CN104638144A - Organic light-emitting device and production method thereof - Google Patents
Organic light-emitting device and production method thereof Download PDFInfo
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Abstract
The invention relates to an organic light-emitting device and a production method thereof. The organic light-emitting device is of a layered structure and comprises an anode conducting substrate, a hole injection layer, a hole transmission layer, a light-emitting layer, an electron transmission layer, an electron injection layer and a cathode layer which are stacked in sequence; the electron injection layer comprises a rubidium compound layer, a ternary doping layer and a rhenium compound layer; the rubidium compound layer is made of rubidium carbonate, rubidium chloride and rubidium nitrate or rubidium sulfate, the ternary doping layer is made of materials of low-work function metal, high-work function metal and metal sulfide. The rubidium compound layer in the electron injection layer is low in melting point and easy to evaporate and plate; work function is low due to existing of metal ions, electron injection barrier between the electron transmission layer and the injection layer can be lowered, and injection of electrons is benefited.
Description
Technical field
The present invention relates to field of optoelectronic devices, particularly relate to a kind of organic electroluminescence device.The invention still further relates to the preparation method of this organic electroluminescence device.
Background technology
1987, C.W.Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.Utilize ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED), its brightness under 10V reaches 1000cd/m
2, its luminous efficiency is 1.51lm/W, the life-span is greater than 100 hours.
But in existing organic electroluminescence device, electron injecting layer is one of important functional layer, in the fabrication process, because the exclusion of water oxygen of electron injecting layer selected materials is indifferent, steam can infiltrate via crack and affect the electrical of thin-film transistor.Selected materials is also unfavorable for the injection being conducive to electronics simultaneously, therefore the transmission rate of electronics is lower, two or three orders of magnitude lower than hole transport speed, therefore, very easily cause the low of exciton recombination probability, and easily make the region of its compound not in light-emitting zone, thus luminous efficiency is reduced.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, provide a kind of organic electroluminescence device and preparation method thereof to improve the light extraction efficiency of organic electroluminescence device.
The present invention is directed to above-mentioned technical problem and the technical scheme proposed is: a kind of organic electroluminescence device, this organic electroluminescence device is layer structure, this layer structure is: the anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually, and described electron injecting layer comprises rubidium compound layer, ternary doping layer and rhenium compound layer; Wherein, the material of described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate;
The material of described ternary doping layer is low workfunction metal, high-work-function metal and metal sulfide composition; The material of described low work function is magnesium, strontium, calcium or ytterbium, and work function is-2.0eV ~-3.5eV;
The material of described high-work-function metal is silver, aluminium, platinum or gold, and work function is-4.0 ~-5.5eV;
The material of described metal sulfide is zinc sulphide, magnesium sulfide, vulcanized sodium or copper sulfide;
The material of described rhenium compound layer is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums.
The doping mass ratio of described low workfunction metal, high-work-function metal and metal sulfide is 4:1:1 ~ 20:10:1.
The thickness of described rubidium compound layer is 5-20nm, and the thickness of described ternary doping layer is 40-80nm, and the thickness of described rhenium compound layer is 2-10nm.
The material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide;
The material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine;
The material of 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, 9,10-bis--β-naphthylene anthracene, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl or oxine aluminium;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole;
The material of described negative electrode is silver, aluminium, platinum or gold.
The present invention also proposes a kind of preparation method of organic electroluminescence device, it comprises the steps: (a) glass after the cleaning prepares conductive anode film by magnetron sputtering apparatus and obtains anode conducting substrate, then on described anode conducting substrate evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively;
B () uses thermal resistance evaporated device on the electron transfer layer that step (a) is obtained, adopt thermal resistance evaporation to prepare rubidium compound layer, then on described rubidium compound layer, thermal resistance evaporation is adopted to prepare ternary doping layer, on described ternary doping layer, thermal resistance evaporation prepares rhenium compound layer again, thus obtains electron injecting layer; Wherein,
The material of described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate;
The material of described ternary doping layer is low workfunction metal, high-work-function metal and metal sulfide composition; The material of described low work function is magnesium, strontium, calcium or ytterbium, and work function is-2.0eV ~-3.5eV;
The material of described high-work-function metal is silver, aluminium, platinum or gold, and work function is-4.0 ~-5.5eV;
The material of described metal sulfide is zinc sulphide, magnesium sulfide, vulcanized sodium or copper sulfide;
The material of described rhenium compound layer is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums.
C () evaporation on the electron injecting layer that step (b) is obtained prepares cathode layer, thus obtain described organic electroluminescence device.
In described step (a), the accelerating voltage of described magnetron sputtering apparatus is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 1 ~ 40W/cm
2; The evaporation rate of described hole transmission layer, luminescent layer and electron transfer layer is 0.1 ~ 1nm/s.
In described step (b), the evaporation rate of described thermal resistance evaporation is 0.1 ~ 1nm/s; The thickness of described rubidium compound layer is 5-20nm, and the thickness of described ternary doping layer is 40-80nm, and the thickness of described rhenium compound layer is 2-10nm.
The evaporation rate of described cathode layer is 1 ~ 10nm/s.
Compared with prior art, there is following advantage in organic electroluminescence devices of the present invention and preparation method thereof:
The performance of each component of described electron injecting layer is as follows: rubidium compound layer due to its fusing point lower, easy evaporation, owing to there being the existence of metal ion, work function is lower, the electron injection potential barrier between electron transfer layer and implanted layer can be reduced, be conducive to the injection of electronics, and metal ion can strengthen the transmission rate of electronics further, the thickness of rubidium compound layer is 5-20nm simultaneously, this thickness is moderate, rubidium compound layer can be avoided blocked up and form cluster, thus form electronic defects and affect the transmission of electric charge, also rubidium compound layer can be avoided too thin and cause electronics to lose transmission path, thus reduction transmission rate,
Ternary doping layer is low workfunction metal, high-work-function metal and metal sulfide composition, low workfunction metal is more active, free electron can movement in a large number, device conducts can be improved, high-work-function metal stable in properties, the stability of low workfunction metal can be improved, avoid oxidation reaction occurs, metal sulfide film forming is better, the electron trap of rete can be effectively avoided to exist, reflection can be produced to light simultaneously, improve light extraction efficiency, simultaneously, low workfunction metal, the doping mass ratio of high-work-function metal and metal sulfide is 4:1:1 ~ 20:10:1, the performance of low workfunction metal and high-work-function metal can be ensured in this scope, also can prevent metal sulfide from too much making material lose activity, thus be unfavorable for transmitting charge carrier, the thickness of ternary doping layer is 40 ~ 80nm in addition, this thickness is moderate, ternary doping layer can be avoided blocked up and form electronic defects, also can avoid too thin and be punctured by electric current, thus organic electroluminescence device is burnt out,
The HOMO energy level of rhenium compound is comparatively dark, can traverse to negative electrode by blocking hole, effectively avoid the generation of hole quenching phenomenon.The thickness of rhenium compound layer is 2 ~ 10nm simultaneously, this thickness is moderate, can avoid blocked up and make passivation layer form cluster, thus form electronic defects and affect the transmission of electric charge, also can avoid too thin and cause electronics to lose transmission path, thus reducing transmission rate.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 1.
Fig. 2 is the graph of a relation of the organic electroluminescence device of embodiment 1 and the current density of comparative example and current efficiency.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
Organic electroluminescence device of the present invention is layer structure, and every layer is followed successively by: anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.
To the preparation method of above-mentioned organic electroluminescence device, specifically comprise the following steps:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
Conductive anode film preparing by the glass 2, after above-mentioned steps cleans and obtain anode conducting substrate, then on anode conducting substrate, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively.
3, then on above-mentioned electron transfer layer, prepare electron injecting layer, electron injecting layer is described electron injecting layer is rubidium compound layer, ternary doping layer and rhenium compound layer form.
First adopt the rubidium compound described in thermal resistance evaporation, its material is rubidium carbonate (Rb
2cO
3), rubidium chloride (RbCl), rubidium nitrate (RbNO
3) or rubidium sulfate (Rb
2sO
4), thickness is 5-20nm;
Adopt ternary doping layer described in thermal resistance evaporation again, its material is low workfunction metal, high-work-function metal and metal sulfide.The material of described low work function is magnesium (Mg), strontium (Sr), calcium (Ca) or ytterbium (Yb).The material of described high-work-function metal is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).The material of described metal sulfide is zinc sulphide (ZnS), magnesium sulfide (MgS), vulcanized sodium (Na
2or copper sulfide (CuS) S).The doping mass ratio of described low workfunction metal, high-work-function metal and metal sulfide is 4:1:1 ~ 20:10:1;
Then adopt thermal resistance evaporation rhenium compound layer, thickness is 40-80nm, and its material is rhenium heptoxide (Re
2o
7), rhenium trioxide (ReO
3), rhenium dioxide (ReO
2) or oxidation two rhenium (Re
2o), thickness is 2-10nm.
4, finally metallic cathode is prepared.
In organic electroluminescence device, material and the thickness of other functional layers are as follows:
Described glass is available glass.
Described anode conducting substrate is indium and tin oxide film (ITO), mix the zinc-oxide film (AZO) of aluminium or mix the zinc-oxide film (IZO) of indium, and adopt magnetron sputtering preparation, thickness is 50-300nm, and be preferably ITO, thickness is 100nm.
Anode conducting substrate comprises conductive anode film and glass, the material of its conductive anode film is conductive oxide, comprise tin indium oxide (ITO), Al-Doped ZnO (AZO), mix indium zinc oxide (IZO) or mix any one of fluorine zinc oxide (FTO), the material of its substrate can be glass, plastics or metal, can make by oneself, also can commercially obtain.In actual applications, the material can other being selected as required suitable is as anode conducting substrate.In actual applications, the anode pattern of required organic electroluminescence device can be prepared on anode conducting substrate.Anode conducting substrate is prior art, does not repeat them here.
Described hole injection layer material adopts molybdenum trioxide (MoO
3), also can adopt tungstic acid (WO
3) or vanadic oxide (V
2o
5), thickness is 20-80nm, is preferably MoO
3, thickness is 25nm.
What described hole mobile material adopted is 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).Thickness is 20-60nm, and be preferably TCTA, thickness is 50nm.
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 (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl (BCzVBi), oxine aluminium (Alq
3), thickness is 5-40nm, and be preferably BCzVBi, thickness is preferably 24nm.
Described electron transfer layer adopts 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI), and thickness is 40-250nm, and be preferably Bphen, thickness is 150nm.
Described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and thickness is 80-250nm, and be preferably Ag, thickness is 150nm.
With embodiment 1 ~ 4, organic electroluminescence device of the present invention and preparation method thereof is illustrated below:
Embodiment 1
As shown in Figure 1, the organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
The anode conducting substrate 101 of glass/IZO, MoO
3the luminescent layer 104 of the hole injection layer 102 of material, the hole transmission layer 103 of TAPC material, ADN material, the electron transfer layer 105 of TPBI material, the rubidium compound layer 106 of RbCl material, the ternary doping layer 107 of Sr:Ag:MgS material, ReO
2the rhenium compound layer 108 of material and the cathode layer 109 of Ag material.Rubidium compound layer 106, ternary doping layer 107 and rhenium compound layer 108 form electron injecting layer.(wherein brace "/" represents layer structure, and colon ": " represents doping mutually).
Above-mentioned organic electroluminescence device is prepared successively as follows:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
2, under the glass after above-mentioned steps 1 being cleaned is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 700V, the magnetic field of 120G and 250W/cm
2power density, use magnetron sputtering apparatus on glass, to prepare material for IZO and the thickness conductive anode film that is 50nm, thus obtained anode conducting substrate 101.
Technological parameter prepared by thermal resistance evaporation, under the preparation of thermal resistance evaporation, is set to the evaporation rate and 8 × 10 of 0.2nm/s by anode conducting substrate 101 transposition 3, then step 2 be prepared into
-4the operating pressure of Pa, use thermal resistance evaporation be prepared in anode conducting substrate 101 successively deposition material for tungstic acid and the thickness hole injection layer 102 that is 25nm, material are 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane and thickness are the hole transmission layer 103 of 50nm, material is 9,10-bis--β-naphthylene anthracene and thickness is the luminescent layer 104 of 24nm, material is N-aryl benzimidazole and thickness is the electron transfer layer 105 of 150nm.
4, then on above-mentioned electron transfer layer 105, rubidium compound layer 106, ternary doping layer 107 and rhenium compound layer 108 is prepared successively:
First adopt thermal resistance evaporation to prepare rubidium compound layer 106, material is RbCl, and obtained thickness is 10nm;
Then the doping mass ratio adopting thermal resistance evaporation to prepare the ternary doping layer 107, Sr:Ag:MgS of Sr:Ag:MgS material on rubidium compound layer 106 is 10:3:1, and obtained thickness is 50nm;
Then on rubidium compound doped layer 107, adopt thermal resistance evaporation rhenium compound layer 108, thickness is 5nm, and material is ReO
2.
5, last evaporation prepares metal cathode layer 109, and evaporation rate is 2nm/s, and material used is silver, and thickness is 80nm, thus obtains required electroluminescent device.
Fig. 2 is the organic electroluminescence device of the present embodiment 1 and the current density of general device and the graph of a relation of current efficiency.
Test and Preparation equipment are high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), 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 structure of described general device is simple glass/ITO/MoO
3/ TCTA/BCzVBi/Bphen/CsF/Ag.In Fig. 2, abscissa is the size of current density, ordinate is the size of luminous efficiency, and curve 1 is the current density of embodiment 1 organic electroluminescence device and the relation curve of luminous efficiency, and curve 2 is the current density of comparative example device and the relation curve of luminous efficiency.
As seen from Figure 2, under different current density, the luminous efficiency of embodiment 1 is all larger than comparative example, luminous efficiency is 5.22lm/W, and comparative example be only 4.11lm/W, , and the luminous efficiency of comparative example declines fast along with the increase of current density, this explanation, electron injecting layer of the present invention can penetrate in organic layer by the metal ion in block electrons implanted layer and negative electrode, reduce the electron injection potential barrier between electron transfer layer and implanted layer, be conducive to the injection of electronics, and the transmission rate of electronics can be strengthened, improve the stability of doped layer, negative electrode can be traversed to by blocking hole, effectively avoid the generation of hole quenching phenomenon.This method is conducive to the luminous efficiency improving device.
Embodiment 2
The layer structure of the organic electroluminescence device of following examples 2-4 is substantially identical with the layer structure of embodiment 1, therefore no longer adds at this and illustrate.
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
The anode conducting substrate of glass/IZO, MoO
3the hole injection layer of material, the hole transmission layer of TAPC material, the luminescent layer of ADN material, the electron transfer layer of TPBI material, Rb
2cO
3the rubidium compound layer of material, the ternary doping layer of Mg:Al:ZnS material, ReO
3the rhenium compound layer of material and the cathode layer of Ag material.Passivation layer, rubidium compound doped layer and rhenium compound layer composition electron injecting layer.(wherein brace "/" represents layer structure, and colon ": " represents doping mutually).
Above-mentioned organic electroluminescence device is prepared successively as follows:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
2, under the glass after above-mentioned steps 1 being cleaned is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 700V, the magnetic field of 120G and 250W/cm
2power density, use magnetron sputtering apparatus on glass, to prepare material for IZO and the thickness conductive anode film that is 50nm, thus obtained anode conducting substrate.
Technological parameter prepared by thermal resistance evaporation, under the preparation of thermal resistance evaporation, is set to the evaporation rate and 8 × 10 of 0.2nm/s by the anode conducting substrate transposition 3, then step 2 be prepared into
-4the operating pressure of Pa, use thermal resistance evaporation be prepared in anode conducting substrate 101 successively deposition material for tungstic acid and the thickness hole injection layer that is 25nm, material are 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane and thickness are the hole transmission layer of 50nm, material is 9,10-bis--β-naphthylene anthracene and thickness be 24nm luminescent layer, material is N-aryl benzimidazole and thickness is the electron transfer layer of 150nm.
4, then on above-mentioned electron transfer layer, rubidium compound layer, ternary doping layer and rhenium compound layer is prepared successively:
First adopt thermal resistance evaporation to prepare rubidium compound layer, material is Rb
2cO
3, obtained thickness is 20nm;
Then on rubidium compound layer, adopt thermal resistance evaporation to prepare the ternary doping layer of Mg:Al:ZnS material, the doping mass ratio of Mg:Al:ZnS is 20:10:1, and obtained thickness is 40nm;
Then on rubidium compound doped layer, adopt thermal resistance evaporation rhenium compound layer, thickness is 2nm, and material is ReO
2.
5, last evaporation prepares metal cathode layer, and evaporation rate is 2nm/s, and material used is Pt, and thickness is 80nm, thus obtains required electroluminescent device.
Embodiment 3
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
The anode conducting substrate of glass/ITO, WO
3the hole injection layer of material, the hole transmission layer of TAPC material, the luminescent layer of ADN material, the electron transfer layer of TPBI material, RbNO
3the rubidium compound layer of material, Ca:Pt:Na
2the ternary doping layer of S material, Re
2o
7the rhenium compound layer of material and the cathode layer of Ag material.Passivation layer, rubidium compound doped layer and rhenium compound layer composition electron injecting layer.(wherein brace "/" represents layer structure, and colon ": " represents doping mutually).
Above-mentioned organic electroluminescence device is prepared successively as follows:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
2, under the glass after above-mentioned steps 1 being cleaned is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 700V, the magnetic field of 120G and 250W/cm
2power density, use magnetron sputtering apparatus on glass, to prepare material for IZO and the thickness conductive anode film that is 50nm, thus obtained anode conducting substrate.
Technological parameter prepared by thermal resistance evaporation, under the preparation of thermal resistance evaporation, is set to the evaporation rate and 5 × 10 of 0.1nm/s by the anode conducting substrate transposition 3, then step 2 be prepared into
-5the operating pressure of Pa, use thermal resistance evaporation be prepared in anode conducting substrate successively deposition material be WO
3, thickness is the hole injection layer of 20nm, material is TAPC, and thickness is the hole transmission layer of 60nm, material is ADN, and thickness is the luminescent layer of 10nm, material is TPBi, and thickness is the electron transfer layer of 200nm.
4, then on above-mentioned electron transfer layer, rubidium compound layer, ternary doping layer and rhenium compound layer is prepared successively:
First adopt thermal resistance evaporation to prepare rubidium compound layer, material is RbNO
3, obtained thickness is 5nm;
Then on rubidium compound layer, adopt thermal resistance evaporation to prepare Ca:Pt:Na
2the ternary doping layer of S material, Ca:Pt:Na
2the doping mass ratio of S is 4:1:1, and obtained thickness is 80nm;
Then on ternary doping layer, adopt thermal resistance evaporation rhenium compound layer, thickness is 10nm, and material is Re
2o
7.
5, last evaporation prepares metal cathode layer, and evaporation rate is 2nm/s, and material used is Ag, and thickness is 100nm, thus obtains required electroluminescent device.
Embodiment 4
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
The anode conducting substrate of glass/IZO, V
2o
5the hole injection layer of material, the hole transmission layer of TCTA material, Alq
3the luminescent layer of material, the electron transfer layer of TAZ material, Rb
2sO
4the rubidium compound layer of material, the ternary doping layer of Yb:Au:CuS material, Re
2the rhenium compound layer of O material and the cathode layer of Ag material.Passivation layer, rubidium compound doped layer and rhenium compound layer composition electron injecting layer.(wherein brace "/" represents layer structure, and colon ": " represents doping mutually).
Above-mentioned organic electroluminescence device is prepared successively as follows:
1, after glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.
2, under the glass after above-mentioned steps 1 being cleaned is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 600V, the magnetic field of 100G and 30W/cm
2power density, use magnetron sputtering apparatus on glass, to prepare material for IZO and the thickness conductive anode film that is 180nm, thus obtained anode conducting substrate.
Technological parameter prepared by thermal resistance evaporation, under the preparation of thermal resistance evaporation, is set to the evaporation rate and 2 × 10 of 0.5nm/s by the anode conducting substrate transposition 3, then step 2 be prepared into
-4the operating pressure of Pa, use thermal resistance evaporation be prepared in anode conducting substrate successively deposition material be V
2o
5, thickness is the hole injection layer of 80nm, material is TCTA, and thickness is the hole transmission layer of 60nm, material is Alq
3, thickness is the luminescent layer of 40nm, material is TAZ, and thickness is the electron transfer layer of 35nm.
4, then on above-mentioned electron transfer layer, rubidium compound layer, ternary doping layer and rhenium compound layer is prepared successively::
First adopt thermal resistance evaporation to prepare rubidium compound layer, material is Rb
2sO
4, obtained thickness is 15nm;
Then on ternary doping layer, adopt thermal resistance evaporation to prepare the ternary doping layer of Yb:Au:CuS material, the doping mass ratio of Yb:Au:CuS is 15:5:1, and obtained thickness is 60nm;
Then on ternary doping layer, adopt thermal resistance evaporation rhenium compound layer, thickness is 6nm, and material is Re
2o.
5, last evaporation prepares metal cathode layer, and evaporation rate is 2nm/s, and material used is Al, and thickness is 250nm, thus obtains required electroluminescent device.
Compared with prior art, organic electroluminescence devices of the present invention and preparation method thereof, there is following advantage: rubidium compound layer due to its fusing point lower, easy evaporation, owing to there being the existence of metal ion, work function is lower, the electron injection potential barrier between electron transfer layer and implanted layer can be reduced, be conducive to the injection of electronics, and metal ion can strengthen the transmission rate of electronics further, ternary doping layer is low workfunction metal, high-work-function metal and metal sulfide composition, low workfunction metal is more active, free electron can movement in a large number, device conducts can be improved, high-work-function metal stable in properties, the stability of low workfunction metal can be improved, avoid oxidation reaction occurs, metal sulfide film forming is better, the electron trap of rete can be effectively avoided to exist, reflection can be produced to light simultaneously, improve light extraction efficiency, the HOMO energy level of rhenium compound is darker, negative electrode can be traversed to by blocking hole, effectively avoid the generation of hole quenching phenomenon.This method is conducive to the luminous efficiency improving device.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection range required by claims.
Claims (8)
1. an organic electroluminescence device, this organic electroluminescence device is layer structure, it is characterized in that, this layer structure is: the anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually, and described electron injecting layer comprises rubidium compound layer, ternary doping layer and rhenium compound layer; Wherein, the material of described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate;
The material of described ternary doping layer is low workfunction metal, high-work-function metal and metal sulfide composition; The material of described low work function is magnesium, strontium, calcium or ytterbium, and work function is-2.0eV ~-3.5eV;
The material of described high-work-function metal is silver, aluminium, platinum or gold, and work function is-4.0 ~-5.5eV;
The material of described metal sulfide is zinc sulphide, magnesium sulfide, vulcanized sodium or copper sulfide;
The material of described rhenium compound layer is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums.
2. organic electroluminescence device according to claim 1, is characterized in that, the doping mass ratio of described low workfunction metal, high-work-function metal and metal sulfide is 4:1:1 ~ 20:10:1.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described rubidium compound layer is 5-20nm, and the thickness of described ternary doping layer is 40-80nm, and the thickness of described rhenium compound layer is 2-10nm.
4. organic electroluminescence device according to claim 1, is characterized in that,
The material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide;
The material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine;
The material of 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, 9,10-bis--β-naphthylene anthracene, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl or oxine aluminium;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole;
The material of described negative electrode is silver, aluminium, platinum or gold.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
A () glass after the cleaning prepares conductive anode film by magnetron sputtering apparatus and obtains anode conducting substrate, then on described anode conducting substrate evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer successively;
B () uses thermal resistance evaporated device on the electron transfer layer that step (a) is obtained, adopt thermal resistance evaporation to prepare rubidium compound layer, then on described rubidium compound layer, thermal resistance evaporation is adopted to prepare ternary doping layer, on described ternary doping layer, thermal resistance evaporation prepares rhenium compound layer again, thus obtains electron injecting layer; Wherein,
The material of described rubidium compound is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate;
The material of described ternary doping layer is low workfunction metal, high-work-function metal and metal sulfide composition; The material of described low work function is magnesium, strontium, calcium or ytterbium, and work function is-2.0eV ~-3.5eV;
The material of described high-work-function metal is silver, aluminium, platinum or gold, and work function is-4.0 ~-5.5eV;
The material of described metal sulfide is zinc sulphide, magnesium sulfide, vulcanized sodium or copper sulfide;
The material of described rhenium compound layer is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums;
C () evaporation on the electron injecting layer that step (b) is obtained prepares cathode layer, thus obtain described organic electroluminescence device.
6. preparation method according to claim 5, is characterized in that, in described step (a), the accelerating voltage of described magnetron sputtering apparatus is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 1 ~ 40 W/cm
2; The evaporation rate of described hole transmission layer, luminescent layer and electron transfer layer is 0.1 ~ 1nm/s.
7. preparation method according to claim 5, is characterized in that, in described step (b), the evaporation rate of described thermal resistance evaporation is 0.1 ~ 1nm/s; The thickness of described rubidium compound layer is 5-20nm, and the thickness of described ternary doping layer is 40-80nm, and the thickness of described rhenium compound layer is 2-10nm.
8. preparation method according to claim 5, is characterized in that, in described step (c), the evaporation rate of described cathode layer is 1 ~ 10nm/s.
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Application publication date: 20150520 |