CN104659227A - Organic electroluminescent device and manufacturing method thereof - Google Patents
Organic electroluminescent device and manufacturing method thereof Download PDFInfo
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- CN104659227A CN104659227A CN201310589173.7A CN201310589173A CN104659227A CN 104659227 A CN104659227 A CN 104659227A CN 201310589173 A CN201310589173 A CN 201310589173A CN 104659227 A CN104659227 A CN 104659227A
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Abstract
The invention discloses an organic electroluminescent device and a manufacturing method thereof. The organic electroluminescent device comprises a glass substrate, a conductive anode, a hole injection layer, a hole transmission layer, a luminous layer, an electron transmission layer, an electron injection layer and a cathode which are stacked in sequence, wherein the electron injection layer comprises a rhenium compound doped layer, a rubidium compound layer and a metal layer which are stacked in sequence; the rhenium compound doped layer is arranged on the surface of the electron transmission layer and made from a mixed material formed by mixing a rhenium compound with a bipolar organic material at a mass ratio of (1:1) to (4:1); the rubidium compound layer is made from rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate; the metal layer is made from low-work-function metal with the work function ranging from -2.0 eV to -3.5 eV. The electron injection layer can effectively improve the luminous efficiency of the 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
1987, C.W.Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.Ultrathin film technology is utilized to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).Under 10V, brightness reaches 1000cd/m
2, its luminous efficiency is 1.51lm/W, and the life-span is greater than 100 hours.
Under the principle of luminosity of OLED is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
In traditional organic electroluminescence device, all low than hole transport speed two or three orders of magnitude of electron transfer rate, therefore, very easily cause the low of exciton recombination probability, further, make the region of exciton compound not at light-emitting zone, thus device light emitting efficiency is reduced.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of organic electroluminescence device and preparation method thereof, described organic electroluminescence device, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described electron injecting layer comprises the rhenium compound doped layer, rubidium compound layer and the metal level that stack gradually, and described electron injecting layer can improve the luminous efficiency of organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the substrate of glass stacked gradually, conductive anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described electron injecting layer comprises the rhenium compound doped layer stacked gradually, rubidium compound layer and metal level, described rhenium compound doped layer is arranged on described electron transfer layer on the surface, the material of described rhenium compound doped layer is rhenium compound and bipolar organic material is composite material that the ratio of 1:1 ~ 4:1 is formed in mass ratio, described rhenium compound is rhenium heptoxide (Re
2o
7), rhenium trioxide (ReO
3), rhenium dioxide (ReO
2) or oxidation two rhenium (Re
2o), described bipolar organic material is 2,4,6-tri-(N-phenyl-1-naphthylamino)-1,3,5-triazines (TRZ4), 2,6-bis-(3-(9H-carbazole-9-base) benzene) pyridine (2,6Dczppy), 3 ', 3 "-(4-(naphthalene-1-base)-4H-1, 2,4-triazole-3,5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) (p-TPAm-NTAZ) or 2, and two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1,3,4-oxadiazoles (CzOXD), the material of described rubidium compound layer is rubidium carbonate (Rb
2cO
3), rubidium chloride (RbCl), rubidium nitrate (RbNO
3) or rubidium sulfate (Rb
2sO
4), the low workfunction metal of the material of described metal level to be work function be-2.0eV ~-3.5eV.
Preferably, described work function is the low work function of-2.0eV ~-3.5eV is magnesium (Mg), strontium (Sr), calcium (Ca) or ytterbium (Yb).
Preferably, the thickness of described rhenium compound doped layer is 10 ~ 30nm, and the thickness of described rubidium compound layer is 1 ~ 5nm, and the thickness of described metal level is 5 ~ 20nm.
Preferably, described conductive anode is the one in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide glass (IZO), and thickness is 50 ~ 300nm, and more preferably, described conductive anode is ITO, and thickness is 160nm.
Preferably, the material of described hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in one, thickness is 20 ~ 80nm.More preferably, the material of described hole injection layer is MoO
3, thickness is 36nm.
Preferably, the material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N; N '-diphenyl-4; one in 4 '-benzidine (NPB), the thickness of described hole transmission layer is 20 ~ 60nm, more preferably; the material of described hole transmission layer is NPB, and thickness is 40nm.
Preferably, 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 (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in one, thickness is 5 ~ 40nm, and more preferably, the material of described luminescent layer is BCzVBi, and thickness is 15nm.
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI), thickness is 40 ~ 250nm, more preferably, the material of described electron transfer layer is Bphen, and thickness is 75nm.
Preferably, the material of described cathode layer is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and the thickness of described cathode layer is 80 ~ 250nm, and more preferably, the material of described cathode layer is Ag, and thickness is 145nm.
Electron injecting layer of the present invention comprises the rhenium compound doped layer stacked gradually, rubidium compound layer and metal level, rhenium compound doped layer is made up of rhenium compound and bipolar organic material, rhenium compound film forming is better, rete planarization can be improved, reduce the existence of rete defect, simultaneously, 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, bipolar organic material has the effect of transporting holes and transmission electronic, the transmission rate of electronics can be improved, simultaneously, reduce the electron injection potential barrier between adjacent layer, improve its electron injection efficiency, rubidium compound fusing point is lower, easy evaporation, owing to there being the existence of rubidium ion, work function is lower, is conducive to the injection of electronics, reduce the electron injection potential barrier between negative electrode and electron injecting layer, improve electron injection efficiency, meanwhile, the easy ejected electron of rubidium, electron concentration is higher, can further improve the transmission rate of electronics, metal level is made up of low workfunction metal (work function is-2.0eV ~-3.5eV), the reflection of light can be improved after low workfunction metal film forming, can reduce the electron injection potential barrier of negative electrode and electron injecting layer, this method is conducive to the luminous efficiency improving device simultaneously.
In described rhenium compound doped layer, the mass ratio of rhenium compound and bipolar organic material is 1:1 ~ 4:1, when the mass ratio of rhenium compound and bipolar organic material is greater than 4:1, electron injection efficiency and electric transmission efficiency little, be unfavorable for injection and the transmission of electronics; When the mass ratio of rhenium compound and bipolar organic material is less than 1:1, electron injecting layer rete defect is more, thus causes electronics cancellation by defect capture.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises following operating procedure:
(1) substrate of glass is provided, dry after cleaning; Adopt the method for magnetron sputtering to prepare anode on the glass substrate, on described anode, then adopt the method for thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively;
(2) prepare electron injecting layer on the electron transport layer, concrete grammar is:
The method of thermal resistance evaporation is adopted to prepare rhenium compound doped layer on the electron transport layer, the material of described rhenium compound doped layer is rhenium compound and bipolar organic material is composite material that the ratio of 1:1 ~ 4:1 is formed in mass ratio, described rhenium compound is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums, described bipolar organic material is 2, 4, 6-tri-(N-phenyl-1-naphthylamino)-1, 3, 5-triazine, 2, 6-bis-(3-(9H-carbazole-9-base) benzene) pyridine, 3 ', 3 "-(4-(naphthalene-1-base)-4H-1, 2, 4-triazole-3, 5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) or 2, two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1, 3, 4-oxadiazole, during described thermal resistance evaporation, pressure is 5 × 10
-5pa ~ 2 × 10
-3pa, described evaporation rate is 0.1 ~ 1nm/s,
Described rhenium compound doped layer adopts the method for thermal resistance evaporation to prepare rubidium compound layer, and the material of described rubidium compound layer is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate, and during described thermal resistance evaporation, pressure is 5 × 10
-5pa ~ 2 × 10
-3pa, evaporation rate is 1 ~ 10nm/s;
Described rubidium compound layer adopts the method for thermal resistance evaporation to prepare described metal level, and the low work function of the material of described metal level to be work function be-2.0eV ~-3.5eV, during described thermal resistance evaporation, pressure is 5 × 10
-5pa ~ 2 × 10
-3pa, evaporation rate is 1 ~ 10nm/s;
(3) on described electron injecting layer, adopt the method for thermal resistance evaporation to prepare negative electrode, obtain described organic electroluminescence device.
Preferably, described work function is the low work function of-2.0eV ~-3.5eV is magnesium (Mg), strontium (Sr), calcium (Ca) or ytterbium (Yb).
Preferably, the thickness of described rhenium compound doped layer is 10 ~ 30nm, and the thickness of described rubidium compound layer is 1 ~ 5nm, and the thickness of described metal level is 5 ~ 20nm.
When adopting the method for thermal resistance evaporation to prepare described rhenium compound doped layer, described evaporation raw material is rhenium compound and bipolar organic material is composite material that the ratio of 1:1 ~ 4:1 is formed in mass ratio.
Preferably, when adopting magnetron sputtering to prepare described anode, accelerating voltage is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 1 ~ 40W/cm
2.
Preferably, the thermal resistance evaporation condition of described hole injection layer and cathode layer is: pressure is 5 × 10
-5pa ~ 2 × 10
-3pa, evaporation rate is 1 ~ 10nm/s.
Preferably, the thermal resistance evaporation condition of described hole transmission layer, electron transfer layer and luminescent layer is: pressure is 5 × 10
-5pa ~ 2 × 10
-3pa, evaporation rate is 0.1 ~ 1nm/s.
Preferably, after described cleaning, substrate of glass is used liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol by dry be operating as successively, removes the organic pollution of glass surface, cleans up rear air-dry.
Preferably, described conductive anode is the one in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide glass (IZO), and thickness is 50 ~ 300nm, and more preferably, described conductive anode is ITO, and thickness is 160nm.
Preferably, the material of described hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in one, thickness is 20 ~ 80nm.More preferably, the material of described hole injection layer is MoO
3, thickness is 36nm.
Preferably, the material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N; N '-diphenyl-4; one in 4 '-benzidine (NPB), the thickness of described hole transmission layer is 20 ~ 60nm, more preferably; the material of described hole transmission layer is NPB, and thickness is 40nm.
Preferably, 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 (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in one, thickness is 5 ~ 40nm, and more preferably, the material of described luminescent layer is BCzVBi, and thickness is 15nm.
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI), thickness is 40 ~ 250nm, more preferably, the material of described electron transfer layer is Bphen, and thickness is 75nm.
Preferably, the material of described cathode layer is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and the thickness of described cathode layer is 80 ~ 250nm, and more preferably, the material of described cathode layer is Ag, and thickness is 145nm.
Electron injecting layer of the present invention comprises the rhenium compound doped layer stacked gradually, rubidium compound layer and metal level, rhenium compound doped layer is made up of rhenium compound and bipolar organic material, rhenium compound film forming is better, rete planarization can be improved, reduce the existence of rete defect, simultaneously, 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, bipolar organic material has the effect of transporting holes and transmission electronic, the transmission rate of electronics can be improved, simultaneously, reduce the electron injection potential barrier between adjacent layer, improve its electron injection efficiency, rubidium compound fusing point is lower, easy evaporation, owing to there being the existence of rubidium ion, work function is lower, is conducive to the injection of electronics, reduce the electron injection potential barrier between negative electrode and electron injecting layer, improve electron injection efficiency, meanwhile, the easy ejected electron of rubidium, electron concentration is higher, can further improve the transmission rate of electronics, metal level is made up of low workfunction metal (work function is-2.0eV ~-3.5eV), the reflection of light can be improved after low workfunction metal film forming, the electron injection potential barrier of negative electrode and electron injecting layer can be reduced simultaneously, can improve the reflection of light after low workfunction metal film forming, this method is conducive to the luminous efficiency improving device.
Preparation method's technique of electron injecting layer of the present invention is simple, and cost is low.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) electron injecting layer provided by the invention improves the luminous efficiency of organic electroluminescence device;
(2) preparation method of electron injecting layer provided by the invention, technique is simple, and cost is low.
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 the organic electroluminescence device that the embodiment of the present invention 1 provides;
Fig. 2 is current density and the luminous efficiency graph of a relation of the embodiment of the present invention 1 and comparative example's 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) first commercially available simple glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up rear air-dry; Then adopt the method for magnetron sputtering to prepare the ITO that thickness is 160nm on the glass substrate, the accelerating voltage of magnetron sputtering is 700V, and magnetic field is 120G, and power density is 25W/cm
2; Then on anode, adopt the method for thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively; Wherein,
The material of hole injection layer is MoO
3, the pressure 8 × 10 adopted during evaporation
-4pa, evaporation rate is 2nm/s, and evaporation thickness is 36nm;
The material of hole transmission layer is NPB, and the pressure adopted during evaporation is 8 × 10
-4pa, evaporation rate is 0.2nm/s, and evaporation thickness is 40nm;
The material of luminescent layer is BCzVBi, and the pressure adopted during evaporation is 8 × 10
-4pa, evaporation rate is 0.2nm/s, and evaporation thickness is 15nm;
The material of electron transfer layer is Bphen, and the pressure adopted during evaporation is 8 × 10
-4pa, evaporation rate is 0.2nm/s, and evaporation thickness is 75nm;
(2) electron injecting layer is prepared;
Adopt the method for thermal resistance evaporation to prepare the rhenium compound doped layer that thickness is 18nm on the electron transport layer, the material of rhenium compound doped layer is ReO
3with CzOXD according to mass ratio be 3:1 formed composite material, the pressure adopted during evaporation is 8 × 10
-4pa, evaporation rate is 0.2nm/s;
Then on rhenium compound doped layer, adopt the method for thermal resistance evaporation to prepare the rubidium compound layer that thickness is 2nm, the material of rubidium compound layer is Rb
2cO
3, the pressure adopted during evaporation is 8 × 10
-4pa, evaporation rate is 2nm/s;
Rubidium compound layer adopts the method for thermal resistance evaporation prepare metal level that thickness is 15nm, the material of metal level is Ca, and the pressure adopted during evaporation is 8 × 10
-4pa, evaporation rate is 2nm/s;
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device, the material of negative electrode is Ag, and thickness is 145nm, the pressure 8 × 10 adopted during evaporation
-4pa, evaporation rate is 2nm/s.
Fig. 1 is the structural representation of organic electroluminescence device prepared by the present embodiment, as shown in Figure 1, organic electroluminescence device prepared by the present embodiment, comprise the substrate of glass 1, conductive anode 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and the negative electrode 8 that stack gradually, electron injecting layer 7 comprises the rhenium compound doped layer 71, rubidium compound layer 72 and the metal level 73 that stack gradually.Concrete structure is expressed as:
Glass/ITO/MoO
3/ NPB/BCzVBi/Bphen/ReO
3: CzOXD(3:1)/Rb
2cO
3/ Ca/Ag, wherein, slash "/" represents and stacks gradually, ReO
3: colon ": " in CzOXD represents mixing, and 3:1 represents the mass ratio of the former and the latter, and the meaning that in Examples hereinafter, each symbol represents is identical.
Embodiment 2
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) first commercially available simple glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up rear air-dry; Then adopt the method for magnetron sputtering to prepare the AZO that thickness is 300nm on the glass substrate, the accelerating voltage of magnetron sputtering is 300V, and magnetic field is 50G, and power density is 40W/cm
2; Then on anode, adopt the method for thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively; Wherein,
The material of hole injection layer is WO
3, the pressure 2 × 10 adopted during evaporation
-3pa, evaporation rate is 10nm/s, and evaporation thickness is 20nm;
The material of hole transmission layer is TAPC, and the pressure adopted during evaporation is 2 × 10
-3pa, evaporation rate is 1nm/s, and evaporation thickness is 45nm;
The material of luminescent layer is ADN, and the pressure adopted during evaporation is 2 × 10
-3pa, evaporation rate is 1nm/s, and evaporation thickness is 10nm;
The material of electron transfer layer is TPBi, and the pressure adopted during evaporation is 2 × 10
-3pa, evaporation rate is 1nm/s, and evaporation thickness is 65nm;
(2) electron injecting layer is prepared;
Adopt the method for thermal resistance evaporation to prepare the rhenium compound doped layer that thickness is 30nm on the electron transport layer, the material of rhenium compound doped layer is Re
2o
7with TRZ4 according to mass ratio be 1:1 formed composite material, the pressure adopted during evaporation is 2 × 10
-3pa, evaporation rate is 1nm/s;
Then on rhenium compound doped layer, adopt the method for thermal resistance evaporation to prepare the rubidium compound layer that thickness is 1nm, the material of rubidium compound layer is Rb
2sO
4, the pressure adopted during evaporation is 2 × 10
-3pa, evaporation rate is 10nm/s;
Rubidium compound layer adopts the method for thermal resistance evaporation prepare metal level that thickness is 5nm, the material of metal level is Sr, and the pressure adopted during evaporation is 2 × 10
-3pa, evaporation rate is 10nm/s;
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device, the material of negative electrode is Al, and thickness is 80nm, the pressure 2 × 10 adopted during evaporation
-3pa, evaporation rate is 10nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the substrate of glass, conductive anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, electron injecting layer comprises the rhenium compound doped layer, rubidium compound layer and the metal level that stack gradually.Concrete structure is expressed as: glass/AZO/WO
3/ TAPC/ADN/TPBi/Re
2o
7: TRZ4(1:1)/Rb
2sO
4/ Sr/Al.
Embodiment 3
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) first commercially available simple glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up rear air-dry; Then adopt the method for magnetron sputtering to prepare the ITO that thickness is 180nm on the glass substrate, the accelerating voltage of magnetron sputtering is 800V, and magnetic field is 200G, and power density is 1W/cm
2; Then on anode, adopt the method for thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively; Wherein,
The material of hole injection layer is MoO
3, the pressure 5 × 10 adopted during evaporation
-5pa, evaporation rate is 1nm/s, and evaporation thickness is 40nm;
The material of hole transmission layer is NPB, and the pressure adopted during evaporation is 5 × 10
-5pa, evaporation rate is 0.1nm/s, and evaporation thickness is 20nm;
The material of luminescent layer is Alq
3, the pressure adopted during evaporation is 5 × 10
-5pa, evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
The material of electron transfer layer is TAZ, and the pressure adopted during evaporation is 5 × 10
-5pa, evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
(2) electron injecting layer is prepared;
Adopt the method for thermal resistance evaporation to prepare the rhenium compound doped layer that thickness is 10nm on the electron transport layer, the material of rhenium compound doped layer is ReO
2with 2,6Dczppy according to mass ratio be 4:1 formed composite material, the pressure adopted during evaporation is 5 × 10
-5pa, evaporation rate is 0.1nm/s;
Then on rhenium compound doped layer, adopt the method for thermal resistance evaporation to prepare the rubidium compound layer that thickness is 5nm, the material of rubidium compound layer is RbCl, and the pressure adopted during evaporation is 5 × 10
-5pa, evaporation rate is 1nm/s;
Rubidium compound layer adopts the method for thermal resistance evaporation prepare metal level that thickness is 20nm, the material of metal level is Mg, and the pressure adopted during evaporation is 5 × 10
-5pa, evaporation rate is 1nm/s;
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device, the material of negative electrode is Pt, and thickness is 250nm, the pressure 5 × 10 adopted during evaporation
-5pa, evaporation rate is 1nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the substrate of glass, conductive anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, electron injecting layer comprises the rhenium compound doped layer, rubidium compound layer and the metal level that stack gradually.Concrete structure is expressed as:
Glass/ITO/MoO
3/ NPB/Alq
3/ TAZ/ReO
2: 2,6Dczppy(4:1)/RbCl/Mg/Pt.
Embodiment 4
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) first commercially available simple glass is used liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface, clean up rear air-dry; Then adopt the method for magnetron sputtering to prepare the IZO that thickness is 50nm on the glass substrate, the accelerating voltage of magnetron sputtering is 600V, and magnetic field is 100G, and power density is 30W/cm
2; Then on anode, adopt the method for thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively; Wherein,
The material of hole injection layer is V
2o
5, the pressure 2 × 10 adopted during evaporation
-4pa, evaporation rate is 6nm/s, and evaporation thickness is 80nm;
The material of hole transmission layer is TCTA, and the pressure adopted during evaporation is 2 × 10
-4pa, evaporation rate is 0.5nm/s, and evaporation thickness is 60nm;
The material of luminescent layer is DCJTB, and the pressure adopted during evaporation is 2 × 10
-4pa, evaporation rate is 0.5nm/s, and evaporation thickness is 5nm;
The material of electron transfer layer is Bphen, and the pressure adopted during evaporation is 2 × 10
-4pa, evaporation rate is 0.5nm/s, and evaporation thickness is 250nm;
(2) electron injecting layer is prepared;
Adopt the method for thermal resistance evaporation to prepare the rhenium compound doped layer that thickness is 12nm on the electron transport layer, the material of rhenium compound doped layer is Re
2o and p-TPAm-NTAZ is the composite material that 3.5:1 is formed according to mass ratio, and the pressure adopted during evaporation is 2 × 10
-4pa, evaporation rate is 0.5nm/s;
Then on rhenium compound doped layer, adopt the method for thermal resistance evaporation to prepare the rubidium compound layer that thickness is 1.5nm, the material of rubidium compound layer is RbNO
3, the pressure adopted during evaporation is 2 × 10
-4pa, evaporation rate is 6nm/s;
Rubidium compound layer adopts the method for thermal resistance evaporation prepare metal level that thickness is 13nm, the material of metal level is Yb, and the pressure adopted during evaporation is 2 × 10
-4pa, evaporation rate is 6nm/s;
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device, the material of negative electrode is Au, and thickness is 100nm, the pressure 2 × 10 adopted during evaporation
-4pa, evaporation rate is 6nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the substrate of glass, conductive anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, electron injecting layer comprises the rhenium compound doped layer, rubidium compound layer and the metal level that stack gradually.Concrete structure is expressed as: glass/IZO/V
2o
5/ TCTA/DCJTB/Bphen/Re
2o:p-TPAm-NTAZ(3.5:1)/RbNO
3/ Yb/Au.
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 that the electron injecting layer in comparative example is individual layer, material is CsF, thickness is 1nm, and the concrete structure of comparative example's organic electroluminescence device is: glass/ITO/MoO
3/ NPB/BCzVBi/Bphen/CsF/Ag, respectively corresponding substrate of glass, conductive anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Effect example
Adopt the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the current-voltage tester Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Konica Minolta company of Japan and colourity, obtain the change curve of luminous efficiency with current density of organic electroluminescence device, to investigate the luminous efficiency of device, tested object is the organic electroluminescence device that embodiment 1 is prepared with comparative example.Test result as shown in Figure 2.
Fig. 2 is the embodiment of the present invention 1 and the luminous efficiency of comparative example's organic electroluminescence device and the graph of a relation of current density.As can be seen from Figure 2, under different current density, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum luminous efficiency of embodiment 1 is 5.65lm/W, and comparative example be only 3.74lm/W, meanwhile, along with the increase of current density, the ratio of the luminous efficiency decay of comparative example is very fast, and the decay of embodiment 1 is slower.This illustrates, electron injecting layer of the present invention can improve the transmission rate of electronics, stops hole traverse to negative electrode and cause hole cancellation, simultaneously, reduce the electron injection potential barrier between electron injecting layer and cathode layer, improve electron injection efficiency, this method is conducive to the luminous efficiency improving device.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, comprises the substrate of glass stacked gradually, conductive anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, is characterized in that, described electron injecting layer comprises the rhenium compound doped layer stacked gradually, rubidium compound layer and metal level, described rhenium compound doped layer is arranged on described electron transfer layer on the surface, the material of described rhenium compound doped layer is rhenium compound and bipolar organic material is the composite material that the ratio of 1:1 ~ 4:1 is formed in mass ratio, and described rhenium compound is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums, described bipolar organic material is 2,4,6-tri-(N-phenyl-1-naphthylamino)-1,3,5-triazines, 2,6-bis-(3-(9H-carbazole-9-base) benzene) pyridine, 3 ', 3 "-(4-(naphthalene-1-base)-4H-1,2,4-triazole-3,5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) or two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 2,5-) phenyl)-1,3,4-oxadiazoles, the material of described rubidium compound layer is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate, the low workfunction metal of the material of described metal level to be work function be-2.0eV ~-3.5eV.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, described work function is the low workfunction metal of-2.0eV ~-3.5eV is magnesium, strontium, calcium or ytterbium.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described rhenium compound doped layer is 10 ~ 30nm, and the thickness of described rubidium compound layer is 1 ~ 5nm, and the thickness of described metal level is 5 ~ 20nm.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole injection layer is the one in molybdenum trioxide, tungstic acid and vanadic oxide.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4 ', 4 "-three (carbazole-9-base) triphenylamine and N; the one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).
6. organic electroluminescence device as claimed in claim 1, it is characterized in that, 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, one in 4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl and oxine aluminium.
7. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, one in 2,4-triazole and N-aryl benzimidazole.
8. a preparation method for organic electroluminescence device, is characterized in that, comprises following operating procedure:
(1) substrate of glass is provided, dry after cleaning; Adopt the method for magnetron sputtering to prepare anode on the glass substrate, on described anode, then adopt the method for thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively;
(2) prepare electron injecting layer on the electron transport layer, concrete grammar is:
The method of thermal resistance evaporation is adopted to prepare rhenium compound doped layer on the electron transport layer, the material of described rhenium compound doped layer is rhenium compound and bipolar organic material is composite material that the ratio of 1:1 ~ 4:1 is formed in mass ratio, described rhenium compound is rhenium heptoxide, rhenium trioxide, rhenium dioxide or oxidation two rheniums, described bipolar organic material is 2, 4, 6-tri-(N-phenyl-1-naphthylamino)-1, 3, 5-triazine, 2, 6-bis-(3-(9H-carbazole-9-base) benzene) pyridine, 3 ', 3 "-(4-(naphthalene-1-base)-4H-1, 2, 4-triazole-3, 5-bis-base) two (N, N-bis-(xenyl)-4-ammonia) or 2, two (4-(9-(2-the ethylhexyl)-9H-carbazole-3-base of 5-) phenyl)-1, 3, 4-oxadiazole, during described thermal resistance evaporation, pressure is 5 × 10
-5pa ~ 2 × 10
-3pa, described evaporation rate is 0.1 ~ 1nm/s,
Described rhenium compound doped layer adopts the method for thermal resistance evaporation to prepare rubidium compound layer, and the material of described rubidium compound layer is rubidium carbonate, rubidium chloride, rubidium nitrate or rubidium sulfate, and during described thermal resistance evaporation, pressure is 5 × 10
-5pa ~ 2 × 10
-3pa, evaporation rate is 1 ~ 10nm/s;
Described rubidium compound layer adopts the method for thermal resistance evaporation to prepare described metal level, and the low workfunction metal of the material of described metal level to be work function be-2.0eV ~-3.5eV, during described thermal resistance evaporation, pressure is 5 × 10
-5pa ~ 2 × 10
-3pa, evaporation rate is 1 ~ 10nm/s;
(3) on described electron injecting layer, adopt the method for thermal resistance evaporation to prepare negative electrode, obtain described organic electroluminescence device.
9. the preparation method of organic electroluminescence device as claimed in claim 8, it is characterized in that, described work function is the low workfunction metal of-2.0eV ~-3.5eV is magnesium, strontium, calcium or ytterbium.
10. the preparation method of organic electroluminescence device as claimed in claim 8, it is characterized in that, the thickness of described rhenium compound doped layer is 10 ~ 30nm, and the thickness of described rubidium compound layer is 1 ~ 5nm, and the thickness of described metal level is 5 ~ 20nm.
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| CN107799571A (en) * | 2017-10-12 | 2018-03-13 | 武汉华星光电半导体显示技术有限公司 | Organic light emitting diode device and display device |
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| CN107799571A (en) * | 2017-10-12 | 2018-03-13 | 武汉华星光电半导体显示技术有限公司 | Organic light emitting diode device and display device |
| US10665804B2 (en) | 2017-10-12 | 2020-05-26 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Organic light emitting diode and display device |
| CN107799571B (en) * | 2017-10-12 | 2020-10-09 | 武汉华星光电半导体显示技术有限公司 | Organic light emitting diode device and display device |
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