CN103972408A - Organic light-emitting device and method for manufacturing same - Google Patents

Organic light-emitting device and method for manufacturing same Download PDF

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Publication number
CN103972408A
CN103972408A CN201310039161.7A CN201310039161A CN103972408A CN 103972408 A CN103972408 A CN 103972408A CN 201310039161 A CN201310039161 A CN 201310039161A CN 103972408 A CN103972408 A CN 103972408A
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layer
evaporation
main part
hole
electroluminescence device
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周明杰
王平
黄辉
陈吉星
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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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Priority to CN201310039161.7A priority Critical patent/CN103972408A/en
Publication of CN103972408A publication Critical patent/CN103972408A/en
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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]
    • H10K50/14—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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
    • H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent 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
    • 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

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses an organic light-emitting device which comprises an anode, a hole injection layer, a first hole transport layer, a first light-emitting layer, a first electron transport layer, a charge generating layer, a second hole transport layer, a second light-emitting layer, a second electron transport layer, an electron injection layer and a cathode. The anode, the hole injection layer, the first hole transport layer, the first light-emitting layer, the first electron transport layer, the charge generating layer, the second hole transport layer, the second light-emitting layer, the second electron transport layer, the electron injection layer and the cathode are sequentially stacked on one another, the charge generating layer is made of host materials and guest materials which are doped in the host materials, the host materials are at least one type of silver, aluminum, platinum and gold selectively, the guest materials comprise hole transport materials and ferric trichloride, a mass ratio of the hole transport materials to the host materials is 1:10-3:10, and a mass ratio of the ferric trichloride to the host materials is 1:50-1:10. The organic light-emitting device has the advantage of high light-emitting efficiency. The invention further provides a method for manufacturing the organic light-emitting device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
The principle of luminosity of organic electroluminescence device 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.But the luminous efficiency of organic electroluminescence device is lower at present.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprises the anode stacking gradually, 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 negative electrode, the material of described charge generation layer comprises material of main part and is entrained in the guest materials in described material of main part, described material of main part is selected from silver, aluminium, at least one in platinum and gold, described guest materials comprises hole mobile material and ferric trichloride, the mass ratio of described hole mobile material and described material of main part is 1:10 ~ 3:10, described hole mobile material is selected from N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine, 9,9'-(1,3-phenyl), two-9H-carbazole, N, N '-(1-naphthyl)-N, N '-diphenyl-9,9-spiral shell two fluorenes and N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4, at least one in 4'-diamines, the mass ratio of described ferric trichloride and described material of main part is 1:50 ~ 1: 10.
In an embodiment, the thickness of described charge generation layer is 1nm ~ 20nm therein.
Therein in an embodiment, the material of described the first luminescent layer and described the second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
Therein in an embodiment, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N; N '-diphenyl-4, at least one in 4 '-benzidine.
In an embodiment, the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1 therein, 10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
A preparation method for organic electroluminescence device, comprises the following steps:
Prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer at anode surface successively evaporation;
Prepare charge generation layer at described the first electron transfer layer surface evaporation, the material of described charge generation layer comprises material of main part and is entrained in the guest materials in described material of main part, described material of main part is selected from silver, aluminium, at least one in platinum and gold, described guest materials comprises hole mobile material and ferric trichloride, the mass ratio of described hole mobile material and described material of main part is 1:10 ~ 3:10, described hole mobile material is selected from N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, N, N '-(1-naphthyl)-N, N '-diphenyl-9, 9-spiral shell two fluorenes and N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, at least one in 4'-diamines, the mass ratio of described ferric trichloride and described material of main part is 1:50 ~ 1:10, described material of main part, described hole mobile material and described ferric trichloride evaporate respectively in three evaporation boats, evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, described material of main part evaporation speed is 1nm/s ~ 10nm/s, and the evaporation speed of described hole mobile material is 0.1nm/s ~ 1nm/s, and the evaporation speed of described ferric trichloride is 0.1nm/s ~ 1nm/s, and
Form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode on described charge generation layer surface successively evaporation.
Therein in an embodiment, the material of described the first luminescent layer and described the second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
Therein in an embodiment, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N; N '-diphenyl-4, at least one in 4 '-benzidine.
In an embodiment, the thickness of described charge generation layer is 1nm ~ 20nm therein.
Therein in an embodiment, before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
Above-mentioned organic electroluminescence device and preparation method thereof, charge generation layer is formed by metal and guest materials doping, metal both can provide electronics, hole can be provided again, the material of main part that is suitable as charge generation layer produces electric charge, doping object is made up of hole mobile material and ferric trichloride, hole mobile material can improve the transmission rate in hole, and ferric trichloride has a large amount of electronics free, can produce more hole, improve the regeneration efficiency of electric charge, simultaneously, also further improved the conductivity of charge generation layer, metal material Main Function is to provide electronics, improve conductivity and the permeability of charge generation layer simultaneously, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the preparation method's of the organic electroluminescence device of an execution mode flow chart;
Fig. 3 is brightness and the luminous efficiency graph of a relation of the organic electroluminescence device prepared of embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the anode 10, hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34, the first electron transfer layer 36, charge generation layer 40, the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and the negative electrode 70 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Hole injection layer 20 is formed at anode 10 surfaces.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably WO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 30nm.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The material of the first hole transmission layer 32 is selected from 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; at least one in 4 '-benzidine (NPB), is preferably TCTA.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 40nm.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The material of the first luminescent layer 34 is selected from 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 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 25nm.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 32.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm ~ 200nm, is preferably 50nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.The material of charge generation layer 40 comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au).Guest materials comprises hole mobile material and ferric trichloride (FeCl 3).The mass ratio of hole mobile material and material of main part is 1:10 ~ 3:10.Hole mobile material is selected from N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), N, N '-(1-naphthyl)-N, N '-diphenyl-9,9-spiral shell two fluorenes (Spiro-NPB) and N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4, at least one in 4'-diamines (TPD).The mass ratio of ferric trichloride and material of main part is 1:50 ~ 1:10.The thickness of charge generation layer 40 is 1nm ~ 20nm.
The second hole transmission layer 52 is formed at the surface of charge generation layer 40.The material of the second hole transmission layer 52 is selected from 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; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 30nm.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 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 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 25nm.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 150nm.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 is selected from cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is formed by metal and guest materials doping, metal both can provide electronics, hole can be provided again, the material of main part that is suitable as charge generation layer produces electric charge, doping object is made up of hole mobile material and ferric trichloride, hole mobile material can improve the transmission rate in hole, and ferric trichloride has a large amount of electronics free, can produce more hole, improve the regeneration efficiency of electric charge, simultaneously, also further improved the conductivity of charge generation layer 40, metal material Main Function is to provide electronics, improve conductivity and the permeability of charge generation layer 40 simultaneously, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device 100, organic electroluminescence device 100 has two luminescence units simultaneously, thereby has brightness and luminous efficiency at double.
Be appreciated that other functional layers also can be set in this organic electroluminescence device 100 as required.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an embodiment, it comprises the following steps:
Step S110, prepare hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34 and the first electron transfer layer 36 at anode surface successively evaporation.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
In present embodiment, before anode 10 surfaces form hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surfaces.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably WO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The first hole transmission layer 32 is prepared by evaporation.The material of the first hole transmission layer 32 is selected from 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; at least one in 4 '-benzidine (NPB), is preferably TCTA.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 40nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The first luminescent layer 34 is prepared by evaporation.The material of the first luminescent layer 34 is selected from 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 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 25nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 32.The first electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm ~ 200nm, is preferably 50nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Step S120, prepare charge generation layer 40 at the surperficial evaporation of the first electron transfer layer 36.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.The material of charge generation layer 40 comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au).Guest materials comprises hole mobile material and ferric trichloride (FeCl 3).The mass ratio of hole mobile material and material of main part is 1:10 ~ 3:10.Hole mobile material is selected from N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), N, N '-(1-naphthyl)-N, N '-diphenyl-9,9-spiral shell two fluorenes (Spiro-NPB) and N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4, at least one in 4'-diamines (TPD).The mass ratio of ferric trichloride and material of main part is 1:50 ~ 1:10.The thickness of charge generation layer 40 is 5nm ~ 30nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, material of main part, hole mobile material and ferric trichloride evaporate respectively in three evaporation boats, material of main part evaporation speed is 1nm/s～10nm/s, and the evaporation speed of hole mobile material is 0.1nm/s ~ 1nm/s, and the evaporation speed of ferric trichloride is 0.1nm/s ~ 1nm/s.
Step S130, prepare the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and negative electrode 70 on charge generation layer 40 surfaces successively evaporation.
The second hole transmission layer 52 is formed at the surface of charge generation layer 40.The material of the second hole transmission layer 52 is selected from 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; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 30nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 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 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 25nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 150nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 is selected from cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device preparation method, technique is simple, and the luminous efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method of organic electroluminescence device provided by the invention is elaborated.
The preparation used of the embodiment of the present invention and comparative example and tester are: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 test electric property of Keithley company of the U.S., CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
Structure prepared by the present embodiment is ITO/WO 3/ TCTA/Alq 3/ TAZ/Au:TPD:FeCl 3/ NPB/Alq 3the organic electroluminescence device of/Bphen/LiF/Ag.
First ITO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Evaporation hole injection layer, material is WO 3, thickness is 30nm; Evaporation the first hole transmission layer, material is TCTA, thickness is 40nm; Evaporation the first luminescent layer, material is Alq 3, thickness is 25nm; Evaporation the first electron transfer layer, material is TAZ, thickness is 50nm; Evaporation charge generation layer, material of main part is Au, guest materials is TPD and FeCl 3, the mass ratio of TPD and Au is 1:5, FeCl 3with the mass ratio 1:25 of Au, thickness is 10nm; Evaporation the second hole transmission layer, material is NPB, thickness is 30nm; Evaporation the second luminescent layer, material is Alq 3, thickness is 25nm; Evaporation the second electron transfer layer, material is Bphen, thickness is 150nm; Evaporation electron injecting layer, material is LiF, thickness is 1nm; Evaporation negative electrode, material is Ag, thickness is 150nm.Finally obtain needed electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -4under Pa, carry out, organic material evaporation speed is 0.5nm/s, FeCl 3evaporation speed be 0.3nm/s, the evaporation speed of metal is 5nm/s.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ITO/WO 3/ TCTA/Alq 3/ TAZ/Au:TPD:FeCl 3/ NPB/Alq 3the organic electroluminescence device (curve 1) of/Bphen/LiF/Ag is ITO/WO with structure prepared by comparative example 3/ TCTA/Alq 3the brightness of the organic electroluminescence device (curve 2) of/TAZ/LiF/Ag and the relation of luminous efficiency.In the organic electroluminescence device that in organic electroluminescence device prepared by comparative example, each layer thickness is prepared with embodiment 1, each layer thickness is identical.
From scheming, can see, under different brightness, all large than comparative example of the luminous efficiency of embodiment 1, the maximum lumen efficiency of organic electroluminescence device prepared by embodiment 1 is 13lm/W, and the luminous efficiency of organic electroluminescence device prepared by comparative example is only 7.8lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer is made up of metal-doped layer, improve the transmission rate in hole, produce more hole, improve the regeneration efficiency of electric charge, simultaneously, also further improved the conductivity of charge generation layer, metal material improves conductivity and the permeability of charge generation layer, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
The luminous efficiency of the organic electroluminescence device that below prepared by each embodiment is all similar with embodiment 1, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/V 2o 5/ NPB/ADN/TPBi/Ag:NPB:FeCl 3/ TCTA/ADN/TAZ/CsN 3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is V 2o 5, thickness is 80nm; Evaporation is prepared the first hole transmission layer, and material is NPB, and thickness is 60nm; Evaporation is prepared the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is TPBi, and thickness is 200nm; Evaporation charge generation layer, material of main part is Ag, guest materials is NPB and FeCl 3, the mass ratio of NPB and Ag is 1:10, FeCl 3with the mass ratio 1:50 of Ag, thickness is 5nm; Evaporation is prepared the second hole transmission layer, and material is TCTA, and thickness is 20nm; Evaporation is prepared the second luminescent layer, and material is ADN, and thickness is 7nm; Evaporation is prepared the second electron transfer layer, and material is TAZ, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is CsN 3, thickness is 0.5nm; Evaporation is prepared negative electrode, and material is Pt, and thickness is 60nm, finally obtains needed electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -3under Pa, carry out, organic material evaporation speed is 0.1nm/s, FeCl 3evaporation speed be 1nm/s, the evaporation speed of metal is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/WO 3/ TAPC/BCzVBi/Bphen/Al:mCP:FeCl 3the organic electroluminescence device of/TCTA/BCzVBi/Bphen/CsF/Al.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is WO 3, thickness is 20nm; Evaporation is prepared the first hole transmission layer, and material is TAPC, and thickness is 30nm; Evaporation is prepared the first luminescent layer, and material is BCzVBi, and thickness is 40nm; Evaporation is prepared the first electron transfer layer, and material is Bphen, and thickness is 200nm; Evaporation is prepared charge generation layer, and material of main part is Al, and guest materials is mCP and FeCl 3, the mass ratio of mCP and Al is 3:10, FeCl 3with the mass ratio 1:20 of Al, thickness is 20nm; Evaporation is prepared the second hole transmission layer, and material is TCTA, and thickness is 60nm; Evaporation is prepared the second luminescent layer, and material is BCzVBi, and thickness is 30nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is CsF, and thickness is 10nm; Evaporation is prepared negative electrode, and material is Al, and thickness is 300nm, finally obtains needed electroluminescent device.Evaporation is 2 × 10 at vacuum pressure -4under Pa, carry out, organic material evaporation speed is 1nm/s, FeCl 3evaporation speed be 0.1nm/s, the evaporation speed of metal is 1nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/MoO 3/ TCTA/DCJTB/Bphen/Pt:Spiro-NPB:FeCl 3/ NPB/DCJTB/TPBi/Cs 2cO 3the organic electroluminescence device of/Au.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is MoO 3, thickness is 30nm; Evaporation is prepared the first hole transmission layer, and material is TCTA, and thickness is 50nm; Evaporation is prepared the first luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation is prepared charge generation layer, and material of main part is Pt, and guest materials is Spiro-NPB and FeCl 3, the mass ratio of Spiro-NPB and Pt is 18:100, FeCl 3with the mass ratio of Pt 1: 10, thickness was 30nm; Evaporation is prepared the second hole transmission layer, and material is NPB, and thickness is 50nm; Evaporation is prepared the second luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the second electron transfer layer, and material is TPBi, and thickness is 100nm; Evaporation is prepared electron injecting layer, and material is Cs 2cO 3, thickness is 2nm; Evaporation is prepared negative electrode, and material is Au, and thickness is 180nm, finally obtains needed electroluminescent device.Evaporation is 8 × 10 at vacuum pressure -4under Pa, carry out, organic material evaporation speed is 0.6nm/s, FeCl 3evaporation speed be 0.5nm/s, the evaporation speed of metal is 2nm/s.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, is characterized in that, comprises the anode stacking gradually, 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 negative electrode, the material of described charge generation layer comprises material of main part and is entrained in the guest materials in described material of main part, described material of main part is selected from silver, aluminium, at least one in platinum and gold, described guest materials comprises hole mobile material and ferric trichloride, the mass ratio of described hole mobile material and described material of main part is 1:10 ~ 3:10, described hole mobile material is selected from N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine, 9,9'-(1,3-phenyl), two-9H-carbazole, N, N '-(1-naphthyl)-N, N '-diphenyl-9,9-spiral shell two fluorenes and N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4, at least one in 4'-diamines, the mass ratio of described ferric trichloride and described material of main part is 1:50 ~ 1:10.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described charge generation layer is 1nm ~ 20nm.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first luminescent layer and described the second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer at anode surface successively evaporation;
Prepare charge generation layer at described the first electron transfer layer surface evaporation, the material of described charge generation layer comprises material of main part and is entrained in the guest materials in described material of main part, described material of main part is selected from silver, aluminium, at least one in platinum and gold, described guest materials comprises hole mobile material and ferric trichloride, the mass ratio of described hole mobile material and described material of main part is 1:10 ~ 3:10, described hole mobile material is selected from N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, N, N '-(1-naphthyl)-N, N '-diphenyl-9, 9-spiral shell two fluorenes and N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, at least one in 4'-diamines, the mass ratio of described ferric trichloride and described material of main part is 1:50 ~ 1:10, described material of main part, described hole mobile material and described ferric trichloride evaporate respectively in three evaporation boats, evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, described material of main part evaporation speed is 1nm/s ~ 10nm/s, and the evaporation speed of described hole mobile material is 0.1nm/s ~ 1nm/s, and the evaporation speed of described ferric trichloride is 0.1nm/s ~ 1nm/s, and
Form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode on described charge generation layer surface successively evaporation.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described the first luminescent layer and described the second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
8. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described charge generation layer is 1nm ~ 20nm.
10. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
CN201310039161.7A 2013-01-31 2013-01-31 Organic light-emitting device and method for manufacturing same Pending CN103972408A (en)

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Application publication date: 20140806