CN103137876A - Organic electroluminescent device and production method thereof - Google Patents
Organic electroluminescent device and production method thereof Download PDFInfo
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Abstract
An organic electroluminescent device comprises a substrate, an anode, a first organic electroluminescent layer, a charge generating layer, a second organic electroluminescent layer and a cathode. The charge generating layer comprises a metal layer, a molybdenum oxide layer and a gold layer which are arranged on the first organic electroluminescent layer in a laminating mode. The metal layer is made of magnesium, aluminum, neodymium, samarium or ytterbium. The organic electroluminescent device is in a laminating structure; the charge generating layer is sequentially connected with the first organic electroluminescent layer and the second organic electroluminescent layer; and the charge generating layer comprises the metal layer, the molybdenum oxide layer and the gold layer which are arranged on the first organic electroluminescent layer in a laminating mode, so that the charge generating layer has the advantages of being high-efficiency in the charge generating property and rapid in the charge transmission property, generating more hole-electron luminous pairs, improving the luminous efficiency of the organic electroluminescent, increasing the current efficiency of the organic electroluminescent device in a multiplied mode along the number of luminous units which are in serious connection and being low in the driving current and high in the luminous efficiency.
Description
[technical field]
The present invention relates to the organic electroluminescence device field, particularly relate to a kind of Organnic electroluminescent device and preparation method thereof.
[background technology]
Organic electroluminescent LED (Organic Light-Emitting Diode), hereinafter to be referred as OLED, have that brightness is high, the material range of choice is wide, driving voltage is low, entirely solidify the characteristics such as active illuminating, have simultaneously high definition, wide viewing angle, and the advantage such as fast response time, a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, be present lot of domestic and foreign researcher's focal point.
Organic electroluminescent LED has a kind of structure of similar sandwich, it is respectively negative electrode and anode up and down, clip the organic material functional layer of single or multiple lift different materials kind and different structure 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, the hole is from anode, electronics is injected into respectively the organic material layer of device work from negative electrode, two kinds of charge carriers form hole-duplet in luminous organic material luminous, and then light sends from electrode one side.
The drive current of existing Organnic electroluminescent device is larger, and luminous efficiency is low, and device lifetime is low, serious restriction the application of 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 metal level, molybdenum oxide layer and the gold layer that stacks gradually on described the first 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 gold layer 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 doped stannum 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 of described negative electrode silver, aluminium, silver-magnesium alloy or magnesium-aluminum alloy.
Preferably, described the first organic electro luminescent layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and the first electron injecting layer that stacks gradually on described anode; Described the second organic electro luminescent layer comprises the second hole injection layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stacks gradually on described gold layer.
Preferably, the material of described the first hole injection layer and the second hole injection layer be CuPc and 4,4 ', 4 " at least a in three (N-3-aminomethyl phenyl-N-phenyl-amino)-triphenylamines;
The material of described the first hole transmission layer and the second hole transmission layer is phenyl beautiful jade, N, N '-two (3-aminomethyl phenyl)-N, and N '-diphenyl-4,4 '-benzidine or 1,3,5-triphenylbenzene;
The material of described the 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 of quinolizine-11-ketone and (oxine)-aluminium, C
2') iridium (acetylacetonate) and 4, the mixture, 4 of 4 '-two (9-carbazole) biphenyl, 4 '-two (2, the 2-diphenylethyllene)-1,1 '-biphenyl, two (4,6-difluorophenyl pyridine-N, C2) pyridine carboxylic acid closes iridium and 4, the mixture, three (2-phenylpyridine) of 4 '-two (9-carbazole) biphenyl closes iridium and 4, the mixture, three (1-phenyl-isoquinolin) of 4 '-two (9-carbazole) biphenyl closes one or more in the mixture of iridium and 4,4 '-two (9-carbazole) biphenyl;
The material of described the 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, 1,2, a kind of in 4-triazole derivative and N-aryl benzimidazole;
The material of described the first electron injecting layer and the second electron injecting layer is lithium fluoride, caesium lithium or sodium fluoride.
A kind of preparation method of Organnic electroluminescent device comprises the steps:
Step 1: substrate is provided;
Step 2: prepare anode on described substrate;
Step 3: prepare successively the first organic electro luminescent layer, charge generating layers and the second organic electro luminescent layer on described anode, described charge generating layers comprises metal level, molybdenum oxide layer and the gold layer that stacks gradually on described the first organic electro luminescent layer, and the material of described metal level is magnesium, aluminium, neodymium, samarium or ytterbium; And
Step 4: evaporation negative electrode on described the second organic electro luminescent layer obtains described Organnic electroluminescent device.
Preferably, step 1 also comprises the washing of substrate, at first substrate is placed on and carries out ultrasonic cleaning in the deionized water that contains washing agent, processes 20 minutes with ultrasonic wave in isopropyl alcohol, acetone successively after cleaning up, and then dries up with nitrogen.
Preferably, in step 2, comprise that also antianode carries out the step of plasma treatment.
Preferably, in step 3, the preparation method of described charge generating layers is: first evaporated metal layer, evaporation molybdenum oxide layer then, last gold evaporation layer.
above-mentioned Organnic electroluminescent device is laminated construction, adopt charge generating layers that the first organic electro luminescent layer and the second organic electro luminescent layer are connected in series, charge generating layers comprises the metal level that stacks gradually on the first organic electro luminescent layer, molybdenum oxide layer and gold layer, this structure makes charge generating layers have efficient charge generation character and charge-transporting matter fast, thereby can produce more hole-electron luminescence pair, make Organnic electroluminescent device can obtain higher luminosity, its current efficiency is along with the number of series connection luminescence unit can increase exponentially.Thereby Organnic electroluminescent device has the character that drive current is little, luminous efficiency is high.
[description of drawings]
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 that embodiment 1 is 2000cd/m with Comparative Examples 1 in initial brightness
2, the variation diagram of service time and brightness.
[embodiment]
Below by embodiment, above-mentioned Organnic electroluminescent device is further set forth.
See also Fig. 1, the Organnic electroluminescent device 100 of an execution mode comprises the substrate 110, anode 120, the first organic electro luminescent layer 130, charge generating layers 140, the second organic electro luminescent layer 150 and the negative electrode 160 that stack gradually.
Anode 120 requires anode transparent as display device.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 doped stannum oxide (ITO), indium doping zinc-oxide (IZO), aluminium-doped zinc oxide (AZO) or Ga-doped zinc oxide (GZO).Unsuitable blocked up for guaranteeing 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 light transmission preferably.
The first organic electro luminescent layer 130 comprises the first hole injection layer 131, the first hole transmission layer 132, the first luminescent layer 133, the first electron transfer layer 134 and the first electron injecting layer 135 that stacks gradually on anode 120.
The material of the first hole injection layer 131 be CuPc (CuPc) and 4,4 ', 4 " at least a in three (N-3-aminomethyl phenyl-N-phenyl-amino)-triphenylamines (m-MTDATA).
The material of the first hole transmission layer 132 is phenyl beautiful jade (NPB), also can be N, N '-two (3-aminomethyl phenyl)-N, and 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, the 2-diphenylethyllene)-1,1 '-biphenyl (DPVBi), two (4,6-difluorophenyl pyridine-N, C2) the pyridine carboxylic acid mixture, three (2-phenylpyridine) that closes iridium (FIrPic) and 4,4 '-two (9-carbazole) biphenyl (CBP) closes iridium (Ir (ppy)
3) and the mixture, three (1-phenyl-isoquinolin) of 4,4 '-two (9-carbazole) biphenyl (CBP) close iridium (Ir (piq)
3) and the mixture of 4,4 '-two (9-carbazole) biphenyl (CBP) 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, a kind of 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 metal level 141, the molybdenum oxide (MoO that stacks gradually 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 to connect the first organic electro luminescent layer 130 and the second organic electro luminescent layer 150, the more important thing is and to produce electric charge, be electronics and hole, and can be with charge transport to luminescence unit, thereby can produce more hole-electron luminescence pair, make Organnic electroluminescent device 100 can obtain higher luminosity, its current efficiency is along with the number of series connection luminescence unit can increase exponentially.
Therefore, the structure of charge generating layers 140 produces significant impact to the performance of Organnic electroluminescent device 100.Efficiently charge generation layer all must have efficient charge generation character and charge-transporting matter fast, just can make 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 gold layer 143.Metal level 141 adopts the preparation of metals of low work content to form, and can effectively reduce the injection barrier between metal level 141 and the first organic electro luminescent layer 130, thereby can improve electron transport efficient.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.Thereby charge generating layers 140 has efficient charge generation character and charge-transporting matter fast.
Loss when passing through charge generating layers 140 for reducing utilizing emitted light is to guarantee the light transmission of Organnic electroluminescent device 100, and 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) layer 142 thickness is 3～10 nanometers, the thickness of gold (Au) layer 143 is 10～20 nanometers.
The second organic electro luminescent layer 150 comprises the second hole injection layer 151, the second hole transmission layer 152, the second luminescent layer 153, the second electron transfer layer 154 and the second electron injecting layer 155 that stacks gradually on gold (Au) layer 143.
The material of the second hole injection layer 151 be CuPc (CuPc) and 4,4 ', 4 " at least a in three (N-3-aminomethyl phenyl-N-phenyl-amino)-triphenylamines (m-MTDATA).
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, the 3 benzothiazole-N of quinolizine-11-ketone (C545T) and (oxine)-aluminium (Alq3), C
2') iridium (acetylacetonate) ((F-Bt) 2Ir (acac)) and 4, the mixture, 4 of 4 '-two (9-carbazole) biphenyl (CBP), 4 '-two (2, the 2-diphenylethyllene)-1,1 '-biphenyl (DPVBi), two (4,6-difluorophenyl pyridine-N, C2) the pyridine carboxylic acid mixture, three (2-phenylpyridine) that closes iridium (FIrPic) and 4,4 '-two (9-carbazole) biphenyl (CBP) closes iridium (Ir (ppy)
3) and the mixture, three (1-phenyl-isoquinolin) of 4,4 '-two (9-carbazole) biphenyl (CBP) close iridium (Ir (piq)
3) and the mixture of 4,4 '-two (9-carbazole) biphenyl (CBP) 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, a kind of 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).
above-mentioned Organnic electroluminescent device 100, adopt charge generating layers 140 that the first organic electro luminescent layer 130 and the second organic electro luminescent layer 150 are connected in series, charge generating layers 140 comprises the metal level 141 that stacks gradually on 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 charge generation character and charge-transporting matter fast, thereby can produce more hole-electron luminescence pair, make Organnic electroluminescent device 100 can obtain higher luminosity, its current efficiency is along with the number of series connection luminescence unit can increase exponentially.Thereby Organnic electroluminescent device 100 has the character that drive current is little, luminous efficiency is high.Because drive current is little, improved the useful life of Organnic electroluminescent device 100, be easy to be extended and applied.
See also 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.At first substrate is placed on substrate and carries out ultrasonic cleaning in the deionized water that contains washing agent through washing, processes 20 minutes with ultrasonic wave in isopropyl alcohol, acetone successively after cleaning up, and then dries up with nitrogen, obtains clean substrate.
Step S120: prepare anode on the substrate of step S110.
In vacuum coating system, evaporation transparent conductive oxide or metal, preparation transparent conductive oxide film or sheet metal are as anode on substrate.
Transparent conductive oxide can be indium doped stannum 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 processing of anode.The anode of Organnic electroluminescent device requires to have higher work content, with the injection barrier in reduction hole, thereby improves the injection efficiency in hole.The work content that anode can improve anode is processed in plasma.
Step S130: prepare successively the first organic electro luminescent layer, charge generating layers and the second electroluminescence layer on the anode of step S120.
The 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 stacks gradually on anode.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 metal level, the molybdenum oxide (MoO that stacks gradually on described the first 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, evaporation molybdenum oxide layer then, last gold evaporation (Au) layer.The preparation of the charge generating layers process of not adulterating, 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 gold layer is 10～20 nanometers.
The 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 stacks gradually on charge generating layers.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 on the 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 need not to carry out the 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 doped stannum oxide (ITO) film for preparing thickness 100 nanometers at its surface sputtering, through after plasma treatment, then be transferred in the vacuum thermal evaporation system, evaporation the first organic electro luminescent layer successively on the ito thin film surface, 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 are 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, prepare at its surface sputtering indium doping zinc-oxide (IZO) film that thickness is 120 nanometers, through after plasma treatment, then be transferred in the vacuum thermal evaporation system, at IZO film surface evaporation the 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 are 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, prepare the aluminium-doped zinc oxide that thickness is 120 nanometers (AZO) film at its surface sputtering, through after plasma treatment, then be transferred in the vacuum thermal evaporation system, at AZO film surface evaporation the 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 are 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, prepare the Ga-doped zinc oxide that thickness is 100 nanometers (GZO) film at its surface sputtering, through after plasma treatment, then be transferred in the vacuum thermal evaporation system, at GZO film surface evaporation the 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 are 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 the low temperature sputtering technology, prepare the aluminium-doped zinc oxide that thickness is 100 nanometers (AZO) film at its surface sputtering, through after plasma treatment, then be transferred in the vacuum thermal evaporation system, in AZO film surface evaporation the 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 are 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 the low temperature sputtering technology, prepare the silver that thickness is 20 nanometers (Ag) layer at its surface sputtering, through after plasma treatment, then be transferred in the vacuum thermal evaporation system, in surperficial evaporation the first organic electro luminescent layer of silver (Ag) 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 are 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, prepare the gold that thickness is 18 nanometers (Au) layer at its surface sputtering, through after plasma treatment, then be transferred in the vacuum thermal evaporation system, at surperficial evaporation the first organic electro luminescent layer of gold (Au) 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 are 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 Examples 1
With reference to embodiment 1, the 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.
See also table 1, the Organnic electroluminescent device of embodiment 1～5 is compared common luminescent device, possesses higher current efficiency and luminosity are arranged.
The luminescent properties data of the device of table 1 embodiment 1～5 and Comparative Examples 1 made
| 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 Examples 1 | 3.2 | 5463 | 11.2 |
Seeing also Fig. 3, is 2000cd/m in initial brightness
2Under, the service time of the luminescent device of the Organnic electroluminescent device of embodiment 1 and Comparative Examples 1 and the variation of brightness, the Organnic electroluminescent device of embodiment 1 has less drive current, so will higher than common device, therefore be conducive to applying of this device its useful life.
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.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. 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 metal level, molybdenum oxide layer and the gold layer that stacks gradually on described the first organic electro luminescent layer, and the material of described metal level is magnesium, aluminium, neodymium, samarium or ytterbium.
2. Organnic electroluminescent device according to claim 1, is characterized in that, 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 gold layer is 10～20 nanometers.
3. 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 doped stannum 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.
4. Organnic electroluminescent device according to claim 1, is characterized in that, material silver, aluminium, silver-magnesium alloy or the magnesium-aluminum alloy of described negative electrode.
5. Organnic electroluminescent device according to claim 1, it is characterized in that, described the first organic electro luminescent layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and the first electron injecting layer that stacks gradually on described anode; Described the second organic electro luminescent layer comprises the second hole injection layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer that stacks gradually on described gold layer.
6. Organnic electroluminescent device according to claim 5, is characterized in that,
The material of described the first hole injection layer and the second hole injection layer be CuPc and 4,4 ', 4 " at least a in three (N-3-aminomethyl phenyl-N-phenyl-amino)-triphenylamines;
The material of described the first hole transmission layer and the second hole transmission layer is phenyl beautiful jade, N, N '-two (3-aminomethyl phenyl)-N, and N '-diphenyl-4,4 '-benzidine or 1,3,5-triphenylbenzene;
The material of described the first luminescent layer and the second luminescent layer 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, two (2-(2-fluorophenyl))-1,3 benzothiazole-N of quinolizine-11-ketone and (oxine)-aluminium, C
2') iridium (acetylacetonate) and 4, the mixture, 4 of 4 '-two (9-carbazole) biphenyl, 4 '-two (2, the 2-diphenylethyllene)-1,1 '-biphenyl, two (4,6-difluorophenyl pyridine-N, C2) pyridine carboxylic acid closes iridium and 4, the mixture, three (2-phenylpyridine) of 4 '-two (9-carbazole) biphenyl closes iridium and 4, the mixture, three (1-phenyl-isoquinolin) of 4 '-two (9-carbazole) biphenyl closes one or more in the mixture of iridium and 4,4 '-two (9-carbazole) biphenyl;
The material of described the 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, 1,2, a kind of in 4-triazole derivative and N-aryl benzimidazole;
The material of described the first electron injecting layer and the second electron injecting layer is lithium fluoride, caesium lithium or sodium fluoride.
7. the preparation method of an Organnic electroluminescent device, is characterized in that, comprises the steps:
Step 1: substrate is provided;
Step 2: prepare anode on described substrate;
Step 3: prepare successively the first organic electro luminescent layer, charge generating layers and the second organic electro luminescent layer on described anode, described charge generating layers comprises metal level, molybdenum oxide layer and the gold layer that stacks gradually on described the first organic electro luminescent layer, and the material of described metal level is magnesium, aluminium, neodymium, samarium or ytterbium; And
Step 4: evaporation negative electrode on described the second organic electro luminescent layer obtains described Organnic electroluminescent device.
8. Organnic electroluminescent device according to claim 7, it is characterized in that, step 1 also comprises the washing of substrate, at first substrate is placed on and carries out ultrasonic cleaning in the deionized water that contains washing agent, processed 20 minutes with ultrasonic wave in isopropyl alcohol, acetone successively after cleaning up, and then dry up with nitrogen.
9. Organnic electroluminescent device according to claim 7, is characterized in that, in step 2, comprises that also antianode carries out the step of plasma treatment.
10. Organnic electroluminescent device according to claim 7, is characterized in that, in step 3, the preparation method of described charge generating layers is: first evaporated metal layer, evaporation molybdenum oxide layer then, last gold evaporation layer.
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