CN104183727A - Organic light emission diode and preparation method thereof - Google Patents
Organic light emission diode and preparation method thereof Download PDFInfo
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- CN104183727A CN104183727A CN201310194853.9A CN201310194853A CN104183727A CN 104183727 A CN104183727 A CN 104183727A CN 201310194853 A CN201310194853 A CN 201310194853A CN 104183727 A CN104183727 A CN 104183727A
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- layer
- hole
- electron transfer
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- transfer layer
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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]
- H10K50/18—Carrier blocking 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Abstract
The invention discloses an organic light emission diode which comprises a glass substrate, an anode, a hole transfer layer, a light-emitting layer, a hole-blocking layer, an electron transfer layer, a cathode and a packaging cover plate which are sequentially stacked. The packaging cover plate and the glass substrate form an enclosure space; the anode, the hole transfer layer, the light-emitting layer, the hole-blocking layer, the electron transfer layer and the cathode are accommodated in the enclosure space; the hole-blocking layer is made of a mixed material formed by indifferent oxide and a hole-blocking material; and the hole-blocking layer can adsorb alkali metal ions diffused form the electron transfer layer, so that the alkali metal ions do not diffuse to the light-emitting layer, and the service life of the device can be improved. The invention also discloses a preparation method of the organic light emission diode.
Description
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode, hereinafter to be referred as OLED), have that brightness is high, material range of choice is wide, driving voltage is low, entirely solidify the characteristics such as active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, be current lot of domestic and foreign researcher's focal point.
Up to the present, although the scientific research personnel of various countries, the whole world is by selecting suitable organic material and rational device structure design, made the indices of device performance be greatly improved, for example adopt the technique of pn doping transport layer, can reduce the starting resistor of device to improve light efficiency, and be conducive to the raising in life-span.For the n doping of electron transfer layer, conventionally adopt alkali metal compound to adulterate, this is because alkali metal work content is low, easily realize n doping effect, but often alkali metal ion volume is little, diffusivity is strong, diffusion length in organic layer is long, and alkali metal ion, except being entrained in transport layer, also likely diffuses in luminescent layer, directly cause the cancellation of exciton, affect light efficiency and the life-span of device.In order to obtain the long-life, stable Organnic electroluminescent device, is necessary to address this problem.
Prior art organic electroluminescence device adopts the electron transfer layer of the alkali metal compound that adulterated, electron transfer layer is after alkali-metal-doped, its electric conductivity has obtained raising, injection and the efficiency of transmission of electronics have been improved simultaneously, but after overdoping, alkali-metal-doped agent easily, to luminescent layer diffusion, directly causes the cancellation of exciton, affects device useful life.
The present invention arranges a hole blocking layer in luminescent layer and electron transfer layer, described hole blocking layer material is the composite material that inert material and hole barrier materials form, inert material itself is difficult to spread, the alkali metal ion that simultaneously can come to diffusion adsorbs, alkali metal ion is no longer spread to luminescent layer, thereby can extend useful life of device, solved the problem that above-mentioned prior art occurs.Meanwhile, hole barrier materials and electron transport material belong to same type material, contribute to the injection of electronics.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise following operating procedure:
(1) on the glass substrate after cleaning up, adopt the method for magnetron sputtering to prepare anode; Vacuum evaporation hole transmission layer and luminescent layer successively on anode layer;
(2) vacuum evaporation hole blocking layer on luminescent layer, described hole blocking layer material is the composite material that indifferent oxide and hole barrier materials form, the mass fraction of described indifferent oxide in hole blocking layer is 5%～10%, and described indifferent oxide is SiO, Sb
2o
3, Bi
2o
3or Nd
2o
5, described hole barrier materials is PBD, Alq3, Bphen, TPBi, BCP or TAZ; Described evaporation pressure is 1 * 10
-5pa～1 * 10
-3pa, described evaporation speed is 0.01nm/s～1nm/s;
(3) vacuum evaporation electron transfer layer and negative electrode successively on hole blocking layer, then on negative electrode, cover encapsulation cover plate, described encapsulation cover plate and glass substrate are connected to form enclosure space by adhesive, described anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode are contained in described enclosure space, obtain described organic electroluminescence device.
Preferably, described hole barrier layer thickness is 5nm～20nm.
Preferably, the material of described electron transfer layer is the composite material that alkali metal compound and electron transport material form, and described alkali metal compound is lithium carbonate (Li
2cO
3), Lithium Azide (LiN
3), lithium fluoride (LiF), cesium azide (CsN
3), cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), potassium borohydride (KBH
4), rubidium carbonate (Rb
2cO
3), lithium nitride (Li
3n) or sodium fluoride (NaF), the mass fraction of described alkali metal compound in electron transfer layer is 5%～50%.
Preferably, described electron transport material is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) or 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, the thickness of described electron transfer layer is 20nm～200nm.
After having prepared negative electrode, on negative electrode, cover encapsulation cover plate and encapsulate, be convenient to test and anti-sealing, the erosion of oxygen to device.
Preferably, described encapsulation cover plate is glass cover-plate.
Preferably, described encapsulation cover plate and glass substrate are connected to form enclosure space by Photocurable adhesive.
More preferably, described Photocurable adhesive is light-solidifying poly acrylic resin or photo-curing epoxy resin.
Preferably, the sputter rate of described anode is 0.2nm/s～2nm/s.
Preferably, described hole transmission layer, luminescent layer, electron transfer layer evaporation condition are: evaporation pressure is 1 * 10
-5pa～1 * 10
-3pa, evaporation speed is 0.01nm/s～1nm/s.
Preferably, the evaporation condition of described negative electrode is: evaporation pressure is 1 * 10
-5pa～1 * 10
-3pa, evaporation speed is 0.2nm/s～2nm/s.
Preferably, described cleaning-drying is that glass substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, after cleaning up, is using isopropyl alcohol successively, and acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Preferably, described anode material is ITO, IZO, AZO or GZO, and thickness is 70nm～200nm.
More preferably, described anode is ITO, and thickness is 100nm.
Preferably, described hole transmission layer material is hole mobile material or doped with the hole mobile material of dopant; Wherein,
Described hole mobile material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), 4, 4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), 2, two (the N of 7-, N-bis-(4-methoxyphenyl) amino)-9, 9-spiral shell two fluorenes (MeO-Sprio-TPD), 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or 1, 1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC), described dopant is 2, 3, 5, 6-tetrafluoro-7, 7 ', 8, 8 '-tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1, 3, 4, 5, 7, 8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones (F6-TNAP) or 2, 2'-(2, 5-dicyano-3, 6-difluoro cyclohexane-2, 5-diene-1, 4-bis-subunits) two malononitrile (F2-HCNQ), the mass fraction of described dopant in hole transmission layer is 2%～30%, is more preferably 5%.
Preferably, described thickness of hole transport layer is 40nm～100nm.
More preferably, described thickness of hole transport layer is 60nm.
Preferably, the material of described luminescent layer is that guest materials is doped to the composite material that material of main part forms, described guest materials is 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) or three (2-phenylpyridines) close iridium (Ir (ppy) 3), described material of main part is 4, 4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq3), 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) or N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), the mass fraction of described guest materials in material of main part is 1%～10%.
Preferably, described luminescent layer also can adopt fluorescent material 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), oxine aluminium (Alq
3), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) or 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene).
Preferably, the thickness of described luminescent layer is 1nm～20nm, and more preferably, thickness is 15nm.
Preferably, the material of described negative electrode is silver (Ag), aluminium (Al), samarium (Sm), (Yb) ytterbium, and Mg-Al alloy or Mg-Ag alloy, thickness is 70nm～200nm.
More preferably, described negative electrode is Ag, and thickness is 100nm.
Prior art organic electroluminescence device adopts the electron transfer layer of the alkali metal compound that adulterated, electron transfer layer is after alkali-metal-doped, its electric conductivity has obtained raising, injection and the efficiency of transmission of electronics have been improved simultaneously, but after overdoping, alkali-metal-doped agent easily, to luminescent layer diffusion, directly causes the cancellation of exciton, affects the useful life of device.
The present invention arranges a hole blocking layer in luminescent layer and electron transfer layer, described hole blocking layer material is the composite material that inert material and hole barrier materials form, inert material itself is difficult to spread, the alkali metal ion that simultaneously can come to diffusion adsorbs, alkali metal ion is no longer spread to luminescent layer, thereby can extend useful life of device, solved the problem that above-mentioned prior art occurs.Meanwhile, hole barrier materials and electron transport material belong to same type material, contribute to the injection of electronics.
The present invention is provided with encapsulation cover plate on negative electrode, can stop better extraneous water, the erosion of oxygen to device, the useful life of further improving device.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) hole blocking layer material of the present invention is the composite material that inert material and hole barrier material material form, inert material itself is difficult to spread, the alkali metal ion that simultaneously can come to diffusion adsorbs, make alkali metal ion no longer to luminescent layer diffusion, thereby the useful life that can improve device;
(2) the present invention is provided with encapsulation cover plate on negative electrode, can stop better extraneous water, the erosion of oxygen to device, the useful life of further improving device.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of organic electroluminescence device, comprise the glass substrate stacking gradually, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and encapsulation cover plate, described encapsulation cover plate and glass substrate form enclosure space, described anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode is contained in described enclosure space, described hole blocking layer material is the composite material that indifferent oxide and hole barrier materials form, material in the described hole blocking layer alkali metal ion that diffusion is come to electron transfer layer adsorbs, alkali metal ion is no longer spread to luminescent layer, avoid the cancellation of exciton, thereby the useful life that can improve device, the invention also discloses the preparation method of this organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the glass substrate stacking gradually, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer and negative electrode and encapsulation cover plate, described encapsulation cover plate and glass substrate form enclosure space, described anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode is contained in described enclosure space, the material of described hole blocking layer is the composite material that indifferent oxide and hole barrier materials form, the mass fraction of described indifferent oxide in hole blocking layer is 5%～10%, described indifferent oxide is silicon monoxide (SiO), antimonous oxide (Sb
2o
3), bismuth oxide (Bi
2o
3) or five oxidation two neodymium (Nd
2o
5), described hole barrier materials is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) or 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, described hole barrier layer thickness is 5nm～20nm.
Preferably, the material of described electron transfer layer is the composite material that alkali metal compound and electron transport material form, and described alkali metal compound is lithium carbonate (Li
2cO
3), Lithium Azide (LiN
3), lithium fluoride (LiF), cesium azide (CsN
3), cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), potassium borohydride (KBH
4), rubidium carbonate (Rb
2cO
3), lithium nitride (Li
3n) or sodium fluoride (NaF), the mass fraction of described alkali metal compound in electron transfer layer is 5%～50%.
Preferably, described electron transport material is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) or 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).
Preferably, the thickness of described electron transfer layer is 20nm～200nm.
After having prepared negative electrode, on negative electrode, cover encapsulation cover plate and encapsulate, be convenient to test and anti-sealing, the erosion of oxygen to device.
Preferably, described encapsulation cover plate and glass substrate are connected to form enclosure space by Photocurable adhesive.
More preferably, described Photocurable adhesive is light-solidifying poly acrylic resin or photo-curing epoxy resin.
Preferably, described encapsulation cover plate is glass cover-plate.
Preferably, described anode material is indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO), and thickness is 70nm～200nm.
More preferably, described anode is ITO, and thickness is 100nm.
Preferably, described hole transmission layer material is hole mobile material or doped with the hole mobile material of dopant; Wherein,
Described hole mobile material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), 4, 4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines (TPD), N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), 2, two (the N of 7-, N-bis-(4-methoxyphenyl) amino)-9, 9-spiral shell two fluorenes (MeO-Sprio-TPD), 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or 1, 1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC), described dopant is 2, 3, 5, 6-tetrafluoro-7, 7 ', 8, 8 '-tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1, 3, 4, 5, 7, 8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones (F6-TNAP) or 2, 2'-(2, 5-dicyano-3, 6-difluoro cyclohexane-2, 5-diene-1, 4-bis-subunits) two malononitrile (F2-HCNQ), the mass fraction of described dopant in hole transmission layer is 2%～30%, is more preferably 5%.
Preferably, described thickness of hole transport layer is 40nm～100nm.
More preferably, described thickness of hole transport layer is 60nm.
Preferably, the material of described luminescent layer is that guest materials is doped to the composite material that material of main part forms, described guest materials is 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) or three (2-phenylpyridines) close iridium (Ir (ppy) 3), described material of main part is 4, 4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq3), 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) or N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), the mass ratio of described guest materials in material of main part is 1%～10%.
Preferably, described luminescent layer also can adopt fluorescent material 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), oxine aluminium (Alq3), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) or 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene).
Preferably, the thickness of described luminescent layer is 1nm～20nm, and more preferably, thickness is 15nm.
Preferably, the material of described negative electrode is silver (Ag), aluminium (Al), samarium (Sm), ytterbium (Yb), Mg-Al alloy or Mg-Ag alloy, and thickness is 70nm～200nm.
More preferably, described negative electrode is Ag, and thickness is 100nm.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in execution mode be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of organic electroluminescence device of the present invention;
Fig. 2 is brightness and the operating time graph of a relation of the embodiment of the present invention 1 and comparative example's 1 organic electroluminescence device.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Embodiment 1
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide glass substrate 1, substrate 1 is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen; In vacuum coating system, adopt the method for magnetron sputtering, on glass substrate 1, prepare anode 2, anode material 2 is ITO, thickness is 100nm; Sputter rate is 2nm/s.Then in vacuum degree, be 1 * 10
-4in the vacuum film coating chamber of Pa, vacuum evaporation hole transmission layer 3 and luminescent layer 4 successively on anode 2, the material of hole transmission layer 3 is doped with the MeO-TPD of F6-TNAP, and the mass fraction of F6-TNAP in hole transmission layer is 5%; Hole transmission layer 3 thickness are 60nm; The material of luminescent layer 4 is DPVBi, and thickness is 15nm, and the evaporation speed of hole transmission layer 3 and luminescent layer 4 is 0.01nm/s;
(2) on luminescent layer 4, prepare hole blocking layer 5, hole blocking layer 5 materials are SiO and Alq
3the mixture forming, the mass fraction of SiO in mixture is 5%, the thickness of hole blocking layer 5 is 5nm; In vacuum degree, be 1 * 10
-4in the vacuum film coating chamber of Pa, carry out evaporation preparation, evaporation speed is 0.01nm/s;
(3) vacuum evaporation electron transfer layer 6 and negative electrode 7 successively on hole blocking layer 5, the material of described electron transfer layer 6 is doped with Li
2cO
3bCP, Li
2cO
3doping mass fraction in electron transfer layer 6 is 10%, and the thickness of electron transfer layer 6 is 40nm; The material of negative electrode 7 is Ag, and thickness is 100nm; Electron transfer layer 6 and negative electrode 7 are all 1 * 10 in vacuum degree
-4in the vacuum film coating chamber of Pa, prepare, the evaporation speed of electron transfer layer 6 is 0.01nm/s; The evaporation speed of described negative electrode 7 is 0.2nm/s.
(4) cover glass cover plate 8 on negative electrode, glass cover-plate 8 is connected with glass substrate 1 by light-solidifying poly acrylic resin, glass substrate 1 and glass cover-plate 8 form enclosure space, and anode 2, hole transmission layer 3, luminescent layer 4, hole blocking layer 5, electron transfer layer 6 and negative electrode 7 are contained in this enclosure space.
Fig. 1 is the structural representation of the organic electroluminescence device prepared of the present embodiment, organic electroluminescence device prepared by the present embodiment, comprises the glass substrate 1, anode 2, hole transmission layer 3, luminescent layer 4, hole blocking layer 5, electron transfer layer 6, negative electrode 7 and the glass cover-plate 8 that stack gradually.Concrete structure is expressed as:
Glass substrate/ITO/F6-TNAP:MeO-TPD/DPVBi/SiO:Alq
3/ Li
2cO
3: BCP/Ag/ glass cover-plate, wherein, slash "/" represents layer structure, SiO:Alq
3and Li
2cO
3: the colon ": " in BCP represents to mix, lower same.
Embodiment 2
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide glass substrate, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.In vacuum coating system, adopt the method for magnetron sputtering, on glass substrate, prepare anode, anode material is GZO, thickness is 70nm; Sputter rate is 0.2nm/s.Then in vacuum degree, be 1 * 10
-3in the vacuum film coating chamber of Pa, vacuum evaporation hole transmission layer and luminescent layer successively on anode, the material of hole transmission layer is the NPB doped with F4-TCNQ, the mass fraction of F4-TCNQ in hole transmission layer is 2%; Thickness of hole transport layer is 40nm; The material of luminescent layer is the TPBi doped with FIrpic, and the doping mass fraction of FIrpic in TPBi is 10%, and light emitting layer thickness is 20nm, and the evaporation speed of hole transmission layer and luminescent layer is 1nm/s;
(2) on luminescent layer, prepare hole blocking layer, hole blocking layer material is Sb
2o
3with the mixture that TAZ forms, Sb
2o
3mass fraction in mixture is 10%, and the thickness of hole blocking layer is 10nm; In vacuum degree, be 1 * 10
-3in the vacuum film coating chamber of Pa, carry out evaporation preparation, evaporation speed is 1nm/s;
(3) vacuum evaporation electron transfer layer and negative electrode successively on hole blocking layer, the material of described electron transfer layer is doped with Cs
2cO
3bphen, Cs
2cO
3doping mass fraction in electron transfer layer is 50%, and the thickness of electron transfer layer is 100nm.The material of negative electrode is Al, and thickness is 200nm.Electron transfer layer and negative electrode are all 1 * 10 in vacuum degree
-3in the vacuum film coating chamber of Pa, prepare, the evaporation speed of electron transfer layer is 1nm/s; The evaporation speed of described negative electrode is 2nm/s.
(4) cover glass cover plate on negative electrode, glass cover-plate is connected with glass substrate by photo-curing epoxy resin, glass substrate and glass cover-plate form enclosure space, and anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer and negative electrode are contained in this enclosure space.
Organic electroluminescence device prepared by the present embodiment, comprises the glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and the glass cover-plate that stack gradually.Concrete structure is expressed as:
Glass substrate/GZO/F4-TCNQ:NPB/Firpic:TPBi/Sb
2o
3: TAZ/Cs
2cO
3: Bphen/Al/ glass cover-plate.
Embodiment 3
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide glass substrate, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.In vacuum coating system, adopt the method for magnetron sputtering, on glass substrate, prepare anode, anode material is AZO, thickness is 200nm; Sputter rate is 1nm/s.Then in vacuum degree, be 1 * 10
-5in the vacuum film coating chamber of Pa, vacuum evaporation hole transmission layer and luminescent layer successively on anode, the material of hole transmission layer is the 2-TNATA doped with F2-TCNQ, the mass fraction of F2-TCNQ in hole transmission layer is 30%; Thickness of hole transport layer is 100nm; The material of luminescent layer is the Alq doped with DCJTB
3, DCJTB is at Alq
3in doping mass fraction be 1%, light emitting layer thickness is 5nm, the evaporation speed of hole transmission layer and luminescent layer is 0.5nm/s;
(2) on luminescent layer, prepare hole blocking layer, hole blocking layer material is Nd
2o
5with the mixture that TPBi forms, Nd
2o
5mass fraction in mixture is 6%, and the thickness of hole blocking layer is 20nm; In vacuum degree, be 1 * 10
-5in the vacuum film coating chamber of Pa, carry out evaporation preparation, evaporation speed is 0.5nm/s;
(3) vacuum evaporation electron transfer layer and negative electrode successively on hole blocking layer, the material of described electron transfer layer is doped with KBH
4alq
3, KBH
4doping mass fraction in electron transfer layer is 20%, and the thickness of electron transfer layer is 200nm.The material of negative electrode is Mg-Al alloy, and thickness is 100nm.Electron transfer layer and negative electrode are all 1 * 10 in vacuum degree
-5in the vacuum film coating chamber of Pa, prepare, the evaporation speed of electron transfer layer is 0.5nm/s; The evaporation speed of described negative electrode is 1nm/s.
(4) cover glass cover plate on negative electrode, glass cover-plate is connected with glass substrate by photo-curing epoxy resin, glass substrate and glass cover-plate form enclosure space, and anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer and negative electrode are contained in this enclosure space.
Organic electroluminescence device prepared by the present embodiment, comprises the glass substrate, anode layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and the glass cover-plate that stack gradually.Concrete structure is expressed as:
Glass substrate/AZO/F2-TCNQ:2-TNATA/DCJTB:Alq
3/ Nd
2o
5: TPBi/KBH
4: Alq
3/ Mg-Al alloy/glass cover-plate.
Embodiment 4
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide glass substrate, substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.In vacuum coating system, adopt the method for magnetron sputtering, on glass substrate, prepare anode, anode material is IZO, thickness is 100nm; Sputter rate is 0.5nm/s.Then in vacuum degree, be 1 * 10
-4in the vacuum film coating chamber of Pa, on anode, evaporation is prepared hole transmission layer and luminescent layer successively, and the material of hole transmission layer is doped with the TPD of F6-TNAP, and the mass fraction of F6-TNAP in hole transmission layer is 10%; Thickness of hole transport layer is 60nm; The material of luminescent layer is doped with Ir (ppy)
3tPBi, Ir (ppy)
3doping mass fraction in TPBi is 10%, and light emitting layer thickness is 12nm, and the evaporation speed of hole transmission layer and luminescent layer is 0.05nm/s;
(2) on luminescent layer, prepare hole blocking layer, hole blocking layer material is Bi
2o
3with the mixture that Bphen forms, Bi
2o
3mass fraction in mixture is 10%, and the thickness of hole blocking layer is 10nm; In vacuum degree, be 1 * 10
-4in the vacuum film coating chamber of Pa, carry out evaporation preparation, evaporation speed is 0.05nm/s;
(3) vacuum evaporation electron transfer layer and negative electrode successively on hole blocking layer, the material of described electron transfer layer is doped with LiN
3bphen, LiN
3doping mass fraction in electron transfer layer is 20%, and the thickness of electron transfer layer is 50nm.The material of negative electrode is Mg-Ag alloy, and thickness is 100nm.Electron transfer layer and negative electrode are all 1 * 10 in vacuum degree
-4in the vacuum film coating chamber of Pa, prepare, the evaporation speed of electron transfer layer is 0.05nm/s; The evaporation speed of described negative electrode is 1.5nm/s.
(4) cover glass cover plate on negative electrode, glass cover-plate is connected with glass substrate by photo-curing epoxy resin, glass substrate and glass cover-plate form enclosure space, and anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer and negative electrode are contained in this enclosure space.
Organic electroluminescence device prepared by the present embodiment, comprises the glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and the glass cover-plate that stack gradually.Concrete structure is expressed as:
Glass substrate/IZO/F6-TNAP:TPD/Ir (ppy)
3: TPBi/Bi
2o
3: Bphen/LiN
3: Bphen/Mg-Ag alloy/glass cover-plate.
Comparative example 1
For being presented as creativeness of the present invention, the present invention is also provided with comparative example, and comparative example 1 is that with the difference of embodiment 1 material of hole blocking layer in comparative example is only Alq
3, the concrete structure of comparative example's organic electroluminescence device is: glass substrate/ITO/F6-TNAP:MeO-TPD/DPVBi/Alq
3/ Li
2cO
3: BCP/Ag/ glass cover-plate, respectively corresponding glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and glass cover-plate.
Comparative example 2
Comparative example 2 is that with the difference of embodiment 2 material of hole blocking layer in comparative example is only TAZ, and the concrete structure of comparative example's organic electroluminescence device is: glass substrate/GZO/F4-TCNQ:NPB/Firpic:TPBi/TAZ/Cs
2cO
3: Bphen/Al/ glass cover-plate, respectively corresponding glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and glass cover-plate.
Comparative example 3
Comparative example 3 is that with the difference of embodiment 3 material of hole blocking layer in comparative example is only TPBi, and the concrete structure of comparative example's organic electroluminescence device is: glass substrate/AZO/F2-TCNQ:2-TNATA/DCJTB:Alq
3/ TPBi/KBH
4: Alq
3/ Mg-Al alloy/glass cover-plate, respectively corresponding glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and glass cover-plate.
Comparative example 4
Comparative example 4 is that with the difference of embodiment 4 material of hole blocking layer in comparative example is only Bphen, and the concrete structure of comparative example's organic electroluminescence device is: glass substrate/IZO/F6-TNAP:TPD/Ir (ppy)
3: TPBi/Bphen/LiN
3: Bphen/Mg-Ag alloy/glass cover-plate, respectively corresponding glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and glass cover-plate.
Effect embodiment
Adopt fiber spectrometer (U.S. marine optics Ocean Optics company, model: USB4000), current-voltage tester (U.S. Keithly company, 2400), colorimeter (Japanese Konica Minolta company, model: CS-100A) the luminescent properties data of test organic electroluminescence device model:.
Table 1 is life-span and the luminous efficiency data of the prepared device of embodiment 1～4 and comparative example 1～4; Fig. 2 is operating time and the relative brightness graph of a relation of embodiment 1 and comparative example's 1 organic electroluminescence device.
Life-span and the luminous efficiency of the device of table 1 embodiment 1～4 and comparative example's 1～4 preparation
Table 1 is embodiment 1,2,3,4 and the luminescent properties data of the device of comparative example 1,2,3,4 mades.As can be seen from the table, hole blocking layer in organic electroluminescence device provided by the invention, by control alkali metal ion in electron transfer layer in organic layer to the diffusion in luminescent layer, therefore avoided the quenching phenomenon of luminescent layer exciton, device improves useful life greatly.Compare comparative example 1,2,3,4, embodiment 1,2, and improved respectively 78%, 75%, 78%, 69% the useful life of the organic electroluminescence device of 3,4 preparations.Wherein lifetime data is to be 1000cd/m in initial brightness
2under, service time when initial brightness 70% is arrived in brightness decay.
From table 1, also can see, the luminous efficiency that the present invention is to provide embodiment and comparative example is more or less the same, and illustrates that arranging of hole blocking layer of the present invention do not exist adverse influence to light efficiency.
Fig. 2 is embodiment 1 and 1 device operation time of comparative example and relative brightness graph of a relation, and ordinate is the ratio of luminosity and original intensity, abscissa be operation use time.When relative brightness is 70%, reached 3200 hours the service time of embodiment 1, and comparative example only has 1800 hours.Explanation is at the device of embodiment 1 and comparative example 1 preparation when decaying to same brightness, and the service time of embodiment is longer than comparative example.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, is characterized in that, comprises the glass substrate stacking gradually, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and encapsulation cover plate, described encapsulation cover plate and glass substrate form enclosure space, described anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode is contained in described enclosure space, and the material of described hole blocking layer is the composite material that indifferent oxide and hole barrier materials form, and the mass fraction of described indifferent oxide in hole blocking layer is 5%～10%, and described indifferent oxide is silicon monoxide, antimonous oxide, bismuth oxide or five oxidation two neodymiums, described hole barrier materials is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole, (oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described hole barrier layer thickness is 5～20nm.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron transfer layer is the composite material that alkali metal compound and electron transport material form, described alkali metal compound is lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate, cesium fluoride, potassium borohydride, rubidium carbonate, lithium nitride or sodium fluoride, and the mass fraction of described alkali metal compound in electron transfer layer is 5%～50%.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described electron transfer layer is 20nm～200nm.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, described encapsulation cover plate is glass cover-plate.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises following operating procedure:
(1) on the glass substrate after cleaning up, adopt the method for magnetron sputtering to prepare anode; Vacuum evaporation hole transmission layer and luminescent layer successively on anode;
(2) vacuum evaporation hole blocking layer on described luminescent layer, described hole blocking layer material is the composite material that indifferent oxide and hole barrier materials form, the mass fraction of described indifferent oxide in hole blocking layer is 5%～10%, described indifferent oxide is silicon monoxide, antimonous oxide, bismuth oxide or five oxidation two neodymiums, described hole barrier materials is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1, 3, 4-oxadiazole, (oxine)-aluminium, 4, 7-diphenyl-o-phenanthroline, 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene or 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole, described evaporation pressure is 1 * 10
-5pa～1 * 10
-3pa, described evaporation speed is 0.01nm/s～1nm/s,
(3) vacuum evaporation electron transfer layer and negative electrode successively on hole blocking layer, then on negative electrode, cover encapsulation cover plate, described encapsulation cover plate and glass substrate are connected to form enclosure space by adhesive, described anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode are contained in described enclosure space, obtain described organic electroluminescence device.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described hole barrier layer thickness is 5nm～20nm.
8. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, the material of described electron transfer layer is the composite material that alkali metal compound and electron transport material form, described alkali metal compound is lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate, cesium fluoride, potassium borohydride, rubidium carbonate, lithium nitride or sodium fluoride, and the mass fraction of described alkali metal compound in electron transfer layer is 5%～50%.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thickness of described electron transfer layer is 20nm～200nm.
10. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described encapsulation cover plate is glass cover-plate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050116633A1 (en) * | 2003-12-02 | 2005-06-02 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element and light-emitting device using the same |
| CN101030625A (en) * | 2007-04-03 | 2007-09-05 | 清华大学 | Organic electroluminescent device |
| CN102916132A (en) * | 2011-08-05 | 2013-02-06 | 海洋王照明科技股份有限公司 | White-light organic electroluminescence device and preparation method thereof |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050116633A1 (en) * | 2003-12-02 | 2005-06-02 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element and light-emitting device using the same |
| CN101030625A (en) * | 2007-04-03 | 2007-09-05 | 清华大学 | Organic electroluminescent device |
| CN102916132A (en) * | 2011-08-05 | 2013-02-06 | 海洋王照明科技股份有限公司 | White-light organic electroluminescence device and preparation method thereof |
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Application publication date: 20141203 |