CN104218162A - Organic light emission diode device and preparation method thereof - Google Patents
Organic light emission diode device and preparation method thereof Download PDFInfo
- Publication number
- CN104218162A CN104218162A CN201310210327.7A CN201310210327A CN104218162A CN 104218162 A CN104218162 A CN 104218162A CN 201310210327 A CN201310210327 A CN 201310210327A CN 104218162 A CN104218162 A CN 104218162A
- Authority
- CN
- China
- Prior art keywords
- layer
- organic
- mixed layer
- electroluminescence device
- hole transmission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/156—Hole transporting layers comprising a multilayered structure
-
- 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
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 hole transmission layer comprises mixed layers and organic layers, which are alternatively stacked, the mixing layers are made of a mixed material formed by organic materials and inorganic oxides, the number of layers of the mixed layers and the organic layers is not less than 2, the mixed layers and the organic layers have the same organic material, so that the hole transmission capacity of the device can be kept. An inorganic oxide material is added in the hole transmission layer, so that the density of a hole transmission material can be improved, and the refractive index of the organic layers is changed, so that an original homogeneous phase structure between each mixing layer and the corresponding organic material layer forms an out-phase structure, and the direction of travel of light is continuously changed, and thus an original light path with the micro-cavity effect does not exist, and the micro-cavity effect is reduced. The invention also discloses a preparation method of the organic light emission diode device.
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, described hole transmission layer comprises alternately laminated mixed layer and organic material layer, mixed layer material is the composite material that organic material and inorganic oxide are formed, can the cavity transmission ability of retainer member.Inorganic oxide material is added in hole transmission layer, the density of hole mobile material can be improved, and change the refractive index of organic layer, make to form out-phase structure by original equal phase structure between mixed layer and organic material layer, the direct of travel of continuous change light, 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 alternately laminated transparent substrates, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described hole transmission layer comprises alternately laminated mixed layer and organic layer, the number of plies of described mixed layer and organic layer is all more than or equal to 2, described mixed layer material is the composite material that inorganic oxide and organic material are formed, and the mass ratio of described inorganic oxide and organic material is 0.3:1 ~ 1:1; Described organic 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 phenyl)-1,1'-biphenyl-4,4'-diamines (TPD) or N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD); Described inorganic oxide is tungstic acid (WO
3), silicon dioxide (SiO
2), five oxidation two neodymium (Nd
2o
5), rhenium trioxide (ReO
3) or molybdenum trioxide (MoO
3); The material of described organic layer is described organic material.
Preferably, the thickness of described mixed layer is 10 ~ 15nm.
Preferably, the thickness of described organic layer is 10 ~ 20nm.
Preferably, the number of plies of described mixed layer and organic layer is 2 ~ 3 layers.
Preferably, described mixed layer contains identical organic material with in organic layer material.
Preferably, the material of described anode is Ag, Al, Au or Pt.
Preferably, the thickness of described anode is 70 ~ 200nm.
Preferably, the material of described negative electrode is Ag, Al or Ag-Mg alloy or Al-Mg alloy.
Preferably, the thickness of described negative electrode is 20 ~ 40nm.
Preferably, described hole injection layer material is Phthalocyanine Zinc (ZnPc), 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).
Preferably, the thickness of described hole injection layer is 5 ~ 10nm.
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 ~ 60nm.
Preferably, described electron injecting layer material is lithium fluoride, cesium fluoride or calcirm-fluoride.
Preferably, the thickness 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 described 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.
Hole transmission layer of the present invention comprises alternately laminated mixed layer and organic layer, when preparing described hole transmission layer, first can prepare mixed layer on hole injection layer, then on mixed layer, organic layer is prepared, described organic layer prepares mixed layer, by that analogy, alternately laminated mixed layer and organic layer is obtained; Also on hole injection layer, first can prepare organic layer, then prepare mixed layer on described organic layer, described mixed layer prepares organic layer, by that analogy, obtain alternately laminated organic layer and mixed layer, meanwhile, the number of plies of described mixed layer and organic layer can be the same or different.
Hole transmission layer of the present invention comprises alternately laminated mixed layer and organic layer, the number of plies of described mixed layer and organic layer is all more than or equal to 2, described mixed layer material is the composite material that organic material and inorganic oxide are formed, mixed layer with in organic layer material containing identical organic material, can the cavity transmission ability of retainer member.Inorganic oxide material is added in hole transmission layer, the density of hole mobile material can be improved, and change the refractive index of organic layer, make to form out-phase structure by original equal phase structure between mixed layer and organic layer, light can reflect at multiple interface when transmitting in this many one-tenth structures, the direct of travel of continuous change light, makes the light path of original generation microcavity effect not exist, thus reduces microcavity effect.
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 magnetron sputtering prepare anode; The method that described anode adopts thermal resistance to evaporate prepares hole injection layer;
(2) on described hole injection layer, hole transmission layer is prepared, described hole transmission layer comprises alternately laminated mixed layer and organic layer, the number of plies of described mixed layer and organic layer is all more than or equal to 2, described mixed layer material is the composite material that organic material and inorganic oxide are formed, and the mass ratio of described inorganic oxide and organic material is 0.3:1 ~ 1:1; Described organic material 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 phenyl)-1,1'-biphenyl-4,4'-diamines or N, N, N', N '-tetramethoxy phenyl)-benzidine; Described inorganic oxide is tungstic acid, silicon dioxide, five oxidation two neodymiums, rhenium trioxide or molybdenum trioxides; The material of described organic layer is described organic material, described organic layer adopts the method preparation of thermal resistance evaporation, and when preparing described mixed layer, thermal resistance evaporates the organic material in described mixed layer, inorganic oxide simultaneously in mixed layer described in electron beam evaporation, operating pressure during described preparation is 1 × 10
-5~ 1 × 10
-3pa, the evaporation rate of described thermal resistance evaporation is 0.1 ~ 1nm/s, and the evaporation rate of described electron beam is 0.1 ~ 0.5nm/s, and the energy density of described electron beam evaporation is 10 ~ 100W/cm
2; The speed ratio of described electron-beam evaporation rate and thermal resistance evaporation rate is 0.3:1 ~ 1:1;
(3) method adopting thermal resistance to evaporate on hole transmission layer prepares luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, obtains described organic electroluminescence device.
Preferably, the thickness of described mixed layer is 10 ~ 15nm.
Preferably, the thickness of described organic layer is 10 ~ 20nm.
Preferably, the number of plies of described mixed layer and organic layer is 2 ~ 3 layers.
Preferably, described mixed layer contains identical organic material with in organic layer material.
Preferably, the thermal resistance evaporation conditions of described hole injection layer and electron transfer layer is: thermal resistance evaporation pressure is 1 × 10
-5pa ~ 1 × 10
-3pa, thermal resistance evaporation rate is 0.1nm/s ~ 1nm/s.
Preferably, the thermal resistance evaporation conditions of described electron injecting layer, negative electrode and anode is: thermal resistance evaporation pressure is 1 × 10
-5pa ~ 1 × 10
-3pa, thermal resistance evaporation rate is 0.2nm/s ~ 5nm/s.
Preferably, the 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.
Hole transmission layer of the present invention comprises alternately laminated mixed layer and organic layer, when preparing described hole transmission layer, first can prepare mixed layer on hole injection layer, then on mixed layer, organic layer is prepared, described organic layer prepares mixed layer, by that analogy, alternately laminated mixed layer and organic layer is obtained; Also on hole injection layer, first can prepare organic layer, then prepare mixed layer on described organic layer, described mixed layer prepares organic layer, by that analogy, obtain alternately laminated organic layer and mixed layer, meanwhile, the number of plies of described mixed layer and organic layer can identical also can not be identical.
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, the material of described anode is Ag, Al, Au or Pt.
Preferably, the thickness of described anode is 70 ~ 200nm.
Preferably, the material of described negative electrode is Ag, Al or Ag-Mg alloy or Al-Mg alloy.
Preferably, the thickness of described negative electrode is 20 ~ 40nm.
Preferably, described hole injection layer material is Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 2-TNATA (4,4', 4''-tri-(2-naphthylphenyl is amino) triphenylamine) or m-MTDATA ((4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine).
Preferably, the thickness of described hole injection layer is 5 ~ 10nm.
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 ~ 60nm.
Preferably, described electron injecting layer material is lithium fluoride, cesium fluoride or calcirm-fluoride.
Preferably, the thickness 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 described 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.
Hole transmission layer of the present invention comprises alternately laminated mixed layer and organic layer, the number of plies of described mixed layer and organic layer is all more than or equal to 2, described mixed layer material is the composite material that organic material and inorganic oxide are formed, mixed layer with in organic layer material containing identical organic material, can the cavity transmission ability of retainer member.Inorganic oxide material is added in hole transmission layer, the density of hole mobile material can be improved, and change the refractive index of organic layer, make to form out-phase structure by original equal phase structure between mixed layer and organic layer, light can reflect at multiple interface when transmitting in this many one-tenth structures, the direct of travel of continuous change light, makes the light path of original generation microcavity effect not exist, thus reduces microcavity effect.
Implement the embodiment of the present invention, there is following beneficial effect:
The present invention comprises alternately laminated mixed layer and organic layer at hole transmission layer of the present invention, improves the cavity transmission ability of device, reduces the microcavity effect of device simultaneously.
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.
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, 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, adopt the method for thermal resistance evaporation to prepare anode and hole injection layer on the glass substrate successively, anode material is Ag, and thickness is 70nm; Thermal resistance evaporation rate is 5nm/s; The material of hole injection layer is ZnPc, and thickness is 10nm; Thermal resistance evaporation rate is 0.1nm/s;
(2) on hole injection layer, mixed layer is prepared, mixed layer prepares organic layer, then prepare mixed layer on organic layer, by that analogy, obtain the hole transport Rotating fields of the mixed layer/organic layer/mixed layer/organic layer/mixed layer/organic layer stacked gradually, slash "/" represents layer structure; The material of mixed layer is Al
2o
3with the composite material that the NPB ratio that take mass ratio as 0.3:1 is formed, the thickness of mixed layer is 10nm, and the material of organic layer is NPB, and thickness is 10nm, when preparing mixed layer, and electron beam evaporation Al
2o
3, the NPB of thermal resistance evaporation simultaneously, adopt the method for steaming altogether to prepare mixed layer, the evaporation rate of electron beam is 0.15nm/s, and the energy density of electron beam evaporation is 10W/cm
2, thermal resistance evaporation rate is 0.5nm/s; Organic layer adopts the method preparation of thermal resistance evaporation, and thermal resistance evaporation rate is 0.5nm/s;
(3) method adopting thermal resistance to evaporate on hole transmission layer prepares luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, the material of luminescent layer is the composite material that FIrpic is doped to CBP formation, the mass ratio of Firpic and CBP is 0.08:1, and thickness is 1nm; The evaporation rate of Firpic is 0.01nm/s; The evaporation rate of CBP is 0.125nm/s; The material of electron transfer layer is Bphen, and thickness is 60nm; Electron injecting layer material is LiF, and thickness is 0.5nm; Negative electrode material is Ag, and thickness is 20nm; The evaporation rate of electron transfer layer is 0.1nm/s; The evaporation rate of electron injecting layer and negative electrode is 0.2nm/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, electron injecting layer 70 and the negative electrode 80 that stack gradually, hole transmission layer 40 comprises the mixed layer 41, organic layer 42, mixed layer 43, organic layer 44, mixed layer 45 and the organic layer 46 that stack gradually; Concrete structure is expressed as:
Glass substrate/Ag/ZnPc/Al
2o
3: NPB/NPB/Al
2o
3: NPB/NPB/Al
2o
3: NPB/NPB/FIrpic:CBP/Bphen/LiF/Ag, wherein, slash "/" represents layer structure, Al
2o
3: the colon ": " in NPB and 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 and hole injection layer on the glass substrate successively, anode material is Al, and thickness is 200nm; Evaporation rate is 1nm/s; The material of hole injection layer is CuPc, and thickness is 5nm; Evaporation rate is 1nm/s;
(2) on hole injection layer, prepare organic layer, then prepare mixed layer on organic layer, by that analogy, obtain the hole transport Rotating fields of the organic layer/mixed layer/organic layer/mixed layer/organic layer stacked gradually, the material of mixed layer is ReO
3with the composite material that the TPD ratio that take mass ratio as 1:1 is formed, the thickness of mixed layer is 15nm, and the material of organic layer is TPD, and thickness is 15nm, when preparing mixed layer, and electron beam evaporation ReO
3, the TPD of thermal resistance evaporation simultaneously, adopt the method for steaming altogether to prepare mixed layer, thermal resistance evaporation rate is 0.1nm/s, and the evaporation rate of electron beam is 0.1nm/s, and the energy density of electron beam evaporation is 100W/cm
2; Organic layer adopts the method preparation of thermal resistance evaporation, and evaporation rate is 0.1nm/s;
(3) method adopting thermal resistance to evaporate on hole transmission layer prepares luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, and the material of luminescent layer is Ir (MDQ)
2(acac) composite material that NPB is formed is doped to, Ir (MDQ)
2(acac) and the mass ratio of NPB be 0.08:1, thickness is 30nm; Ir (MDQ)
2(acac) evaporation rate is 0.01nm/s; The evaporation rate of NPB is 0.125nm/s; The material of electron transfer layer is TPBi, and thickness is 20nm; Electron injecting layer material is CsF, and thickness is 0.5nm; Negative electrode material is Al, and thickness is 20nm; The evaporation rate of electron transfer layer is 1nm/s; The evaporation rate of electron injecting layer and negative electrode is 1nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, hole transmission layer comprises the organic layer, mixed layer, organic layer, mixed layer and the organic layer that stack gradually; Concrete structure is expressed as:
Glass substrate/Al/CuPc/TPD/ReO
3: TPD/TPD/ReO
3: TPD/TPD/Ir (MDQ)
2(acac): NPB/TPBi/CsF/Al.
Embodiment 3
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 thermal resistance evaporation to prepare anode and hole injection layer on the glass substrate successively, anode material is Au, and thickness is 100nm; Evaporation rate is 2nm/s; The material of hole injection layer is m-MTDATA, and thickness is 10nm; Evaporation rate is 0.5nm/s;
(2) on hole injection layer, prepare mixed layer, mixed layer prepares organic layer, then prepare mixed layer on organic layer, by that analogy, obtain the hole transport Rotating fields of the mixed layer/organic layer/mixed layer/organic layer/mixed layer stacked gradually; The material of mixed layer is MoO
3with the composite material that the TCTA ratio that take mass ratio as 0.5:1 is formed, the thickness of mixed layer is 10nm, and the material of organic layer is TCTA, and thickness is 20nm, when preparing mixed layer, and electron beam evaporation MoO
3, the TCTA of thermal resistance evaporation simultaneously, adopt the method for steaming altogether to prepare mixed layer, the evaporation rate of electron beam is 0.5nm/s, and the energy density of electron beam evaporation is 50W/cm
2; Thermal resistance evaporation rate is 1nm/s; Organic layer adopts the method preparation of thermal resistance evaporation, and evaporation rate is 1nm/s;
(3) method adopting thermal resistance to evaporate on hole transmission layer prepares luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, and the material of luminescent layer is Ir (ppy)
3be doped to the composite material that TPBi is formed, Ir (ppy)
3be 0.15:1 with the mass ratio of TPBi, thickness is 20nm; Ir (ppy)
3evaporation rate be 0.15nm/s; The evaporation rate of TPBi is 1nm/s; The material of electron transfer layer is Alq
3, thickness is 40nm; Electron injecting layer material is NaF, and thickness is 1nm; Negative electrode material is Mg-Ag alloy, and thickness is 40nm; The evaporation rate of electron transfer layer is 0.5nm/s; The evaporation rate of electron injecting layer and negative electrode is 2nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, hole transmission layer comprises the mixed layer, organic layer, mixed layer, organic layer, the mixed layer that stack gradually; Concrete structure is expressed as:
Glass substrate/Au/m-MTDATA/MoO
3: TCTA/TCTA/MoO
3: TCTA/TCTA/MoO
3: TCTA/Ir (ppy)
3: 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 thermal resistance evaporation to prepare anode and hole injection layer on the glass substrate successively, anode material is Pt, and thickness is 80nm; Evaporation rate is 5nm/s; The material of hole injection layer is 2-TNATA, and thickness is 5nm; Evaporation rate is 0.1nm/s;
(2) on hole injection layer, prepare organic layer, then prepare mixed layer on organic layer, by that analogy, obtain the hole transport Rotating fields of the organic layer/mixed layer/organic layer/mixed layer stacked gradually, the material of mixed layer is Nd
2o
5with the composite material that the MeO-TPD ratio that take mass ratio as 0.4:1 is formed, the thickness of mixed layer is 10nm, and the material of organic layer is MeO-TPD, and thickness is 10nm, when preparing mixed layer, and electron beam evaporation Nd
2o
5, the MeO-TPD of thermal resistance evaporation simultaneously, prepare mixed layer by the method for steaming altogether, the evaporation rate of electron beam is 0.2nm/s, and the energy density of electron beam evaporation is 10W/cm
2; Organic layer adopts the method preparation of thermal resistance evaporation, and evaporation rate is 0.5nm/s;
(3) method adopting thermal resistance to evaporate on hole transmission layer prepares luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, and the material of luminescent layer is that DCJTB is doped to Alq
3the composite material formed, DCJTB and Alq
3mass ratio is 0.01:1, and thickness is 5nm; The evaporation rate of DCJTB is 0.01nm/s; Alq
3evaporation rate be 1nm/s; The material of electron transfer layer is BCP, and thickness is 40nm; Electron injecting layer material is LiF, and thickness is 2nm; Negative electrode material is Mg-Al, and thickness is 35nm; The evaporation rate of electron transfer layer is 0.1nm/s; The evaporation rate of electron injecting layer and negative electrode is 5nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, hole transmission layer comprises the organic layer, mixed layer, organic layer and the mixed layer that stack gradually; Concrete structure is expressed as:
Glass substrate/Pt/2-TNATA/MeO-TPD/Nd
2o
5: MeO-TPD/MeO-TPD/Nd
2o
5: MeO-TPD/DCJTB:Alq
3/ 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 1, with the difference of embodiment 1, comparative example 1 is that the material of comparative example 1 hole-transporting layer is only NPB, the concrete structure of comparative example 1 organic electroluminescence device is: glass substrate/Ag/ZnPc/NPB/FIrpic:CBP/Bphen/LiF/Ag is corresponding glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode respectively.
Comparative example 2
With the difference of embodiment 2, comparative example 2 is that the material of comparative example's hole-transporting layer is only TPD, the concrete structure of comparative example 2 organic electroluminescence device is: glass substrate/Al/CuPc/TPD/Ir (MDQ)
2(acac): NPB/TPBi/CsF/Al.Corresponding glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode respectively.
Comparative example 3
With the difference of embodiment 3, comparative example 3 is that the material of comparative example's hole-transporting layer is only TCTA, the concrete structure of comparative example 3 organic electroluminescence device is: glass substrate/Au/m-MTDATA/TCTA/Ir (ppy)
3: TPBi/Alq
3/ NaF/Mg-Ag; Corresponding glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode respectively.
Comparative example 4
With the difference of embodiment 4, comparative example 4 is that the material of comparative example's hole-transporting layer is only MeO-TPD, the concrete structure of comparative example 4 organic electroluminescence device is: glass substrate/Pt/2-TNATA/MeO-TPD/DCJTB:Alq
3/ BCP/LiF/Mg-Al.Corresponding glass substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode respectively.
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 | 472nm | 54nm |
| Comparative example 1 | 467nm | 32nm |
| Embodiment 2 | 620nm | 49nm |
| Comparative example 2 | 612nm | 25nm |
| Embodiment 3 | 513nm | 56nm |
| Comparative example 3 | 509nm | 31nm |
| Embodiment 4 | 602nm | 41nm |
| Comparative example 4 | 598nm | 22nm |
In prior art, in the organic electroluminescent organic electroluminescence device of top emitting, owing to there is microcavity effect, luminescent spectrum is narrowed, thus the half-peak breadth numerical value of luminescent spectrum peak wavelength can diminish, as can be seen from Table 1, the half-peak breadth of the luminescent spectrum measured by organic electroluminescence device prepared by the embodiment of the present invention is compared with comparative example, the embodiment of the present invention has wider half-peak breadth, illustrates that organic electroluminescence device prepared by 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, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, it is characterized in that, described hole transmission layer comprises alternately laminated mixed layer and organic layer, the number of plies of described mixed layer and organic layer is all more than or equal to 2, the material of described mixed layer is the composite material that inorganic oxide and organic material are formed, and the mass ratio of described inorganic oxide and organic material is 0.3:1 ~ 1:1; Described organic material 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 phenyl)-1,1'-biphenyl-4,4'-diamines or N, N, N', N '-tetramethoxy phenyl)-benzidine; Described inorganic oxide is tungstic acid, silicon dioxide, five oxidation two neodymiums, rhenium trioxide or molybdenum trioxides; The material of described organic layer is described organic material.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described mixed layer is 10 ~ 15nm, and the thickness of described organic layer is 10 ~ 20nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, described mixed layer contains identical organic material with in organic layer material.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, the number of plies of described mixed layer and organic layer is 2 ~ 3 layers.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole injection layer is Phthalocyanine Zinc, CuPc, 4,4', 4''-tri-(2-naphthylphenyl is amino) triphenylamine or (4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine).
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. 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 magnetron sputtering prepare anode; Anode adopt the method that thermal resistance is evaporated prepare hole injection layer;
(2) on described hole injection layer, hole transmission layer is prepared, described hole transmission layer comprises alternately laminated mixed layer and organic layer, the number of plies of described mixed layer and organic layer is all more than or equal to 2, described mixed layer material is the composite material that inorganic oxide and organic material are formed, and the mass ratio of described inorganic oxide and organic material is 0.3:1 ~ 1:1; Described organic material 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 phenyl)-1,1'-biphenyl-4,4'-diamines or N, N, N', N '-tetramethoxy phenyl)-benzidine; Described inorganic oxide is tungstic acid, silicon dioxide, five oxidation two neodymiums, rhenium trioxide or molybdenum trioxides; The material of described organic layer is described organic material, described organic layer adopts the method preparation of thermal resistance evaporation, when preparing described mixed layer, organic material in described mixed layer adopts the method preparation of thermal resistance evaporation, inorganic oxide in described mixed layer adopts the method preparation of electron beam evaporation, and operating pressure during described preparation is 1 × 10
-5~ 1 × 10
-3pa, the evaporation rate of described thermal resistance evaporation is 0.1 ~ 1nm/s, and the evaporation rate of described electron beam is 0.1 ~ 0.5nm/s, and the energy density of described electron beam evaporation is 10 ~ 100W/cm
2; The speed ratio of described electron-beam evaporation rate and thermal resistance evaporation rate is 0.3:1 ~ 1:1;
(3) thermal resistance Evaporation preparation luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively on hole transmission layer, obtain described organic electroluminescence device.
8. the preparation method of organic electroluminescence device as claimed in claim 7, it is characterized in that, the thickness of described mixed layer is 10 ~ 15nm, and the thickness of described organic layer is 10 ~ 20nm.
9. the preparation method of organic electroluminescence device as claimed in claim 7, is characterized in that, described mixed layer contains identical organic material with in organic layer material.
10. the preparation method of organic electroluminescence device as claimed in claim 7, it is characterized in that, the number of plies of described mixed layer and organic layer is 2 ~ 3 layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310210327.7A CN104218162A (en) | 2013-05-30 | 2013-05-30 | Organic light emission diode device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310210327.7A CN104218162A (en) | 2013-05-30 | 2013-05-30 | Organic light emission diode device and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104218162A true CN104218162A (en) | 2014-12-17 |
Family
ID=52099462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310210327.7A Pending CN104218162A (en) | 2013-05-30 | 2013-05-30 | Organic light emission diode device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104218162A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107104193A (en) * | 2017-05-03 | 2017-08-29 | 上海大学 | Composite hole transporting layer, LED device structure with multilayer periodically doping structure, using and preparation method |
| CN107546244A (en) * | 2016-06-28 | 2018-01-05 | 三星显示有限公司 | Display device |
| CN112768613A (en) * | 2021-01-11 | 2021-05-07 | 昆山国显光电有限公司 | Organic light emitting device and display panel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010043043A1 (en) * | 2000-01-07 | 2001-11-22 | Megumi Aoyama | Organic electroluminescent display panel and organic electroluminescent device used therefor |
| CN1398146A (en) * | 2002-08-13 | 2003-02-19 | 清华大学 | Electroluminescent organic device |
| CN101383400A (en) * | 2008-10-07 | 2009-03-11 | 中国科学院长春应用化学研究所 | Organic light emitting device using high conductive hole transport material as hole transport layer |
-
2013
- 2013-05-30 CN CN201310210327.7A patent/CN104218162A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010043043A1 (en) * | 2000-01-07 | 2001-11-22 | Megumi Aoyama | Organic electroluminescent display panel and organic electroluminescent device used therefor |
| CN1398146A (en) * | 2002-08-13 | 2003-02-19 | 清华大学 | Electroluminescent organic device |
| CN101383400A (en) * | 2008-10-07 | 2009-03-11 | 中国科学院长春应用化学研究所 | Organic light emitting device using high conductive hole transport material as hole transport layer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107546244A (en) * | 2016-06-28 | 2018-01-05 | 三星显示有限公司 | Display device |
| CN107546244B (en) * | 2016-06-28 | 2021-12-28 | 三星显示有限公司 | Display device |
| US11476440B2 (en) | 2016-06-28 | 2022-10-18 | Samsung Display Co., Ltd. | Display apparatus including touch sensing unit with low-density silicon nitride layer |
| CN107104193A (en) * | 2017-05-03 | 2017-08-29 | 上海大学 | Composite hole transporting layer, LED device structure with multilayer periodically doping structure, using and preparation method |
| CN112768613A (en) * | 2021-01-11 | 2021-05-07 | 昆山国显光电有限公司 | Organic light emitting device and display panel |
| CN112768613B (en) * | 2021-01-11 | 2022-10-28 | 昆山国显光电有限公司 | Organic light emitting device and display panel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103219471A (en) | Top-emitting organic electroluminescent device based on semi-transparent composite negative electrode and preparation method for top-emitting organic electroluminescent device | |
| CN104934544A (en) | Organic electroluminescent light emitting device and preparation method thereof | |
| CN104051655A (en) | Inverted organic light emission diode device and manufacturing method thereof | |
| CN104218162A (en) | Organic light emission diode device and preparation method thereof | |
| CN103594653A (en) | Top-emitting organic electroluminescent device and preparation method thereof | |
| CN102842682A (en) | Stacked organic electroluminescence device and manufacturing method thereof | |
| CN104183746A (en) | White light organic light emitting device and manufacturing method thereof | |
| CN104183775A (en) | Cathode and manufacturing method thereof, and organic light emitting device and manufacturing method thereof | |
| CN104218156A (en) | Organic light emission diode device and preparation method thereof | |
| CN104183718A (en) | Organic light emission diode and preparation method thereof | |
| CN104576954A (en) | Organic electroluminescent component and manufacturing method thereof | |
| CN104051653A (en) | Inversion-type organic light-emitting device and preparation method thereof | |
| CN104078604A (en) | White organic light-emitting diode and manufacturing method thereof | |
| CN104183722A (en) | White-light organic light emission diode and preparation method thereof | |
| CN102790180A (en) | Transmission organic electroluminescent device with color conversion layer outside | |
| CN104218178A (en) | Organic light emission diode device and fabrication method thereof | |
| CN104681739A (en) | Organic light emission diode and preparation method thereof | |
| CN104078572A (en) | White organic light-emitting diode and manufacturing method thereof | |
| CN104681726A (en) | Organic light emission diode and preparation method thereof | |
| CN104183713A (en) | Top-emission organic light emission diode and preparation method thereof | |
| CN104183773A (en) | Organic light emitting device (OLED) and manufacturing method thereof | |
| CN104638161A (en) | White-light OLED (organic light-emitting device) and production method thereof | |
| CN104183761A (en) | Inverted organic light emission diode and preparation method thereof | |
| CN103928631A (en) | Organic electroluminescence apparatus and preparation method thereof | |
| CN104078576A (en) | White organic light-emitting diode and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141217 |