CN102810646A - Laminated organic electroluminescence device and preparation method thereof - Google Patents
Laminated organic electroluminescence device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a laminated organic electroluminescence device, which comprises an anode, a cathode, two organic electroluminescence layers which are arranged between the anode and the cathode and an electric charge generating layer which is arranged between the two electroluminescence layers. The electric charge generating layer of the laminated organic electroluminescence device is a single-layer structure and made of hole-transport material which is doped with few electronic injection materials and hole-transport materials, so that the problem of the high starting voltage of the device caused by the weakness of an interface because of the electric charge generating layer of a multilayer structure can be avoided, and the starting voltage of the organic electroluminescence device can be reduced. Meanwhile, the electric charge generating layer is made of the hole-transport material which is doped with the electron injection material and the hole injection material, so that the regeneration, injection and transportation capacity of electrons and holes can be improved, the compounding possibility of the electrons and holes can be improved, and the luminescence efficiency can be improved. The invention also provides a preparation method of the laminated organic electroluminescence device.
Description
[technical field]
The present invention relates to the electroluminescence field, relate in particular to a kind of lamination organic electroluminescence device and preparation method thereof.
[background technology]
1987, the C.W.Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.Utilize the ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, brightness reaches 1000cd/m under the 10V
2, luminous efficiency is that 1.51lm/W, life-span were greater than 100 hours.
The principle of luminosity of OLED is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and the hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton move under electric field action, gives luminescent material with NE BY ENERGY TRANSFER, and excitation electron is from the ground state transition to excitation state, excited energy is through the radiation inactivation, generation photon, release luminous energy.At present, in order to improve luminosity and luminous efficiency, increasing research is to be main with laminated device; This structure normally is together in series several luminescence units as articulamentum with charge generation layer, compares with unit component, and the laminated construction device often has energy efficiency and luminosity at double; The original intensity of lamination OLED is bigger; When under identical current density, measuring, be converted into the original intensity of unit component, stacked device has the long life-span; And this laminated device also can be easily becomes white light with the luminescence unit series hybrid of different colours, thereby realizes the emission of white light.
The charge generation layer of laminated device must have electronics power of regeneration and hole power of regeneration, and has reasonable injectability, could effectively electronics and hole be injected into each luminescence unit, thereby realizes the white light emission of device.Traditional laminated device be utilize two or more have the hole is injected or electronics injects material as charge generating layers (like Cs:BCP/V
2O
5), or n type and p type doped layer as charge generation layer (like n type (Alq
3: Li) with p type (NPB:FeCl
3)), or Al-WO
3-Au etc. are linked in sequence a plurality of luminescence units and constitute.But this charge generation layer has sandwich construction, has certain boundary defect (like the variation of the contact resistance between layer and the layer) between each layer, thereby makes that the starting resistor of laminated device is higher.
[summary of the invention]
Based on this, be necessary to provide lower lamination organic electroluminescence device of a kind of starting resistor and preparation method thereof.
A kind of lamination organic electroluminescence device comprises: anode, negative electrode, the charge generation layers that are positioned at two organic electro luminescent layer of said anode and said negative electrode centre and are positioned at two said organic electro luminescent layer centres;
The material of said charge generation layer is the hole mobile material of electronics injection material and hole-injecting material of having mixed; Wherein, the doping mass ratio of said electronics injection material is 1%～10%, and the doping mass ratio of said hole-injecting material is 1%～20%.
Preferably, said hole mobile material is N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, N; N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine, 1,3; 5-triphenylbenzene or 4,4,4 ,-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine.
Preferably, said electronics injection material is Cs
2CO
3, CsN
3, CsF, LiF, Li
2O or Li
2CO
3
Preferably, said hole-injecting material is 2,3,5,6-tetrafluoro-7; 7,8,8 ,-four cyano-benzoquinone's bismethane, 4,4; 4-three (naphthyl-phenyl-ammonium) triphenylamine, 4,4,4-three (naphthyl-1-phenyl-ammonium) triphenylamine or 4,4,4-three (naphthyl-2-phenyl-ammonium) triphenylamine.
Preferably, the thickness of said charge generation layer is 5nm～30nm.
A kind of preparation method of lamination organic electroluminescence device comprises the steps:
Step 1, anode is provided;
Step 2, form two organic electro luminescent layer and be positioned at two charge generation layers in the middle of the said organic electro luminescent layer at the surperficial vapor deposition of one on said anode; The material of said charge generation layer is the hole mobile material of electronics injection material and hole-injecting material of having mixed; Wherein, the doping mass ratio of said electronics injection material is 1%～10%, and the doping mass ratio of said hole-injecting material is 1%～20%;
Step 3, forming negative electrode away from the organic electro luminescent layer of said anode surface vapor deposition.
Preferably, in the step 2, said hole mobile material is N, N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine, N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine, 1,3,5-triphenylbenzene or 4; 4,4 ,-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine.
Preferably, in the step 2, said electronics injection material is Cs
2CO
3, CsN
3, CsF, LiF, Li
2O or Li
2CO
3
Preferably, in the step 2, said hole-injecting material is 2,3,5,6-tetrafluoro-7; 7,8,8 ,-four cyano-benzoquinone's bismethane, 4,4; 4-three (naphthyl-phenyl-ammonium) triphenylamine, 4,4,4-three (naphthyl-1-phenyl-ammonium) triphenylamine or 4,4,4-three (naphthyl-2-phenyl-ammonium) triphenylamine.
Preferably, in the step 2, said charge generation layer thickness is 5nm～30nm.
The charge generation layer of this lamination organic electroluminescence device is a single layer structure; Material is the hole mobile material that is doped with little electrons injection material and hole mobile material; Avoided because the charge generation layer of sandwich construction owing to boundary defect causes device starting resistor problem of higher, has reduced the starting resistor of organic electroluminescence device.Simultaneously; The material of charge generation layer is the hole mobile material of electronics injection material and hole-injecting material of having mixed; Can improve regeneration, injection and the transmittability in electronics and hole, thereby improve the recombination probability in electronics and hole, thereby improve luminous efficiency.
[description of drawings]
Fig. 1 is the structural representation of the lamination organic electroluminescence device of an execution mode;
Fig. 2 is the preparation flow figure of lamination organic electroluminescence device shown in Figure 1;
Fig. 3 is the current density and the energy efficiency graph of a relation of the embodiment 1 and the lamination organic electroluminescence device of Comparative Examples preparation.
[embodiment]
Below in conjunction with accompanying drawing and specific embodiment lamination organic electroluminescence device and preparation method thereof is done further description.
The lamination organic electroluminescence device of an execution mode as shown in Figure 1 comprises anode, negative electrode, is positioned at two organic electro luminescent layer of anode and negative electrode centre and is positioned at the middle charge generation layer of two organic electro luminescent layer.
In the present embodiment, the number of organic electro luminescent layer is two, and the number of charge generation layer is one; In other embodiment, organic electro luminescent layer also can be three, four or more, and charge generation layer is two, three or more, is provided with a charge generation layer in the middle of per two adjacent organic electro luminescent layer.
The material of anode can be indium tin oxide glass, fluorine-containing tin oxide glass, the zinc oxide of mixing aluminium, magnesium-indium oxide, nickel-tungsten oxide, metal nitride, metal selenide or metal sulfide.
The material of negative electrode can be silver (Ag), aluminium (Al), magnesium silver alloy or gold (Au), and thickness is 20nm～200nm.The material of negative electrode is preferably Ag, and thickness is preferably 150nm.
Each organic electro luminescent layer structure can be identical, also can be inequality.Organic electro luminescent layer can comprise the following structure that is arranged in order: hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer.Hole injection layer more is close to anode than electron injecting layer.
Special; Organic electro luminescent layer can only comprise luminescent layer, all the other each layer structures, as: hole injection layer, hole transmission layer, electronic barrier layer, hole blocking layer, electron transfer layer and electron injecting layer; Can add arbitrarily according to demand, also can not add.
The material of hole injection layer can be molybdenum trioxide (MoO
3), tungstic acid (WO
3), barium oxide (VO
x).VO
xCan be vanadic oxide (V
2O
5).The thickness of hole injection layer is 20nm～60nm, is preferably 40nm.
The material of hole transmission layer and electronic barrier layer can be 1,1-two [4-[N, N '-two (p-tolyl) amino] phenyl] cyclohexane (TAPC), N, N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine (TPD), 4,4 '; 4 " three (carbazole-9-yl) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine (NPB), 1,3,5-triphenylbenzene (TDAPB) or CuPc (CuPc).The thickness of hole transmission layer is 20nm～80nm, and the thickness of electronic barrier layer is 2nm～10nm.The material of hole transmission layer is preferably NPB, and thickness is preferably 40nm.The material of electronic barrier layer is preferably TAPC, and thickness is preferably 5nm.
The material of luminescent layer can be four-tert-butyl group perylene (TBP), 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-two-β-naphthylene anthracene (AND), two (2-methyl-oxine)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1; 1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq
3), two (4,6-difluorophenyl pyridine-N, C
2) the pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-four (1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) and closes iridium (Ir (MDQ)
2(acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)
2(acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq)
3) and three (2-phenylpyridines) close iridium (Ir (ppy)
3) at least a.As far as phosphorescent light-emitting materials, luminescent layer can carry out the mixing and doping preparation with one or both of hole mobile material or electron transport material, and its doping mass ratio is 1%～20%; As far as fluorescence luminescent material, then can be separately as luminescent material as luminescent layer, like Alq
3, this moment, thickness was 20nm.
The material of electron transfer layer and hole blocking layer can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 2,5-two (1-naphthyl)-1,3,4-diazole (BND), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (like TAZ), N-aryl benzimidazole (TPBI) or quinoxaline derivant (TPQ).The thickness of electron transfer layer is 40nm～80nm, and the thickness of hole blocking layer is 3nm～10nm.The material of electron transfer layer is preferably Bphen, and thickness is preferably 60nm.The material of hole blocking layer is preferably TPBi, and thickness is preferably 5nm.
The material of electron injecting layer can be Cs
2CO
3, CsN
3, LiF, CsF, CaF
2, MgF
2Or NaF, thickness is 0.5nm～5nm.Electron injecting layer also can adopt the doping of material of material and the electron transfer layer of above-mentioned electron injecting layer, and the material doping mass ratio of electron injecting layer is 20%～60%, and this moment, the thickness of electron injecting layer was 20nm～60nm.The material of electron injecting layer is preferably the CsN that mixed
3Bphen, CsN
3The doping mass ratio is preferably 20%, and the thickness of electron injecting layer is preferably 40nm.
The material of charge generation layer is the hole transport performance material of electronics injection material and hole-injecting material of having mixed, and thickness is 5nm～30nm.
The electronics injection material is that the doping mass ratio of main body is 1%～10% with the hole mobile material.Hole-injecting material is that the doping mass ratio of main body is 1%～20% with the hole mobile material.
Hole mobile material can be N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4; 4 '-benzidine (TPD), N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine (NPB), 1,3,5-triphenylbenzene (TDAPB) or 4; 4,4 ,-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine (m-MTDATA).
The electronics injection material is selected cesium salt or lithium salts among the present invention.General, can enumerate like Cs
2CO
3, CsN
3, CsF, LiF, Li
2O and Li
2CO
3Because the electronics injectability of cesium salt and lithium salts is stronger, only need a small amount of doping can reach the electronics regenerability, and the optical property of charge generation layer is not had very big influence, more help the application of lamination organic electroluminescence device.
Hole-injecting material can be 2,3,5,6-tetrafluoro-7; 7,8,8 ,-four cyano-benzoquinone's bismethane (F4-TCNQ), 4; 4,4-three (naphthyl-phenyl-ammonium) triphenylamine (NATA), 4,4; 4-three (naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) or 4,4,4-three (naphthyl-2-phenyl-ammonium) triphenylamine (2T-NATA).
The charge generation layer of this lamination organic electroluminescence device is a single layer structure; Material is the hole mobile material that is doped with little electrons injection material and hole mobile material; Avoided since the charge generation layer of sandwich construction owing to boundary defect causes device starting resistor problem of higher, this lamination organic electroluminescence device starting resistor is lower.
Simultaneously; The material of charge generation layer is the hole mobile material of electronics injection material and hole-injecting material of having mixed; Can improve regeneration, injection and the transmittability in electronics and hole, thereby improve the recombination probability in electronics and hole, thereby improve luminous efficiency.
In addition; The hole mobile material and the hole mobile material of this lamination organic electroluminescence device are organic molecule; Because tangible total reflection or absorption can not take place in the optical property and the luminescent layer basically identicals such as refractive index of organic molecule, can effectively reduce phenomenons such as reflection; Improved light extraction efficiency, the luminous efficiency of device is improved.
The preparation method of above-mentioned lamination organic electroluminescence device as shown in Figure 2 comprises the steps.
S10, anode is provided.
S20, form two organic electro luminescent layer and be positioned at the charge generation layer in the middle of two organic electro luminescent layer at the surperficial vapor deposition of one on anode.
With two organic electro luminescent layer and a charge generation layer is example, is formed with organic electroluminescent layer, charge generation layer and organic electro luminescent layer on surface of anode vapor deposition successively.
The material of charge generation layer is the hole transport performance material of electronics injection material and hole-injecting material of having mixed, and thickness is 5nm～30nm.
The electronics injection material is that the doping mass ratio of main body is 1%～10% with the hole mobile material.Hole-injecting material is that the doping mass ratio of main body is 1%～20% with the hole mobile material.
Hole mobile material can be N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4; 4 '-benzidine (TPD), N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine (NPB), 1,3,5-triphenylbenzene (TDAPB) or 4; 4,4 ,-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine (m-MTDATA).
The electronics injection material is selected cesium salt or lithium salts among the present invention.General, can enumerate like Cs
2CO
3, CsN
3, CsF, LiF, Li
2O and Li
2CO
3Because the electronics injectability of cesium salt and lithium salts is stronger, only need a small amount of doping can reach the electronics regenerability, and the optical property of charge generation layer is not had very big influence, more help the application of lamination organic electroluminescence device.
Hole-injecting material can be 2,3,5,6-tetrafluoro-7; 7,8,8 ,-four cyano-benzoquinone's bismethane (F4-TCNQ), 4; 4,4-three (naphthyl-phenyl-ammonium) triphenylamine (NATA), 4,4; 4-three (naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) or 4,4,4-three (naphthyl-2-phenyl-ammonium) triphenylamine (2T-NATA).
If prepare plural organic electro luminescent layer, method is the same basically, and the vapor deposition that superposes successively gets final product.
S30, forming negative electrode away from the organic electro luminescent layer of anode surface vapor deposition, obtain the lamination organic electroluminescence device.
The preparation method of this lamination organic electroluminescence device, with respect to the multilayer charge generation layer that traditional lamination organic electroluminescence device adopts, the preparation process is comparatively simple.
Be the specific embodiment part below, preparation of using and tester are: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure＜1 * 10
-32602), electroluminescent spectrum tester (U.S. photo research company, model: PR650) and screen intensity meter (Beijing Normal University, model: ST-86LA) Pa), current-voltage tester (U.S. Keithly company, model:.
Embodiment 1
As anode, vapor deposition hole injection layer successively on anode: material is MoO with indium tin oxide glass (ITO)
3, thickness is 40nm, hole transmission layer: material is NPB, thickness is 40nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 20nm then, material is 2T-NATA and the CsN of having mixed
3M-MTDATA.2T-NATA is that the doping mass ratio of main body is 2% with m-MTDATA, CsN
3The doping mass ratio that with m-MTDATA is main body is 1%.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB, and thickness is 40nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Ag at last, and thickness is 150nm, obtains needed lamination organic electroluminescence device.
Embodiment 2
As anode, vapor deposition hole injection layer successively on anode: material is MoO with fluorine-containing tin oxide glass (FTO)
3, thickness is 20nm, hole transmission layer: material is NPB, thickness is 40nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 80nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 10nm then, material is 2T-NATA and the CsN of having mixed
3M-MTDATA.2T-NATA is that the doping mass ratio of main body is 2% with m-MTDATA, CsN
3The doping mass ratio that with m-MTDATA is main body is 1%.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB, and thickness is 60nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 80nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Ag at last, and thickness is 200nm, obtains needed lamination organic electroluminescence device.
Embodiment 3
As anode, vapor deposition hole injection layer successively on anode: material is MoO with indium tin oxide glass (ITO)
3, thickness is 20nm, hole transmission layer: material is NPB, thickness is 40nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 40nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 5nm then, material is 1T-NATA and the CsN of having mixed
3M-MTDATA.1T-NATA is that the doping mass ratio of main body is 2% with m-MTDATA, CsN
3The doping mass ratio that with m-MTDATA is main body is 1%.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB, and thickness is 20nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Ag at last, and thickness is 20nm, obtains needed lamination organic electroluminescence device.
Embodiment 4
As anode, vapor deposition hole injection layer successively on anode: material is WO with indium tin oxide glass (ITO)
3Thickness is 50nm, hole transmission layer: material is TAPC; Thickness is 30nm, luminescent layer: material is TBP; Thickness is 25nm and electron transfer layer: material is BND, and thickness is 50nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 20nm then, material are the m-MTDATA of 2T-NATA and LiF of having mixed.2T-NATA is that the doping mass ratio of main body is 2% with m-MTDATA, and LiF is that the doping mass ratio of main body is 5% with m-MTDATA.Vapor deposition hole transmission layer successively on charge generation layer then: material is TAPC; Thickness is 30nm, luminescent layer: material is TBP; Thickness is 25nm and electron transfer layer: material is BND; Thickness is 50nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Al at last, and thickness is 50nm, obtains needed lamination organic electroluminescence device.
Embodiment 5
As anode, vapor deposition hole injection layer successively on anode: material is V with indium tin oxide glass (ITO)
2O
5, thickness is 60nm, hole transmission layer: material is TPD, thickness is 20nm, luminescent layer: material is Ir (ppy)
3, thickness is 20nm and electron transfer layer: material is Bphen, and thickness is 60nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 15nm then, material is 2T-NATA and the CsN of having mixed
3M-MTDATA.2T-NATA is that the doping mass ratio of main body is 10% with m-MTDATA, CsN
3The doping mass ratio that with m-MTDATA is main body is 7%.Vapor deposition hole transmission layer successively on charge generation layer then: material is TPD, and thickness is 40nm, luminescent layer: material is Ir (ppy)
3, thickness is 20nm and electron transfer layer: material is Bphen, and thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Au at last, and thickness is 120nm, obtains needed lamination organic electroluminescence device.
Embodiment 6
As anode, vapor deposition hole injection layer successively on anode: material is WO with the zinc oxide glass (AZO) of mixing aluminium
3Thickness is 25nm, hole transmission layer: material is CuPc; Thickness is 45nm, luminescent layer: material is FIrpic; Thickness is 15nm and electron transfer layer: material is TAZ, and thickness is 55nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 30nm then, material are the m-MTDATA of 2T-NATA and CsF of having mixed.2T-NATA is that the doping mass ratio of main body is 20% with m-MTDATA, and CsF is that the doping mass ratio of main body is 1% with m-MTDATA.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB; Thickness is 40nm, luminescent layer: material is FIrpic; Thickness is 15nm and electron transfer layer: material is PBD; Thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is the magnesium silver alloy at last, and thickness is 150nm, obtains needed lamination organic electroluminescence device.
Embodiment 7
As anode, vapor deposition hole injection layer successively on anode: material is WO with magnesium-indium oxide glass (MZO)
3Thickness is 35nm, hole transmission layer: material is TDAPB; Thickness is 30nm, luminescent layer: material is DCJTI; Thickness is 20nm and electron transfer layer: material is TPQ, and thickness is 60nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 20nm then, material is F4-TCNQ and the CsN of having mixed
3M-MTDATA.F4-TCNQ is that the doping mass ratio of main body is 2% with m-MTDATA, CsN
3The doping mass ratio that with m-MTDATA is main body is 10%.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB, and thickness is 40nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Au at last, and thickness is 40nm, obtains needed lamination organic electroluminescence device.
Embodiment 8
As anode, vapor deposition hole injection layer successively on anode: material is MoO with metal sulfide (CdS)
3Thickness is 55nm, hole transmission layer: material is NPB; Thickness is 40nm, luminescent layer: material is FIr6; Thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 20nm then, material is NATA and the Cs of having mixed
2CO
3NPB.NATA is that the doping mass ratio of main body is 1% with NPB, Cs
2CO
3The doping mass ratio that with NPB is main body is 1%.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB; Thickness is 40nm, luminescent layer: material is FIr6; Thickness is 20nm and electron transfer layer: material is PBD; Thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Ag at last, and thickness is 80nm, obtains needed lamination organic electroluminescence device.
Embodiment 9
As anode, vapor deposition hole injection layer successively on anode: material is MoO with metal selenide (ZnSe)
3Thickness is 25nm, hole transmission layer: material is NPB; Thickness is 40nm, luminescent layer: material is TBP; Thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 20nm then, material is 2T-NATA and the CsN of having mixed
3TPD.2T-NATA is that the doping mass ratio of main body is 2% with TPD, CsN
3The doping mass ratio that with TPD is main body is 1%.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB; Thickness is 40nm, luminescent layer: material is TBP; Thickness is 20nm and electron transfer layer: material is PBD; Thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Al at last, and thickness is 180nm, obtains needed lamination organic electroluminescence device.
Embodiment 10
As anode, vapor deposition hole injection layer successively on anode: material is MoO with indium tin oxide glass
3Thickness is 20nm, hole transmission layer: material is NPB; Thickness is 40nm, luminescent layer: material is BALQ; Thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.The thick charge generation layer of vapor deposition 20nm then, material is 1T-NATA and the CsN of having mixed
3TPD.1T-NATA is that the doping mass ratio of main body is 2% with TPD, CsN
3The doping mass ratio that with TPD is main body is 2%.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB; Thickness is 40nm, luminescent layer: material is BALQ; Thickness is 20nm and electron transfer layer: material is PBD; Thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Au at last, and thickness is 20nm, obtains needed lamination organic electroluminescence device.
Comparative Examples
As anode, vapor deposition hole injection layer successively on anode: material is MoO with indium tin oxide glass
3, thickness is 40nm, hole transmission layer: material is NPB, thickness is 40nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.Mixed the m-MTDATA layer of 2T-NATA and the MoO that mixed of vapor deposition successively then
3CsN
3Layer, 2T-NATA is that the doping mass ratio of main body is 7% with m-MTDATA, MoO
3With CsN
3For the doping mass ratio of main body is 15%.Vapor deposition hole transmission layer successively on charge generation layer then: material is NPB, and thickness is 40nm, luminescent layer: material is Alq
3, thickness is 20nm and electron transfer layer: material is PBD, and thickness is 60nm, obtains comprising second organic electro luminescent layer of hole transmission layer, luminescent layer and electron transfer layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Ag at last, and thickness is 150nm, obtains needed lamination organic electroluminescence device.
Be illustrated in figure 3 as the current density and the energy efficiency graph of a relation of the embodiment 1 and the lamination organic electroluminescence device of Comparative Examples preparation.
As can be seen from the figure, under same current density, the energy efficiency of the lamination organic electroluminescence device of the energy effciency ratio Comparative Examples preparation of the lamination organic electroluminescence device of embodiment 1 preparation is high.The maximum power efficiency of the lamination organic electroluminescence device of embodiment 1 preparation is 10.6lm/W, and the maximum power efficiency of traditional lamination organic electroluminescence device is 9.8lm/W.Can explain thus; The lamination organic electroluminescence device of embodiment 1 preparation is doped with the charge generation layer of the little electrons injection material and the organic molecule material with hole transport performance of the organic molecule with hole transport performance through use; Effectively reduced the adverse effect factor such as reflectivity and absorptivity of charge generation layer; The luminous efficiency of device is improved, finally makes the energy efficiency of device be improved.
Above embodiment has only expressed several kinds of execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, 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 accompanying claims.
Claims (10)
1. a lamination organic electroluminescence device is characterized in that, comprising: anode, negative electrode, the charge generation layers that are positioned at two organic electro luminescent layer of said anode and said negative electrode centre and are positioned at two said organic electro luminescent layer centres;
The material of said charge generation layer is the hole mobile material of electronics injection material and hole-injecting material of having mixed; Wherein, the doping mass ratio of said electronics injection material is 1%～10%, and the doping mass ratio of said hole-injecting material is 1%～20%.
2. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, said hole mobile material is N, N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine, N, N '-(1-naphthyl)-N, N '-diphenyl-4; 4 '-benzidine, 1,3,5-triphenylbenzene or 4; 4,4 ,-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine.
3. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, said electronics injection material is Cs
2CO
3, CsN
3, CsF, LiF, Li
2O or Li
2CO
3
4. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, said hole-injecting material is 2,3; 5,6-tetrafluoro-7,7,8; 8 ,-four cyano-benzoquinone's bismethane, 4,4,4-three (naphthyl-phenyl-ammonium) triphenylamine, 4; 4,4-three (naphthyl-1-phenyl-ammonium) triphenylamine or 4,4,4-three (naphthyl-2-phenyl-ammonium) triphenylamine.
5. like each described lamination organic electroluminescence device in the claim 1～4, it is characterized in that the thickness of said charge generation layer is 5nm～30nm.
6. the preparation method of a lamination organic electroluminescence device is characterized in that, comprises the steps:
Step 1, anode is provided;
Step 2, form two organic electro luminescent layer and be positioned at two charge generation layers in the middle of the said organic electro luminescent layer at the surperficial vapor deposition of one on said anode; The material of said charge generation layer is the hole mobile material of electronics injection material and hole-injecting material of having mixed; Wherein, the doping mass ratio of said electronics injection material is 1%～10%, and the doping mass ratio of said hole-injecting material is 1%～20%;
Step 3, forming negative electrode away from the organic electro luminescent layer of said anode surface vapor deposition.
7. the preparation method of lamination organic electroluminescence device as claimed in claim 6 is characterized in that, in the step 2, said hole mobile material is N; N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, N, N '-(1-naphthyl)-N; N '-diphenyl-4,4 '-benzidine, 1,3,5-triphenylbenzene or 4; 4,4 ,-three (N-3-aminomethyl phenyl-N-phenyl-amino) triphenylamine.
8. the preparation method of lamination organic electroluminescence device as claimed in claim 6 is characterized in that, in the step 2, said electronics injection material is Cs
2CO
3, CsN
3, CsF, LiF, Li
2O or Li
2CO
3
9. the preparation method of lamination organic electroluminescence device as claimed in claim 6 is characterized in that, in the step 2, said hole-injecting material is 2,3; 5,6-tetrafluoro-7,7,8; 8 ,-four cyano-benzoquinone's bismethane, 4,4,4-three (naphthyl-phenyl-ammonium) triphenylamine, 4; 4,4-three (naphthyl-1-phenyl-ammonium) triphenylamine or 4,4,4-three (naphthyl-2-phenyl-ammonium) triphenylamine.
10. like the preparation method of each described lamination organic electroluminescence device in the claim 6～9, it is characterized in that in the step 2, said charge generation layer thickness is 5nm～30nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972406A (en) * | 2013-01-31 | 2014-08-06 | 海洋王照明科技股份有限公司 | Organic light-emitting device and method for manufacturing same |
| CN104078568A (en) * | 2013-03-29 | 2014-10-01 | 海洋王照明科技股份有限公司 | Organic light-emitting diode and preparation method thereof |
| CN107611271A (en) * | 2017-08-10 | 2018-01-19 | 上海天马有机发光显示技术有限公司 | Organic light emitting diode, display panel and display device |
| CN114447238A (en) * | 2020-10-30 | 2022-05-06 | 财团法人纺织产业综合研究所 | Electroluminescent wire |
| WO2024192675A1 (en) * | 2023-03-21 | 2024-09-26 | 京东方科技集团股份有限公司 | Organic electroluminescent device and display apparatus |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843062A (en) * | 2003-08-25 | 2006-10-04 | 株式会社半导体能源研究所 | Electrode for organic device and electronic device employing same |
| CN101359721A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Top radiation organic EL part with optical spectrum adjustable |
| CN101694849A (en) * | 2009-09-22 | 2010-04-14 | 昆山维信诺显示技术有限公司 | Organic electroluminescence lamination device |
| WO2010048920A1 (en) * | 2008-10-31 | 2010-05-06 | Osram Opto Semiconductors Gmbh | Radiation-emitting device |
-
2011
- 2011-06-03 CN CN2011101497573A patent/CN102810646A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843062A (en) * | 2003-08-25 | 2006-10-04 | 株式会社半导体能源研究所 | Electrode for organic device and electronic device employing same |
| CN101359721A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Top radiation organic EL part with optical spectrum adjustable |
| WO2010048920A1 (en) * | 2008-10-31 | 2010-05-06 | Osram Opto Semiconductors Gmbh | Radiation-emitting device |
| CN101694849A (en) * | 2009-09-22 | 2010-04-14 | 昆山维信诺显示技术有限公司 | Organic electroluminescence lamination device |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972406A (en) * | 2013-01-31 | 2014-08-06 | 海洋王照明科技股份有限公司 | Organic light-emitting device and method for manufacturing same |
| CN104078568A (en) * | 2013-03-29 | 2014-10-01 | 海洋王照明科技股份有限公司 | Organic light-emitting diode and preparation method thereof |
| CN107611271A (en) * | 2017-08-10 | 2018-01-19 | 上海天马有机发光显示技术有限公司 | Organic light emitting diode, display panel and display device |
| CN114447238A (en) * | 2020-10-30 | 2022-05-06 | 财团法人纺织产业综合研究所 | Electroluminescent wire |
| CN114447238B (en) * | 2020-10-30 | 2024-02-02 | 财团法人纺织产业综合研究所 | Electroluminescent wire |
| WO2024192675A1 (en) * | 2023-03-21 | 2024-09-26 | 京东方科技集团股份有限公司 | Organic electroluminescent device and display apparatus |
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Application publication date: 20121205 |