CN104183726A - Organic light emission diode and preparation method thereof - Google Patents
Organic light emission diode and preparation method thereof Download PDFInfo
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- CN104183726A CN104183726A CN201310194852.4A CN201310194852A CN104183726A CN 104183726 A CN104183726 A CN 104183726A CN 201310194852 A CN201310194852 A CN 201310194852A CN 104183726 A CN104183726 A CN 104183726A
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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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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; and the hole-blocking layer not only can block holes from transmitting to the electron transfer layer, but also can block the alkali metal ions in the electron transfer layer form diffusing to the light-emitting layer, so that carrier transmission efficiency is improved, and highly-efficient luminous efficiency can be obtained favorably. 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.
For this reason, researcher has been developed a series of materials as barrier layer, BAlq for example, Alq
3, TPBi, these barrier layers have good film forming, but its thermal stability is general, can be used for stopping the diffusion of alkali metal ion.But barrier layer also has another important function to be, it needs blocking hole transmission to arrive electron transfer layer, thereby avoids causing that radiationless luminous exciton is compound between luminescent layer and electron transfer layer.For this barrier effect, need material to there is the high orbit that lower HOMO(has occupied the energy level of electronics) energy level, and need to there is higher electron mobility, and just can be conducive to the transmission of electronics, improve light efficiency and useful life.Therefore and the blocking capability in hole, existing barrier layer is poor, need one deck not only can blocking hole but also can stop the hole blocking layer of alkali metal ion.
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 zinc sulphide, zinc selenide or zinc telluridse, the alkali metal ion that described hole blocking layer attract electrons transport layer diffusion is come, alkali metal ion is no longer spread to luminescent layer, avoid the cancellation of exciton, blocking hole is transferred to electron transfer layer simultaneously, thereby avoid causing that radiationless luminous exciton is compound.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, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and the encapsulation cover plate that stack gradually, 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 are contained in described enclosure space, and described hole blocking layer material is zinc sulphide (ZnS), zinc selenide (ZnSe) or zinc telluridse ZnTe).
Preferably, described hole barrier layer thickness is 5nm～30nm.
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, 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.
In order to improve light efficiency, hole mobile material of the present invention adopts the hole transmission layer of doped structure.
Preferably, described hole transmission layer material is the hole mobile material doped with 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, the thickness of described hole transmission layer is 40nm～100nm.
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 (Alq
3), 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 (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), 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.
Hole blocking layer material of the present invention is ZnS, ZnSe or ZnTe, conduction level is followed successively by ZnS (3.3eV), ZnSe (3.7eV), ZnTe (3.5eV), valence-band level is followed successively by ZnS (6.9eV), ZnSe (6.3eV), ZnTe (5.9eV), the lumo energy of electron transport material is-2.7eV～(3.3) eV that the HOMO energy level of electron transport material is-5.8～(6.4eV); The valence-band level of hole blocking layer material has been occupied the high orbit of the energy level of electronics lower than the HOMO(of electric transmission shaped material) numerical value of energy level, therefore can carry out hole barrier, reduce hole and electronics and in electron transfer layer, form radiationless luminous recombination probability.The conduction level of hole blocking layer material does not occupy the minimum track of the energy level of electronics lower than the LUMO(of electric transmission shaped material) energy level, so electronics can jump in the conduction band in hole blocking layer by the lumo energy from electron transfer layer.Hole blocking layer adopts the method preparation of vacuum thermal evaporation, and the density of the film preparing is higher, and thermal stability is higher, and the barrier effect of alkali metal ion is also had to remarkable result, has extended the useful life of device.
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 zinc sulphide, zinc selenide or zinc telluridse; Described evaporation pressure is 1 * 10
-5pa～1 * 10
-3pa, evaporation speed is 0.2nm/s～2nm/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～30nm.
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 sputtering 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, acetone in ultrasonic wave, to process 20 minutes, and then dry up with nitrogen successively.
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.
In order to improve light efficiency, hole mobile material of the present invention adopts the hole transmission layer of doped structure.
Preferably, described hole transmission layer material is the hole mobile material doped with 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 TAPC(1, 1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane), 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 (Alq
3), 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.
Hole blocking layer material of the present invention is ZnS, ZnSe or ZnTe, and conduction level is followed successively by ZnS (3.3eV), ZnSe (3.7eV), ZnTe (3.5eV), valence-band level is followed successively by ZnS (6.9eV), ZnSe (6.3eV), ZnTe (5.9eV).The lumo energy of electron transport material is-2.7eV～(3.3) eV that the HOMO energy level of electron transport material is-5.8eV～(6.4) eV; The valence-band level of hole blocking layer material has been occupied the high orbit of the energy level of electronics lower than the HOMO(of electric transmission shaped material) numerical value of energy level, therefore can carry out hole barrier, reduce hole and electronics and in electron transfer layer, form radiationless luminous recombination probability.The conduction level of hole blocking layer material does not occupy the minimum track of the energy level of electronics lower than the LUMO(of electric transmission shaped material) energy level, so electronics can jump in the conduction band in hole blocking layer by the lumo energy from electron transfer layer.Hole blocking layer adopts the method preparation of vacuum thermal evaporation, and the density of the film preparing is higher, and thermal stability is higher, and the barrier effect of alkali metal ion is also had to remarkable result, has extended the useful life of device.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) hole blocking layer material of the present invention is ZnS, ZnSe or ZnTe, can blocking hole to the transmission of electron transfer layer, alkali metal ion in all right block electrons transport layer is to the diffusion of luminescent layer, improve the conductivity of material, thereby improve carrier transport efficiency, be conducive to obtain efficient luminescent device; Hole blocking layer preparation method of the present invention is simple simultaneously, and the hole blocking layer film heat stability preparing is high;
(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.
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 the MeO-TPD doped with F6-TNAP, 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 10nm, and the evaporation rate 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 ZnS, and 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 rate is 0.2nm/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 rate of electron transfer layer 6 is 0.01nm/s; The evaporation rate 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/ZnS/Li
2cO
3: BCP/Ag/ glass cover-plate, wherein, slash "/" represents layer structure, 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 rate of hole transmission layer and luminescent layer is 1nm/s;
(2) on luminescent layer, prepare hole blocking layer, hole blocking layer material is ZnS, 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 rate is 2nm/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 rate of electron transfer layer is 1nm/s; The evaporation rate of described negative electrode is 2nm/s.
(4) cover glass cover plate on negative electrode, glass cover-plate is connected with glass substrate by light-solidifying poly acrylic 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/ZnS/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 rate of hole transmission layer and luminescent layer is 0.5nm/s;
(2) on luminescent layer, prepare hole blocking layer, hole blocking layer material is ZnTe, 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 rate 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 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 rate of electron transfer layer is 0.5nm/s; The evaporation rate 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/ ZnTe/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 rate of hole transmission layer and luminescent layer is 0.05nm/s;
(2) on luminescent layer, prepare hole blocking layer, hole blocking layer material is ZnSe, and the thickness of hole blocking layer is 30nm; In vacuum degree, be 1 * 10
-4in the vacuum film coating chamber of Pa, carry out evaporation preparation, evaporation rate is 1.5nm/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 LiN
3tPBi, 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 rate of electron transfer layer is 0.05nm/s; The evaporation rate 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/ZnSe/LiN
3: TPBi/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 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 BAlq
3, the concrete structure of comparative example's organic electroluminescence device is: glass substrate/GZO/F4-TCNQ:NPB/Firpic:TPBi/BAlq
3/ 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 Alq
3, the concrete structure of comparative example's organic electroluminescence device is: glass substrate/AZO/F2-TCNQ:2-TNATA/DCJTB:Alq
3/ Alq
3/ 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 Alq
3, the concrete structure of comparative example's organic electroluminescence device is: glass substrate/IZO/F6-TNAP:TPD/Ir (ppy)
3: TPBi/Alq
3/ LiN
3: TPBi/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 84%, 70%, 74%, 78% 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.The present invention is to provide embodiment 1,2,3,4 compare with the luminous efficiency of comparative example, and its luminous efficiency has improved respectively 55%, 47%, 54% and 33%.
Fig. 2 is device operation time and the relative brightness graph of a relation of embodiment 1 and comparative example 1 preparation, and ordinate is the ratio of luminosity and original intensity, abscissa be operation use time.When relative brightness is 70%, reached 3900 hours the service time of embodiment 1, and comparative example only has 1900 hours.Explanation is at device 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, it is characterized in that, comprise the glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode and the encapsulation cover plate that stack gradually, 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 are contained in described enclosure space, and described hole blocking layer material is zinc sulphide, zinc selenide or zinc telluridse.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described hole blocking layer is 5nm～30nm.
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 luminescent layer, described hole blocking layer material is zinc sulphide, zinc selenide or zinc telluridse; Described evaporation pressure is 1 * 10
-5pa～1 * 10
-3pa, evaporation speed is 0.2nm/s～2nm/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～30nm.
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 |
|---|---|---|---|---|
| CN114512615A (en) * | 2021-12-29 | 2022-05-17 | 电子科技大学 | Organic photoelectric detector based on organic-metal ion chelated electron transport layer |
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| US20030117068A1 (en) * | 2001-12-20 | 2003-06-26 | Stephen Forrest | Organic optoelectronic device structures |
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| US20030117068A1 (en) * | 2001-12-20 | 2003-06-26 | Stephen Forrest | Organic optoelectronic device structures |
| CN1959997A (en) * | 2005-11-01 | 2007-05-09 | 富士胶片株式会社 | Photoconductive layer forming radiation image taking panel and radiation image taking panel |
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Application publication date: 20141203 |