CN104078569A - Organic light-emitting diode and preparation method thereof - Google Patents

Organic light-emitting diode and preparation method thereof Download PDF

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Publication number
CN104078569A
CN104078569A CN201310109254.2A CN201310109254A CN104078569A CN 104078569 A CN104078569 A CN 104078569A CN 201310109254 A CN201310109254 A CN 201310109254A CN 104078569 A CN104078569 A CN 104078569A
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layer
metal oxide
evaporation
oxide
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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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active 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]
    • H10K50/18—Carrier blocking 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • 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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  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

An organic light-emitting diode comprises a positive pole, a hole injection layer, a first hole transport layer, a first light-emitting layer, a first electron transport layer, a charge generation layer, a second hole transport layer, a second light-emitting layer, a second electron transport layer, an electron injection layer and a negative pole which are stacked in sequence. The charge generation layer comprises an n-type layer and a p-type layer. An n-type layer material comprises a metal oxide and a fullerene compound doped in the metal oxide, a p-type material comprises a metal oxide and a lanthanide oxide doped in the metal oxide, and the organic light-emitting diode is high in light-emitting efficiency. The invention further provides a preparation method for preparing the organic light-emitting diode.

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, 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, described charge generation layer comprises N-shaped layer and p-type layer, and described N-shaped layer material comprises metal oxide and is entrained in the fullerene compound in metal oxide, wherein, fullerene compound is selected from 6, 6-phenyl-C61-butyric acid acid methyl esters, 6, 6-phenyl-C71-butyric acid acid methyl esters, one in football alkene and carbon 70, the mass ratio of fullerene compound and metal oxide is 1:20～1:2, described p-type material comprises metal oxide and is entrained in the lanthanide oxide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the mass ratio of described lanthanide oxide and metal oxide is 1:10～1:2.
The thickness of described N-shaped layer is 5nm～20nm, and the thickness of described p-type layer is 10nm～40nm.
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.
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.
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.
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, described charge generation layer comprises N-shaped layer and p-type layer, and described N-shaped layer material comprises metal oxide and is entrained in the fullerene compound in metal oxide, wherein, fullerene compound is selected from 6, 6-phenyl-C61-butyric acid acid methyl esters, 6, 6-phenyl-C71-butyric acid acid methyl esters, one in football alkene and carbon 70, the mass ratio of fullerene compound and metal oxide is 1:20～1:2, described p-type material comprises metal oxide and is entrained in the lanthanide oxide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the mass ratio of described lanthanide oxide and metal oxide is 1:10～1:2, evaporation is 2 × 10 at vacuum pressure -3～5 × 10 -5under Pa, carry out, described metal oxide and described fullerene compound evaporate respectively in two evaporation boats, described metal oxide evaporation speed is 0.1nm/s～10nm/s, the evaporation speed of described fullerene compound is 1nm/s～10nm/s, described metal oxide and described lanthanide oxide evaporate respectively in two evaporation boats, and the evaporation speed of described lanthanide oxide is 1nm/s～10nm/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.
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.
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.
The thickness of described N-shaped layer is 5nm～20nm, and the thickness of described p-type layer is 10nm～40nm.
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 N-shaped layer and p-type layer, wherein, N-shaped layer material comprises metal oxide and is entrained in the fullerene compound in metal oxide, p-type material comprises metal oxide and is entrained in the lanthanide oxide in described metal oxide, N-shaped layer can block charge produces the hole producing in layer and traverses in N-shaped electronic shell and lose with electron recombination, play the effect stopping, and the electric transmission speed of fullerene compound is very fast, with power of regeneration and the transmission performance that can improve electronics after doped metallic oxide, p-type material metal oxide filming performance is good, lanthanide oxide work function is lower, HOMO energy level comparison match with organic material, can strengthen the injectability in hole, improve light extraction efficiency, 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 one 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, and charge generation layer 40 comprises N-shaped layer 401 and p-type layer 402.
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 MoO 3.The thickness of hole injection layer 20 is 20nm～80nm, is preferably 40nm.
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 TAPC.The thickness of the first hole transmission layer 32 is 20nm～60nm, is preferably 30nm.
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 BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, is preferably 30nm.
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 60nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.Charge generation layer 40, charge generation layer 40 comprises N-shaped layer 401 and p-type layer 402, the material of N-shaped layer 401 comprises metal oxide and is entrained in the fullerene compound in metal oxide.Wherein, fullerene compound is selected from 6, 6-phenyl-C61-butyric acid acid methyl esters, 6, 6-phenyl-C71-butyric acid acid methyl esters, one in football alkene and carbon 70, the mass ratio of fullerene compound and metal oxide is 1:20～1:2, described p-type material comprises metal oxide and is entrained in the lanthanide oxide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the mass ratio of described lanthanide oxide and metal oxide is 1:10～1:2.The thickness of described N-shaped layer is 5nm～20nm, and the thickness of described p-type layer is 10nm～40nm.
The second hole transmission layer 52 is formed at the surface of doped layer 402.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 TCTA.The thickness of the second hole transmission layer 52 is 20nm～60nm, is preferably 25nm.
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 BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, is preferably 30nm.
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 60nm.
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 180nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is formed by N-shaped layer and p-type layer, wherein, N-shaped layer material comprises metal oxide and is entrained in the fullerene compound in metal oxide, p-type material comprises metal oxide and is entrained in the lanthanide oxide in described metal oxide, N-shaped layer can block charge produces the hole producing in layer and traverses in N-shaped electronic shell and lose with electron recombination, play the effect stopping, and the electric transmission speed of fullerene compound is very fast, with power of regeneration and the transmission performance that can improve electronics after doped metallic oxide, p-type material metal oxide filming performance is good, lanthanide oxide work function is lower, HOMO energy level comparison match with organic material, can strengthen the injectability in hole, improve light extraction efficiency, 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 MoO 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 TAPC.The thickness of the first hole transmission layer 32 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 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 BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, 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 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 60nm.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, and charge generation layer 40 comprises N-shaped layer 401 and p-type layer 402, and the material of N-shaped layer 401 comprises metal oxide and is entrained in the fullerene compound in metal oxide.Wherein, fullerene compound is selected from 6, 6-phenyl-C61-butyric acid acid methyl esters, 6, 6-phenyl-C71-butyric acid acid methyl esters, one in football alkene and carbon 70, the mass ratio of fullerene compound and metal oxide is 1:20～1:2, described p-type material comprises metal oxide and is entrained in the lanthanide oxide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the mass ratio of described lanthanide oxide and metal oxide is 1:10～1:2.The thickness of described N-shaped layer is 5nm～20nm, and the thickness of described p-type layer is 10nm～40nm.The thickness of described N-shaped layer is 10nm～30nm, and the thickness of described p-type layer is 20nm～60nm.Evaporation is 2 × 10 at vacuum pressure -3～5 × 10 -5under Pa, carry out, evaporation is 2 × 10 at vacuum pressure -3～5 × 10 -5under Pa, carry out, described metal oxide and described fullerene compound evaporate respectively in two evaporation boats, described metal oxide evaporation speed is 1nm/s～10nm/s, the evaporation speed of described fullerene compound is 1nm/s～10nm/s, described metal oxide and described lanthanide oxide evaporate respectively in two evaporation boats, and the evaporation speed of described lanthanide oxide is 1nm/s～10nm/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 surface successively evaporation.
The second hole transmission layer 52 is formed at the surface of doped layer 402.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 TCTA.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 BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, 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 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 180nm.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/MoO 3/ TAPC/BCzVBi/TAZ/PC71BM:MoO 3/ PrO 2: MoO 3the organic electroluminescence device of/TCTA/BCzVBi/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 MoO 3, thickness is 40nm; Evaporation the first hole transmission layer, material is TAPC, thickness is 25nm; Evaporation the first luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the first electron transfer layer, material is TAZ, thickness is 60nm; Evaporation charge generation layer, the metal oxide layer material in N-shaped material is MoO 3, fullerene compound is PC71BM, PC71BM and MoO 3mass ratio be 3:20, thickness is 15nm, the middle lanthanide oxide in p-type material is PrO 2, metal oxide layer material is MoO 3, wherein, PrO 2with MoO 3mass ratio be 1:5,, thickness is 25nm; Evaporation the second hole transmission layer, material is TCTA, thickness is 30nm; Evaporation the second luminescent layer, material is BCzVBi, thickness is 30nm; 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 180nm.Finally obtain needed electroluminescent device.Evaporation is 8 × 10 at vacuum pressure -5under Pa, carry out, metal oxide evaporation speed is 8nm/s, and the evaporation speed of fullerene compound is 1.2nm/s, and the evaporation speed of lanthanide oxide is 4nm/s.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ITO/MoO 3/ TAPC/BCzVBi/TAZ/PC71BM:MoO 3/ PrO 2: MoO 3the organic electroluminescence device (curve 1) of/TCTA/BCzVBi/Bphen/LiF/Ag is ito glass/MoO with structure prepared by comparative example 3/ TAPC/BCzVBi/Bphen/LiF/Al(curve 2) brightness 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 4.6lm/W, and the luminous efficiency of organic electroluminescence device prepared by comparative example is only 3.0lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer is formed by N-shaped layer and p-type layer, N-shaped layer can block charge produces the hole producing in layer and traverses in N-shaped electronic shell and lose with electron recombination, play the effect stopping, and the electric transmission speed of fullerene compound is very fast, with power of regeneration and the transmission performance that can improve electronics after doped metallic oxide, p-type material metal oxide filming performance is good, lanthanide oxide work function is lower, HOMO energy level comparison match with organic material, can strengthen the injectability in hole, 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/PC61BM:WO 3/ Pr 2o 3: WO 3/ TCTA/ADN/Bphen/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, the metal oxide layer material in N-shaped material is WO 3, fullerene compound is PC61BM, PC61BM and WO 3mass ratio be 1:20, thickness is 5nm, the middle lanthanide oxide in p-type material is Pr 2o 3, metal oxide layer material is WO 3, wherein, Pr 2o 3with WO 3mass ratio be 1:2,, thickness is 10nm; Evaporation is prepared the second hole transmission layer, and material is TCTA, and thickness is 20nm, the second luminescent layer, and material is ADN, thickness is 7nm; 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 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 2 × 10 at vacuum pressure -3under Pa, carry out, metal oxide evaporation speed is 1nm/s, and the evaporation speed of fullerene compound is 10nm/s, and the evaporation speed of lanthanide oxide is 1nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/MoO 3/ TAPC/Alq 3/ TAZ/C60:V 2o 5/ Yb 2o 3: WO 3/ NPB/Alq 3the organic electroluminescence device of/TPBi/CsF/Ag.
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 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 Alq 3, thickness is 40nm; Evaporation is prepared the first electron transfer layer, and material is TAZ, and thickness is 200nm; Evaporation is prepared charge generation layer, and the metal oxide layer material in N-shaped material is V 2o 5, fullerene compound is C60, C60 and V 2o 5mass ratio be 2:5, thickness is 20nm, the middle lanthanide oxide in p-type material is Yb 2o 3, metal oxide layer material is WO 3, wherein, Yb 2o 3with WO 3mass ratio be 1:10,, thickness is 40nm; Evaporation is prepared the second hole transmission layer, and material is NPB, and thickness is 60nm; Evaporation is prepared the second luminescent layer, and material is Alq 3, thickness is 30nm; Evaporation is prepared the second electron transfer layer, and material is TPBi, 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 Ag, and thickness is 300nm, finally obtains needed electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -5under Pa, carry out, metal oxide evaporation speed is 10nm/s, and the evaporation speed of fullerene compound is 1nm/s, and the evaporation speed of lanthanide oxide is 10nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/V 2o 5/ NPB/DCJTB/Bphen/C70:MoO 3/ Sm 2o 3: V 2o 5/ NPB/DCJTB/Bphen/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 V 2o 5, thickness is 30nm; Evaporation is prepared the first hole transmission layer, and material is NPB, 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 the metal oxide layer material in N-shaped material is MoO 3, fullerene compound is C70, C70 and MoO 3mass ratio be 1:4, thickness is 10nm, the middle lanthanide oxide in p-type material is Sm 2o 3, metal oxide layer material is V 2o 5, wherein, Sm 2o 3with V 2o 5mass ratio be 3:7,, thickness is 15nm; Evaporation is prepared the second hole transmission layer, and material is NPB, and thickness is 50nm, the second luminescent layer, and material is DCJTB, thickness is 5nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, 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, metal oxide evaporation speed is 4nm/s, and the evaporation speed of fullerene compound is 3nm/s, and the evaporation speed of lanthanide oxide is 6nm/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, it is characterized in that, 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, described charge generation layer comprises N-shaped layer and p-type layer, and described N-shaped layer material comprises metal oxide and is entrained in the fullerene compound in metal oxide, wherein, fullerene compound is selected from 6, 6-phenyl-C61-butyric acid acid methyl esters, 6, 6-phenyl-C71-butyric acid acid methyl esters, one in football alkene and carbon 70, the mass ratio of fullerene compound and metal oxide is 1:20～1:2, described p-type material comprises metal oxide and is entrained in the lanthanide oxide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the mass ratio of described lanthanide oxide and metal oxide is 1:10～1:2.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described N-shaped layer is 5nm～20nm, and the thickness of described p-type layer is 10nm～40nm.
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, described charge generation layer comprises N-shaped layer and p-type layer, and described N-shaped layer material comprises metal oxide and is entrained in the fullerene compound in metal oxide, wherein, fullerene compound is selected from 6, 6-phenyl-C61-butyric acid acid methyl esters, 6, 6-phenyl-C71-butyric acid acid methyl esters, one in football alkene and carbon 70, the mass ratio of fullerene compound and metal oxide is 1:20～1:2, described p-type material comprises metal oxide and is entrained in the lanthanide oxide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the mass ratio of described lanthanide oxide and metal oxide is 1:10～1:2, evaporation is 2 × 10 at vacuum pressure -3～5 × 10 -5under Pa, carry out, described metal oxide and described fullerene compound evaporate respectively in two evaporation boats, described metal oxide evaporation speed is 1nm/s～10nm/s, the evaporation speed of described fullerene compound is 1nm/s～10nm/s, described metal oxide and described lanthanide oxide evaporate respectively in two evaporation boats, and the evaporation speed of described lanthanide oxide is 1nm/s～10nm/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 N-shaped layer is 5nm～20nm, and the thickness of described p-type layer is 10nm～40nm.
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.
CN201310109254.2A 2013-03-29 2013-03-29 Organic light-emitting diode and preparation method thereof Pending CN104078569A (en)

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CN1913731A (en) * 2006-08-28 2007-02-14 清华大学 Organic electroluminescence device
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CN102197507A (en) * 2008-10-28 2011-09-21 密执安州立大学董事会 Stacked white OLED having separate red, green and blue sub-elements
US20120126208A1 (en) * 2010-11-22 2012-05-24 Idemitsu Kosan Co., Ltd. Organic electroluminescence device
CN102544385A (en) * 2012-01-19 2012-07-04 友达光电股份有限公司 Serial connection type organic light-emitting component
CN102810644A (en) * 2011-06-03 2012-12-05 海洋王照明科技股份有限公司 Laminated organic electroluminescent device and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1913731A (en) * 2006-08-28 2007-02-14 清华大学 Organic electroluminescence device
CN102197507A (en) * 2008-10-28 2011-09-21 密执安州立大学董事会 Stacked white OLED having separate red, green and blue sub-elements
CN101447555A (en) * 2008-12-29 2009-06-03 中国科学院长春应用化学研究所 Laminated organic electro-luminescent device of an organic semiconductor-based hetero-junction electric-charge generating layer taken as a connecting layer and preparation method thereof
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Application publication date: 20141001