CN102810644A - Laminated organic electroluminescent device and preparation method thereof - Google Patents
Laminated organic electroluminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a laminated organic electroluminescent device which comprises an anode, a cathode, two organic electroluminescent layers and a charge generation layer, wherein the charge generation layer is positioned between the two organic electroluminescent layers which are positioned between the anode and the cathode. The charge generation layer comprises an n-type doped layer, a bipolar metal oxide layer and a p-type doped layer, wherein the bipolar metal oxide layer has an electron generation capacity and a hole generation capacity simultaneously, and the n-type doped layer is closer to the anode than the p-type doped layer. The bipolar metal oxide layer has functions of n-type materials and p-type materials simultaneously and can generate holes and electrons concurrently, so that hole and electron generation of the charge generation layer can be further guaranteed, efficiency of the laminated organic electroluminescent device can be improved, and application of the laminated device is facilitated. The invention further provides a preparation method of the laminated organic electroluminescent 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 current 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.Research at present many be utilize n type and p type doped layer as charge generation layer (like n type (Alq
3: Li) with p type (NPB: FeCl
3)) be linked in sequence a plurality of luminescence units and constitute, but this charge generation layer is limited to the power of regeneration in electronics and hole, adopts the luminous efficiency of lamination organic electroluminescence device of this charge generation layer lower.
[summary of the invention]
Based on this, be necessary to provide higher lamination organic electroluminescence device of a kind of luminous efficiency and preparation method thereof.
A kind of lamination organic electroluminescence device comprises: anode, negative electrode, two organic electro luminescent layer between said anode and said negative electrode and the charge generation layer that is positioned at said two organic electro luminescent layer centre;
Said charge generation layer comprises the following structure that stacks gradually: n type doped layer, have bipolarity metal oxide layer and a p type doped layer that electronics and hole produce ability simultaneously; Said n type doped layer more is close to said anode than said p type doped layer; The material of said n type doped layer is the electron transport material of metallic compound of having mixed, and the material of said p type doped layer is the organic hole transferring material of organic hole injection material of having mixed.
Preferably, the material of said bipolarity metal oxide layer is MoO
3, WoO
3Or V
2O
5
Preferably, the thickness of said bipolarity metal oxide layer is 2nm～10nm.
Preferably, the mass ratio of the doping of metallic compound described in the electron transport material of the said metallic compound that mixed is 5%～60%.
Preferably, said metallic compound is Cs
2CO
3, CsN
3, CsF, LiF or Li
2CO
3
Said electron transport material is an oxine aluminium, 1,2,4-triazole derivative, N-aryl benzimidazole, 4,7-diphenyl-1,10-phenanthroline or two (2-methyl-oxine)-(4-xenol) aluminium.
Preferably, said n type doped layer thickness is 5nm～20nm.
Preferably, the mass ratio of the doping of organic hole injection material described in the organic hole transferring material of the said organic hole injection material that mixed is 1%～10%.
Preferably, said organic hole injection 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;
Said organic hole transferring 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 p type doped layer thickness is 5nm～40nm.
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 the charge generation layer in the middle of said two organic electro luminescent layer at the surperficial vapor deposition of one on said anode; Said charge generation layer comprises the following structure that stacks gradually: n type doped layer, bipolarity metal oxide layer and p type doped layer, and said n type doped layer more is close to said anode than said p type doped layer; The material of said n type doped layer is the electron transport material of metallic compound of having mixed, and the material of said p type doped layer is the organic hole transferring material of organic hole injection material of having mixed;
Step 3, forming negative electrode away from the organic electro luminescent layer of said anode surface vapor deposition.
This lamination organic electroluminescence device is through adding the bipolarity metal oxide layer that has electronics and hole generation ability simultaneously between n type doped layer and p type doped layer; Middle bipolarity metal oxide layer plays the effect of n type material and p type material simultaneously; Can produce hole and electronics simultaneously; Further guarantee the hole of charge generation layer and the generation of electronics, made the efficient of lamination organic electroluminescence device be improved, more helped the application of laminated device.
[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 current 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 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 two charge generation layers in the middle of the adjacent organic electro luminescent layer.
In the present embodiment, organic electro luminescent layer is two, and 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 between per two adjacent organic electro luminescent layer.
The anode material can be indium tin oxide glass, fluorine-containing tin oxide glass, the zinc oxide of mixing aluminium, magnesium-indium oxide, metal selenide or metal sulfide.
The negative electrode material can be silver (Ag), aluminium (A1), magnesium silver alloy or gold (Au), and thickness is 20～200nm.Wherein, the negative electrode material 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 hole injection layer material can be molybdenum trioxide (MoO
3), tungstic acid (WO
3), barium oxide (VO
x).VO
xCan be vanadic oxide (V
2O
5) thickness is 20nm～60nm, is preferably 40nm.
Hole transmission layer and electronic barrier layer material 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).Thickness of hole transport layer is 20nm～80nm, and electronic barrier layer thickness is 2nm～10nm.The hole transmission layer material is preferably NPB, and thickness is preferably 40nm.The electronic barrier layer material is preferably TAPC, and thickness can be 5nm.
The luminescent layer material 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 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.
Electron transfer layer and hole blocking layer material 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 electric transmission layer thickness is 40nm～80nm, and the hole barrier layer thickness is 3nm～10nm.The electron transfer layer material is preferably Bphen, and thickness is preferably 60nm.The hole blocking layer material is preferably TPBi, and thickness is preferably 5nm.
The electron injecting layer material 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 above-mentioned electron injecting layer material and electron transport material, and the material doped ratio of electron injecting layer is 20%～60%, and this moment, electron injecting layer thickness was 20nm～60nm.The electron injecting layer material is preferably the CsN that mixed
3Bphen, CsN
3Doping ratio is preferably 20%, and electron injecting layer thickness is preferably 40nm.
Charge generation layer comprises the following structure that stacks gradually: n type doped layer, have bipolarity metal oxide layer and the p type doped layer that electronics and hole produce ability simultaneously, n type doped layer more is close to anode than p type doped layer.
N type doped layer material is the electron transport material of metallic compound of having mixed, and thickness is 5nm～20nm, and wherein the mass ratio that mixes of metallic compound is 5%～60%.Metallic compound is Cs
2CO
3, CsN
3, CsF, LiF or Li
2CO
3, electron transport material is oxine aluminium (Alq
3), 1,2,4-triazole derivative (like TAZ), N-aryl benzimidazole (TPBI), 4,7-diphenyl-1,10-phenanthroline (Bphen) or two (2-methyl-oxine)-(4-xenol) aluminium (BALQ).
Bipolarity metal oxide layer material is MoO
3, WoO
3Or V
2O
5, thickness is 2nm～10nm.
P type doped layer material is the organic hole transferring material of organic hole injection material of having mixed, and thickness is 5nm～40nm, and the mass ratio that the organic hole injection material mixes is 1%～10%.The organic hole injection material is 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 organic hole transferring material is 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).
This lamination organic electroluminescence device is through adding the bipolarity metal oxide layer that has electronics and hole generation ability simultaneously between n type doped layer and p type doped layer; Constitute the structure of n type doped layer/bipolarity metal oxide layer/p type doped layer; Middle bipolarity metal oxide layer plays the effect of n type material and p type material simultaneously; Can produce hole and electronics simultaneously; Further guarantee the hole of charge generation layer and the generation of electronics, made the efficient of lamination organic electroluminescence device be improved, more helped the application of laminated device.
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.
Charge generation layer comprises the following structure that stacks gradually: n type doped layer, bipolarity metal oxide layer and p type doped layer, n type doped layer more is close to anode than p type doped layer.
N type doped layer material is the electron transport material of metallic compound of having mixed, and thickness is 5nm～20nm, and wherein the mass ratio that mixes of metallic compound is 5%～60%.Metallic compound is Cs
2CO
3, CsN
3, CsF, LiF or Li
2CO
3, electron transport material is an oxine aluminium, 1,2,4-triazole derivative, N-aryl benzimidazole, 4,7-diphenyl-1,10-phenanthroline or two (2-methyl-oxine)-(4-xenol) aluminium.
Bipolarity metal oxide layer material is MoO
3, WoO
3Or V
2O
5, thickness is 2nm～10nm.
P type doped layer material is the organic hole transferring material of organic hole injection material of having mixed, and thickness is 5nm～40nm, and the mass ratio that the organic hole injection material mixes is 1%～10%.The organic hole injection 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, the organic hole transferring 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.
If prepare plural organic electro luminescent layer, method is the same basically, and vapor deposition gets final product successively.
S30, forming negative electrode away from the organic electro luminescent layer of anode surface vapor deposition, obtain the lamination organic electroluminescence device.
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 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.Evaporating n type doped layer then, material is the Cs that mixed
2CO
3Bphen, thickness is 7nm, wherein Cs
2CO
3Doping ratio be 40%.Follow vapor deposition bipolarity metal oxide layer, material is MoO
3, thickness is 5nm.Last vapor deposition p type doped layer, material are the m-MTDATA of F4-TCNQ of having mixed, and thickness is 10nm, and wherein the doping ratio of F4-TCNQ is 2%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent 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 thick, the hole transmission layer of 40nm: material is NPB, thickness is 40nm, luminescent layer: material is Alq
3Thickness 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.Evaporating n type doped layer then, material is the Cs that mixed
2CO
3Bphen, thickness is 15nm, wherein Cs
2CO
3Doping ratio be 40%.Follow vapor deposition bipolarity metal oxide layer, material is MoO
3, thickness is 5nm.Last vapor deposition p type doped layer, material are the m-MTDATA of F4-TCNQ of having mixed, and thickness is 15nm, and wherein the doping ratio of F4-TCNQ is 2%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Ag at last, and thickness is that 150nm obtains needed lamination organic electroluminescence device.
Embodiment 3
As anode, vapor deposition hole injection layer successively on anode: material is MoO with fluorine-containing tin oxide glass glass (FTO)
3, thickness is thick, the hole transmission layer of 20nm: material is NPB, thickness is 60nm, luminescent layer: material is Alq
3Thickness is 15nm 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.Evaporating n type doped layer then, material is the Cs that mixed
2CO
3Bphen, thickness is 5nm, wherein Cs
2CO
3Doping ratio be 40%.Follow vapor deposition bipolarity metal oxide layer, material is MoO
3, thickness is 15nm.Last vapor deposition p type doped layer, material are the m-MTDATA of F4-TCNQ of having mixed, and thickness is 5nm, and wherein the doping ratio of F4-TCNQ is 2%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Ag at last, and thickness is that 200nm obtains needed lamination organic electroluminescence device.
Embodiment 4
As anode, vapor deposition hole injection layer successively on anode: material is MoO with indium tin oxide glass (ITO)
3, thickness is 60nm, hole transmission layer: material is NPB, thickness is 20nm, luminescent layer: material is Alq
3, thickness is 25nm and electron transfer layer: material is Bphen, and thickness is 40nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.Evaporating n type doped layer then, material is the Cs that mixed
2CO
3Bphen, thickness is 7nm, wherein Cs
2CO
3Doping ratio be 50%.Follow vapor deposition bipolarity metal oxide layer, material is MoO
3, thickness is 5nm.Last vapor deposition p type doped layer, material are the m-MTDATA of F4-TCNQ of having mixed, and thickness is 10nm, and wherein the doping ratio of F4-TCNQ is 5%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent 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 5
As anode, vapor deposition hole injection layer successively on anode: material is WO with the zinc oxide glass (AZO) of mixing aluminium
3Thickness is 40nm, hole transmission layer: material is TAPC; Thickness is 20nm, luminescent layer: material is BALQ; Thickness is 25nm and electron transfer layer: material is Bphen, and thickness is 80nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.Evaporating n type doped layer then, material is the Cs that mixed
2CO
3Bphen, thickness is 7nm, wherein Cs
2CO
3Doping ratio be 20%.Follow vapor deposition bipolarity metal oxide layer, material is MoO
3, thickness is 5nm.Last vapor deposition p type doped layer, material are the m-MTDATA of F4-TCNQ of having mixed, and thickness is 40nm, and wherein the doping ratio of F4-TCNQ is 1%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Al at last, and thickness is 60nm, obtains needed lamination organic electroluminescence device.
Embodiment 6
As anode, vapor deposition hole injection layer successively on anode: material is V with magnesium-indium oxide glass (MZO)
2O
5Thickness is 50nm, hole transmission layer: material is CuPc; Thickness is 40nm, luminescent layer: material is TBP; 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.Evaporating n type doped layer then, material are the Alq of CsF of having mixed
3, thickness is 7nm, wherein the doping ratio of CsF is 25%.Follow vapor deposition bipolarity metal oxide layer, material is MoO
3, thickness is 5nm.Last vapor deposition p type doped layer, material are the m-MTDATA of F4-TCNQ of having mixed, and thickness is 10nm, and wherein the doping ratio of F4-TCNQ is 2%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent 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 7
As anode, vapor deposition hole injection layer successively on anode: material is WO with metal sulfide (CdS) glass
3Thickness is 40nm, hole transmission layer: material is TPD; 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.Evaporating n type doped layer then, material is the Cs that mixed
2CO
3Bphen, thickness is 7nm, wherein Cs
2CO
3Doping ratio be 40%.Follow vapor deposition bipolarity metal oxide layer, material is MoO
3, thickness is 5nm.Last vapor deposition p type doped layer, material are the F4-TCNQ of NPB of having mixed, and thickness is 10nm, and wherein the doping ratio of NPB is 15%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent 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 8
As anode, vapor deposition hole injection layer successively on anode: material is WO with indium tin oxide glass (ITO)
3Thickness is 30nm, hole transmission layer: material is TDAPB; Thickness is 80nm, luminescent layer: material is AND; Thickness is 20nm and electron transfer layer: material is TPQ, and thickness is 40nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.Evaporating n type doped layer then, material is the CsN that mixed
3Bphen, thickness is 7nm, wherein CsN
3Doping ratio be 45%.Follow vapor deposition bipolarity metal oxide layer, material is V
2O
5, thickness is 10nm.Last vapor deposition p type doped layer, material are the m-MTDATA of F4-TCNQ of having mixed, and thickness is 10nm, and wherein the doping ratio of F4-TCNQ is 2%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent layer.At the surperficial vapor deposition negative electrode of second organic electro luminescent layer, material is Au at last, and thickness is 30nm, obtains needed lamination organic electroluminescence device.
Embodiment 9
As anode, vapor deposition hole injection layer successively on anode: material is MoO with indium tin oxide glass (ITO)
3, thickness is 60nm, hole transmission layer: material is NPB, thickness is 80nm, luminescent layer: material is Ir (ppy)
3, thickness is 20nm and electron transfer layer: material is TPBI, and thickness is 60nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.Evaporating n type doped layer then, material is the Cs that mixed
2CO
3Bphen, thickness is 7nm, wherein Cs
2CO
3Doping ratio be 40%.Follow vapor deposition bipolarity metal oxide layer, material is WO
3, thickness is 5nm.Last vapor deposition p type doped layer, material are the m-MTDATA of 2T-NATA of having mixed, and thickness is 25nm, and wherein the doping ratio of 2T-NATA is 2%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent 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 metal selenide (ZnSe) glass
3Thickness is 25nm, hole transmission layer: material is TCTA; Thickness is 40nm, luminescent layer: material is DCJTI; Thickness is 25nm and electron transfer layer: material is Bphen, and thickness is 45nm, obtains comprising first organic electro luminescent layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.Evaporating n type doped layer then, material is the Li that mixed
2CO
3Bphen, thickness is 7nm, wherein Li
2CO
3Doping ratio be 60%.Follow vapor deposition bipolarity metal oxide layer, material is WO
3, thickness is 5nm.Last vapor deposition p type doped layer, material are the m-MTDATA of 1T-NATA of having mixed, and thickness is 10nm, and wherein the doping ratio of 1T-NATA is 10%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent 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 (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 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.Evaporating n type doped layer then, material is the Cs that mixed
2CO
3Bphen, thickness is 7nm, wherein Cs
2CO
3Doping ratio be 40%.Last vapor deposition p type doped layer, material are the m-MTDATA of F4-TCNQ of having mixed, and thickness is 10nm, and wherein the doping ratio of F4-TCNQ is 2%.Continue vapor deposition structure second organic electro luminescent layer consistent then with first organic electro luminescent 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.
The current density and the current efficiency graph of a relation of the embodiment 1 as shown in Figure 3 and the lamination organic electroluminescence device of Comparative Examples preparation.
By finding out among the figure; Under identical current density; The current efficiency of the lamination organic electroluminescence optical device of embodiment 1 preparation has explained that greater than the lamination organic electroluminescence device of Comparative Examples preparation the interpolation of bipolarity metal oxide layer has improved the luminous efficiency of lamination organic electroluminescence device.
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, be positioned at two organic electro luminescent layer in the middle of said anode and the said negative electrode and be positioned at the charge generation layer in the middle of said two organic electro luminescent layer;
Said charge generation layer comprises the following structure that stacks gradually: n type doped layer, have bipolarity metal oxide layer and a p type doped layer that electronics and hole produce ability simultaneously; Said n type doped layer more is close to said anode than said p type doped layer; The material of said n type doped layer is the electron transport material of metallic compound of having mixed, and the material of said p type doped layer is the organic hole transferring material of organic hole injection material of having mixed.
2. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the material of said bipolarity metal oxide layer is MoO
3, WoO
3Or V
2O
5
3. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the thickness of said bipolarity metal oxide layer is 2nm～10nm.
4. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the mass ratio that metallic compound described in the material of n type doped layer mixes in the electron transport material of the said metallic compound that mixed is 5%～60%.
5. lamination organic electroluminescence device as claimed in claim 4 is characterized in that, said metallic compound is Cs
2CO
3, CsN
3, CsF, LiF or Li
2CO
3
Said electron transport material is an oxine aluminium, 1,2,4-triazole derivative, N-aryl benzimidazole, 4,7-diphenyl-1,10-phenanthroline or two (2-methyl-oxine)-(4-xenol) aluminium.
6. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, said n type doped layer thickness is 5nm～20nm.
7. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, the mass ratio that organic hole injection material described in the organic hole transferring material of the said organic hole injection material that mixed mixes is 1%～10%.
8. lamination organic electroluminescence device as claimed in claim 7 is characterized in that, said organic hole injection 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;
Said organic hole transferring 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.
9. lamination organic electroluminescence device as claimed in claim 1 is characterized in that, said p type doped layer thickness is 5nm～40nm.
10. the preparation method like each described lamination organic electroluminescence device in the claim 1～9 is characterized in that, comprises the steps:
Step 1, anode is provided;
Step 2, form two organic electro luminescent layer and be positioned at the charge generation layer in the middle of said two organic electro luminescent layer at the surperficial vapor deposition of one on said anode; Said charge generation layer comprises the following structure that stacks gradually: n type doped layer, bipolarity metal oxide layer and p type doped layer, and said n type doped layer more is close to said anode than said p type doped layer; The material of said n type doped layer is the electron transport material of metallic compound of having mixed, and the material of said p type doped layer is the organic hole transferring material of organic hole injection material of having mixed;
Step 3, forming negative electrode away from the organic electro luminescent layer of said anode surface vapor deposition.
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