CN104183789A - Organic light emitting diode and preparation method thereof - Google Patents
Organic light emitting diode and preparation method thereof Download PDFInfo
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- CN104183789A CN104183789A CN201310193624.5A CN201310193624A CN104183789A CN 104183789 A CN104183789 A CN 104183789A CN 201310193624 A CN201310193624 A CN 201310193624A CN 104183789 A CN104183789 A CN 104183789A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
Abstract
The invention discloses an organic light emitting diode which comprises a conductive anode substrate, a hole injection layer, a hole transfer layer, a light-emitting layer, an electron transfer layer, an electron injection layer and a cathode layer which are stacked in sequence. The light-emitting layer is made of mixture formed by mixing a guest material, a first host material and a second host material. According to the organic light emitting diode, the mass ratio of the guest material and the first host material in the light-emitting layer increases gradually from the side close to the hole transfer layer to the side away from the hole transfer layer; and the mass ratio of the guest material and the second host material decreases gradually from the side close to the hole transfer layer to the side away from the hole transfer layer, so that energy conversion efficiency of the host and guest is improved through the gradual mixing of the host materials and the guest material. The invention also discloses a preparation method of the organic light emitting diode.
Description
Technical field
The present invention relates to organic electroluminescent field, relate in particular to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) has advantages of that some are unique: (1) OLED belongs to diffused area source, does not need to obtain large-area white light source by extra light-conducting system as light-emitting diode (LED); (2) due to the diversity of luminous organic material, the OLED illumination light of design color as required, no matter be little Molecule OLEDs at present, or polymer organic LED (PLED) has all obtained and has comprised the light of white-light spectrum at interior all colours; (3) OLED can make on as glass, pottery, metal, plastic or other material at multiple substrate, freer when this makes to design lighting source; (4) adopt the mode of making OLED demonstration to make OLED illumination panel, can in illumination, show information; (5) OLED also can be used as controlled look in illuminator, allows user to regulate light atmosphere according to individual demand.
The luminous efficiency of organic electroluminescence device is to evaluate the important indicator of organic electroluminescence device performance always.The material of the luminescent layer of traditional organic electroluminescence device normally Uniform Doped the material of main part of guest materials, because the energy conversion efficiency of Subjective and Objective is relatively low, cause the luminous efficiency of traditional organic electroluminescence device poor.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually;
The material of described luminescent layer is the mixture that guest materials, the first material of main part and the second material of main part are mixed to form;
The mass ratio of guest materials described in described luminescent layer and described the first material of main part improves from the side near described hole transmission layer to the side echelon away from described hole transmission layer;
The mass ratio of guest materials described in described luminescent layer and described the second material of main part reduces from the side near described hole transmission layer to the side echelon away from described hole transmission layer;
Described guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] closes iridium;
Described the first material of main part is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or the 3-tert-butyl group-9,10-bis-(2-naphthalene) anthracene;
Described the second material of main part is 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, 4,7-diphenyl-1,10-phenanthroline or N-aryl benzimidazole;
The mass ratio of guest materials described in described luminescent layer and described the first material of main part is 1.2～10.8:100;
The mass ratio of guest materials described in described luminescent layer and described the second material of main part is 0.2～4.8:100.
In one embodiment, described luminescent layer is made up of the first luminescent layer stacking gradually and thickness is identical, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer, and described the first luminescent layer is laminated on described hole transmission layer;
Described in described the first luminescent layer, described the second luminescent layer, described the 3rd luminescent layer and described the 4th luminescent layer, guest materials increases progressively than echelon with the quality of described the first material of main part;
Described in described the first luminescent layer, described the second luminescent layer, described the 3rd luminescent layer and described the 4th luminescent layer, guest materials successively decreases than echelon with the quality of described the second material of main part.
In one embodiment, the mass ratio of guest materials and described the first material of main part described in described the 4th luminescent layer is 1.5 times of mass ratio of described guest materials in described the first luminescent layer and described the first material of main part;
The mass ratio of guest materials and described the second material of main part described in described the 3rd luminescent layer is 2 times of mass ratio of guest materials described in described the 4th luminescent layer and described the second material of main part;
And the described guest materials in described the 4th luminescent layer and the mass ratio of described the first material of main part are 9 times of mass ratio of described guest materials in described the 4th luminescent layer and described the second material of main part.
In one embodiment, the thickness of described luminescent layer is 10nm～30nm.
In one embodiment, the material of described hole injection layer is the hole mobile material doped with metal oxide;
Described metal oxide is MoO
3, WO
3, V
2o
5or ReO
3;
Described hole mobile material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
The mass ratio of described metal oxide and described hole mobile material is 25～35:100;
The thickness of described hole injection layer is 10nm～15nm.
In one embodiment, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
The thickness of described hole transmission layer is 30nm～50nm.
In one embodiment, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The thickness of described electron transfer layer is 10nm～60nm.
In one embodiment, the material of described electron injecting layer is the electron transport material doped with the first salt and the second salt;
Described the first salt is LiF, LiN
3, Li
3n, CsF, CsN
3or Cs
3n;
Described the second salt is Li
2sO
4, Na
2sO
4, K
2sO
4, Rb
2sO
4or Cs
2sO
4;
Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The mass ratio of described the first salt and described electron transport material is 25～35:100;
The mass ratio of described the second salt and described electron transport material is 6～25:100;
The thickness of described electron injecting layer is 15nm～45nm.
A preparation method for organic electroluminescence device, comprises the steps:
Conductive anode substrate is carried out to surface preparation;
In described conductive anode substrate, evaporation forms hole injection layer and hole transmission layer successively;
On described hole transmission layer, evaporation forms luminescent layer, the material of described luminescent layer is guest materials, the mixture that the first material of main part and the second material of main part are mixed to form, the mass ratio of guest materials described in described luminescent layer and described the first material of main part improves from the side near described hole transmission layer to the side echelon away from described hole transmission layer, the mass ratio of guest materials described in described luminescent layer and described the second material of main part reduces from the side near described hole transmission layer to the side echelon away from described hole transmission layer, described guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] closes iridium, described the first material of main part is 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or the 3-tert-butyl group-9, 10-bis-(2-naphthalene) anthracene, described the second material of main part is 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene, 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, 4, 7-diphenyl-1, 10-phenanthroline or N-aryl benzimidazole, the mass ratio of guest materials described in described luminescent layer and described the first material of main part is 1.2～10.8:100, the mass ratio of guest materials described in described luminescent layer and described the second material of main part is 0.2～4.8:100, and
On described luminescent layer, evaporation forms electron transfer layer, electron injecting layer and cathode layer successively.
In one embodiment, described on described hole transmission layer evaporation form the step of luminescent layer and be:
On described hole transmission layer, evaporation forms the first identical luminescent layer of thickness successively, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer, described the first luminescent layer, described the second luminescent layer, described the 3rd luminescent layer and described the 4th luminescent layer form described luminescent layer, described the first luminescent layer, described the second luminescent layer, described in described the 3rd luminescent layer and described the 4th luminescent layer, guest materials increases progressively than echelon with the quality of described the first material of main part, described the first luminescent layer, described the second luminescent layer, described in described the 3rd luminescent layer and described the 4th luminescent layer, guest materials successively decreases than echelon with the quality of described the second material of main part.
In the luminescent layer of this organic electroluminescence device, the mass ratio of guest materials and the first material of main part improves from the side near hole transmission layer to the side echelon away from hole transmission layer, the mass ratio of guest materials and the second material of main part reduces from the side near hole transmission layer to the side echelon away from hole transmission layer, by the gradual mixing of material of main part and guest materials, improve the energy conversion efficiency of Subjective and Objective.With respect to traditional organic electroluminescence device, the luminous efficiency of this organic electroluminescence device is higher.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the structural representation of the luminescent layer of an embodiment of organic electroluminescence device as shown in Figure 1;
Fig. 3 is the preparation method's of organic electroluminescence device flow chart as shown in Figure 1.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
The organic electroluminescence device of an execution mode as shown in Figure 1, comprises the conductive anode substrate 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and the cathode layer 70 that stack gradually.
Conductive anode substrate 10 can be indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).At one, preferably in embodiment, conductive anode substrate 10 is indium tin oxide glass (ITO).
The thickness of the conductive layer of anode conducting substrate 10 can be 80nm～150nm.
The material of hole injection layer 20 can be the hole mobile material doped with metal oxide.
Metal oxide can be MoO
3, WO
3, V
2o
5or ReO
3.
Hole mobile material can be N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC).
The mass ratio of metal oxide and hole mobile material is 25～35:100.
The thickness of hole injection layer 20 can be 10nm～15nm.
The material of hole transmission layer 30 can be N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC).
The thickness of hole transmission layer 30 can be 30nm～50nm.
The material of luminescent layer 40 can be the mixture that guest materials, the first material of main part and the second material of main part are mixed to form.
The mass ratio of guest materials and the first material of main part is 1.2～10.8:100.
The mass ratio of guest materials and the second material of main part is 0.2～4.8:100.
The first material of main part is different with the second material of main part.
Guest materials can be that three (2-phenylpyridines) close iridium (Ir (ppy)
3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy)
3).
The first material of main part can be 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) or the 3-tert-butyl group-9,10-bis-(2-naphthalene) anthracene (MADN).
The second material of main part can be 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] (OXD-7), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene (PO15), 4,7-diphenyl-1,10-phenanthroline (Bphen) or N-aryl benzimidazole (TPBI).
The thickness of luminescent layer 40 can be 10nm～30nm.
In luminescent layer 40, the mass ratio of guest materials and the first material of main part improves to the side echelon away from hole transmission layer 30 from the side near hole transmission layer 30, and the mass ratio of guest materials and the second material of main part reduces from the side near hole transmission layer 30 to the side echelon away from hole transmission layer 30.
In conjunction with Fig. 2, in a specific embodiment, luminescent layer 40 is made up of the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47 that stack gradually and thickness is identical, and the first luminescent layer 41 is laminated on hole transmission layer 30.
The material of the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47 is the mixture that guest materials, the first material of main part and the second material of main part are mixed to form, and in above-mentioned each layer, guest materials and the mass ratio of the first material of main part and the mass ratio of guest materials and the second material of main part are single value.
In the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47, guest materials increases progressively than echelon with the quality of the first material of main part, and in the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47, guest materials successively decreases than echelon with the quality of the second material of main part.
In the present embodiment, the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47 four-layer structure composition luminescent layer 40 altogether that thickness is identical.In other embodiments, can also form luminescent layer 40 by two-layer structure, three-decker, five-layer structure, six layers of structure, seven-layer structure etc.
In the present embodiment, in the 4th luminescent layer 47, the mass ratio of guest materials and the first material of main part is 1.5 times of mass ratio of guest materials in the first luminescent layer 41 and the first material of main part, in the 3rd luminescent layer 45, the mass ratio of guest materials and the second material of main part is 2 times of mass ratio of guest materials and the second material of main part in the 4th luminescent layer 47, and the mass ratio of guest materials in the 4th luminescent layer 47 and the first material of main part is 9 times of mass ratio of guest materials in the 4th luminescent layer 47 and the second material of main part.That is to say, in the present embodiment, remember that guest materials in the 4th luminescent layer 47 and the mass ratio of the second material of main part are a, again owing to being echelon doping, the mass ratio of the guest materials in the 3rd luminescent layer 45 and the second material of main part is 2a, guest materials in the second luminescent layer 43 and the mass ratio of the second material of main part are 3a, in the first luminescent layer 41, the mass ratio of guest materials and the second material of main part is 4a, guest materials in the first luminescent layer 41 and the mass ratio of the first material of main part are 6a, guest materials in the second luminescent layer 43 and the mass ratio of the first material of main part are 7a, guest materials in the 3rd luminescent layer 45 and the mass ratio of the first material of main part are 8a, guest materials in the 4th luminescent layer 47 and the mass ratio of the first material of main part are 9a.
In other embodiment, in the 4th luminescent layer 47, the mass ratio of guest materials and the first material of main part can not be also 1.5 times of mass ratio of guest materials in the first luminescent layer 41 and the first material of main part, in the 3rd luminescent layer 45, the mass ratio of guest materials and the second material of main part can not be also 2 times of mass ratio of guest materials and the second material of main part in the 4th luminescent layer 47, and the mass ratio of guest materials in the 4th luminescent layer 47 and the first material of main part can not be also 9 times of mass ratio of guest materials in the 4th luminescent layer 47 and the second material of main part.
The material of electron transfer layer 50 can be 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Electron transfer layer 50 can thickness be 10nm～60nm.
The material of electron injecting layer 60 can be the electron transport material doped with the first salt and the second salt.
The first salt can be LiF, LiN
3, Li
3n, CsF, CsN
3or Cs
3n.
The second salt can Li
2sO
4, Na
2sO
4, K
2sO
4, Rb
2sO
4or Cs
2sO
4.
Electron transport material can be 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
The mass ratio of the first salt and electron transport material is 25～35:100.
The mass ratio of the second salt and electron transport material is 6～25:100.
The thickness of electron injecting layer 60 can be 15nm～45nm.
The material of cathode layer 70 can be silver (Ag), aluminium (Al) or gold (Au).
The thickness of cathode layer 70 can be 50nm～200nm.
In the luminescent layer 40 of this organic electroluminescence device, the mass ratio of guest materials and the first material of main part improves from the side near hole transmission layer 30 to the side echelon away from hole transmission layer 30, in luminescent layer 40, the mass ratio of guest materials and the second material of main part reduces from the side near hole transmission layer 30 to the side echelon away from hole transmission layer 30, by the gradual mixing of material of main part and guest materials, improve the energy conversion efficiency of Subjective and Objective.With respect to traditional organic electroluminescence device, the luminous efficiency of this organic electroluminescence device is higher.
The preparation method of above-mentioned organic electroluminescence device as shown in Figure 3, comprises the steps:
S10, conductive anode substrate 10 is carried out to surface preparation.
Conductive anode substrate 10 can be indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).At one, preferably in embodiment, conductive anode substrate 10 is indium tin oxide glass (ITO).
The thickness of the conductive layer of anode conducting substrate 10 can be 80nm～150nm.
The operation of surface preparation can be: successively conductive anode substrate 10 is carried out to liquid detergent cleaning, washed with de-ionized water, acetone cleaning and ethanol and clean, obtain clean conductive anode substrate 10.Then the conductive layer of clean conductive anode substrate 10 is carried out to surface activation process, increase oxygen content and the work function of the conductive layer of conductive anode substrate 10.
All in triplicate, each scavenging period is 5min in above-mentioned cleaning, and be 5min interval time.Meanwhile, above-mentioned cleaning all adopts supersonic wave cleaning machine to carry out.
Surface activation process can be for adopting ultraviolet-ozone (UV-ozone) to process 30～50 minutes the anode after cleaning-drying.
S20, in conductive anode substrate 10, evaporation forms hole injection layer 20 and hole transmission layer 30 successively.
Obviously, hole injection layer 20 is formed on the conductive layer of conductive anode substrate 10.
In present embodiment, be 1 × 10 in vacuum degree
-5pa～1 × 10
-3pa, evaporation rate is
condition under, on the conductive layer of conductive anode substrate 10 evaporation form hole injection layer 20.
The material of hole injection layer 20 can be the hole mobile material doped with metal oxide.
Metal oxide can be MoO
3, WO
3, V
2o
5or ReO
3.
Hole mobile material can be N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC).
The mass ratio of metal oxide and hole mobile material is 25～35:100.
The thickness of hole injection layer 20 can be 10nm～15nm.
In present embodiment, be 1 × 10 in vacuum degree
-5pa～1 × 10
-3pa, evaporation rate is
condition under, on hole injection layer 20 evaporation form hole transmission layer 30.
The material of hole transmission layer 30 can be N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC).
The thickness of hole transmission layer 30 can be 30nm～50nm.
S30, on hole transmission layer 30 evaporation form luminescent layer 40.
In present embodiment, be 1 × 10 in vacuum degree
-5pa～1 × 10
-3pa, evaporation rate is
condition under, on hole transmission layer 30 evaporation form luminescent layer 40.
The material of luminescent layer 40 can be the mixture that guest materials, the first material of main part and the second material of main part are mixed to form.
The mass ratio of guest materials and the first material of main part is 1.2～10.8:100.
The mass ratio of guest materials and the second material of main part is 0.2～4.8:100.
The first material of main part is different with the second material of main part.
Guest materials can be that three (2-phenylpyridines) close iridium (Ir (ppy)
3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy)
3).
The first material of main part can be 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) or the 3-tert-butyl group-9,10-bis-(2-naphthalene) anthracene (MADN).
The second material of main part can be 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] (OXD-7), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene (PO15), 4,7-diphenyl-1,10-phenanthroline (Bphen) or N-aryl benzimidazole (TPBI).
The thickness of luminescent layer 40 can be 10nm～30nm.
In luminescent layer 40, the mass ratio of guest materials and the first material of main part improves to the side echelon away from hole transmission layer 30 from the side near hole transmission layer 30, and the mass ratio of guest materials and the second material of main part reduces from the side near hole transmission layer 30 to the side echelon away from hole transmission layer 30.
In conjunction with Fig. 2, in a specific embodiment, luminescent layer 40 is made up of the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47 that stack gradually and thickness is identical, and the first luminescent layer 41 is laminated on hole transmission layer 30.
The material of the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47 is the mixture that guest materials, the first material of main part and the second material of main part are mixed to form, and in above-mentioned each layer, guest materials and the mass ratio of the first material of main part and the mass ratio of guest materials and the second material of main part are single value.
In the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47, guest materials increases progressively than echelon with the quality of the first material of main part, and in the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47, guest materials successively decreases than echelon with the quality of the second material of main part.
In the present embodiment, the first luminescent layer 41, the second luminescent layer 43, the 3rd luminescent layer 45 and the 4th luminescent layer 47 four-layer structure composition luminescent layer 40 altogether that thickness is identical.In other embodiments, can also form luminescent layer 40 by two-layer structure, three-decker, five-layer structure, six layers of structure, seven-layer structure etc.
In the present embodiment, in the 4th luminescent layer 47, the mass ratio of guest materials and the first material of main part is 1.5 times of mass ratio of guest materials in the first luminescent layer 41 and the first material of main part, in the 3rd luminescent layer 45, the mass ratio of guest materials and the second material of main part is 2 times of mass ratio of guest materials and the second material of main part in the 4th luminescent layer 47, and the mass ratio of guest materials in the 4th luminescent layer 47 and the first material of main part is 9 times of mass ratio of guest materials in the 4th luminescent layer 47 and the second material of main part.That is to say, in the present embodiment, remember that guest materials in the 4th luminescent layer 47 and the mass ratio of the second material of main part are a, again owing to being echelon doping, the mass ratio of the guest materials in the 3rd luminescent layer 45 and the second material of main part is 2a, guest materials in the second luminescent layer 43 and the mass ratio of the second material of main part are 3a, in the first luminescent layer 41, the mass ratio of guest materials and the second material of main part is 4a, guest materials in the first luminescent layer 41 and the mass ratio of the first material of main part are 6a, guest materials in the second luminescent layer 43 and the mass ratio of the first material of main part are 7a, guest materials in the 3rd luminescent layer 45 and the mass ratio of the first material of main part are 8a, guest materials in the 4th luminescent layer 47 and the mass ratio of the first material of main part are 9a.
In other embodiment, in the 4th luminescent layer 47, the mass ratio of guest materials and the first material of main part can not be also 1.5 times of mass ratio of guest materials in the first luminescent layer 41 and the first material of main part, in the 3rd luminescent layer 45, the mass ratio of guest materials and the second material of main part can not be also 2 times of mass ratio of guest materials and the second material of main part in the 4th luminescent layer 47, and the mass ratio of guest materials in the 4th luminescent layer 47 and the first material of main part can not be also 9 times of mass ratio of guest materials in the 4th luminescent layer 47 and the second material of main part.
S40, on luminescent layer 40 successively evaporation form electron transfer layer 50, electron injecting layer 60 and cathode layer 70.
In present embodiment, in vacuum degree 1 × 10
-5pa～1 × 10
-3pa, evaporation rate
condition under, on luminescent layer 40 evaporation form electron transfer layer 50.
The material of electron transfer layer 50 can be 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Electron transfer layer 50 can thickness be 10nm～60nm.
In present embodiment, in vacuum degree 1 × 10
-5pa～1 × 10
-3pa, evaporation rate
condition under, on electron transfer layer 50 evaporation form electron injecting layer 60.
The material of electron injecting layer 60 can be the electron transport material doped with the first salt and the second salt.
The first salt can be LiF, LiN
3, Li
3n, CsF, CsN
3or Cs
3n.
The second salt can Li
2sO
4, Na
2sO
4, K
2sO
4, Rb
2sO
4or Cs
2sO
4.
Electron transport material can be 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
The mass ratio of the first salt and electron transport material is 25～35:100.
The mass ratio of the second salt and electron transport material is 6～25:100.
The thickness of electron injecting layer 60 can be 15nm～45nm.
In present embodiment, in vacuum degree 1 × 10
-5pa～1 × 10
-3pa, evaporation rate
condition under, on electron injecting layer 60 evaporation form cathode layer 70.
The material of cathode layer 70 can be silver (Ag), aluminium (Al) or gold (Au).
The thickness of cathode layer 70 can be 50nm～200nm.
In the luminescent layer 40 of the organic electroluminescence device that the preparation method of this organic electroluminescence device prepares, the mass ratio of guest materials and the first material of main part improves from the side near hole transmission layer 30 to the side echelon away from hole transmission layer 30, in luminescent layer 40, the mass ratio of guest materials and the second material of main part reduces from the side near hole transmission layer 30 to the side echelon away from hole transmission layer 30, by the gradual mixing of material of main part and guest materials, improve the energy conversion efficiency of Subjective and Objective.With respect to traditional organic electroluminescence device, the luminous efficiency of this organic electroluminescence device is higher.
Be below specific embodiment and comparative example part, the test and the Preparation equipment that in embodiment, use comprise: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 test electric property of Keithley company of the U.S., CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually.Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and successively ito glass is carried out to liquid detergent cleaning, washed with de-ionized water, acetone cleaning and ethanol and clean, and all in triplicate, each scavenging period is 5min in above-mentioned cleaning, and be 5min interval time.Then the ITO layer of the ito glass cleaning is carried out to surface activation process, increase oxygen content and the work function of ITO layer.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the ITO of ito glass layer evaporation form hole injection layer.The material of hole injection layer is the MoO that adulterated
3nPB, MoO
3with the mass ratio of NPB be 30:100, the thickness of hole injection layer is 12.5nm.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole injection layer evaporation form hole transmission layer.The material of hole transmission layer is NPB, and the thickness of hole transmission layer is 40nm.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole transmission layer, evaporation forms the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer successively.The first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer composition luminescent layer.The material of the first luminescent layer is Ir (ppy)
3, the mixture that is mixed to form of TCTA and OXD-7, Ir (ppy)
3with the mass ratio of TCTA be 7.2:100, Ir (ppy)
3with the mass ratio of OXD-7 be 4.8:100.The material of the second luminescent layer is Ir (ppy)
3, the mixture that is mixed to form of TCTA and OXD-7, Ir (ppy)
3with the mass ratio of TCTA be 8.4:100, Ir (ppy)
3with the mass ratio of OXD-7 be 3.6:100.The material of the 3rd luminescent layer is Ir (ppy)
3, the mixture that is mixed to form of TCTA and OXD-7, Ir (ppy)
3with the mass ratio of TCTA be 9.6:100, Ir (ppy)
3with the mass ratio of OXD-7 be 2.4:100.The material of the 4th luminescent layer is Ir (ppy)
3, the mixture that is mixed to form of TCTA and OXD-7, Ir (ppy)
3with the mass ratio of TCTA be 10.8:100, Ir (ppy)
3with the mass ratio of OXD-7 be 1.2:100.The thickness of the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer is all identical, and the gross thickness of luminescent layer is 30nm.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the 4th luminescent layer evaporation form electron transfer layer.The material of electron transfer layer is Bphen, and the thickness of electron transfer layer is 35nm.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron transfer layer evaporation form electron injecting layer.The material of electron injecting layer is doped with LiF and Li
2sO
4bphen, the mass ratio of LiF and Bphen is 30:100, Li
2sO
4with the mass ratio of Bphen be 15:100, the thickness of electron injecting layer is 35nm.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron injecting layer evaporation form cathode layer.The material of cathode layer is Ag, and the thickness of cathode layer is 125nm.
Embodiment 2
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually.Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and successively ito glass is carried out to liquid detergent cleaning, washed with de-ionized water, acetone cleaning and ethanol and clean, and all in triplicate, each scavenging period is 5min in above-mentioned cleaning, and be 5min interval time.Then the ITO layer of the ito glass cleaning is carried out to surface activation process, increase oxygen content and the work function of ITO layer.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the ITO of ito glass layer evaporation form hole injection layer.The material of hole injection layer is the WO that adulterated
3tCTA, WO
3with the mass ratio of TCTA be 25:100, the thickness of hole injection layer is 10nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole injection layer evaporation form hole transmission layer.The material of hole transmission layer is TCTA, and the thickness of hole transmission layer is 30nm.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole transmission layer, evaporation forms the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer successively.The first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer composition luminescent layer.The material of the first luminescent layer is Ir (ppy)
2(acac), the mixture that is mixed to form of mCP and BCP, Ir (ppy)
2(acac) be 6:100 with the mass ratio of mCP, Ir (ppy)
2(acac) be 4:100 with the mass ratio of BCP.The material of the second luminescent layer is Ir (ppy)
2(acac), the mixture that is mixed to form of mCP and BCP, Ir (ppy)
2(acac) be 7:100 with the mass ratio of mCP, Ir (ppy)
2(acac) be 3:100 with the mass ratio of BCP.The material of the 3rd luminescent layer is Ir (ppy)
2(acac), the mixture that is mixed to form of mCP and BCP, Ir (ppy)
2(acac) be 8:100 with the mass ratio of mCP, Ir (ppy)
2(acac) be 2:100 with the mass ratio of BCP.The material of the 4th luminescent layer is Ir (ppy)
2(acac), the mixture that is mixed to form of mCP and BCP, Ir (ppy)
2(acac) be 9:100 with the mass ratio of mCP, Ir (ppy)
2(acac) be 1:100 with the mass ratio of BCP.The thickness of the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer is all identical, and the gross thickness of luminescent layer is 27nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the 4th luminescent layer evaporation form electron transfer layer.The material of electron transfer layer is BCP, and the thickness of electron transfer layer is 10nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron transfer layer evaporation form electron injecting layer.The material of electron injecting layer is doped with LiN
3and Na
2sO
4bCP, LiN
3with the mass ratio of BCP be 25:100, Na
2sO
4with the mass ratio of BCP be 25:100, the thickness of electron injecting layer is 45nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron injecting layer evaporation form cathode layer.The material of cathode layer is Al, and the thickness of cathode layer is 50nm.
Embodiment 3
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually.Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and successively ito glass is carried out to liquid detergent cleaning, washed with de-ionized water, acetone cleaning and ethanol and clean, and all in triplicate, each scavenging period is 5min in above-mentioned cleaning, and be 5min interval time.Then the ITO layer of the ito glass cleaning is carried out to surface activation process, increase oxygen content and the work function of ITO layer.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the ITO of ito glass layer evaporation form hole injection layer.The material of hole injection layer is the V that adulterated
2o
5cBP, V
2o
5with the mass ratio of CBP be 35:100, the thickness of hole injection layer is 15nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole injection layer evaporation form hole transmission layer.The material of hole transmission layer is CBP, and the thickness of hole transmission layer is 50nm.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole transmission layer, evaporation forms the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer successively.The first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer composition luminescent layer.The material of the first luminescent layer is Ir (mppy)
3, the mixture that is mixed to form of CBP and PO15, Ir (mppy)
3with the mass ratio of CBP be 4.8:100, Ir (mppy)
3with the mass ratio of PO15 be 3.2:100.The material of the second luminescent layer is Ir (mppy)
3, the mixture that is mixed to form of CBP and PO15, Ir (mppy)
3with the mass ratio of CBP be 5.6:100, Ir (mppy)
3with the mass ratio of PO15 be 2.4:100.The material of the 3rd luminescent layer is Ir (mppy)
3, the mixture that is mixed to form of CBP and PO15, Ir (mppy)
3with the mass ratio of CBP be 6.4:100, Ir (mppy)
3with the mass ratio of PO15 be 1.6:100.The material of the 4th luminescent layer is Ir (mppy)
3, the mixture that is mixed to form of CBP and PO15, Ir (mppy)
3with the mass ratio of CBP be 7.2:100, Ir (mppy)
3with the mass ratio of PO15 be 0.8:100.The thickness of the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer is all identical, and the gross thickness of luminescent layer is 24nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the 4th luminescent layer evaporation form electron transfer layer.The material of electron transfer layer is BAlq, and the thickness of electron transfer layer is 60nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron transfer layer evaporation form electron injecting layer.The material of electron injecting layer is doped with Li
3n and K
2sO
4bAlq, Li
3the mass ratio of N and BAlq is 35:100, K
2sO
4with the mass ratio of BAlq be 6:100, the thickness of electron injecting layer is 15nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron injecting layer evaporation form cathode layer.The material of cathode layer is Au, and the thickness of cathode layer is 200nm.
Embodiment 4
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually.Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and successively ito glass is carried out to liquid detergent cleaning, washed with de-ionized water, acetone cleaning and ethanol and clean, and all in triplicate, each scavenging period is 5min in above-mentioned cleaning, and be 5min interval time.Then the ITO layer of the ito glass cleaning is carried out to surface activation process, increase oxygen content and the work function of ITO layer.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the ITO of ito glass layer evaporation form hole injection layer.The material of hole injection layer is the ReO that adulterated
3tPD, ReO
3with the mass ratio of TPD be 30:100, the thickness of hole injection layer is 13nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole injection layer evaporation form hole transmission layer.The material of hole transmission layer is TPD, and the thickness of hole transmission layer is 40nm.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole transmission layer, evaporation forms the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer successively.The first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer composition luminescent layer.The material of the first luminescent layer is Ir (ppy)
3, the mixture that is mixed to form of TPD and Bphen, Ir (ppy)
3with the mass ratio of TPD be 4.8:100, Ir (ppy)
3with the mass ratio of Bphen be 3.2:100.The material of the second luminescent layer is Ir (ppy)
3, the mixture that is mixed to form of TPD and Bphen, Ir (ppy)
3with the mass ratio of TPD be 5.6:100, Ir (ppy)
3with the mass ratio of Bphen be 2.4:100.The material of the 3rd luminescent layer is Ir (ppy)
3, the mixture that is mixed to form of TPD and Bphen, Ir (ppy)
3with the mass ratio of TPD be 6.4:100, Ir (ppy)
3with the mass ratio of Bphen be 1.6:100.The material of the 4th luminescent layer is Ir (ppy)
3, the mixture that is mixed to form of TPD and Bphen, Ir (ppy)
3with the mass ratio of TPD be 7.2:100, Ir (ppy)
3with the mass ratio of Bphen be 0.8:100.The thickness of the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer is all identical, and the gross thickness of luminescent layer is 24nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the 4th luminescent layer evaporation form electron transfer layer.The material of electron transfer layer is Alq3, and the thickness of electron transfer layer is 30nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron transfer layer evaporation form electron injecting layer.The material of electron injecting layer is doped with CsF and Rb
2sO
4alq
3, CsF and Alq
3mass ratio be 30:100, Rb
2sO
4and Alq
3mass ratio be 10:100, the thickness of electron injecting layer is 30nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron injecting layer evaporation form cathode layer.The material of cathode layer is Ag, and the thickness of cathode layer is 100nm.
Embodiment 5
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually.Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and successively ito glass is carried out to liquid detergent cleaning, washed with de-ionized water, acetone cleaning and ethanol and clean, and all in triplicate, each scavenging period is 5min in above-mentioned cleaning, and be 5min interval time.Then the ITO layer of the ito glass cleaning is carried out to surface activation process, increase oxygen content and the work function of ITO layer.
Be 1 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the ITO of ito glass layer evaporation form hole injection layer.The material of hole injection layer is the MoO that adulterated
3tAPC, MoO
3with the mass ratio of TAPC be 25:100, the thickness of hole injection layer is 10nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole injection layer evaporation form hole transmission layer.The material of hole transmission layer is TAPC, and the thickness of hole transmission layer is 40nm.
Be 1 × 10 in vacuum degree
-4pa, evaporation rate
condition under, on hole transmission layer, evaporation forms the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer successively.The first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer composition luminescent layer.The material of the first luminescent layer is Ir (ppy)
2(acac), the mixture that is mixed to form of TAPC and TPBI, Ir (ppy)
2(acac) and the mass ratio of TAPC be 3.6:100, Ir (ppy)
2(acac) and the mass ratio of TPBI be 2.4:100.The material of the second luminescent layer is Ir (ppy)
2(acac), the mixture that is mixed to form of TAPC and TPBI, Ir (ppy)
2(acac) and the mass ratio of TAPC be 4.2:100, Ir (ppy)
2(acac) and the mass ratio of TPBI be 1.8:100.The material of the 3rd luminescent layer is Ir (ppy)
2(acac), the mixture that is mixed to form of TAPC and TPBI, Ir (ppy)
2(acac) and the mass ratio of TAPC be 4.8:100, Ir (ppy)
2(acac) and the mass ratio of TPBI be 1.2:100.The material of the 4th luminescent layer is Ir (ppy)
2(acac), the mixture that is mixed to form of TAPC and TPBI, Ir (ppy)
2(acac) and the mass ratio of TAPC be 5.4:100, Ir (ppy)
2(acac) and the mass ratio of TPBI be 0.6:100.The thickness of the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer is all identical, and the gross thickness of luminescent layer is 20nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the 4th luminescent layer evaporation form electron transfer layer.The material of electron transfer layer is TAZ, and the thickness of electron transfer layer is 50nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron transfer layer evaporation form electron injecting layer.The material of electron injecting layer is doped with CsN
3and Cs
2sO
4tAZ, CsN
3with the mass ratio of TAZ be 30:100, Cs
2sO
4with the mass ratio of TAZ be 10:100, the thickness of electron injecting layer is 30nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron injecting layer evaporation form cathode layer.The material of cathode layer is Al, and the thickness of cathode layer is 100nm.
Embodiment 6
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually.Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and successively ito glass is carried out to liquid detergent cleaning, washed with de-ionized water, acetone cleaning and ethanol and clean, and all in triplicate, each scavenging period is 5min in above-mentioned cleaning, and be 5min interval time.Then the ITO layer of the ito glass cleaning is carried out to surface activation process, increase oxygen content and the work function of ITO layer.
Be 1 × 10 in vacuum degree
-3pa, evaporation rate
condition under, on the ITO of ito glass layer evaporation form hole injection layer.The material of hole injection layer is the WO that adulterated
3nPB, WO
3with the mass ratio of NPB be 30:100, the thickness of hole injection layer is 12nm.
Be 1 × 10 in vacuum degree
-3pa, evaporation rate
condition under, on hole injection layer evaporation form hole transmission layer.The material of hole transmission layer is NPB, and the thickness of hole transmission layer is 40nm.
Be 1 × 10 in vacuum degree
-3pa, evaporation rate
condition under, on hole transmission layer, evaporation forms the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer successively.The first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer composition luminescent layer.The material of the first luminescent layer is Ir (mppy)
3, the mixture that is mixed to form of MADN and OXD-7, Ir (mppy)
3with the mass ratio of MADN be 1.2:100, Ir (mppy)
3with the mass ratio of OXD-7 be 0.8:100.The material of the second luminescent layer is Ir (mppy)
3, the mixture that is mixed to form of MADN and OXD-7, Ir (mppy)
3with the mass ratio of MADN be 1.4:100, Ir (mppy)
3with the mass ratio of OXD-7 be 0.6:100.The material of the 3rd luminescent layer is Ir (mppy)
3, the mixture that is mixed to form of MADN and OXD-7, Ir (mppy)
3with the mass ratio of MADN be 1.6:100, Ir (mppy)
3with the mass ratio of OXD-7 be 0.4:100.The material of the 4th luminescent layer is Ir (mppy)
3, the mixture that is mixed to form of MADN and OXD-7, Ir (mppy)
3with the mass ratio of MADN be 1.8:100, Ir (mppy)
3with the mass ratio of OXD-7 be 0.2:100.The thickness of the first luminescent layer, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer is all identical, and the gross thickness of luminescent layer is 10nm.
Be 1 × 10 in vacuum degree
-3pa, evaporation rate
condition under, on the 4th luminescent layer evaporation form electron transfer layer.The material of electron transfer layer is TPBI, and the thickness of electron transfer layer is 30nm.
Be 1 × 10 in vacuum degree
-3pa, evaporation rate
condition under, on electron transfer layer evaporation form electron injecting layer.The material of electron injecting layer is doped with Cs
3n and Cs
2sO
4tPBI, Cs
3the mass ratio of N and TPBI is 30:100, Cs
2sO
4with the mass ratio of TPBI be 10:100, the thickness of electron injecting layer is 30nm.
Be 1 × 10 in vacuum degree
-3pa, evaporation rate
condition under, on electron injecting layer evaporation form cathode layer.The material of cathode layer is Al, and the thickness of cathode layer is 100nm.
Comparative example
A kind of organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually.Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and successively ito glass is carried out to liquid detergent cleaning, washed with de-ionized water, acetone cleaning and ethanol and clean, and all in triplicate, each scavenging period is 5min in above-mentioned cleaning, and be 5min interval time.Then the ITO layer of the ito glass cleaning is carried out to surface activation process, increase oxygen content and the work function of ITO layer.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on the ITO of ito glass layer evaporation form hole injection layer.The material of hole injection layer is the V that adulterated
2o
5cBP, V
2o
5with the mass ratio of CBP be 30:100, the thickness of hole injection layer is 12nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole injection layer evaporation form hole transmission layer.The material of hole transmission layer is TCTA, and the thickness of hole transmission layer is 40nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on hole transmission layer evaporation form luminescent layer.The material of luminescent layer is the Ir that adulterated (ppy)
3mADN, Ir (ppy)
3with the mass ratio of MADN be 7:100, the thickness of luminescent layer is 20nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on luminescent layer evaporation form electron transfer layer.The material of electron transfer layer is Bphen, and the thickness of electron transfer layer is 40nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron transfer layer evaporation form electron injecting layer.The material of electron injecting layer is doped with Cs
3the Bphen of N, Cs
3the mass ratio of N and Bphen is 28:100, and the thickness of electron injecting layer is 32.5nm.
Be 5 × 10 in vacuum degree
-5pa, evaporation rate
condition under, on electron injecting layer evaporation form cathode layer.The material of cathode layer is Al, and the thickness of cathode layer is 138nm.
Adopt luminance meter CS-100A and digital sourcemeter Keithley2400 synchro measure, the organic electroluminescence device that embodiment 1～6 and comparative example are made carries out luminous efficiency testing experiment, by programming Control with can be calculated test result as shown in the table:
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example |
| Efficiency (lm/W) | 27.1 | 26.3 | 25.7 | 25.0 | 24.5 | 23.8 | 13.2 |
The luminous efficiency of the organic electroluminescence device that the luminous efficiency of the organic electroluminescence device that embodiment 1～embodiment 6 prepares as can be seen from the above table prepares apparently higher than comparative example, has approximately improved more than 0.8 times.
Above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an organic electroluminescence device, is characterized in that, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually;
The material of described luminescent layer is the mixture that guest materials, the first material of main part and the second material of main part are mixed to form;
The mass ratio of guest materials described in described luminescent layer and described the first material of main part improves from the side near described hole transmission layer to the side echelon away from described hole transmission layer;
The mass ratio of guest materials described in described luminescent layer and described the second material of main part reduces from the side near described hole transmission layer to the side echelon away from described hole transmission layer;
Described guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] closes iridium;
Described the first material of main part is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or the 3-tert-butyl group-9,10-bis-(2-naphthalene) anthracene;
Described the second material of main part is 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, 4,7-diphenyl-1,10-phenanthroline or N-aryl benzimidazole;
The mass ratio of guest materials described in described luminescent layer and described the first material of main part is 1.2～10.8:100;
The mass ratio of guest materials described in described luminescent layer and described the second material of main part is 0.2～4.8:100.
2. organic electroluminescence device according to claim 1, it is characterized in that, described luminescent layer is made up of the first luminescent layer stacking gradually and thickness is identical, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer, and described the first luminescent layer is laminated on described hole transmission layer;
Described in described the first luminescent layer, described the second luminescent layer, described the 3rd luminescent layer and described the 4th luminescent layer, guest materials increases progressively than echelon with the quality of described the first material of main part;
Described in described the first luminescent layer, described the second luminescent layer, described the 3rd luminescent layer and described the 4th luminescent layer, guest materials successively decreases than echelon with the quality of described the second material of main part.
3. organic electroluminescence device according to claim 1, it is characterized in that, the mass ratio of guest materials and described the first material of main part described in described the 4th luminescent layer is 1.5 times of mass ratio of described guest materials in described the first luminescent layer and described the first material of main part;
The mass ratio of guest materials and described the second material of main part described in described the 3rd luminescent layer is 2 times of mass ratio of guest materials described in described the 4th luminescent layer and described the second material of main part;
And the described guest materials in described the 4th luminescent layer and the mass ratio of described the first material of main part are 9 times of mass ratio of described guest materials in described the 4th luminescent layer and described the second material of main part.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described luminescent layer is 10nm～30nm.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described hole injection layer is the hole mobile material doped with metal oxide;
Described metal oxide is MoO
3, WO
3, V
2o
5or ReO
3;
Described hole mobile material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
The mass ratio of described metal oxide and described hole mobile material is 25～35:100;
The thickness of described hole injection layer is 10nm～15nm.
6. organic electroluminescence device according to claim 1, is characterized in that, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
The thickness of described hole transmission layer is 30nm～50nm.
7. organic electroluminescence device according to claim 1, it is characterized in that, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The thickness of described electron transfer layer is 10nm～60nm.
8. organic electroluminescence device according to claim 1, is characterized in that, the material of described electron injecting layer is the electron transport material doped with the first salt and the second salt;
Described the first salt is LiF, LiN
3, Li
3n, CsF, CsN
3or Cs
3n;
Described the second salt is Li
2sO
4, Na
2sO
4, K
2sO
4, Rb
2sO
4or Cs
2sO
4;
Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The mass ratio of described the first salt and described electron transport material is 25～35:100;
The mass ratio of described the second salt and described electron transport material is 6～25:100;
The thickness of described electron injecting layer is 15nm～45nm.
9. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Conductive anode substrate is carried out to surface preparation;
In described conductive anode substrate, evaporation forms hole injection layer and hole transmission layer successively;
On described hole transmission layer, evaporation forms luminescent layer, the material of described luminescent layer is guest materials, the mixture that the first material of main part and the second material of main part are mixed to form, the mass ratio of guest materials described in described luminescent layer and described the first material of main part improves from the side near described hole transmission layer to the side echelon away from described hole transmission layer, the mass ratio of guest materials described in described luminescent layer and described the second material of main part reduces from the side near described hole transmission layer to the side echelon away from described hole transmission layer, described guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] closes iridium, described the first material of main part is 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or the 3-tert-butyl group-9, 10-bis-(2-naphthalene) anthracene, described the second material of main part is 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene, 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, 4, 7-diphenyl-1, 10-phenanthroline or N-aryl benzimidazole, the mass ratio of guest materials described in described luminescent layer and described the first material of main part is 1.2～10.8:100, the mass ratio of guest materials described in described luminescent layer and described the second material of main part is 0.2～4.8:100, and
On described luminescent layer, evaporation forms electron transfer layer, electron injecting layer and cathode layer successively.
10. the preparation method of organic electroluminescence device according to claim 1, is characterized in that, described on described hole transmission layer evaporation form the step of luminescent layer and be:
On described hole transmission layer, evaporation forms the first identical luminescent layer of thickness successively, the second luminescent layer, the 3rd luminescent layer and the 4th luminescent layer, described the first luminescent layer, described the second luminescent layer, described the 3rd luminescent layer and described the 4th luminescent layer form described luminescent layer, described the first luminescent layer, described the second luminescent layer, described in described the 3rd luminescent layer and described the 4th luminescent layer, guest materials increases progressively than echelon with the quality of described the first material of main part, described the first luminescent layer, described the second luminescent layer, described in described the 3rd luminescent layer and described the 4th luminescent layer, guest materials successively decreases than echelon with the quality of described the second material of main part.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713151A (en) * | 2018-12-29 | 2019-05-03 | 武汉天马微电子有限公司 | The preparation method and display device of display panel, light-emitting component |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1822409A (en) * | 2006-01-10 | 2006-08-23 | 陕西科技大学 | Inorganic salt blended organic electroluminescence light emitting display device |
| KR100684109B1 (en) * | 2006-01-24 | 2007-02-16 | (주)그라쎌 | Electroluminescent compounds and organic electroluminescent device using the same |
| CN101378612A (en) * | 2007-08-31 | 2009-03-04 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic appliance |
| CN102709475A (en) * | 2012-06-01 | 2012-10-03 | 吉林大学 | Organic semiconductor device by using alkali metal rubidium compound as buffer layer or electron injection layer |
-
2013
- 2013-05-22 CN CN201310193624.5A patent/CN104183789A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1822409A (en) * | 2006-01-10 | 2006-08-23 | 陕西科技大学 | Inorganic salt blended organic electroluminescence light emitting display device |
| KR100684109B1 (en) * | 2006-01-24 | 2007-02-16 | (주)그라쎌 | Electroluminescent compounds and organic electroluminescent device using the same |
| CN101378612A (en) * | 2007-08-31 | 2009-03-04 | 株式会社半导体能源研究所 | Light-emitting element, light-emitting device, and electronic appliance |
| CN102709475A (en) * | 2012-06-01 | 2012-10-03 | 吉林大学 | Organic semiconductor device by using alkali metal rubidium compound as buffer layer or electron injection layer |
Non-Patent Citations (3)
| Title |
|---|
| DONGGE MA等: "Improved ef?ciency by a graded emissive region in organiclight-emitting diodes", 《APPLIED PHYSIC LETTERS》, 27 March 2002 (2002-03-27) * |
| JUN LIU等: "Improved efficiency of blue phosphorescence organic light-emitting diodes with irregular stepwise-doping emitting layers", 《PHYSICA STATUS SOLIDI A》, 16 January 2013 (2013-01-16) * |
| NICHOLAS C. ERICKSON等: "Highly efficient, single-layer organic light-emitting devices based on a graded-composition emissive layer", 《APPLIED PHYSIC LETTERS》, 27 August 2010 (2010-08-27) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713151A (en) * | 2018-12-29 | 2019-05-03 | 武汉天马微电子有限公司 | The preparation method and display device of display panel, light-emitting component |
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