CN104218177A - Organic light emission diode device and preparation method thereof - Google Patents
Organic light emission diode device and preparation method thereof Download PDFInfo
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- CN104218177A CN104218177A CN201310210275.3A CN201310210275A CN104218177A CN 104218177 A CN104218177 A CN 104218177A CN 201310210275 A CN201310210275 A CN 201310210275A CN 104218177 A CN104218177 A CN 104218177A
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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
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
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- 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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- 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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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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Abstract
The invention discloses an organic light emission diode device. The organic light emission diode device comprises a transparent substrate, an anode, a hole injection layer, a hole transmission layer, a luminous layer, an electronic transmission layer, an electronic injection layer and a cathode, which are stacked in sequence, wherein the organic light emission diode device further comprises a micro-cavity effect damage layer, the micro-cavity effect damage layer is made of a hybrid material formed by doping metal elements in an electronic transmission material, and the refractive index of the micro-cavity effect damage layer and the refractive index of the electronic transmission layer made of a pure organic material have some differences. A metal element material is bombarded on the organic material by the energy provided by a high-energy electron beam in a process of evaporation of the electron beam, so that an original film formation surface is no longer in a smooth form, when the ray is transmitted in an interface structure, the ray is subjected to refraction and diffuse reflection on the interface, and thus an original light path with the micro-cavity effect does not exist, and the micro-cavity effect is reduced.
Description
Technical field
The present invention relates to field of organic electroluminescence, particularly a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode, hereinafter referred to as OLED), there is the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate 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 of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.
At present, the development of OLED is very rapid, and in order to obtain its more application, simpler manufacture craft, researchers develop the OLED light-emitting device of various structures, such as top emitting light-emitting device, inverted type light-emitting device.Be applied at present in the OLED of display unit, the structure of usual employing top emitting, this is because display unit needs opaque silicon materials as substrate usually, bright dipping can only, from the cathode emission at top, can adopt metallic film as the anode with reflection simultaneously.But top emitting device has stronger microcavity effect usually, the emission spectrum of device is launched and narrows, the transmitting particularly for white light or other mixed-color light is unfavorable.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of organic electroluminescence device, comprise the transparent substrates, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, also comprise microcavity effect breakable layer, the material of described microcavity effect breakable layer is the composite material that metal simple-substance is entrained in electron transport material formation, and the described refractive index of microcavity effect breakable layer and the electron transfer layer of pure organic materials exist certain difference.In the process of electron beam evaporation, metal simple-substance material bombards on the organic material by the energy that the electron beam of high energy provides, original film formation surface is made to be no longer smooth form, can reflect at interface when light is transmitted in this interfacial structure, and in this irregular film surface generation diffuse reflection, the light path of original generation microcavity effect is not existed, thus reduces microcavity effect; 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 transparent substrates stacked gradually, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, also comprise microcavity effect breakable layer, described electron transfer layer, described microcavity effect breakable layer and described electron injecting layer stack gradually, or described microcavity effect breakable layer is sandwich is arranged in described electron transfer layer, described electron transfer layer is separated into the first electron transfer layer be arranged on described luminescent layer surface, with the second electron transfer layer be arranged on described microcavity effect breakable layer surface, the thickness of described first electron transfer layer is 20nm ~ 60nm, and the material of described microcavity effect breakable layer is the composite material that metal simple-substance is entrained in electron transport material formation, and the mass ratio of described metal simple-substance and electron transport material is 0.3:1 ~ 1:1, described metal simple-substance is gold (Au), aluminium (Al), silver (Ag), platinum (Pt) or nickel (Ni), described electron transport material is oxine aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP).
Preferably, the thickness of described microcavity effect breakable layer is 20 ~ 40nm.
Preferably, the material of described electron transfer layer is oxine aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP).
Preferably, described electric transmission layer thickness is 20 ~ 80nm.
The thickness of described first electron transfer layer is 20nm ~ 60nm, and described luminescent layer and described microcavity effect breakable layer are separated, and prevents from producing destruction at the described microcavity effect breakable layer of preparation to the organic material in luminescent layer.
Preferably, described anode material is Ag, Al, Au or Pt.
Preferably, the thickness of described anode is 70 ~ 200nm.
Preferably, the material of described negative electrode is silver (Ag), aluminium (Al), silver-colored magnesium alloy or almag.
Preferably, the thickness of described negative electrode is 20 ~ 40nm.
Preferably, the material Phthalocyanine Zinc (ZnPc) of described hole injection layer, CuPc (CuPc), 4,4', 4''-tri-(2-naphthylphenyl is amino) triphenylamine (2-TNATA) or (4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), the thickness of described hole injection layer is 5 ~ 10nm.
Preferably, described hole transmission layer material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyls)-1,1'-biphenyl-4,4'-diamines (TPD) or N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), described thickness of hole transport layer is 20nm ~ 60nm.
Preferably, the material of described electron injecting layer is LiF, CsF or NaF.
Preferably, the material of described electron injecting layer is 0.5 ~ 2nm.
Preferably, the material of described luminescent layer is the composite material that guest materials is doped to material of main part formation, described guest materials is 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (FIrpic), two (4, 6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction 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-Ji) 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 and material of main part is 0.01:1 ~ 0.15:1.
Preferably, described luminescent layer also can adopt fluorescent material, described fluorescent material is 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi), 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene) or dimethylquinacridone (DMQA).
Preferably, the thickness of described luminescent layer is 1nm ~ 30nm.
Preferably, described transparent substrates is glass substrate or transparent polymer film.
More preferably, described transparent substrates is glass substrate.
Organic electroluminescence device of the present invention comprises microcavity effect breakable layer, described microcavity effect breakable layer adopts the method that metal simple-substance and electron transport material evaporate jointly to prepare, in the process of electron beam evaporation, metal simple-substance material bombards on electron transport material by the energy that the electron beam of high energy provides, original film formation surface is made to be no longer smooth form, the refractive index of microcavity effect breakable layer and the electron transfer layer of pure organic materials is made to there is certain difference, finally make light can reflect when electron transfer layer and the transmission of microcavity effect breakable layer interface, and in this irregular film surface generation diffuse reflection, the light path of original generation microcavity effect is not existed, thus microcavity effect is reduced.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise following operating procedure:
(1) transparent substrates after cleaning up adopt the method for vacuum evaporation or electron beam evaporation prepare anode; Method anode adopting thermal resistance evaporate prepares hole injection layer, hole transmission layer and luminescent layer successively;
(2) method of thermal resistance evaporation is adopted to prepare electron transfer layer on the light-emitting layer, then described microcavity effect breakable layer is prepared on the electron transport layer, the last method adopting thermal resistance to evaporate on described microcavity effect breakable layer prepares described electron injecting layer, or
The method of thermal resistance evaporation is adopted to prepare the first electron transfer layer on the light-emitting layer, the thickness of described first electron transfer layer is 20nm ~ 60nm, then on described first electron transfer layer, prepare described microcavity effect breakable layer, the method finally adopting thermal resistance to evaporate on described microcavity effect breakable layer prepares the second electron transfer layer and described electron injecting layer successively; Described first electron transfer layer is identical with described second electron transfer layer material;
The material of described microcavity effect breakable layer is the composite material that metal simple-substance is entrained in electron transport material formation, and the mass ratio of described metal simple-substance and electron transport material is 0.3:1 ~ 1:1; Described metal simple-substance is gold, aluminium, silver, platinum or nickel, and described electron transport material is oxine aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene; When preparing described microcavity effect breakable layer, electron beam evaporation metal simple-substance, simultaneously thermal resistance evaporated electron transferring material, make metal simple-substance and electron transport material jointly form microcavity effect breakable layer, described evaporation pressure is 1 × 10
-5~ 1 × 10
-3pa, the evaporation rate of described electron transport material is 2 ~ 5nm/s, and described electron beam evaporation speed is 1 ~ 5nm/s; The speed ratio of described electron beam evaporation speed and thermal resistance evaporation rate is 0.3:1 ~ 1:1;
(3) method adopting thermal resistance to evaporate on described electron injecting layer prepares negative electrode, obtains described organic electroluminescence device.
Preferably, the thickness of described microcavity effect breakable layer is 20 ~ 40nm.
Preferably, the material of described electron transfer layer is oxine aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP).
Preferably, described first electron transfer layer is all identical with preparation method with the second electron transfer layer material, and described thermal resistance evaporation pressure is 1 × 10
-5pa ~ 1 × 10
-3pa, thermal resistance evaporation rate is 0.1nm/s ~ 5nm/s.
Preferably, described electric transmission layer thickness is 20 ~ 80nm.
The thickness of described first electron transfer layer is 20nm ~ 60nm, and described luminescent layer and described microcavity effect breakable layer are separated, and prevents from producing destruction at the described microcavity effect breakable layer of preparation to the organic material in luminescent layer.
Preferably, described hole injection layer, hole transmission layer and electron transfer layer thermal resistance evaporation conditions are: thermal resistance evaporation pressure is 1 × 10
-5pa ~ 1 × 10
-3pa, thermal resistance evaporation rate is 0.1nm/s ~ 5nm/s.
Preferably, the thermal resistance evaporation rate of described luminescent layer is 0.01nm/s ~ 1nm/s, and the evaporation rate of described guest materials and material of main part is than being 0.01:1 ~ 0.15:1.
Preferably, the thermal resistance evaporation conditions of described electron injecting layer and negative electrode is: thermal resistance evaporation pressure is 1 × 10
-5pa ~ 1 × 10
-3pa, thermal resistance evaporation rate is 0.2nm/s ~ 5nm/s.
Preferably, described transparent substrates is glass substrate or transparent polymer film.
More preferably, described transparent substrates is glass substrate.
Preferably, described in clean up be placed on by transparent substrates in the deionized water containing washing agent to carry out ultrasonic cleaning, successively at use isopropyl alcohol after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Preferably, described anode material is Ag, Al, Au or Pt.
Preferably, the thickness of described anode is 70 ~ 200nm.
Transparent substrates adopt the method for vacuum evaporation or electron beam evaporation prepare anode.
Preferably, described thermal resistance evaporation pressure is 1 × 10
-5pa ~ 1 × 10
-3pa, described thermal resistance evaporation rate is 0.2nm/s ~ 5nm/s, and described electron beam evaporation speed is 1 ~ 5nm/s.
Preferably, the material of described negative electrode is silver (Ag), aluminium (Al), silver-colored magnesium alloy or almag.
Preferably, the thickness of described negative electrode is 20 ~ 40nm.
Preferably, the material Phthalocyanine Zinc (ZnPc) of described hole injection layer, CuPc (CuPc), 4,4', 4''-tri-(2-naphthylphenyl is amino) triphenylamine (2-TNATA) or (4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), the thickness of described hole injection layer is 5 ~ 10nm.
Preferably, described hole transmission layer material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyls)-1,1'-biphenyl-4,4'-diamines (TPD) or N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), described thickness of hole transport layer is 20nm ~ 60nm.
Preferably, the material of described electron injecting layer is LiF, CsF or NaF.
Preferably, the material of described electron injecting layer is 0.5 ~ 2nm.
Preferably, the material of described luminescent layer is the composite material that guest materials is doped to material of main part formation, described guest materials is 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (FIrpic), two (4, 6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction 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-Ji) 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 and material of main part is 0.01:1 ~ 0.15:1.
Preferably, described luminescent layer also can adopt fluorescent material, described fluorescent material is 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi), 5,6,11,12-tetraphenyl naphthonaphthalene (Rubrene) or dimethylquinacridone (DMQA).
Preferably, the thickness of described luminescent layer is 1nm ~ 30nm.
Organic electroluminescence device of the present invention comprises microcavity effect breakable layer, described microcavity effect breakable layer adopts the method that metal simple-substance and electron transport material evaporate jointly to prepare, in the process of electron beam evaporation, metal simple-substance material bombards on electron transport material by the energy that the electron beam of high energy provides, original film formation surface is made to be no longer smooth form, the refractive index of microcavity effect breakable layer and the electron transfer layer of pure organic materials is made to there is certain difference, finally make light can reflect when electron transfer layer and the transmission of microcavity effect breakable layer interface, and in this irregular film surface generation diffuse reflection, the light path of original generation microcavity effect is not existed, thus microcavity effect is reduced.
Implement the embodiment of the present invention, there is following beneficial effect:
Organic electroluminescence device of the present invention comprises microcavity effect breakable layer, the light path of original generation microcavity effect is not existed, thus reduces microcavity effect.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, be briefly described to the accompanying drawing used required in execution mode below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of organic electroluminescence device prepared by the embodiment of the present invention 1;
Fig. 2 is the structural representation of organic electroluminescence device prepared by the embodiment of the present invention 2.
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 transparent substrates, be placed on by substrate in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen; Be 1 × 10 at pressure
-3in the vacuum coating system of Pa, transparent substrates adopts the method that thermal resistance is evaporated prepare anode, anode material is Ag, and thickness is 70nm; Evaporation rate is 5nm/s; On anode, thermal resistance evaporates hole injection layer, hole transmission layer and luminescent layer successively, and hole injection layer material is ZnPc, and thickness is 10nm, and evaporation rate is 0.2nm/s, and hole transmission layer material is NPB, and thickness is 30nm, and evaporation rate is 0.2nm/s; Luminescent layer material is that FIrpic is entrained in the composite material formed in CBP, and the mass ratio of FIrpic and CBP is 0.08:1, and the evaporation rate of light emitting layer thickness to be the evaporation rate of 10nm, Firpic be 0.01nm/s, CBP is 0.125nm/s;
(2) on luminescent layer, adopt the method for vacuum evaporation to prepare electron transfer layer, the material of electron transfer layer is Bphen, and thickness is 20nm; Evaporation rate is 0.5nm/s; Then by metal A g deposited by electron beam evaporation, also thermal resistance evaporates Bphen simultaneously, and wherein the evaporation rate of metal A g is the evaporation rate of 1.5nm/s, Bphen is 5nm/s, form the microcavity effect breakable layer that thickness is 20nm on the electron transport layer, the mass ratio of Ag and Bphen is 0.3:1; The method that microcavity effect breakable layer adopts thermal resistance to evaporate prepares electron injecting layer, and the material of electron injecting layer is LiF, and thickness is 0.5nm, and evaporation rate is 1nm/s;
(3) on electron injecting layer, adopt the method that thermal resistance is evaporated to prepare negative electrode, the material of negative electrode is Ag, and thickness is 20nm, and evaporation rate is 1nm/s.
Fig. 1 is the structural representation of organic electroluminescence device prepared by the present embodiment, organic electroluminescence device prepared by the present embodiment, comprise the glass substrate 10, anode 20, hole injection layer 30, hole transmission layer 40, luminescent layer 50, electron transfer layer 60, microcavity effect breakable layer 70, electron injecting layer 80 and the negative electrode 90 that stack gradually, concrete structure is expressed as:
Glass substrate/Ag/ZnPc/NPB/ FIrpic:CBP/Bphen/Ag:Bphen/LiF/Ag, wherein, slash "/" represents layer structure, and the colon ": " in FIrpic:CBP represents mixing, lower same.
Embodiment 2
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide glass substrate, be placed on by substrate in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen; Be 1 × 10 at pressure
-5in the vacuum coating system of Pa, adopt the method for thermal resistance evaporation to prepare anode on the glass substrate, anode material is Al, and thickness is 200nm; Evaporation rate is 0.2nm/s; On anode, thermal resistance evaporates hole injection layer, hole transmission layer and luminescent layer successively, and hole injection layer material is CuPc, and thickness is 5nm, and evaporation rate is 0.2nm/s; Hole transmission layer material is TPD, and thickness is 60nm, and evaporation rate is 0.5nm/s; Luminescent layer material is Ir (MDQ)
2(acac) be entrained in the composite material formed in NPB, the mass ratio of Ir (MDQ) 2 (acac) and NPB is 0.08:1, and light emitting layer thickness is 15nm, Ir (MDQ)
2(acac) evaporation rate is the evaporation rate of 0.05nm/s, NPB is 0.625nm/s;
(2) on luminescent layer, adopt the method for vacuum evaporation to prepare the first electron transfer layer, the material of the first electron transfer layer is TPBi, and thickness is 60nm; Evaporation rate is 0.5nm/s; Then by metal A u deposited by electron beam evaporation, also thermal resistance evaporates TPBi simultaneously, and wherein the evaporation rate of metal A u is the evaporation rate of 1nm/s, TPBi is 2nm/s, first electron transfer layer is formed the microcavity effect breakable layer that thickness is 20nm, and the mass ratio of Au and TPBi is 0.5:1; Then on microcavity effect breakable layer, prepare the second electron transfer layer, the material of the second electron transfer layer and preparation method are with the first electron transfer layer, and the thickness of the second electron transfer layer is 20nm; The method that second electron transfer layer adopts thermal resistance to evaporate prepares electron injecting layer, and the material of electron injecting layer is CsF, and thickness is 0.5nm, and evaporation rate is 0.1nm/s;
(3) on electron injecting layer, adopt the method that thermal resistance is evaporated to prepare negative electrode, the material of negative electrode is Al, and thickness is 20nm, and evaporation rate is 0.2nm/s.
Fig. 2 is the structural representation of organic electroluminescence device prepared by the embodiment of the present invention 2; Organic electroluminescence device prepared by the present embodiment, comprise the glass substrate 10, anode 20, hole injection layer 30, hole transmission layer 40, luminescent layer 50, first electron transfer layer 60a, microcavity effect breakable layer 70, second electron transfer layer 60b, electron injecting layer 80 and the negative electrode 90 that stack gradually, concrete structure is expressed as:
Glass substrate/Al/CuPc/TPD/Ir (MDQ)
2(acac): NPB/TPBi/Au:TPBi/TPBi/CsF/Al.
Embodiment 3
(1) provide glass substrate, be placed on by substrate in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen; Be 1 × 10 at pressure
-4in the vacuum coating system of Pa, adopt the method for electron beam evaporation to prepare anode on the glass substrate, anode material is Au, and thickness is 100nm; Evaporation rate is 1nm/s; On anode, thermal resistance evaporates hole injection layer, hole transmission layer and luminescent layer successively, and hole injection layer material is m-MTDATA, and thickness is 10nm, and evaporation rate is 0.1nm/s; Hole transmission layer material is TCTA, and thickness is 20nm, and evaporation rate is 0.5nm/s; Luminescent layer material is Ir (ppy)
3be entrained in the composite material formed in TPBi, Ir (ppy)
3be 0.15:1 with the mass ratio of TPBi, light emitting layer thickness is 30nm, Ir (ppy)
3evaporation rate be the evaporation rate of 0.15nm/s, TPBi be 1nm/s;
(2) on luminescent layer, adopt the method for vacuum evaporation to prepare the first electron transfer layer, the material of the first electron transfer layer is Alq
3, thickness is 20nm; Evaporation rate is 0.5nm/s; Then by Pt metal deposited by electron beam evaporation, also thermal resistance evaporates Alq simultaneously
3, wherein the evaporation rate of Pt metal is 5nm/s, Alq
3evaporation rate be 5nm/s, the first electron transfer layer is prepared the microcavity effect breakable layer that thickness is 40nm, Pt and Alq
3mass ratio be 1:1; Microcavity effect breakable layer is prepared the second electron transfer layer, the material of the material of the second electron transfer layer and same first electron transfer layer of preparation method and preparation method, thickness is 20nm; The method that second electron transfer layer adopts thermal resistance to evaporate prepares electron injecting layer, and the material of electron injecting layer is NaF, and thickness is 1nm, and evaporation rate is 5nm/s;
(3) on electron injecting layer, adopt the method that thermal resistance is evaporated to prepare negative electrode, the material of negative electrode is Mg-Ag, and thickness is 40nm, and evaporation rate is 5nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, the first electron transfer layer, microcavity effect breakable layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, concrete structure is expressed as:
Glass substrate/Au/m-MTDATA/TCTA/Ir (ppy)
3: TPBi/Alq
3/ Pt:TPBi/Alq
3/ NaF/Mg-Ag.
Embodiment 4
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide glass substrate, be placed on by substrate in the deionized water containing washing agent and carry out ultrasonic cleaning, use isopropyl alcohol successively after cleaning up, acetone processes 20 minutes in ultrasonic wave, and then dries up with nitrogen; Be 1 × 10 at pressure
-4in the vacuum coating system of Pa, adopt the method for electron beam evaporation to prepare anode on the glass substrate, anode material is Pt, and thickness is 80nm; Evaporation rate is 5nm/s; On anode, thermal resistance evaporates hole injection layer, hole transmission layer and luminescent layer successively, and hole injection layer material is 2-TNATA, and thickness is 5nm, and evaporation rate is 5nm/s; Hole transmission layer material is MeO-TPD, and thickness is 40nm, and evaporation rate is 0.2nm/s; Luminescent layer material is that DCJTB is entrained in the composite material formed in Alq3, DCJTB and Alq
3mass ratio be 0.01:1, the evaporation rate of light emitting layer thickness to be the evaporation rate of 1nm, Firpic be 0.01nm/s, CBP is 1nm/s;
(2) on luminescent layer, adopt the method for vacuum evaporation to prepare the first electron transfer layer, the material of the first electron transfer layer is BCP, and thickness is 30nm; Evaporation rate is 0.5nm/s; Then by W metal deposited by electron beam evaporation, also thermal resistance evaporates BCP simultaneously, and wherein the evaporation rate of W metal is the evaporation rate of 2nm/s, BCP is 5nm/s, first electron transfer layer is prepared the microcavity effect breakable layer that thickness is 40nm, and the mass ratio of Ni and BCP is 0.4:1; Then on microcavity effect breakable layer, prepare the second electron transfer layer, the material of the material of the second electron transfer layer and same first electron transfer layer of preparation method and preparation method, thickness is 10nm; The method that second electron transfer layer adopts thermal resistance to evaporate prepares electron injecting layer, and the material of electron injecting layer is LiF, and thickness is 2nm, and evaporation rate is 1nm/s;
(3) on electron injecting layer, adopt the method that thermal resistance is evaporated to prepare negative electrode, the material of negative electrode is Mg-Al, and thickness is 35nm, and evaporation rate is 1nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, the first electron transfer layer, microcavity effect breakable layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, concrete structure is expressed as:
Glass substrate/Pt/2-TNATA/MeO-TPD/ DCJTB:Alq3/BCP/Ni:BCP/ BCP/LiF/Mg-Al.
Comparative example 1
For being presented as creativeness of the present invention, the present invention is also provided with comparative example, comparative example 1 is do not have microcavity effect breakable layer in comparative example 1 with the difference of embodiment 1, the material of electron transfer layer is Bphen, concrete structure is: glass substrate/Ag/ZnPc/NPB/FIrpic:CBP/Bphen/LiF/Ag, respectively corresponding glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Comparative example 2
Comparative example 2 is do not have microcavity effect breakable layer in comparative example 2 with the difference of embodiment 2, and the material of electron transfer layer is TPBi, and concrete structure is: glass substrate/Al/CuPc/TPD/Ir (MDQ)
2(acac): NPB/TPBi/Ag:TPBi/TPBi/CsF/Al, difference corresponding glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Comparative example 3
Comparative example 3 is do not have microcavity effect breakable layer in comparative example 3 with the difference of embodiment 3, and the material of electron transfer layer is Alq3, and concrete structure is: glass substrate/Au/m-MTDATA/TCTA/Ir (ppy)
3: TPBi/Alq
3/ NaF/Mg-Ag, respectively corresponding glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Comparative example 4
Comparative example 4 is do not have microcavity effect breakable layer in comparative example 4 with the difference of embodiment 4, and the material of electron transfer layer is BCP, and concrete structure is: glass substrate/Pt/2-TNATA/MeO-TPD/DCJTB:Alq
3/ BCP/LiF/Mg-Al, respectively corresponding glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Effect example
Table 1 is the spectrum half-peak breadth data of embodiment and comparative example's test.
The spectrum half-peak breadth data that table 1 embodiment 1 ~ 4 and comparative example 1 ~ 4 test
| ? | Peak wavelength | Half-peak breadth |
| Embodiment 1 | 470nm | 46nm |
| Comparative example 1 | 468nm | 30nm |
| Embodiment 2 | 619nm | 45nm |
| Comparative example 2 | 612nm | 26nm |
| Embodiment 3 | 519nm | 43nm |
| Comparative example 3 | 515nm | 30nm |
| Embodiment 4 | 604nm | 45nm |
| Comparative example 4 | 598nm | 31nm |
In prior art, in the Organnic electroluminescent device of top emitting, owing to there is microcavity effect, luminescent spectrum is narrowed, and thus the half-peak breadth numerical value of luminescent spectrum peak wavelength can diminish, as can be seen from Table 1, the invention provides in scheme of the invention, the half-peak breadth of the luminescent spectrum measured by the embodiment of the present invention is compared with comparative example, and embodiment 1 ~ 4 half-peak breadth obviously wider than contrast comparative example 1 ~ 4, illustrates that the present invention effectively reduces the microcavity effect of device.
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, comprise the transparent substrates stacked gradually, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, it is characterized in that, also comprise microcavity effect breakable layer, described electron transfer layer, described microcavity effect breakable layer and described electron injecting layer stack gradually, or described microcavity effect breakable layer is sandwich is arranged in described electron transfer layer, described electron transfer layer is separated into the first electron transfer layer be arranged on described luminescent layer surface, with the second electron transfer layer be arranged on described microcavity effect breakable layer surface, the thickness of described first electron transfer layer is 20nm ~ 60nm, and the material of described microcavity effect breakable layer is the composite material that metal simple-substance is entrained in electron transport material formation, and the mass ratio of described metal simple-substance and electron transport material is 0.3:1 ~ 1:1, described metal simple-substance is gold, aluminium, silver, platinum or nickel, and described electron transport material is oxine aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described microcavity effect breakable layer is 20 ~ 40nm.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron transfer layer is oxine aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described anode is silver, aluminium, gold or platinum.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron injecting layer is lithium fluoride, cesium fluoride or sodium fluoride.
6. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described luminescent layer is fluorescent material, or guest materials is doped to the composite material of material of main part formation, described guest materials is 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium, two (4, 6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, three (1-phenyl-isoquinolin) close iridium or three (2-phenylpyridines) close iridium, described material of main part is 4, 4'-bis-(9-carbazole) biphenyl, oxine aluminium, 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines, the mass ratio of described guest materials and material of main part is 0.01:1 ~ 0.15:1, described fluorescent material is 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl, 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl, 5,6,11,12-tetraphenyl naphthonaphthalene or dimethylquinacridone.
7. organic electroluminescence device as claimed in claim 1, it 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-base) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyls)-1,1'-biphenyl-4,4'-diamines or N, N, N', N '-tetramethoxy phenyl)-benzidine.
8. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material Phthalocyanine Zinc of described hole injection layer, CuPc, 4,4', 4''-tri-(2-naphthylphenyl is amino) triphenylamine or (4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine.
9. a preparation method for organic electroluminescence device, is characterized in that, comprises following operating procedure:
(1) transparent substrates after cleaning up adopt the method for vacuum evaporation or electron beam evaporation prepare anode; Method anode adopting thermal resistance evaporate prepares hole injection layer, hole transmission layer and luminescent layer successively;
(2) method of thermal resistance evaporation is adopted to prepare electron transfer layer on the light-emitting layer, then described microcavity effect breakable layer is prepared on the electron transport layer, the last method adopting thermal resistance to evaporate on described microcavity effect breakable layer prepares described electron injecting layer, or
The method of thermal resistance evaporation is adopted to prepare the first electron transfer layer on the light-emitting layer, the thickness of described first electron transfer layer is 20nm ~ 60nm, then on described first electron transfer layer, prepare described microcavity effect breakable layer, the method finally adopting thermal resistance to evaporate on described microcavity effect breakable layer prepares the second electron transfer layer and described electron injecting layer successively; Described first electron transfer layer is identical with described second electron transfer layer material;
The material of described microcavity effect breakable layer is the composite material that metal simple-substance is entrained in electron transport material formation, and the mass ratio of described metal simple-substance and electron transport material is 0.3:1 ~ 1:1; Described metal simple-substance is gold, aluminium, silver, platinum or nickel, and described electron transport material is oxine aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene; When preparing described microcavity effect breakable layer, electron beam evaporation metal simple-substance, simultaneously thermal resistance evaporated electron transferring material, make metal simple-substance and electron transport material jointly form described microcavity effect breakable layer, described evaporation pressure is 1 × 10
-5~ 1 × 10
-3pa, the thermal resistance evaporation rate of described electron transport material is 2 ~ 5nm/s, and described electron beam evaporation speed is 1 ~ 5nm/s; The speed ratio of described electron beam evaporation speed and thermal resistance evaporation rate is 0.3:1 ~ 1:1;
(3) method adopting thermal resistance to evaporate on described electron injecting layer prepares negative electrode, obtains described organic electroluminescence device.
10. the preparation method of organic electroluminescence device as claimed in claim 9, it is characterized in that, the thickness of described microcavity effect breakable layer is 20 ~ 40nm.
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| US20020180349A1 (en) * | 2001-03-08 | 2002-12-05 | Xerox Corporation | Display devices with organic-metal mixed layer |
| CN102468446A (en) * | 2010-11-18 | 2012-05-23 | 海洋王照明科技股份有限公司 | Cathode injection material, and manufacturing method and application thereof |
| CN102983284A (en) * | 2012-12-06 | 2013-03-20 | 吉林大学 | Top transmitting white light organic electroluminescent device with weak perspective effect |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020180349A1 (en) * | 2001-03-08 | 2002-12-05 | Xerox Corporation | Display devices with organic-metal mixed layer |
| CN102468446A (en) * | 2010-11-18 | 2012-05-23 | 海洋王照明科技股份有限公司 | Cathode injection material, and manufacturing method and application thereof |
| CN102983284A (en) * | 2012-12-06 | 2013-03-20 | 吉林大学 | Top transmitting white light organic electroluminescent device with weak perspective effect |
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Application publication date: 20141217 |