is little, luminous efficiency is high.
A kind of Organnic electroluminescent device, comprise the substrate, anode, the first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and the negative electrode that stack gradually, described charge generating layers comprises the metal level, molybdenum oxide layer and the layer gold that are sequentially laminated in the first described organic electro luminescent layer, and the material of described metal level is magnesium, aluminium, neodymium, samarium or ytterbium.
Preferably, the thickness of described metal level is 2 ~ 5 nanometers, and the thickness of described molybdenum oxide layer is 3 ~ 10 nanometers, and the thickness of described layer gold is 10 ~ 20 nanometers.
Preferably, described anode is transparent conductive oxide film or metal anode, and the material of described transparent conductive oxide film is indium doping tin oxide, indium doping zinc oxide, aluminium-doped zinc oxide or Ga-doped zinc oxide, and the material of described metal anode is silver or golden.
Preferably, the material silver of described negative electrode, aluminium, silver-magnesium alloy or magnesium-aluminum alloy.
Preferably, described first organic electro luminescent layer comprises the first hole injection layer be sequentially laminated on described anode, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and the first electron injecting layer; Described second organic electro luminescent layer comprises the second hole injection layer be sequentially laminated in described layer gold, the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer.
Preferably, the material of described first hole injection layer and the second hole injection layer is CuPc and 4,4 ', the 4 " at least one in-three (N-3-methylphenyl-N-phenyl-amino)-triphenylamine;
The material of described first hole transmission layer and the second hole transmission layer is phenyl beautiful jade, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine or 1,3,5-triphenylbenzene;
The material of described first luminescent layer and the second luminescent layer is 10-(2-[4-morpholinodithio)-2,3,6,7-tetrahydrochysene-1,1,7,7,-tetramethyl l-1H, 5H, 11H-[1] benzopyran ketone group [6,7,8-ij] mixture, two (2-(2-fluorophenyl))-1,3 benzothiazole-N, C of quinolizine-11-ketone and (oxine)-aluminium
2') iridium (acetylacetonate) and 4, the mixture, 4 of 4 '-two (9-carbazole) biphenyl, 4 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl, two (4,6-difluorophenyl pyridinato-N, C2) pyridine carboxylic acid closes iridium and 4, mixture, three (the 2-phenylpyridines) of 4 '-two (9-carbazole) biphenyl close iridium and 4, mixture, three (the 1-phenyl-isoquinolin) of 4 '-two (9-carbazole) biphenyl close iridium and 4, one or more in the mixture of 4 '-two (9-carbazole) biphenyl;
The material of described first electron transfer layer and the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, oxine aluminium, 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, 1, one in 2,4-triazole derivative and N-aryl benzimidazole;
The material of described first electron injecting layer and the second electron injecting layer is lithium fluoride, caesium lithium or sodium fluoride.
A preparation method for Organnic electroluminescent device, comprises the steps:
Step one: substrate is provided;
Step 2: prepare anode over the substrate;
Step 3: prepare the first organic electro luminescent layer, charge generating layers and the second organic electro luminescent layer on described anode successively, described charge generating layers comprises the metal level, molybdenum oxide layer and the layer gold that are sequentially laminated in the first described organic electro luminescent layer, and the material of described metal level is magnesium, aluminium, neodymium, samarium or ytterbium; And
Step 4: evaporation negative electrode in described second organic electro luminescent layer, obtains described Organnic electroluminescent device.
Preferably, step one also comprises the washing of substrate, is first placed on by substrate in the deionized water containing washing agent and carries out ultrasonic cleaning, after cleaning up successively in isopropyl alcohol, acetone with ultrasonic wave process 20 minutes, and then to dry up with nitrogen.
Preferably, in step 2, also comprise the step that antianode carries out plasma treatment.
Preferably, in step 3, the preparation method of described charge generating layers is: first evaporated metal layer, then evaporation molybdenum oxide layer, last evaporation layer gold.
Above-mentioned Organnic electroluminescent device is laminated construction, charge generating layers is adopted the first organic electro luminescent layer and the second organic electro luminescent layer to be connected in series, charge generating layers comprises the metal level be sequentially laminated in the first organic electro luminescent layer, molybdenum oxide layer and layer gold, this structure makes charge generating layers have efficient electric charge and produces character and transferring charge character fast, thus it is right to produce more hole-electron luminescence, make Organnic electroluminescent device can obtain higher luminosity, its current efficiency can increase exponentially along with the number of serial light emitting cell.Thus, Organnic electroluminescent device has the character that drive current is little, luminous efficiency is high.
[accompanying drawing explanation]
Fig. 1 is the structural representation of the Organnic electroluminescent device of an execution mode;
Fig. 2 is preparation method's flow chart of the Organnic electroluminescent device of an execution mode;
Fig. 3 is embodiment 1 is 2000cd/m with comparative example 1 at starting brightness
2, the variation diagram of service time and brightness.
[embodiment]
Below by way of embodiment, above-mentioned Organnic electroluminescent device is set forth further.
Refer to Fig. 1, the Organnic electroluminescent device 100 of an execution mode, comprise the substrate 110, anode 120, first organic electro luminescent layer 130, charge generating layers 140, second organic electro luminescent layer 150 and the negative electrode 160 that stack gradually.
Substrate 110 can be glass substrate or polyethersulfone resin substrate.Glass substrate or polyethersulfone resin substrate are all transparent substrates, to ensure light transmittance.
As display device, anode 120 requires that anode is transparent.Anode 120 can be transparent conductive oxide film or metal anode.Transparent conductive oxide film has the higher transparency.The material of transparent conductive oxide film can be indium doping tin oxide (ITO), indium doping zinc oxide (IZO), aluminium-doped zinc oxide (AZO) or Ga-doped zinc oxide (GZO).Unsuitable blocked up for ensureing light transmittance anode 120 thickness.Preferably, the thickness of transparent conductive oxide film is 100 ~ 120 nanometers.The material of metal anode can be silver (Ag) or gold (Au), and sheet metal also has good light transmission.
First organic electro luminescent layer 130 comprises the first hole injection layer 131, first hole transmission layer 132, first luminescent layer 133, first electron transfer layer 134 and the first electron injecting layer 135 be sequentially laminated on anode 120.
" at least one in-three (N-3-methylphenyl-N-phenyl-amino)-triphenylamine (m-MTDATA) that the material of the first hole injection layer 131 is CuPc (CuPc) and 4,4 ', 4.
The material of the first hole transmission layer 132 is phenyl beautiful jade (NPB), also can be N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) or 1,3,5-triphenylbenzene (TDAPB).
The material of the first luminescent layer 133 is 10-(2-[4-morpholinodithio)-2,3,6,7-tetrahydrochysene-1,1,7,7 ,-tetramethyl 1-1H, 5H, 11H-[1] benzopyran ketone group [6,7,8-ij] quinolizine-11-ketone (C545T) and (oxine)-aluminium (Alq
3) mixture, (2-(2-fluorophenyl))-1,3 benzothiazole-N, C
2') iridium (acetylacetonate) ((F-Bt) 2Ir (acac)) and 4, the mixture, 4 of 4 '-two (9-carbazole) biphenyl (CBP), 4 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl (DPVBi), two (4,6-difluorophenyl pyridinato-N, C2) pyridine carboxylic acid closes iridium (FIrPic) and the mixture of 4,4 '-two (9-carbazole) biphenyl (CBP), three (2-phenylpyridines) close iridium (Ir (ppy)
3) and the mixture of 4,4 '-two (9-carbazole) biphenyl (CBP), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) and 4,4 '-two (9-carbazole) biphenyl (CBP) mixture in one or more.
The material of the first electron transfer layer 134 is 4,7-diphenyl-1,10-phenanthroline (BPhen), oxine aluminium (Alq3), 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), 1, one in 2,4-triazole derivative (TAZ) and N-aryl benzimidazole (TPBI).
The material of the first electron injecting layer 135 is lithium fluoride (LiF), caesium lithium (CsF) or sodium fluoride (NaF).
Charge generating layers 140 comprises the metal level 141, the molybdenum oxide (MoO that are sequentially laminated on the first electron injecting layer 135
3) layer 142 and gold (Au) layer 143.The material of metal level 141 is magnesium (Mg), aluminium (Al), neodymium (Nd), samarium (Sm) or ytterbium (Yb).
Charge generating layers 140 not only plays a part connection first organic electro luminescent layer 130 and the second organic electro luminescent layer 150, the more important thing is and can produce electric charge, i.e. electronics and hole, and can by charge transport in luminescence unit, thus it is right to produce more hole-electron luminescence, make Organnic electroluminescent device 100 can obtain higher luminosity, its current efficiency can increase exponentially along with the number of serial light emitting cell.
Therefore, the structure of charge generating layers 140 produces significant impact to the performance of Organnic electroluminescent device 100.Efficient charge generation layer all must have efficient electric charge and produce character and transferring charge character fast, could obtain efficient lamination Organnic electroluminescent device.Charge generating layers 140 is for comprising metal level 141, molybdenum oxide (MoO
3) three-decker of layer 142 and layer gold 143.Metal level 141 adopts the preparation of metals of low work content to form, and effectively can reduce the injection barrier between metal level 141 and the first organic electro luminescent layer 130, thus can improve electron transport efficiency.Under DC Electric Field, molybdenum oxide (MoO
3) layer 142 can produce electric charge effectively.The work content of gold (Au) is higher, and gold (Au) layer 143 can improve the injection efficiency in hole.Thus, charge generating layers 140 has efficient electric charge and produces character and transferring charge character fast.
For reducing utilizing emitted light by loss during charge generating layers 140 to ensure the light transmission of Organnic electroluminescent device 100, the thickness of charge generating layers 140 is unsuitable blocked up.Preferably, the thickness of metal level 141 is 2 ~ 5 nanometers, molybdenum oxide (MoO
3) thickness of layer 142 is 3 ~ 10 nanometers, the thickness of gold (Au) layer 143 is 10 ~ 20 nanometers.
Second organic electro luminescent layer 150 comprises the second hole injection layer 151, second hole transmission layer 152, second luminescent layer 153, second electron transfer layer 154 and the second electron injecting layer 155 be sequentially laminated on gold (Au) layer 143.
" at least one in-three (N-3-methylphenyl-N-phenyl-amino)-triphenylamine (m-MTDATA) that the material of the second hole injection layer 151 is CuPc (CuPc) and 4,4 ', 4.
The material of the second hole transmission layer 152 is phenyl beautiful jade (NPB), also can be N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) or 1,3,5-triphenylbenzene (TDAPB).
The material of the second luminescent layer 153 is 10-(2-[4-morpholinodithio)-2,3,6,7-tetrahydrochysene-1,1,7,7,-tetramethyl 1-1H, 5H, 11H-[1] benzopyran ketone group [6,7,8-ij] mixture, (2-(2-fluorophenyl))-1,3 benzothiazole-N, C of quinolizine-11-ketone (C545T) and (oxine)-aluminium (Alq3)
2') iridium (acetylacetonate) ((F-Bt) 2Ir (acac)) and 4, the mixture, 4 of 4 '-two (9-carbazole) biphenyl (CBP), 4 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl (DPVBi), two (4,6-difluorophenyl pyridinato-N, C2) pyridine carboxylic acid closes iridium (FIrPic) and the mixture of 4,4 '-two (9-carbazole) biphenyl (CBP), three (2-phenylpyridines) close iridium (Ir (ppy)
3) and the mixture of 4,4 '-two (9-carbazole) biphenyl (CBP), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) and 4,4 '-two (9-carbazole) biphenyl (CBP) mixture in one or more.
The material of the second electron transfer layer 154 is 4,7-diphenyl-1,10-phenanthroline (BPhen), oxine aluminium (Alq3), 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), 1, one in 2,4-triazole derivative (TAZ) and N-aryl benzimidazole (TPBI).
The material of the second electron injecting layer 155 is lithium fluoride (LiF), caesium lithium (CsF) or sodium fluoride (NaF).
Negative electrode 160 is metal electrode, can be silver (Ag) layer, aluminium (Al) layer, silver-magnesium alloy (Ag-Mg) layer or magnesium-aluminum alloy (Mg-Al) layer.
Above-mentioned Organnic electroluminescent device 100, charge generating layers 140 is adopted first organic electro luminescent layer 130 and the second organic electro luminescent layer 150 to be connected in series, charge generating layers 140 comprises the metal level 141 be sequentially laminated in the first organic electro luminescent layer 130, molybdenum oxide layer 142 and gold (Au) layer 143, this structure makes charge generating layers 140 have efficient electric charge and produces character and transferring charge character fast, thus it is right to produce more hole-electron luminescence, make Organnic electroluminescent device 100 can obtain higher luminosity, its current efficiency can increase exponentially along with the number of serial light emitting cell.Thus, Organnic electroluminescent device 100 has the character that drive current is little, luminous efficiency is high.Because drive current is little, improves the useful life of Organnic electroluminescent device 100, be easy to be extended and applied.
Refer to Fig. 2, the preparation method of the Organnic electroluminescent device of an execution mode, comprises the steps:
Step S110: substrate is provided.
Substrate can be glass substrate or polyethersulfone resin substrate.Substrate, through washing, is first placed in the deionized water containing washing agent and carries out ultrasonic cleaning by substrate, after cleaning up successively in isopropyl alcohol, acetone with ultrasonic wave process 20 minutes, and then to dry up with nitrogen, obtain clean substrate.
Step S120: prepare anode on the substrate of step S110.
In vacuum coating system, evaporation transparent conductive oxide or metal, substrate is prepared transparent conductive oxide film or sheet metal as anode.
Transparent conductive oxide can be indium doping tin oxide (ITO), indium doping zinc oxide (IZO), aluminium-doped zinc oxide (AZO) or Ga-doped zinc oxide (GZO).Metal can be silver (Ag) or gold (Au).
Step S120 also comprises the plasma process of anode.The anode of Organnic electroluminescent device requires to have higher work content, to reduce the injection barrier in hole, thus improves the injection efficiency in hole.Plasma process anode can improve the work content of anode.
Step S130: prepare the first organic electro luminescent layer, charge generating layers and the second electroluminescence layer on the anode of step S120 successively.
First organic electro luminescent layer is included in the first hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and the first electronics input layer that anode stacks gradually.In preparation process, evaporation prepares the first hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and the first electronics input layer successively.
Charge generating layers comprises the metal level, the molybdenum oxide (MoO that are sequentially laminated in the first described organic electro luminescent layer
3) layer and gold (Au) layer.The material of metal level can be magnesium (Mg), aluminium (Al), neodymium (Nd), samarium (Sm) or ytterbium (Yb).In preparation process, first evaporated metal layer, then evaporation molybdenum oxide layer, last gold evaporation (Au) layer.The preparation of charge generating layers is not adulterated process, and preparation process is very simple.
The thickness of metal level is 2 ~ 5 nanometers, molybdenum oxide (MoO
3) thickness of layer is 3 ~ 10 nanometers, the thickness of layer gold is 10 ~ 20 nanometers.
Second organic electro luminescent layer is included in the second hole injection layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electronics input layer that charge generating layers stacks gradually.In preparation process, evaporation prepares the second hole injection layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electronics input layer successively.
Step S140: evaporation negative electrode in second organic electro luminescent layer of step S130, obtains Organnic electroluminescent device.
The material of negative electrode can be silver (Ag), aluminium (Al), silver-magnesium alloy (Ag-Mg) or magnesium-aluminum alloy (Mg-Al).
The preparation method of above-mentioned Organnic electroluminescent device, the preparation of charge generating layers, without the need to carrying out doping process, only needs thermal evaporation just can prepare, and preparation process is very simple, and preparation cost is low, is easy to industrialization.
It is below specific embodiment.
Embodiment 1
After glass substrate is cleaned up, in vacuum sputter system, indium doping tin oxide (ITO) film of thickness 100 nanometer is prepared at its surface sputtering, after plasma treatment, then be transferred in vacuum thermal evaporation system, in ito thin film surface successively evaporation first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and negative electrode.
The structure of the first prepared organic electro luminescent layer is:
m-MTDATA/NPB/Ir(ppy)
3:CBP/Alq
3/LiF。
The structure of the second prepared organic electro luminescent layer is:
m-MTDATA/NPB/Ir(ppy)
3:CBP/Alq
3/LiF。
The structure of prepared charge generating layers is Mg/MoO
3/ Au, thickness is respectively 3 nanometers, 5 nanometers, 15 nanometers.
Described device architecture is glass substrate/ITO/m-MTDATA/NPB/Ir (ppy)
3: CBP/Alq
3/ LiF/Mg/MoO
3/ Au/m-MTDATA/NPB/Ir (ppy)
3: CBP/Alq
3/ LiF/Ag.
Embodiment 2
After glass substrate is cleaned up, in vacuum sputter system, indium doping zinc oxide (IZO) film that thickness is 120 nanometers is prepared at its surface sputtering, after plasma treatment, then be transferred in vacuum thermal evaporation system, in IZO film surface evaporation first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and negative electrode.
The structure of the first prepared organic electro luminescent layer is:
CuPc/TPD/FIrPic:CBP/TPBi/CsF。
The structure of the second prepared organic electro luminescent layer is:
m-MTDATA/TPD/(F-BT)
2Ir(acac):CBP/TPBi/CsF。
The structure of charge generating layers used is Yb/MoO
3/ Au, thickness is respectively 2 nanometers, 3 nanometers, 10 nanometers.
Described device architecture is glass substrate/IZO/CuPc/TPD/FIrPic:CBP/TPBi/CsF/Yb/MoO
3/ Au/m-MTDATA/TPD/ (F-BT)
2ir (acac): CBP/TPBi/CsF/Al.
Embodiment 3
After glass substrate is cleaned up, in vacuum sputter system, aluminium-doped zinc oxide (AZO) film that thickness is 120 nanometers is prepared at its surface sputtering, after plasma treatment, then be transferred in vacuum thermal evaporation system, in AZO film surface evaporation first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and negative electrode.
The structure of the first prepared organic electro luminescent layer is:
CuPc/NPB/DPVBi/Alq
3/NaF。
The structure of the second prepared organic electro luminescent layer is:
CuPc/TDAPB/DPVBi/Bphen/NaF。
The structure of charge generating layers used is Sm/MoO
3/ Au, thickness is respectively 5 nanometers, 10 nanometers, 20 nanometers.
Described device architecture is glass substrate/AZO/CuPc/NPB/DPVBi/Alq
3/ NaF/Sm/MoO
3/ Au/CuPc/TDAPB/DPVBi/Bphen/NaF/Ag-Mg.
Embodiment 4
After glass substrate is cleaned up, in vacuum sputter system, Ga-doped zinc oxide (GZO) film that thickness is 100 nanometers is prepared at its surface sputtering, after plasma treatment, then be transferred in vacuum thermal evaporation system, in GZO film surface evaporation first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and negative electrode.
The structure of the first prepared organic electro luminescent layer is:
CuPc/NPB/FIrPic:CBP/PBD/NaF。
The structure of the second prepared organic electro luminescent layer is:
CuPc/PBD/Ir(piq)
3:CBP/Bphen/NaF。
The structure of charge generating layers used is Nd/MoO
3/ Au, thickness is respectively 4 nanometers, 8 nanometers, 15 nanometers.
Described device architecture is glass substrate/GZO/CuPc/NPB/FIrPic:CBP/PBD/NaF/Sm/MoO
3/ Au/CuPc/PBD/Ir (piq)
3: CBP/Bphen/NaF/Al-Mg.
Embodiment 5
After polyethersulfone resin (PES) substrate is cleaned up, in vacuum sputter system, utilize low-temperature sputter technology, aluminium-doped zinc oxide (AZO) film that thickness is 100 nanometers is prepared at its surface sputtering, after plasma treatment, be then transferred in vacuum thermal evaporation system, in AZO film surface evaporation first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and negative electrode.
The structure of the first prepared organic electro luminescent layer is:
m-MTDATA/NPB/DPVBi/TAZ/LiF/Al。
The structure of the second prepared organic electro luminescent layer is;
m-MTDATA/NPB/C545T:Alq
3/TAZ/CsF。
The structure of charge generating layers used is Al/MoO
3/ Au, thickness is respectively 3 nanometers, 8 nanometers, 15 nanometers.
Described device architecture is PES/AZO/m-MTDATA/NPB/DPVBi/TAZ/LiF/Al/MoO
3/ Au/m-MTDATA/NPB/C545T:Alq
3/ TAZ/CsF/Al-Mg.
Embodiment 6
After polyethersulfone resin (PES) substrate is cleaned up, in vacuum sputter system, utilize low-temperature sputter technology, silver (Ag) layer that thickness is 20 nanometers is prepared at its surface sputtering, after plasma treatment, be then transferred in vacuum thermal evaporation system, in silver (Ag) layer surface evaporation first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and negative electrode.
The structure of the first prepared organic electro luminescent layer is:
m-MTDATA/NPB/DPVBi/TAZ/LiF。
The structure of the second prepared organic electro luminescent layer is:
m-MTDATA/TPD/C545T:Alq
3/TAZ/CsF。
The structure of charge generating layers used is Al/MoO
3/ Au, thickness is respectively 3 nanometers, 8 nanometers, 15 nanometers.
Described device architecture is PES/Ag/m-MTDATA/NPB/DPVBi/TAZ/LiF/Al/MoO
3/ Au/m-MTDATA/TPD/C545T:Alq
3/ TAZ/CsF/Al-Mg.
Embodiment 7
After glass substrate is cleaned up, in vacuum sputter system, gold (Au) layer that thickness is 18 nanometers is prepared at its surface sputtering, after plasma treatment, then be transferred in vacuum thermal evaporation system, in gold (Au) layer surface evaporation first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and negative electrode.
The structure of the first prepared organic electro luminescent layer is:
CuPc/NPB/FIrPic:CBP/PBD/NaF。
The structure of the second prepared organic electro luminescent layer is:
CuPc/PBD/Ir(piq)
3:CBP/Bphen/NaF。
The structure of charge generating layers used is Nd/MoO
3/ Au, thickness is respectively 4 nanometers, 8 nanometers, 15 nanometers.
Described device architecture is glass substrate/Au/CuPc/NPB/FIrPic:CBP/PBD/NaF/Sm/MoO
3/ Au/CuPc/PBD/Ir (piq)
3: CBP/Bphen/NaF/Al-Mg.
Comparative example 1
With reference to embodiment 1, making structure is glass substrate/ITO/m-MTDATA/NPB/Ir (ppy)
3: CBP/Alq
3the device of/LiF/Ag, this device is not provided with charge generating layers.
Refer to table 1, the Organnic electroluminescent device of embodiment 1 ~ 5 compares common luminescent device, has higher current efficiency and luminosity.
The luminescent properties data of table 1 embodiment 1 ~ 5 and the device made by comparative example 1
| Starting resistor (V) | Brightness (cd/m during 10V 2) | Current efficiency (cd/A) | |
| Embodiment 1 | 5.4 | 21832 | 28.3 |
| Embodiment 2 | 5.5 | 17783 | 20.1 |
| Embodiment 3 | 5.7 | 14583 | 19.5 |
| Embodiment 4 | 5.5 | 20345 | 24.1 |
| Embodiment 5 | 5.8 | 12764 | 17.5 |
| Comparative example 1 | 3.2 | 5463 | 11.2 |
Referring to Fig. 3, is 2000cd/m at starting brightness
2under, the Organnic electroluminescent device of embodiment 1 and the service time of luminescent device of comparative example 1 and the change of brightness, the Organnic electroluminescent device of embodiment 1 has less drive current, is therefore higher than common device its useful life, is therefore conducive to applying of this device.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 (9)
1. an Organnic electroluminescent device, it is characterized in that, comprise the substrate, anode, the first organic electro luminescent layer, charge generating layers, the second organic electro luminescent layer and the negative electrode that stack gradually, described charge generating layers comprises the metal level, molybdenum oxide layer and the layer gold that are sequentially laminated in the first described organic electro luminescent layer, and the material of described metal level is magnesium, aluminium or neodymium;
The thickness of described metal level is 2 ~ 5 nanometers, and the thickness of described molybdenum oxide layer is 3 ~ 10 nanometers, and the thickness of described layer gold is 10 ~ 20 nanometers;
The thickness of described anode is 100 ~ 120 nanometers.
2. Organnic electroluminescent device according to claim 1, it is characterized in that, described anode is transparent conductive oxide film or metal anode, the material of described transparent conductive oxide film is indium doping tin oxide, indium doping zinc oxide, aluminium-doped zinc oxide or Ga-doped zinc oxide, and the material of described metal anode is silver or golden.
3. Organnic electroluminescent device according to claim 1, is characterized in that, the material silver of described negative electrode, aluminium, silver-magnesium alloy or magnesium-aluminum alloy.
4. Organnic electroluminescent device according to claim 1, it is characterized in that, described first organic electro luminescent layer comprises the first hole injection layer be sequentially laminated on described anode, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and the first electron injecting layer; Described second organic electro luminescent layer comprises the second hole injection layer be sequentially laminated in described layer gold, the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer.
5. Organnic electroluminescent device according to claim 4, is characterized in that,
The material of described first hole injection layer and the second hole injection layer is CuPc and 4,4', the 4 " at least one in-three (N-3-methylphenyl-N-phenyl-amino)-triphenylamine;
The material of described first hole transmission layer and the second hole transmission layer is phenyl beautiful jade, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,3,5-triphenylbenzene;
The material of described first luminescent layer and the second luminescent layer is 10-(2-[4-morpholinodithio)-2,3,6,7-tetrahydrochysene-1,1,7,7,-tetramethyl l-1H, 5H, 11H-[1] benzopyran ketone group [6,7,8-ij] mixture, two (2-(2-fluorophenyl))-1,3 benzothiazoles-N, C of quinolizine-11-ketone and (oxine)-aluminium
2') iridium (acetylacetonate) and 4, the mixture, 4 of 4'-bis-(9-carbazole) biphenyl, 4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl, two (4,6-difluorophenyl pyridinato-N, C2) pyridine carboxylic acid closes iridium and 4, mixture, three (the 2-phenylpyridines) of 4'-bis-(9-carbazole) biphenyl close iridium and 4, the mixture of 4'-bis-(9-carbazole) biphenyl, three (1-phenyl-isoquinolin) close in the mixture of iridium and 4,4'-bis-(9-carbazole) biphenyl one or more;
The material of described first electron transfer layer and the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, oxine aluminium, 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, 1, one in 2,4-triazole derivative and N-aryl benzimidazole;
The material of described first electron injecting layer and the second electron injecting layer is lithium fluoride, caesium lithium or sodium fluoride.
6. a preparation method for Organnic electroluminescent device, is characterized in that, comprises the steps:
Step one: substrate is provided;
Step 2: prepare anode over the substrate;
Step 3: prepare the first organic electro luminescent layer, charge generating layers and the second organic electro luminescent layer on described anode successively, described charge generating layers comprises the metal level, molybdenum oxide layer and the layer gold that are sequentially laminated in the first described organic electro luminescent layer, and the material of described metal level is magnesium, aluminium or neodymium; And
Step 4: evaporation negative electrode in described second organic electro luminescent layer, obtains described Organnic electroluminescent device;
The thickness of described metal level is 2 ~ 5 nanometers, and the thickness of described molybdenum oxide layer is 3 ~ 10 nanometers, and the thickness of described layer gold is 10 ~ 20 nanometers;
The thickness of described anode is 100 ~ 120 nanometers.
7. the preparation method of Organnic electroluminescent device according to claim 6, it is characterized in that, step one also comprises the washing of substrate, first substrate is placed in the deionized water containing washing agent and carries out ultrasonic cleaning, after cleaning up successively in isopropyl alcohol, acetone with ultrasonic wave process 20 minutes, and then to dry up with nitrogen.
8. the preparation method of Organnic electroluminescent device according to claim 6, is characterized in that, in step 2, also comprises the step that antianode carries out plasma treatment.
9. the preparation method of Organnic electroluminescent device according to claim 6, is characterized in that, in step 3, the preparation method of described charge generating layers is: first evaporated metal layer, then evaporation molybdenum oxide layer, last evaporation layer gold.
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