CN104218156A - 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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- CN104218156A CN104218156A CN201310208443.5A CN201310208443A CN104218156A CN 104218156 A CN104218156 A CN 104218156A CN 201310208443 A CN201310208443 A CN 201310208443A CN 104218156 A CN104218156 A CN 104218156A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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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 an electronic injection auxiliary layer, which is clamped between the electronic transmission layer and the electronic injection layer, the electronic injection auxiliary layer has a lower high LUMO (Lowest Unoccupied Molecular Orbital) energy level, and electrons only need to overcome a small barrier when injected to the luminous layer from the electronic injection layer, so that the injection efficiency of the electrons is improved, and thus lower starting voltage and higher lighting effect are implemented. 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.
Organic electroluminescent LED has a kind of structure of similar sandwich, it is negative electrode and anode up and down respectively, the organic material functional layer of single or multiple lift different materials kind and different structure is clipped between two electrodes, be followed successively by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer.Organic electroluminescence device is carrier injection type luminescent device, after anode and negative electrode add operating voltage, hole is from anode, electronics is injected into the organic material layer of device work respectively from negative electrode, two kinds of charge carriers form hole-electron to luminescence in luminous organic material, and then light sends from electrode side.
Organic electroluminescence device of the prior art, usual employing metal material is as negative electrode, but the metal electrode usually adopted is as Ag, Al, and its work content reaches 4.2eV, and to common are organic electronic transferring material such as the lumo energy of TPBi be 2.7eV, potential barrier between bi-material reaches 1.5eV, when electronics is injected into organic material from metal electrode, needs to overcome larger injection barrier, therefore electronics is lower in injection efficiency, makes the starting resistor of device higher.Researcher is had to adopt the electron injecting layer adding one deck thin layer between metal electrode and organic material at present, normally metal oxide, utilize the internal electric field that metal oxide produces, the energy level changed between metal electrode and organic material distributes, thus reduction potential barrier, but the injection barrier reduced is limited.
In prior art, organic electroluminescence device adopts metal material as negative electrode usually, but the metal electrode usually adopted is as Ag, Al, and its work content reaches 4.2eV, and to common are organic electronic transferring material such as the lumo energy of TPBi be 2.7eV, potential barrier between bi-material reaches 1.5eV, when electronics is injected into organic material from metal electrode, needs to overcome larger injection barrier, therefore electronics is lower in injection efficiency, makes the starting resistor of device higher.Researcher is had to adopt the electron injecting layer adding one deck thin layer between metal electrode and organic material at present, normally metal oxide, utilize the internal electric field that metal oxide produces, the energy level changed between metal electrode and organic material distributes, thus reduction potential barrier, but the injection barrier reduced is limited.
At organic electroluminescence device provided by the invention, be provided with electron injection auxiliary layer between described electron transfer layer and electron injecting layer, the material of electron injection auxiliary layer is oxine lithium (Liq), lithium acetate (CH
3cOOLi) or four (oxine) boron lithium (LiBq4), electron injection auxiliary layer has higher lumo energy, lumo energy as Liq is 3.1eV, and for TPBi, the potential barrier that electronics is injected into TPBi from Liq has reduced to below 0.4eV.And electronics only needs to overcome very little potential barrier when electron injecting layer is injected into electron injection auxiliary layer, electronics is made first to be injected in electron injection auxiliary layer through less potential barrier like this, then be injected in electron transfer layer through a little potential barrier again, change the potential barrier that original disposable needs overcome into two stages overcoming, thus improve the injection efficiency of electronics, thus realize lower starting resistor and higher light efficiency.
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; Method anode adopting thermal resistance evaporate prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively;
(2) adopt the method for thermal resistance evaporation to prepare described electron injection auxiliary layer on the electron transport layer, the material of described electron injection auxiliary layer is Liq, CH
3cOOLi or LiBq4, the evaporation pressure of described electron injection auxiliary layer is 1 × 10
-5pa ~ 1 × 10
-3pa, described evaporation rate is 0.1nm/s ~ 1nm/s;
(3) on described electron injection auxiliary layer, adopt the method for electron beam evaporation to prepare described electron injecting layer, on electron injecting layer, then adopt the method that thermal resistance is evaporated to prepare negative electrode, obtain described organic electroluminescence device.
Preferably, the thickness of described electron injection auxiliary layer is 2 ~ 10nm.
Preferably, the material of described electron injecting layer is aluminium oxide (Al
2o
3), silicon dioxide (SiO
2), molybdenum trioxide (MoO
3) or titanium dioxide (TiO
2).
Preferably, the thickness of described electron injecting layer is 0.5 ~ 2nm.
Preferably, the material of described electron transfer layer is oxine aluminium (Alq
3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP).
Preferably, the material of described negative electrode is silver, aluminium, silver-colored magnesium alloy or almag.
Preferably, the sputter rate of described anode is 1nm/s ~ 5nm/s, and the accelerating voltage of magnetron sputtering is 300 ~ 800V, power density 10 ~ 40W/cm
2.
Preferably, described electron injecting layer electron beam evaporation speed is 0.1nm/s ~ 0.2nm/s; The energy density of electron beam evaporation is 10 ~ 100W/cm
2.
Preferably, described hole injection layer, hole transmission layer and electron transfer layer thermal resistance evaporation conditions are: evaporation pressure is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Preferably, the evaporation rate of described luminescent layer is 0.01nm/s ~ 1nm/s, and the thermal resistance 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 negative electrode is: evaporation pressure is 1 × 10
-5pa ~ 1 × 10
-3pa, 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 indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO), and thickness is 70nm ~ 200nm.
Preferably, the material Phthalocyanine Zinc (ZnPc) of described hole injection layer, CuPc (CuPc), ranadylic phthalocyanine (VOPc) or TiOPc (TiOPc), the thickness of described hole injection layer is 10 ~ 30nm.
Preferably, described hole transmission layer material is N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), N; N '-diphenyl-N; N '-two (3-aminomethyl phenyl)-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 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 '-two (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 '-two (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 4,4 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl (DPVBi), 4,4 '-bis-[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 ~ 20nm.
At organic electroluminescence device provided by the invention, be provided with electron injection auxiliary layer between described electron transfer layer and electron injecting layer, the material of electron injection auxiliary layer is oxine lithium (Liq), lithium acetate (CH
3cOOLi) or four (oxine) boron lithium (LiBq4), electron injection auxiliary layer has higher lumo energy, lumo energy as Liq is 3.1eV, and for TPBi, the potential barrier that electronics is injected into TPBi from Liq has reduced to below 0.4eV.And electronics only needs to overcome very little potential barrier when electron injecting layer is injected into electron injection auxiliary layer, electronics is made first to be injected in electron injection auxiliary layer through less potential barrier like this, then be injected in electron transfer layer through a little potential barrier again, change the potential barrier that original disposable needs overcome into two stages overcoming, thus improve the injection efficiency of electronics, thus realize lower starting resistor and higher light efficiency.
Implement the embodiment of the present invention, there is following beneficial effect:
Organic electroluminescence device of the present invention is provided with electron injection auxiliary layer, described electron injection auxiliary layer is between described electron transfer layer and described electron injecting layer, improve electron injection efficiency, thus make the starting resistor of device reduce, and the light efficiency of luminescent device can be improved.
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 stacked gradually, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, also comprise electron injection auxiliary layer, described electron injection auxiliary layer is located between described electron transfer layer and described electron injecting layer, electron injection auxiliary layer has lower high lumo energy, electronics only needs to overcome very little potential barrier when electron injecting layer is injected into electron injection auxiliary layer, thus improve the injection efficiency of electronics, thus realize lower starting resistor and higher light efficiency.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, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, also comprise electron injection auxiliary layer, described electron injection auxiliary layer is located between described electron transfer layer and described electron injecting layer, and described electron injection auxiliary layer material is oxine lithium (Liq), lithium acetate (CH
3cOOLi) or four (oxine) boron lithium (LiBq4).
Preferably, the thickness of described electron injection auxiliary layer is 2 ~ 10nm.
Preferably, the material of described electron injecting layer is aluminium oxide (Al
2o
3), silicon dioxide (SiO
2), molybdenum trioxide (MoO
3) or titanium dioxide (TiO
2).
Preferably, the thickness of described electron injecting layer is 0.5 ~ 2nm.
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, the thickness of described electron transfer layer is 20 ~ 60nm.
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 70 ~ 200nm.
Preferably, the material of described anode is indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO), and thickness is 70nm ~ 200nm.
Preferably, the material Phthalocyanine Zinc (ZnPc) of described hole injection layer, CuPc (CuPc), ranadylic phthalocyanine (VOPc) or TiOPc (TiOPc), the thickness of described hole injection layer is 10 ~ 30nm.
Preferably, described hole transmission layer material is N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), N; N '-diphenyl-N; N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD) or N; N; N ', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), the thickness of described hole transmission layer is 20nm ~ 60nm.
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 '-two (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 '-two (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 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl (DPVBi), 4,4 '-bis-[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 ~ 20nm.
Preferably, described transparent substrates is glass substrate or transparent polymer film.
More preferably, described transparent substrates is glass substrate.
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 voltage and the current density graph of a relation of the embodiment of the present invention 1 and comparative example 1 organic electroluminescence device.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Embodiment 1
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) provide glass substrate, 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 in vacuum degree
-3in the vacuum coating system of Pa, adopt the method for magnetron sputtering, prepare anode on the glass substrate, anode material is ITO, and thickness is 70nm; Sputter rate is 1nm/s, and the accelerating voltage of magnetron sputtering is 300V, power density 10W/cm
2; Then be 1 × 10 in vacuum degree
-3in the vacuum film coating chamber of Pa, on anode, thermal resistance evaporates hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively, and hole injection layer material is ZnPc, thickness is 20nm, hole transmission layer material is NPB, and thickness is 40nm, and luminescent layer material is Ir (MDQ)
2(acac) composite material formed in NPB is entrained in, Ir (MDQ)
2(acac) be 0.1:1 with the mass ratio of NPB, light emitting layer thickness is 15nm, Ir (MDQ)
2(acac) evaporation rate is 0.01nm/s; The evaporation rate of NPB is 0.1nm/s; The material of electron transfer layer is Bphen, and thickness is 60nm; The evaporation pressure of hole injection layer, hole transmission layer and electron transfer layer is 1 × 10
-3pa, evaporation rate is 0.1nm/s;
(2) adopt the method for thermal resistance evaporation to prepare electron injection auxiliary layer on the electron transport layer, material is Liq, and thickness is 2nm; Evaporation rate is 0.1nm/s;
(3) on electron injection auxiliary layer, adopt the method for electron beam evaporation to prepare electron injecting layer, material is Al
2o
3, thickness is 1nm, and the evaporation rate of electron beam is 0.1nm/s, and the energy density of electron beam evaporation is 10W/cm
2; Thermal resistance evaporation cathode on electron injecting layer, negative electrode material is argent (Ag), and thickness is 70nm, and evaporation rate is 5nm/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 injection auxiliary layer 70, electron injecting layer 80 and the negative electrode 90 that stack gradually, concrete structure is expressed as:
Glass substrate/ITO/ZnPc/NPB/Ir (MDQ)
2(acac): NPB/Bphen/Liq/Al
2o
3/ Ag, wherein, slash "/" represents layer structure, Ir (MDQ)
2(acac): the colon ": " in NPB represents mixing, lower same.
The starting resistor of organic electroluminescence device, luminosity and luminous efficiency prepared by testing example 1; Adopt the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
The test result of organic electroluminescence device prepared by embodiment 1 is: device starting resistor is 3.4V, and luminosity is 1000cd/m
2time luminous efficiency be 15.5lm/W.
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; In vacuum coating system, adopt the method for magnetron sputtering, prepare anode on the glass substrate, anode material is IZO, and thickness is 200nm; Sputter rate is 5nm/s, and the accelerating voltage of magnetron sputtering is 800V, power density 40W/cm
2; Then be 1 × 10 in vacuum degree
-5in the vacuum film coating chamber of Pa, on anode, thermal resistance evaporates hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively, and hole injection layer material is CuPc, thickness is 10nm, hole transmission layer material is TPD, and thickness is 60nm, and 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 20nm, Ir (ppy)
3evaporation rate be 0.15nm/s; The evaporation rate of TPBi is 1nm/s;
The material of electron transfer layer is TPBi, and thickness is 60nm; The evaporation pressure of hole injection layer, hole transmission layer and electron transfer layer is 1 × 10
-5pa, evaporation rate is 0.1nm/s;
(2) adopt the method for thermal resistance evaporation to prepare electron injection auxiliary layer on the electron transport layer, material is CH
3cOOLi, thickness is 5nm; Evaporation rate is 0.1nm/s;
(3) on electron injection auxiliary layer, adopt the method for electron beam evaporation to prepare electron injecting layer, material is SiO
2, thickness is 0.5nm, and the evaporation rate of electron beam is 0.2nm/s; The energy density of electron beam evaporation is 100W/cm
2; Thermal resistance evaporation cathode on electron injecting layer, negative electrode material is argent (Ag), and thickness is 200nm, and evaporation rate 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 injection auxiliary layer, electron injecting layer and the negative electrode that stack gradually, concrete structure is expressed as:
Glass substrate/IZO/CuPc/TPD/Ir (ppy)
3: TPBi/TPBi/CH
3cOOLi/SiO
2/ Ag.
The test result of organic electroluminescence device prepared by embodiment 2 is: starting resistor is 3.5V, and luminosity is 1000cd/m
2time luminous efficiency be 19.2m/W.
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; In vacuum coating system, adopt the method for magnetron sputtering, prepare anode on the glass substrate, anode material is AZO, and thickness is 100nm; Sputter rate is 2nm/s, and the accelerating voltage of magnetron sputtering is 600V, power density 20W/cm
2; Then be 1 × 10 in vacuum degree
-4in the vacuum film coating chamber of Pa, on anode, thermal resistance evaporates hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively, and hole injection layer material is VOPc, thickness is 30nm, hole transmission layer material is m-MTDATA, and thickness is 20nm, and luminescent layer material is that DCJTB is entrained in Alq
3the composite material of middle formation, DCJTB and Alq
3mass ratio be the evaporation rate of 0.01:1, DCJTB be 0.01nm/s; Alq
3evaporation rate be 1nm/s; Light emitting layer thickness is 1nm, and the material of electron transfer layer is BCP, and thickness is 20nm; The evaporation pressure of hole injection layer, hole transmission layer and electron transfer layer is 1 × 10
-4pa, evaporation rate is 1nm/s;
(2) adopt the method for thermal resistance evaporation to prepare electron injection auxiliary layer on the electron transport layer, material is LiBq4, and thickness is 10nm; Evaporation rate is 1nm/s;
(3) on electron injection auxiliary layer, adopt the method for electron beam evaporation to prepare electron injecting layer, material is TiO
2, thickness is 0.5nm, and the evaporation rate of electron beam is 0.2nm/s, and the energy density of electron beam evaporation is 60W/cm
2;
Thermal resistance evaporation cathode on electron injecting layer, negative electrode material is almag, and thickness is 100nm, and evaporation rate is 0.2nm/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 injection auxiliary layer, electron injecting layer and the negative electrode that stack gradually, concrete structure is expressed as:
Glass substrate/AZO/VOPc/m-MTDATA/DCJTB:Alq
3/ BCP/LiBq4/TiO
2/ Al-Mg.
The test result of organic electroluminescence device prepared by embodiment 3 is: starting resistor is 3.4V, and luminosity is 1000cd/m
2time luminous efficiency be 12.3lm/W.
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; In vacuum coating system, adopt the method for magnetron sputtering, prepare anode on the glass substrate, anode material is GZO, and thickness is 120nm; Sputter rate is 2nm/s, and the accelerating voltage of magnetron sputtering is 400V, power density 20W/cm
2; Then be 1 × 10 in vacuum degree
-4in the vacuum film coating chamber of Pa, on anode, thermal resistance evaporates hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively, hole injection layer material is TiOPc, thickness is 10nm, hole transmission layer material is MeO-TPD, and thickness is 40nm, and luminescent layer material is DMQA, light emitting layer thickness is 12nm, and the material of electron transfer layer is Alq
3, thickness is 35nm; The evaporation pressure of hole injection layer, luminescent layer, hole transmission layer and electron transfer layer is 1 × 10
-4pa, evaporation rate is 0.2nm/s; The evaporation rate of DMQA is 0.01nm/s;
(2) adopt the method for thermal resistance evaporation to prepare electron injection auxiliary layer on the electron transport layer, material is Liq, and thickness is 5nm; Evaporation rate is 0.2nm/s;
(3) on electron injection auxiliary layer, adopt the method for electron beam evaporation to prepare electron injecting layer, material is MoO
3, thickness is 0.5nm, and the evaporation rate of electron beam is 0.2nm/s, and the energy density of electron beam evaporation is 60W/cm
2; Thermal resistance evaporation cathode on electron injecting layer, negative electrode material is silver-colored magnesium alloy, and thickness is 120nm, 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, electron transfer layer, electron injection auxiliary layer, electron injecting layer and the negative electrode that stack gradually, concrete structure is expressed as:
Glass substrate/GZO/TiOPc/MeO-TPD/DMQA/Alq
3/ Liq/MoO
3/ Ag-Mg.
The test result of organic electroluminescence device prepared by embodiment 4 is: starting resistor is 3.5V, and luminosity is 1000cd/m
2time luminous efficiency be 10.2lm/W.
Comparative example
For being presented as creativeness of the present invention, the present invention is also provided with comparative example, the difference of comparative example and embodiment 1 is do not have electron injection auxiliary layer in comparative example, and the concrete structure of comparative example's organic electroluminescence device is: glass substrate/ITO/ZnPc/NPB/Ir (MDQ)
2(acac): NPB/Bphen/Al
2o
3/ 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's test result: starting resistor is 4.1V, luminosity is 1000cd/m
2time luminous efficiency be 8.1lm/W.
Effect example
Fig. 2 is the Current density-voltage characteristic curve of embodiment 1 and comparative example.As can be seen from Figure 2, under identical driving voltage, the drive current of device that device drive current prepared by embodiment 1 is prepared higher than comparative example, if voltage is when 6V, the drive current density that embodiment 1 obtains is 71.9mA/cm
2, and comparative example only obtains 38.4mA/cm
2drive current.Therefore, the present invention arranges the injection process that electron injection auxiliary layer is more conducive to electronics between electron transfer layer and electron injecting layer.
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, also comprise electron injection auxiliary layer, described electron injection auxiliary layer is located between described electron transfer layer and described electron injecting layer, and described electron injection auxiliary layer material is oxine lithium, lithium acetate or four (oxine) boron lithium.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described electron injection auxiliary layer is 2 ~ 10nm.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron injecting layer is aluminium oxide, silicon dioxide, molybdenum trioxide or titanium dioxide.
4. 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.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described negative electrode is silver, aluminium, silver-colored magnesium alloy or almag.
6. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole injection layer is Phthalocyanine Zinc, CuPc, ranadylic phthalocyanine or TiOPc.
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 '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine, N; N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4; 4 '-diamines or N; N, N ', N '-tetramethoxy phenyl) and-benzidine.
8. 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 '-two (9-carbazole) biphenyl, oxine aluminium, 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene or N, N '-diphenyl-N, N '-two (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 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl, 4,4 '-bis-[4-(di-p-tolyl is amino) styryl] biphenyl, 5,6,11,12-tetraphenyl naphthonaphthalene or dimethylquinacridone.
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 magnetron sputtering prepare anode; Method anode adopting thermal resistance evaporate prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively;
(2) method of thermal resistance evaporation is adopted to prepare described electron injection auxiliary layer on the electron transport layer, the material of described electron injection auxiliary layer is oxine lithium, lithium acetate or four (oxine) boron lithium, and the evaporation pressure of described electron injection auxiliary layer is 1 × 10
-5pa ~ 1 × 10
-3pa, described evaporation rate is 0.1nm/s ~ 1nm/s;
(3) on described electron injection auxiliary layer, adopt the method for electron beam evaporation to prepare described electron injecting layer, the method that described electron injecting layer adopts thermal resistance to evaporate 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 electron injection auxiliary layer is 2 ~ 10nm.
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