CN104051643A - Laminated organic electroluminescent device and manufacturing method thereof - Google Patents
Laminated organic electroluminescent device and manufacturing method thereof Download PDFInfo
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- CN104051643A CN104051643A CN201310078434.9A CN201310078434A CN104051643A CN 104051643 A CN104051643 A CN 104051643A CN 201310078434 A CN201310078434 A CN 201310078434A CN 104051643 A CN104051643 A CN 104051643A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
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Abstract
The invention discloses a laminated organic electroluminescent device. The laminated organic electroluminescent device comprises an anode, a first function layer, a charge generation layer, a second function layer and a cathode which are sequentially laminated, wherein the charge generation layer comprises a bipolar metal oxide layer and a rhenium oxide layer which are sequentially laminated, the bipolar metal oxide layer is much closer to the anode than the rhenium oxide layer, the bipolar metal oxide layer has relatively strong transmittance in a visible light scope, the bipolar metal oxide layer is taken as an electron injection layer of the laminated organic electroluminescent device and has electron injection and electron transmission capabilities, and the rhenium oxide layer improves hole injection and transmission capabilities. The laminated organic electroluminescent device can effectively improve electron and hole regeneration capabilities, and thereby light emitting efficiency is improved. The invention further provides a manufacturing method for the laminated organic electroluminescent device.
Description
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of laminated organic electroluminescent device and preparation method thereof.
Background technology
1987, the C.W.Tang of Eastman Kodak company of the U.S. and VanSlyke reported the breakthrough in organic electroluminescent research.Utilize ultrathin film technology 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, the life-span is greater than 100 hours.
The principle of luminosity of OLED is based under the effect of extra electric field, and 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.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.At present, in order to improve luminosity and luminous efficiency, increasing research is taking laminated device as main, this structure is normally together in series several luminescence units as articulamentum with charge generation layer, compared with unit component, multilayer devices often has current efficiency and luminosity at double, at present research many be utilize two or more to have that hole is injected or material of electronic injection as charge generating layers (as Cs:BCP/V
2o
5), or N-shaped and p-type doped layer as charge generation layer (as N-shaped (Alq
3: Li) and p-type (NPB:FeCl
3)) or Al-WO
3-Au etc. are linked in sequence multiple luminescence units and form, but this charge generation layer at least needs to carry out more than twice operation, brings certain complexity to preparation.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of laminated organic electroluminescent device, comprise the anode, the first functional layer, charge generation layer, the second functional layer and the negative electrode that stack gradually, charge generation layer comprises the bipolarity metal oxide layer that stacks gradually and the oxide skin(coating) of rhenium, and described bipolarity metal oxide layer is more close to described anode than the oxide skin(coating) of rhenium; Bipolarity metal oxide layer has stronger transmitance in visible-range, and bipolarity metal oxide layer, as the electron injecting layer of laminated device, plays electronic injection and electron transport ability, and the oxide of rhenium improves injection and the transmittability in hole.Meanwhile, the present invention also provides a kind of preparation method of above-mentioned laminated organic electroluminescent device, and the present invention prepares charge generation layer and only uses the method for evaporation to prepare, and method is simple.
First aspect, the invention provides a kind of laminated organic electroluminescent device, comprise the anode, the first functional layer, charge generation layer, the second functional layer and the negative electrode that stack gradually, described charge generation layer comprises the bipolarity metal oxide layer that stacks gradually and the oxide skin(coating) of rhenium, and described bipolarity metal oxide layer is more close to described anode than the oxide skin(coating) of rhenium; Described bipolarity metal oxide layer material is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in one, the oxide skin(coating) material of described rhenium is rhenium dioxide (ReO
2), rhenium heptoxide (Re
2o
7), rhenium sesquioxide (Re
2o
3) and oxidation two rhenium (Re
2o) one in, the first functional layer and the second functional layer include luminescent layer.
Preferably, described bipolarity metal oxide layer thickness is 5～20nm.
Preferably, the oxide skin(coating) thickness of described rhenium is 2～10nm.
Preferably, described the first functional layer comprises the hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually.
Preferably, described the second functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the electron injecting layer that stack gradually.
In the present embodiment, functional layer is two, and charge generation layer is one; In other embodiment, luminescent layer can be also three, four or more, and charge generation layer is two, three or more, between every two adjacent functional layers, is provided with a charge generation layer.
The functional layer structure of each lamination organic electroluminescence device can be identical, also can be not identical.The first functional layer and the second functional layer can only comprise luminescent layer, all the other each layer of structures, as: hole injection layer, hole transmission layer, electronic barrier layer, hole blocking layer, electron transfer layer and electron injecting layer, can add arbitrarily according to demand, also can not add.
Preferably, described anode substrate is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Preferably, described hole injection layer material is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in one, thickness is 20～80nm;
More preferably, described hole injection layer material is WO
3, thickness is 50nm.
Preferably, described the first hole transmission layer and the second hole transmission layer material are 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, the one in 4 '-benzidine (NPB), thickness is 20～60nm.
More preferably, the first hole transmission layer material is NPB, and thickness is 40nm, and the second hole transmission layer material is TCTA, and thickness is 60nm.
Preferably, described the first luminescent layer and the second luminescent layer material are 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in one, thickness is 5～40nm.
More preferably, described the first luminescent layer and the second luminescent layer material are Alq
3, thickness is 15nm.
Preferably, described the first electron transfer layer is identical with the second electron transfer layer material, be 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI), thickness is 40～200nm.
More preferably, described the first electron transfer layer material is TPBI, and thickness is 60nm, and described the second electron transfer layer material is TAZ, and thickness is 80nm.
Preferably, described electron injecting layer material is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) in one, thickness is 0.5～10nm;
More preferably, described electron injecting layer material is LiF, and thickness is 0.7nm.
Preferably, described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and thickness is 60～300nm.
More preferably, described negative electrode is Ag, and thickness is 100nm.
Adopt the oxide skin(coating) of bipolarity metal oxide layer and rhenium as the charge generation layer of laminated organic electroluminescent device, bipolarity metal oxide has stronger transmitance (90%～95%) in visible-range, and can be used as the electron injecting layer of laminated organic electroluminescent device, improve injection and the transmission of electronics, and the be about-6.5eV of oxide work function of rhenium, be suitable as hole injection layer, improve injection and the transmittability in hole, therefore, can be used as the hole injection layer of laminated organic electroluminescent device, improve injection and the transmission in hole, charge generation layer can effectively improve the power of regeneration in electronics and hole, thereby raising luminous efficiency.
Second aspect, the invention provides a kind of preparation method of laminated organic electroluminescent device, comprises following operating procedure:
Required size anode is provided, dry after cleaning;
At described anode surface successively evaporation the first functional layer and charge generation layer; Described charge generation layer comprises the bipolarity metal oxide layer that stacks gradually and the oxide skin(coating) of rhenium, and described bipolarity metal oxide layer is more close to described anode than the oxide skin(coating) of rhenium; Described bipolarity metal oxide layer material is the one in molybdenum trioxide, tungstic acid and vanadic oxide; The oxide skin(coating) material of described rhenium is the one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums; The oxide skin(coating) evaporation condition of bipolarity metal oxide layer and rhenium is: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 1～10nm/s;
Evaporation the second functional layer and negative electrode successively on charge generation layer, finally obtain laminated organic electroluminescent device.
Preferably, described the first functional layer comprises the hole injection layer, the first cave transport layer, the first luminescent layer and the first electron transfer layer that stack gradually, all can adopt the method preparation of evaporation.
Preferably, described the second functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the electron injecting layer that stack gradually, all can adopt the method preparation of evaporation.
Preferably, described bipolarity metal oxide layer thickness is 5～20nm.
Preferably, the oxide skin(coating) thickness of described rhenium is 2～10nm.
Preferably, the evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 1～10nm/s.
Preferably, described the first hole transmission layer, the first luminescent layer, the first electron transfer layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 0.1～1nm/s.
Preferably, described anode substrate is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Preferably, described in the anode of required size is provided, concrete operations are: anode substrate is carried out to photoetching treatment, be then cut into needed size.
Preferably, anode is used successively liquid detergent by being operating as that described cleaning is dried afterwards, deionized water, and acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry.
Preferably, described hole injection layer material is molybdenum trioxide MoO
3, WO
3and V
2o
5in one, thickness is 20～80nm;
More preferably, hole injection layer material is WO
3, thickness is 50nm.
Preferably, the first described hole transmission layer is identical with the second hole transmission layer material, is the one in TAPC, TCTA and NPB, and thickness is 20～60nm.
More preferably, the first hole transmission layer material is for being NPB, and thickness is 40nm, and the second hole transmission layer material is TCTA, and thickness is 60nm.
Preferably, described the first luminescent layer and the second luminescent layer material are DCJTB, ADN, BCzVBi and Alq
3in one, thickness is 5～40nm.
More preferably, described the first luminescent layer and the second luminescent layer material are Alq
3, thickness is 15nm.
Preferably, the first and second described electron transfer layer materials are identical, are the one in Bphen, TAZ and TPBI, and thickness is 40～200nm.
More preferably, described the first electron transfer layer is TPBI, and thickness is 60nm, and described the second electron transfer layer is TAZ, and thickness is 80nm.
Preferably, described electron injecting layer material is Cs
2cO
3, CsF, CsN
3with the one in LiF, thickness is 0.5～10nm;
More preferably, described electron injecting layer is preferably LiF, and thickness is 0.7nm.
Preferably, described negative electrode is the one in Ag, Al, Pt and Au, and thickness is 60～300nm.
More preferably, described negative electrode is Ag, and thickness is 100nm.
Adopt the oxide skin(coating) of bipolarity metal oxide layer and rhenium as the charge generation layer of laminated organic electroluminescent device, bipolarity metal oxide has stronger transmitance (90%～95%) in visible-range, simultaneously, bipolarity metal oxide can be used as the electron injecting layer of laminated device, improve injection and the transmission of electronics, and the be about-6.5eV of oxide work function of rhenium, be suitable as hole injection layer, improve injection and the transmittability in hole, therefore, can be used as the hole injection layer of laminated organic electroluminescent device, improve injection and the transmission in hole, charge generation layer can effectively improve the power of regeneration in electronics and hole, thereby raising luminous efficiency.The present invention prepares charge generation layer and only uses the method for evaporation to prepare, and method is simple.
Brief description of the drawings
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in execution mode be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of the embodiment of the present invention 3 laminated organic electroluminescent devices;
Fig. 2 is brightness and the luminous efficiency graph of a relation of the embodiment of the present invention 3 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 laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected ito glass, first anode is carried out to photoetching treatment, is then cut into 2 × 2cm
2square anode, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation the first luminescent layer on anode, the material of the first luminescent layer is Alq
3, evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 15nm;
(2) evaporation charge generation layer on the first luminescent layer, first evaporation bipolarity metal oxide layer on the first luminescent layer, bipolarity metal oxide layer material is MoO
3, thickness is 10nm, evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s, and then on bipolarity metal oxide layer, evaporation is prepared the oxide skin(coating) of rhenium, and the oxide skin(coating) material of rhenium is Re
2o
7, thickness is 15nm, evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s;
(3) evaporation the second luminescent layer and negative electrode successively on the oxide skin(coating) of rhenium, same to step (1) first luminescent layer of the second luminescent layer material and preparation method, the material of negative electrode is Ag, and thickness is 100nm, and evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s.
Embodiment 2
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected AZO glass, first anode is carried out to photoetching treatment, is cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation the first luminescent layer on anode, the material of the first luminescent layer is DCJTB, evaporation pressure is 2 × 10
-4pa, evaporation speed is 1nm/s, evaporation thickness is 5nm;
(2) evaporation charge generation layer on the first luminescent layer, first evaporation bipolarity metal oxide layer on the first luminescent layer, bipolarity metal oxide layer material is WO
3, thickness is 5nm, evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, and then on bipolarity metal oxide layer, evaporation is prepared the oxide skin(coating) of rhenium, and the oxide skin(coating) material of rhenium is Re
2o
3, thickness is 10nm, when evaporation, pressure is 2 × 10
-4pa, evaporation speed is 10nm/s;
(3) evaporation the second luminescent layer and negative electrode successively on the oxide skin(coating) of rhenium, the second luminescent layer material is BCzVBi, same to step (1) first luminescent layer of preparation method, thickness is 40nm, and the material of negative electrode is Pt, and thickness is 60nm, and when evaporation, pressure is 2 × 10
-4pa, evaporation speed is 10nm/s.
Embodiment 3
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected ito glass, first anode is carried out to photoetching treatment, is cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is WO
3, thickness is 50nm, evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s; The first hole transmission layer material is NPB, and thickness is 40nm, and the material of the first luminescent layer is Alq
3, thickness is 15nm, and the first electron transfer layer material is TPBI, and thickness is 60nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation bipolarity metal oxide layer on the first electron transfer layer, bipolarity metal oxide layer material is MoO
3, thickness is 10nm, evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s, and then on bipolarity metal oxide layer, evaporation is prepared the oxide skin(coating) of rhenium, and the oxide skin(coating) material of rhenium is Re
2o
7, thickness is 15nm, evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on the oxide skin(coating) of rhenium, the second hole transmission layer material is TCTA, thickness is 60nm, same step (1) first luminescent layer of the second luminescent layer material and preparation method, the second electron transfer layer material is TAZ, thickness is 80nm, electron injecting layer material is LiF, thickness is 0.7nm, and the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s; The material of negative electrode is Ag, and thickness is 100nm, and evaporation pressure is 5 × 10
-3pa, evaporation speed is 1nm/s.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, organic electroluminescence device prepared by the present embodiment, comprise the anode 1, hole injection layer 2, the first hole transmission layer 3, the first luminescent layer 4, the first electron transfer layer 5, charge generation layer 6, the second hole transmission layer 7, the second luminescent layer 8, the second electron transfer layer 9, electron injecting layer 10 and the negative electrode 11 that stack gradually, charge generation layer comprises the bipolarity metal oxide layer 61 that stacks gradually and the oxide skin(coating) 62 of rhenium.Concrete structure is expressed as:
Ito glass/WO
3/ NPB/Alq
3/ TPBI/MoO
3/ Re
2o
7/ TCTA/Alq
3/ TAZ/LiF/Ag.
Embodiment 4
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected AZO glass, first anode is carried out to photoetching treatment, is cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is V
2o
5, thickness is 80nm, evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s; The first hole transmission layer material is TCTA, and thickness is 60nm, and the material of the first luminescent layer is DCJTB, thickness is 5nm, the first electron transfer layer material is Bphen, and thickness is 40nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 2 × 10
-4pa, evaporation speed is 1nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation bipolarity metal oxide layer on the first electron transfer layer, bipolarity metal oxide layer material is WO
3, thickness is 5nm, evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s, and then on bipolarity metal oxide layer, evaporation is prepared the oxide skin(coating) of rhenium, and the oxide skin(coating) material of rhenium is Re
2o
3, thickness is 10nm, evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on the oxide skin(coating) of rhenium, the second hole transmission layer material is TAPC, thickness is 20nm, the second luminescent layer material is BCzVBi, thickness is 40nm, same to step (1) first luminescent layer of the second luminescent layer preparation method, and the second electron transfer layer material is TAZ, thickness is 200nm, and electron injecting layer material is CsN
3, thickness is 0.5nm, the second hole transmission layer, luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 2 × 10
-4pa, evaporation speed is 1nm/s; The material of negative electrode is Pt, and thickness is 60nm, and evaporation pressure is 2 × 10
-4pa, evaporation speed is 10nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises the bipolarity metal oxide layer that stacks gradually and the oxide skin(coating) of rhenium.Concrete structure is expressed as:
AZO glass/V
2o
5/ TCTA/DCJTB/Bphen/WO
3/ Re
2o
3/ TAPC/BCzVBi/TAZ/CsN
3/ Pt.
Embodiment 5
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected IZO glass, first anode is carried out to photoetching treatment, is cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is WO
3, thickness is 20nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s; The first hole transmission layer material is NPB, and thickness is 30nm, and the material of the first luminescent layer is ADN, thickness is 10nm, the first electron transfer layer material is TPBI, and thickness is 40nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 1 × 10
-3pa, evaporation speed is 0.5nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation bipolarity metal oxide layer on the first electron transfer layer, bipolarity metal oxide layer material is V
2o
5, thickness is 20nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s, and then on bipolarity metal oxide layer, evaporation is prepared the oxide skin(coating) of rhenium, and the oxide skin(coating) material of rhenium is ReO
2, thickness is 2nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on the oxide skin(coating) of rhenium, the second hole transmission layer material is TCTA, thickness is 60nm, the second luminescent layer material is DCJTB, thickness is 5nm, same to step (1) first luminescent layer of the second luminescent layer preparation method, and the second electron transfer layer material is Bphen, thickness is 40nm, and electron injecting layer material is Cs
2cO
3, thickness is 10nm, the second hole transmission layer, luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 1 × 10
-3pa, evaporation speed is 1nm/s; The material of negative electrode is Al, and thickness is 300nm, and evaporation pressure is 1 × 10
-3pa, evaporation speed is 10nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises the bipolarity metal oxide layer that stacks gradually and the oxide skin(coating) of rhenium.Concrete structure is expressed as:
IZO glass/WO
3/ NPB/ADN/TPBI/V
2o
5/ ReO
2/ TCTA/DCJTB/Bphen/Cs
2cO
3/ Al.
Embodiment 6
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected IZO glass, first anode is carried out to photoetching treatment, is cut into 2 × 2cm
2square, then use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is MoO
3, thickness is 30nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s; The first hole transmission layer material is TAPC, and thickness is 50nm, and the material of the first luminescent layer is BCzVBi, thickness is 40nm, the first electron transfer layer material is TAZ, and thickness is 200nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 1 × 10
-3pa, evaporation speed is 0.5nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation bipolarity metal oxide layer on the first electron transfer layer, bipolarity metal oxide layer material is V
2o
5, thickness is 8nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s, and then on bipolarity metal oxide layer, evaporation is prepared the oxide skin(coating) of rhenium, and the oxide skin(coating) material of rhenium is Re
2o, thickness is 5nm, evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s;
(3) evaporation the second hole transmission layer successively on the oxide skin(coating) of rhenium, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, the second hole transmission layer material is TCTA, thickness is 50nm, the second luminescent layer material is BCzVBi, thickness is 35nm, same step (1) first luminescent layer of the second luminescent layer preparation method, the second electron transfer layer material is TAZ, thickness is 100nm, electron injecting layer material is CsF, thickness is 2nm, the second hole transmission layer, luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition is: evaporation pressure is 1 × 10
-3pa, evaporation speed is 0.5nm/s, the material of negative electrode is Au, and thickness is 100nm, and evaporation pressure is 1 × 10
-3pa, evaporation speed is 5nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises the bipolarity metal oxide layer that stacks gradually and the oxide skin(coating) of rhenium.Concrete structure is expressed as:
IZO glass/MoO
3/ TAPC/BCzVBi/TAZ/V
2o
5/ Re
2o/TCTA/BCzVBi/TAZ/CsF/Au.
Comparative example
For being presented as creativeness of the present invention, the present invention is also provided with comparative example, comparative example is existing organic electroluminescence device, comprise the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, the concrete structure of comparative example's organic electroluminescence device is: ito glass/WO
3/ NPB/Alq
3/ TAZ/LiF/Ag, the thickness of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode is respectively: 50nm, 40nm, 15nm, 60nm, 0.7nm and 100nm.
Effect embodiment
Adopt fiber spectrometer (marine optics Ocean Optics company of the U.S., model: USB4000), current-voltage tester (Keithly company of the U.S., 2400), colorimeter (Japanese Konica Minolta company model:, model: CS-100A) test organic electroluminescence device brightness with luminous efficiency change curve, to investigate the luminous efficiency of device, tested object is embodiment 3 and comparative example's organic electroluminescence device.Test result as shown in Figure 2.Fig. 2 is the embodiment of the present invention 3 and the brightness of comparative example's organic electroluminescence device and the graph of a relation of luminous efficiency.
From Fig. 2, can find out, under different brightness, all large than comparative example of the luminous efficiency of embodiment 3, the maximum lumen efficiency of embodiment 3 is 16.2lm/W, and that comparative example is only 9.7lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, a kind of laminated organic electroluminescent device of the present invention, adopt the oxide skin(coating) of bipolarity metal oxide layer and rhenium as the charge generation layer of laminated device, the injection and the transmission that improve electronics, effectively improve the power of regeneration in electronics and hole, thereby improve luminous efficiency.
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. a laminated organic electroluminescent device, it is characterized in that, comprise the anode, the first functional layer, charge generation layer, the second functional layer and the negative electrode that stack gradually, described charge generation layer comprises the bipolarity metal oxide layer that stacks gradually and the oxide skin(coating) of rhenium, and described bipolarity metal oxide layer is more close to described anode than the oxide skin(coating) of rhenium; Described bipolarity metal oxide layer material is the one in molybdenum trioxide, tungstic acid and vanadic oxide, the oxide skin(coating) material of described rhenium is the one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums, and the first functional layer and the second functional layer include luminescent layer.
2. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, described bipolarity metal oxide layer thickness is 5～20nm.
3. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, the oxide skin(coating) thickness of described rhenium is 2～10nm.
4. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, described the first functional layer comprises the hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually.
5. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, described the second functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the electron injecting layer that stack gradually.
6. a preparation method for laminated organic electroluminescent device, is characterized in that, comprises following operating procedure:
Required size anode is provided, dry after cleaning;
At described anode surface successively evaporation the first functional layer and charge generation layer; Described charge generation layer comprises the bipolarity metal oxide layer that stacks gradually and the oxide skin(coating) of rhenium, and described bipolarity metal oxide layer is more close to described anode than the oxide skin(coating) of rhenium; Described bipolarity metal oxide layer material is the one in molybdenum trioxide, tungstic acid and vanadic oxide; The oxide skin(coating) material of described rhenium is the one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums; The oxide skin(coating) evaporation condition of bipolarity metal oxide layer and rhenium is: evaporation pressure is 2 × 10
-4～5 × 10
-3pa, evaporation speed is 1～10nm/s;
Evaporation the second functional layer and negative electrode successively on charge generation layer, finally obtain laminated organic electroluminescent device.
7. the preparation method of laminated organic electroluminescent device as claimed in claim 6, it is characterized in that, described the first functional layer comprises the hole injection layer, the first cave transport layer, the first luminescent layer and the first electron transfer layer that stack gradually, all can adopt the method preparation of evaporation.
8. the preparation method of laminated organic electroluminescent device as claimed in claim 6, it is characterized in that, described the second functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the electron injecting layer that stack gradually, all can adopt the method preparation of evaporation.
9. the preparation method of laminated organic electroluminescent device as claimed in claim 6, is characterized in that, described bipolarity metal oxide layer thickness is 5～20nm.
10. the preparation method of laminated organic electroluminescent device as claimed in claim 6, is characterized in that, the oxide skin(coating) thickness of described rhenium is 2～10nm.
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