CN104218161A - Organic light emission device and fabrication method thereof - Google Patents
Organic light emission device and fabrication method thereof Download PDFInfo
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- CN104218161A CN104218161A CN201310210287.6A CN201310210287A CN104218161A CN 104218161 A CN104218161 A CN 104218161A CN 201310210287 A CN201310210287 A CN 201310210287A CN 104218161 A CN104218161 A CN 104218161A
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- H10K50/00—Organic light-emitting devices
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Abstract
The embodiment of the invention provides an organic light emission device and a fabrication method thereof. The device comprises a substrate, an anode, a hole injection layer, a hole transmission layer, a light emission layer, an electron transmission layer, a first electron injection auxiliary layer, a second electron injection auxiliary layer and a cathode which are sequentially laminated, wherein the material of the first electron injection auxiliary layer is zinc oxide, the material of the second electron injection auxiliary layer is selected from at least one of lithium fluoride, cesium fluoride, sodium fluoride and potassium fluoride, and the material of the cathode is silver, aluminum, aluminum magnesium alloy or silver magnesium alloy. In the embodiment of the invention, the first electron injection auxiliary layer and the second electron injection auxiliary layer are arranged in the organic light emission device having the substrate, the anode, the hole injection layer, the hole transmission layer, the light emission layer, the electron transmission layer and the anode, the electron injection efficiency can be improved, and hole transmission to the cathode is prevented, so that the starting voltage of the organic light emission device can be reduced, and the luminous efficiency of the organic light emission device is improved.
Description
Technical field
The present invention relates to field of organic electroluminescence, particularly a kind of Organnic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescent LED (Organic Light Emission Diode, 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.Therefore organic electroluminescent LED is the focus of the concern 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, clip the organic material functional layer of single or multiple lift different materials kind and different structure between two electrodes, be followed successively by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and 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.
Up to the present, although the scientific research personnel of whole world various countries is by selecting suitable organic material and the rational design to device architecture, the indices of device performance has been made to be greatly improved, but at present owing to driving the electric current of luminescent device larger, luminous efficiency is low, and device lifetime is low, in order to realize the practical of organic electroluminescence device, it is little that people are eager to find a kind of drive current, the Organnic electroluminescent device that luminous efficiency is high.
Summary of the invention
The embodiment of the present invention provides a kind of Organnic electroluminescent device and preparation method thereof, can reduce the starting resistor of Organnic electroluminescent device, and provides its luminous efficiency.
On the one hand, provide a kind of Organnic electroluminescent device, described device comprises substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the first electron injection auxiliary layer, second electron injection auxiliary layer and the negative electrode of stacked above one another; The material of described first electron injection auxiliary layer is zinc oxide, and the material of described second electron injection auxiliary layer is lithium fluoride, cesium fluoride, sodium fluoride, at least one in potassium fluoride, and the material of described negative electrode is silver, aluminium, almag or silver-colored magnesium alloy.
Wherein, the thickness of described first electron injection auxiliary layer is 1 ~ 4nm.
Wherein, the thickness of described second electron injection auxiliary layer is 0.5 ~ 2nm.
Wherein, described substrate is transparency carrier.
Wherein, the material of described anode is indium tin oxide, indium-zinc oxide, aluminium zinc oxide or gallium zinc oxide, and the thickness of described anode is 70 ~ 200nm.
Wherein, the material of described hole injection layer is Phthalocyanine Zinc, CuPc, ranadylic phthalocyanine, TiOPc, and the thickness of described hole injection layer is 10-30nm.
Wherein, 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-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines or N, N, N', N '-tetramethoxy phenyl-benzidine, the thickness of described hole transmission layer is 20-60nm.
Wherein, described luminescent layer 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 and three (2-phenylpyridine) and close one or more luminescent materials and material of main part in iridium and adulterate and form, described material of main part is CBP(4, 4'-bis-(9-carbazole) biphenyl), Alq
3(oxine aluminium), TPBi (1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene) or NPB (N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines), the mass ratio of described luminescent material and described material of main part is 1:100 ~ 15:100, or, described luminescent layer is 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl, DPAVBi (4, 4'-two [4-(di-p-tolyl is amino) styryl] biphenyl), 5, 6, 11, at least one in 12-tetraphenyl naphthonaphthalene and dimethylquinacridone, the thickness of described luminescent layer is 1 ~ 20nm.
Wherein, 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, described electric transmission layer thickness is 20-60nm.
On the other hand, provide a kind of preparation method of Organnic electroluminescent device, the method comprises:
Substrate is provided;
Anode is prepared at described substrate surface vacuum splashing and plating;
At described anode surface successively vacuum evaporation hole injection layer, hole transmission layer, luminescent layer and electron transfer layer;
Prepare the first electron injection auxiliary layer by electron beam evaporation plating on the electron transport layer, the material of described first electron injection auxiliary layer is zinc oxide;
Described first electron injection auxiliary layer prepares the second electron injection auxiliary layer by thermal resistance evaporation, and the material of described second electron injection auxiliary layer is alkali-metal fluoride;
At described second electron injection auxiliary layer vacuum evaporation negative electrode, obtain Organnic electroluminescent device.
The embodiment of the present invention is by being arranged in the Organnic electroluminescent device with substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and anode by the first electron injection auxiliary layer and the second electron injection auxiliary layer, electron injection efficiency can be improved, and blocking hole is to the transmission of negative electrode, thus the starting resistor of Organnic electroluminescent device can be reduced, and improve its luminous efficiency.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is 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 the Organnic electroluminescent device that the embodiment of the present invention provides;
Fig. 2 is the Current density-voltage characteristic curve of the Organnic electroluminescent device in embodiment 1 and comparative example 1.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Fig. 1 shows the structural representation of the Organnic electroluminescent device that the embodiment of the present invention provides.Organnic electroluminescent device 100 comprises the substrate 10, anode 20, hole injection layer 30, hole transmission layer 40, luminescent layer 50, electron transfer layer 60, first electron injection auxiliary layer 70, second electron injection auxiliary layer 80 and the negative electrode 90 that superpose in turn.
Substrate 10 is transparency carrier, such as, and glass substrate.
The material of anode 20 can be transparent conductive oxide film, and preferably, the material of anode 20 is indium tin oxide (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) or gallium zinc oxide (GZO).Preferably, the thickness of anode 20 is 70-200nm.
The material of hole injection layer 30 is selected from Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc).Preferably, the thickness of hole injection layer 30 is 10-30nm.
The material of hole transmission layer 40 is hole mobile material, such as, the material of hole transmission layer 40 is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), 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).Preferably, the thickness of hole transmission layer is 20-60nm.
Preferably, luminescent layer 50 is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic close iridium (FIrpic), two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) and three (2-phenylpyridines) close iridium (Ir (ppy)
3) etc. one or more and material of main part of luminescent material adulterate and form, material of main part can select CBP(4,4'-bis-(9-carbazole) biphenyl), Alq
3(oxine aluminium), TPBi (1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene) or NPB (N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines), the mass ratio of luminescent material and material of main part is 1:100 ~ 15:100.Luminescent layer 50 also can adopt 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), DPAVBi (4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl), 5, at least one in the fluorescent materials such as 6,11,12-tetraphenyl naphthonaphthalene (Rubrene) and dimethylquinacridone (DMQA).Preferably, the thickness of luminescent layer is between 1 ~ 20nm.
The material of electron transfer layer 60 electron transfer layer is electron transport material, such as, and oxine aluminium (Alq
3), 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, electron transfer layer 60 thickness is 20-60nm.
First electron injection auxiliary layer 70 can be zinc oxide (ZnO).Preferably, the thickness of auxiliary layer 70 is injected in the second hole is 1 ~ 4nm.
The material of the second electron injection auxiliary layer 80 is selected from alkali-metal fluoride, preferably, comprises lithium fluoride (LiF), cesium fluoride (CsF), sodium fluoride (NaF), at least one in potassium fluoride (KF) etc.Preferably, the thickness of the first electron injection auxiliary layer 80 is 0.5 ~ 2nm.
Negative electrode 90 material can select the one in metal A g, AlAg-Mg alloy and Al-Mg alloy.Preferably, the thickness of negative electrode 90 is between 70 ~ 200nm.
The concrete preparation method of the Organnic electroluminescent device that the embodiment of the present invention provides, comprises the steps:
Prepare anode 20 at substrate 10 surface vacuum sputter, the material of anode 20 can be transparent conductive oxide, and operating pressure during preparation can be 1 × 10
-5~ 1 × 10
-3pa, magnetron sputtering speed are 1 ~ 5nm/s, the accelerating voltage of sputtering is 300 ~ 800v, the power density of sputtering is 10 ~ 40w/cm
2;
Prepare hole injection layer 30 on the surface of anode 20 successively vacuum evaporation, hole transmission layer 40, luminescent layer 50 and electron transfer layer 60, operating pressure during evaporation can be 1 × 10
-5~ 1 × 10
-3pa, evaporation rate is 0.1 ~ 1nm/s;
On electron transfer layer 60, the material that deposited by electron beam evaporation technique prepares the first electron injection auxiliary layer 70, first electron injection auxiliary layer 60 can be zinc oxide; Can be 1 × 10 in operating pressure
-5~ 1 × 10
-3the evaporation rate of Pa, electron beam is 0.1 ~ 0.2nm/s, the energy density of electron beam evaporation is 10 ~ 100w/cm
2condition under carry out electron beam evaporation plating;
The material that first electron injection auxiliary layer 70 is used thermal resistance Evaporation preparation second electron injection auxiliary layer 80, second electron injection auxiliary layer 70 is alkali-metal fluoride; Can be 1 × 10 in operating pressure
-5~ 1 × 10
-3pa carries out thermal resistance evaporation;
Second electron injection auxiliary layer 80 prepares negative electrode 90, can be, such as, pressure is 1 × 10
-5~ 1 × 10
-3pa, evaporation rate are vacuum evaporation negative electrode 90 under the condition of 0.2 ~ 5nm/s.
It is pointed out that the present invention is that the Organnic electroluminescent device 100 that entity provides can also require to add other functional layers according to other.
The embodiment of the present invention, by adding electron injection auxiliary layer (i.e. the first electron injection auxiliary layer 70 and the second electron injection auxiliary layer 80) between the electron transfer layer 60 and negative electrode 90 of Organnic electroluminescent device 100, can improve the injectability of electronics.Wherein, the alkali metal compounds such as LiF, CsF, LiF, CsF in the second electron injection auxiliary layer 80, Li, Cs atom that of dissociating when evaporating is easy to be formed with metal A l, Ag etc. the key of such as Li-Al, thus electronics is injected into Organnic electroluminescent device 100 from negative electrode 90 by alkali metal compounds such as LiF.And adopt ZnO as the first electron injection auxiliary layer 70, this is because the conduction band of ZnO and valence-band level are respectively-4.35eV and-7.72eV, its conduction level is lower, be conducive to the injection of electronics, for common electron transport material, such as TPBi, its HOMO highest occupied molecular orbital (Highest Occupied Molecular Orbital, HOMO) energy level is generally 6.2eV, therefore there is from needing to overcome ZnO during TPBi transmission arrival negative electrode 90 potential barrier brought in hole, hole can be stoped like this to be injected in negative electrode 90, thus ensure that more charge carrier is luminous in luminescent layer 50.Therefore, by arranging the first electron injection auxiliary layer 70 and the second electron injection auxiliary layer 80, electronics ratio can be made to be easier to be injected in electron transfer layer 70, controlling hole simultaneously and being difficult to arrive negative electrode 90, thus realizing the specular removal of Organnic electroluminescent device 100.
More specifically introduce below in conjunction with embodiment 1 ~ 4 and comparative example 1 couple of the present invention:
Embodiment 1
The structure of Organnic electroluminescent device is glass substrate/ITO/CuPc/NPB/Ir (MDQ)
2(acac): NPB/Bphen/ZnO/LiF/Ag.
The preparation of this Organnic electroluminescent device comprises the following steps and preparation technology:
The operating pressure of preparation is 1 × 10
-3pa, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal is 5nm/s, and the sputtering rate of oxide semiconductor film is 1nm/s, and the evaporation rate of electron beam is 0.1nm/s, and the energy density of electron beam evaporation is 10W/cm
2, the accelerating voltage of magnetron sputtering is 300V, and power density is 10W/cm
2.
Prepare anode at light-transparent substrate surface vacuum sputter, material is ITO, and thickness is 70nm;
On described anode surface surface successively Evaporation preparation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer.
Hole injection layer material is CuPc (CuPc), thickness is 30nm, hole transport layer material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), thickness is 20nm, and emitting layer material is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac) material of main part N) is entrained in, in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), Ir (MDQ)
2(acac) be 10:100 with the mass ratio of NPB, light emitting layer thickness is 15nm, and the material of electron transfer layer is 4,7-diphenyl-o-phenanthroline (Bphen), and thickness is 30nm.
Deposited by electron beam evaporation prepares the first electron injection auxiliary layer on the electron transport layer, and material is zinc oxide (ZnO), and thickness is 1nm;
Adopt thermal resistance Evaporation preparation second electron injection auxiliary layer at the first electron injecting layer, material is lithium fluoride (LiF), and thickness is 0.5nm;
Evaporation preparation negative electrode on the second electron injection auxiliary layer, cathode material is argent (Ag), and thickness is 70nm.
Test result: starting resistor 3.5V, luminosity is 1000cd/m
2time luminous efficiency be 12.5lm/W.
Embodiment 2
The structure of organic electroluminescence device is glass substrate/IZO/ZnPc/TPD/Ir (ppy)
3: TPBi/TPBi/ZnO/CsF/Al.
The preparation of this Organnic electroluminescent device comprises the following steps and preparation technology:
The operating pressure of preparation is 1 × 10
-5pa, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal is 2nm/s, and the sputtering rate of oxide semiconductor film is 5nm/s, and the evaporation rate of electron beam is 0.2nm/s, and the energy density of electron beam evaporation is 100W/cm
2, the accelerating voltage of magnetron sputtering is 800V, power density 40W/cm
2.
Prepare anode at light-transparent substrate surface vacuum sputter, material is IZO, and thickness is 200nm;
At described anode surface successively Evaporation preparation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer.
Hole injection layer material is Phthalocyanine Zinc (ZnPc), thickness is 10nm, hole transport layer material is N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), thickness is 60nm, and emitting layer material is that phosphor material three (2-phenylpyridine) closes iridium (Ir (ppy)
3) be entrained in material of main part 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), Ir (ppy)
3be 10:100 with the mass ratio of TPBi, light emitting layer thickness is 20nm, and the material of electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), and thickness is 60nm.
Deposited by electron beam evaporation prepares the first electron injection auxiliary layer on the electron transport layer, and material is zinc oxide (ZnO), and thickness is 4nm;
Adopt thermal resistance Evaporation preparation second electron injection auxiliary layer at the first electron injecting layer, material is cesium fluoride (CsF), and thickness is 1nm;
Second electron injecting layer prepares negative electrode, and cathode material is metal A g, and thickness is 200nm.
Test result: starting resistor 3.7V, luminosity is 1000cd/m
2time luminous efficiency be 14.4lm/W.
Embodiment 3
The structure of organic electroluminescence device is glass substrate/AZO/VOPc/m-MTDATA/DCJTB:Alq
3/ BCP/ZnO/NaF/Al-Mg.
The preparation of this Organnic electroluminescent device comprises the following steps and preparation technology:
The operating pressure of preparation is 1 × 10
-4pa, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal is 1nm/s, and the sputtering rate of oxide semiconductor film is 2nm/s, and the evaporation rate of electron beam is 0.2nm/s, and the energy density of electron beam evaporation is 60W/cm
2, the accelerating voltage of magnetron sputtering is 600V, power density 20W/cm
2.
Prepare anode at light-transparent substrate surface vacuum sputter, material is AZO, and thickness is 100nm;
At described anode surface successively Evaporation preparation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer;
The material of hole injection layer is ranadylic phthalocyanine (VOPc), thickness is 20nm, hole transport layer material is 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), thickness is 40nm, emitting layer material is fluorescent material 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB) is entrained in material of main part oxine aluminium (Alq
3) in, DCJTB and Alq
3mass ratio be 1:100, light emitting layer thickness is 1nm, and the material of electron transfer layer is 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), and thickness is 40nm;
Deposited by electron beam evaporation prepares the first electron injection auxiliary layer on the electron transport layer, and material is zinc oxide (ZnO), and thickness is 2nm;
Adopt thermal resistance Evaporation preparation second electron injection auxiliary layer at the first electron injecting layer, material is sodium fluoride (NaF), and thickness is 0.5nm;
Second electron injecting layer prepares negative electrode, and cathode material is Al-Mg alloy, and thickness is 100nm.
Test result: starting resistor 3.7V, luminosity is 1000cd/m
2time luminous efficiency be 8.2lm/W.
Embodiment 4
The structure of organic electroluminescence device is glass substrate/GZO/TiOPc/MeO-TPD/DPVBi/Alq
3/ ZnO/KF/Ag-Mg.
The preparation of this Organnic electroluminescent device comprises the following steps and preparation technology:
The operating pressure of preparation is 1 × 10
-4pa, the evaporation rate of organic material is 0.5nm/s, and the evaporation rate of metal is 1nm/s, and the sputtering rate of oxide semiconductor film is 2nm/s, and the evaporation rate of electron beam is 0.1nm/s, and the energy density of electron beam evaporation is 80W/cm
2, the accelerating voltage of magnetron sputtering is 400V, power density 20W/cm
2.。
Prepare anode at light-transparent substrate surface vacuum sputter, material is GZO, and thickness is 120nm;
At described anode surface successively Evaporation preparation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, and negative electrode.
Hole injection layer material is TiOPc (TiOPc), and thickness is 10nm, and hole transport layer material is N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD), thickness is 40nm, emitting layer material is fluorescent material 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), light emitting layer thickness is 15nm, and the material of electron transfer layer is oxine aluminium (Alq
3), thickness is 35nm;
Deposited by electron beam evaporation prepares the second electron injection auxiliary layer on the electron transport layer, and material is zinc oxide (ZnO), and thickness is 3nm;
Adopt thermal resistance Evaporation preparation first electron injection auxiliary layer at the second electron injecting layer, material is potassium fluoride (KF), and thickness is 1nm;
Second electron injecting layer prepares negative electrode, and cathode material is Ag-Mg alloy, and thickness is 120nm.
Test result: starting resistor 3.9V, luminosity is 1000cd/m
2time luminous efficiency be 6.8lm/W.
Comparative example 1
The material of electron injection auxiliary layer is made into organic material LiF single layer structure, thickness is 1nm, does not adopt ZnO as electron injecting layer, and all the other are all with embodiment 1.
Test result: starting resistor 3.8V, luminosity is 1000cd/m
2time luminous efficiency be 9.8lm/W.
Preparation equipment in the embodiment of the present invention is high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd).In addition, adopt the USB4000 fiber spectrometer testing electroluminescent spectrum of marine optics (Ocean Optics) company of the U.S., adopt the Keithley2400 current/voltage tester test electric property of Keithley company of the U.S., adopt CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Fig. 2 is the Current density-voltage characteristic curve of embodiment 1 and comparative example 1.As can be seen from the figure, under identical driving voltage, employing bielectron in embodiment 1 injects the Organnic electroluminescent device of auxiliary layer, its drive current is higher than the Organnic electroluminescent device adopting single electron to inject the comparative example 1 of auxiliary layer, such as, voltage is when 6V, and the drive current density that embodiment 1 obtains is 82.5mA/cm
2, and adopt single electron implanted layer only to obtain 54.2mA/cm
2drive current.Therefore, the bielectron adopted in the embodiment of the present invention injects the injection that auxiliary layer is more conducive to electronics, thus can reduce the starting resistor of Organnic electroluminescent device, and improves its luminous efficiency.
Above disclosedly be only present pre-ferred embodiments, certainly can not limit the interest field of the present invention with this, therefore according to the equivalent variations that the claims in the present invention are done, still belong to the scope that the present invention is contained.
Claims (10)
1. an Organnic electroluminescent device, is characterized in that, described device comprises substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the first electron injection auxiliary layer, second electron injection auxiliary layer and the negative electrode of stacked above one another; The material of described first electron injection auxiliary layer is zinc oxide, and the material of described second electron injection auxiliary layer is lithium fluoride, cesium fluoride, sodium fluoride, at least one in potassium fluoride, and the material of described negative electrode is silver, aluminium, almag or silver-colored magnesium alloy.
2. Organnic electroluminescent device as claimed in claim 1, it is characterized in that, the thickness of described first electron injection auxiliary layer is 1 ~ 4nm.
3. Organnic electroluminescent device as claimed in claim 1, it is characterized in that, the thickness of described second electron injection auxiliary layer is 0.5 ~ 2nm.
4. Organnic electroluminescent device as claimed in claim 1, it is characterized in that, described substrate is transparency carrier.
5. Organnic electroluminescent device as claimed in claim 1, it is characterized in that, the material of described anode is indium tin oxide, indium-zinc oxide, aluminium zinc oxide or gallium zinc oxide, and the thickness of described anode is 70 ~ 200nm.
6. Organnic electroluminescent device as claimed in claim 1, it is characterized in that, the material of described hole injection layer is Phthalocyanine Zinc, CuPc, ranadylic phthalocyanine, TiOPc, and the thickness of described hole injection layer is 10-30nm.
7. Organnic electroluminescent 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-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyls)-1,1'-biphenyl-4,4'-diamines or N, N, N', N '-tetramethoxy phenyl-benzidine, the thickness of described hole transmission layer is 20-60nm.
8. Organnic electroluminescent device as claimed in claim 1, it is characterized in that, described luminescent layer 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 and three (2-phenylpyridine) and close one or more luminescent materials and material of main part in iridium and adulterate and form, described material of main part is CBP(4, 4'-bis-(9-carbazole) biphenyl), Alq
3(oxine aluminium), TPBi (1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene) or NPB (N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines), the mass ratio of described luminescent material and described material of main part is 1:100 ~ 15:100, or, described luminescent layer is 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl, DPAVBi (4, 4'-two [4-(di-p-tolyl is amino) styryl] biphenyl), 5, 6, 11, at least one in 12-tetraphenyl naphthonaphthalene and dimethylquinacridone, the thickness of described luminescent layer is 1 ~ 20nm.
9. Organnic electroluminescent 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, described electric transmission layer thickness is 20-60nm.
10. a preparation method for Organnic electroluminescent device, is characterized in that, described method comprises:
Substrate is provided;
Anode is prepared at described substrate surface vacuum splashing and plating;
At described anode surface successively vacuum evaporation hole injection layer, hole transmission layer, luminescent layer and electron transfer layer;
Prepare the first electron injection auxiliary layer by electron beam evaporation plating on the electron transport layer, the material of described first electron injection auxiliary layer is zinc oxide;
Described first electron injection auxiliary layer prepares the second electron injection auxiliary layer by thermal resistance evaporation, and the material of described second electron injection auxiliary layer is alkali-metal fluoride;
Described second electron injection auxiliary layer prepares negative electrode, obtains Organnic electroluminescent device.
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