CN104051642A - Laminated organic electroluminescent device and manufacturing method thereof - Google Patents

Laminated organic electroluminescent device and manufacturing method thereof Download PDF

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Publication number
CN104051642A
CN104051642A CN201310078340.1A CN201310078340A CN104051642A CN 104051642 A CN104051642 A CN 104051642A CN 201310078340 A CN201310078340 A CN 201310078340A CN 104051642 A CN104051642 A CN 104051642A
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layer
evaporation
organic electroluminescent
electroluminescent device
thickness
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周明杰
王平
黄辉
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

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 an n-type layer, a conductive metal simple substance layer and a p-type layer which are sequentially laminated, the n-type layer is much closer to the anode than the p-type layer, materials of the n-type layer and the p-type layer are respectively bipolar metal oxide, the bipolar metal oxide facilitates hole injection and electron injection and can further improve hole and electron transmission rates, so the bipolar metal oxide can be taken as the charge generation layer capable of further generating a hole and electrons, moreover, the bipolar metal oxide further has the injection and transmission effects, so the bipolar metal oxide can be further taken as the injection and transmission layer; the conductive metal simple substance layer can effectively improve conductivity of the charge generation layer, reduces internal resistance of the device and can effectively improve light emitting efficiency. The invention further provides a manufacturing method for the laminated organic electroluminescent device.

Description

A kind of laminated organic electroluminescent device and preparation method thereof
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 U.S. Eastman Kodak company 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 to take laminated device as main, this structure is normally together in series several luminescence units as articulamentum with charge generation layer, compare 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 a plurality of luminescence units and form, but this charge generation layer at least needs to carry out more than twice operation, to preparation, brings certain complexity.
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, described charge generation layer comprises N-shaped layer, conducting metal simple substance layer and the p-type layer stacking gradually, and described N-shaped layer is more close to described anode than p-type layer; The material of described p-type layer and N-shaped layer is bipolarity metal oxide, thereby bipolarity metal oxide can be used as charge generation layer regeneration hole and electronics, because bipolarity metal oxide has concurrently, inject and transmitting effect simultaneously, therefore can be used as and inject and transport layer; Conducting metal simple substance layer can effectively improve the conductivity of charge generation layer, reduces device internal resistance, and this laminated device can effectively improve luminous efficiency.Meanwhile, the present invention also provides a kind of preparation method of above-mentioned laminated organic electroluminescent device, and the present invention prepares the method preparation that charge generation layer is only used evaporation, 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 N-shaped layer, conducting metal simple substance layer and the p-type layer stacking gradually, and described N-shaped layer is more close to described anode than p-type layer; The material of described p-type layer and N-shaped layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in a kind of, described the first functional layer and the second functional layer include luminescent layer.
Preferably, described p-type layer and N-shaped layer thickness are 5～20nm.
Preferably, described conducting metal simple substance layer material is a kind of in silver (Ag), aluminium (Al), platinum (Pt) and golden (Au), and thickness is 1～10nm.
Preferably, described the first functional layer comprises hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stacking 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 stacking gradually.
In the present embodiment, functional layer is two, and charge generation layer is one; In other embodiment, luminescent layer also can be 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, can not add yet.
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 a kind of, thickness is 20～80nm;
More preferably, described hole injection layer material is V 2o 5, 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, a kind of in 4 '-benzidine (NPB), thickness is 20～60nm.
More preferably, the first hole transmission layer material is TAPC, 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 a kind of, 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, a kind of 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 Bphen, 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 a kind of, thickness is 0.5～10nm;
More preferably, described electron injecting layer material is CsF, 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.
Sky of the present invention has been opened a kind of laminated organic electroluminescent device, this device adopts bipolarity metal oxide respectively as p-type layer and the N-shaped layer of charge generation layer, the middle conducting metal simple substance layer of using is as interval, form bipolarity metal oxide/conducting metal/bipolarity metal oxide structures, bipolarity metal oxide is all more favourable to the injection of the injection in hole and electronics, can improve the transmission rate of hole and electronics simultaneously, therefore, thereby can be used as charge generation layer regeneration hole and electronics, bipolarity metal oxide has concurrently and injects and transmitting effect simultaneously, can be used as and inject and transport layer, conducting metal simple substance layer can effectively improve the conductivity of charge generation layer, reduces device internal resistance, and this laminated device can effectively improve 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 N-shaped layer, conducting metal simple substance layer and the p-type layer stacking gradually, and described N-shaped layer is more close to described anode than p-type layer; The material of described p-type layer and N-shaped layer is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide; The evaporation condition of described p-type layer, N-shaped layer and conducting metal simple substance layer 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 hole injection layer, the first cave transport layer, the first luminescent layer and the first electron transfer layer stacking gradually, and 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 stacking gradually, and all can adopt the method preparation of evaporation.
In the present embodiment, functional layer is two, and charge generation layer is one; In other embodiment, luminescent layer also can be 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, can not add yet.
Preferably, described p-type layer and N-shaped layer thickness are 5～20nm.
Preferably, described conducting metal simple substance layer material is a kind of in silver, aluminium, platinum and gold, and thickness is 1～10nm.
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, being operating as that described cleaning is dried afterwards used liquid detergent successively by anode, deionized water, and acetone, ethanol, 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 a kind of, thickness is 20～80nm;
More preferably, hole injection layer material is V 2o 5, thickness is 50nm.
Preferably, the first described hole transmission layer is identical with the second hole transmission layer material, is a kind of in TAPC, TCTA and NPB, and thickness is 20～60nm.
More preferably, the first hole transmission layer material is for being TAPC, 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 a kind of, 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 a kind of 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 Bphen, and thickness is 80nm.
Preferably, described electron injecting layer material is Cs 2cO 3, CsF, CsN 3a kind of with in LiF, thickness is 0.5～10nm;
More preferably, described electron injecting layer is preferably CsF, and thickness is 0.7nm.
Preferably, described negative electrode is a kind of in Ag, Al, Pt and Au, and thickness is 60～300nm.
More preferably, described negative electrode is Ag, and thickness is 100nm.
Sky of the present invention has been opened a kind of laminated organic electroluminescent device, this device adopts bipolarity metal oxide respectively as p-type layer and the N-shaped layer of charge generation layer, the middle conducting metal simple substance layer of using is as interval, form bipolarity metal oxide/conducting metal/bipolarity metal oxide structures, bipolarity metal oxide is all more favourable to the injection of the injection in hole and electronics, can improve the transmission rate of hole and electronics simultaneously, therefore, thereby can be used as charge generation layer regeneration hole and electronics, simultaneously, bipolarity metal oxide has concurrently and injects and transmitting effect, can be used as and inject and transport layer, conducting metal simple substance layer can effectively improve the conductivity of charge generation layer, reduces device internal resistance, and this laminated device can effectively improve luminous efficiency.The present invention prepares the method preparation that charge generation layer is only used evaporation, and method is simple.
Accompanying drawing explanation
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 skills, 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 current density 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 cut into 2 * 2cm 2square, then use successively liquid detergent, deionized water, acetone, ethanol, 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, evaporating n type layer on the first luminescent layer first, N-shaped layer material is MoO 3, thickness is 10nm, evaporation pressure is 5 * 10 -3pa, evaporation speed is 1nm/s, and then on N-shaped layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Ag, and thickness is 5nm, evaporation pressure is 5 * 10 -3pa, evaporation speed is 1nm/s; Finally on conducting metal simple substance layer, evaporation is prepared P type layer, and material, thickness and the preparation method of P type layer and N-shaped layer are identical;
(3) at P type layer successively evaporation the second luminescent layer and negative electrode, same 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, 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, evaporating n type layer on the first luminescent layer first, N-shaped layer material is V 2o 5, thickness is 20nm, evaporation pressure is 2 * 10 -4pa, evaporation speed is 10nm/s, and then on N-shaped layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Al, and thickness is 1nm, during evaporation, pressure is 2 * 10 -4pa, evaporation speed is 10nm/s; Finally on conducting metal simple substance layer, evaporation is prepared p-type layer, and p-type layer material is WO 3, thickness is 5nm;
(3), at p-type layer successively evaporation the second luminescent layer and negative electrode, the second luminescent layer material is BCzVBi, same step (1) first luminescent layer of preparation method, and thickness is 40nm, and the material of negative electrode is Pt, and thickness is 60nm, and during 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, 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 50nm, evaporation pressure is 5 * 10 -3pa, evaporation speed is 1nm/s; The first hole transmission layer material is TAPC, 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, evaporating n type layer on the first electron transfer layer first, N-shaped layer material is MoO 3, thickness is 10nm, evaporation pressure is 5 * 10 -3pa, evaporation speed is 1nm/s, and then on N-shaped layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Ag, and thickness is 5nm, evaporation pressure is 5 * 10 -3pa, evaporation speed is 1nm/s; Finally on conducting metal simple substance layer, evaporation is prepared P type layer, and material, thickness and the preparation method of P type layer and N-shaped layer are identical;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on P type layer, 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 Bphen, thickness is 80nm, electron injecting layer material is CsF, 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 N-shaped layer 61, conducting metal simple substance layer 62 and the P type layer 63 stacking gradually.Concrete structure is expressed as: ito glass/V 2o 5/ TAPC/Alq 3/ TPBI/MoO 3/ Ag/MoO 3/ TCTA/Alq 3/ Bphen/CsF/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 then cut into 2 * 2cm 2square, then use successively liquid detergent, deionized water, acetone, ethanol, 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, evaporating n type layer on the first electron transfer layer first, N-shaped layer material is V 2o 5, thickness is 80nm, evaporation pressure is 2 * 10 -4pa, evaporation speed is 10nm/s, and then on N-shaped layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Al, and thickness is 1nm, evaporation pressure is 2 * 10 -4pa, evaporation speed is 10nm/s; Finally on conducting metal simple substance layer, evaporation is prepared P type layer, and P type layer material is WO 3, thickness is 5nm, preparation method and N-shaped layer are prepared identical;
(3) at P type layer successively evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, the second hole transmission layer material is TAPC, thickness is 20nm, the second luminescent layer material is BCzVBi, thickness is 40nm, same 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 N-shaped layer, conducting metal simple substance layer and the P type layer stacking gradually.Concrete structure is expressed as: AZO glass/V 2o 5/ TCTA/DCJTB/Bphen/V 2o 5/ Al/WO 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, 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, evaporating n type layer on the first electron transfer layer first, N-shaped layer material is MoO 3, thickness is 5nm, evaporation pressure is 1 * 10 -3pa, evaporation speed is 5nm/s, and then on N-shaped layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Pt, and thickness is 10nm, evaporation pressure is 1 * 10 -3pa, evaporation speed is 5nm/s; Finally on conducting metal simple substance layer, evaporation is prepared P type layer, and P type layer material is V 2o 5, thickness is 20nm, preparation method and N-shaped layer are prepared identical;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on P type layer, the second hole transmission layer material is TCTA, thickness is 60nm, the second luminescent layer material is DCJTB, thickness is 5nm, same 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 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 N-shaped layer, conducting metal simple substance layer and the P type layer stacking gradually.Concrete structure is expressed as: IZO glass/WO 3/ NPB/ADN/TPBI/MoO 3/ Pt/V 2o 5/ 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, 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, evaporating n type layer on the first electron transfer layer first, N-shaped layer material is WO 3, thickness is 20nm, evaporation pressure is 1 * 10 -3pa, evaporation speed is 10nm/s, and then on N-shaped layer, evaporation is prepared conducting metal simple substance layer, and conducting metal simple substance layer material is Au, and thickness is 8nm, evaporation pressure is 1 * 10 -3pa, evaporation speed is 10nm/s; Finally on conducting metal simple substance layer, evaporation is prepared P type layer, and P type layer material is WO 3, thickness is 2nm, preparation method and N-shaped layer are prepared identical;
(3) evaporation the second hole transmission layer successively on P type layer, 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 LiF, thickness is 0.5nm, 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 1nm/s, the material of negative electrode is Au, and thickness is 100nm, 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 N-shaped layer, conducting metal simple substance layer and the P type layer stacking gradually.Concrete structure is expressed as: IZO glass/MoO 3/ TAPC/BCzVBi/TAZ/WO 3/ Au/WO 3/ TCTA/BCzVBi/TAZ/LiF/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/V 2o 5/ TAPC/Alq 3/ Bphen/CsF/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, 80nm, 0.7nm and 100nm.
Effect embodiment
Adopt fiber spectrometer (U.S. marine optics Ocean Optics company, model: USB4000), current-voltage tester (U.S. Keithly company, 2400), colorimeter (Japanese Konica Minolta company model:, model: CS-100A) brightness of test organic electroluminescence device is 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 current density of comparative example's organic electroluminescence device and the graph of a relation of luminous efficiency.
From Fig. 2, can find out, under different current densities, the luminous efficiency of embodiment 3 is large than comparative example all, the maximum lumen efficiency of embodiment 3 is 13.2lm/W, and that comparative example is only 6.8lm/W, and the luminous efficiency of comparative example along with the increase of current density fast-descending, this explanation, adopt bipolarity metal oxide respectively as p-type layer and the N-shaped layer of charge generation layer, the middle conducting metal simple substance layer of using is as interval, can improve the transmission rate of hole and electronics simultaneously, simultaneously as injecting and transport layer, effectively improve the conductivity of charge generation layer, reduce device internal resistance, this laminated device can effectively 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 N-shaped layer, conducting metal simple substance layer and the p-type layer stacking gradually, and described N-shaped layer is more close to described anode than p-type layer; The material of described p-type layer and N-shaped layer is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide, and described 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 p-type layer and N-shaped layer thickness are 5～20nm.
3. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, described conducting metal simple substance layer material is a kind of in silver, aluminium, platinum and gold, and thickness is 1～10nm.
4. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, described the first functional layer comprises hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stacking 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 stacking 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 N-shaped layer, conducting metal simple substance layer and the p-type layer stacking gradually, and described N-shaped layer is more close to described anode than p-type layer; The material of described p-type layer and N-shaped layer is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide; The evaporation condition of described p-type layer, N-shaped layer and conducting metal simple substance layer 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 hole injection layer, the first cave transport layer, the first luminescent layer and the first electron transfer layer stacking gradually, and 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 stacking gradually, and 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 p-type layer and N-shaped layer thickness are 5～20nm.
10. the preparation method of laminated organic electroluminescent device as claimed in claim 6, is characterized in that, described conducting metal simple substance layer material is a kind of in silver, aluminium, platinum and gold, and thickness is 1～10nm.
CN201310078340.1A 2013-03-12 2013-03-12 Laminated organic electroluminescent device and manufacturing method thereof Pending CN104051642A (en)

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Application publication date: 20140917