CN104253231A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

Info

Publication number
CN104253231A
CN104253231A CN201310261057.2A CN201310261057A CN104253231A CN 104253231 A CN104253231 A CN 104253231A CN 201310261057 A CN201310261057 A CN 201310261057A CN 104253231 A CN104253231 A CN 104253231A
Authority
CN
China
Prior art keywords
layer
metal
evaporation
electroluminescence device
hafnium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310261057.2A
Other languages
Chinese (zh)
Inventor
周明杰
黄辉
张振华
王平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201310261057.2A priority Critical patent/CN104253231A/en
Publication of CN104253231A publication Critical patent/CN104253231A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H10K50/155—Hole transporting layers comprising dopants
    • 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
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • 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
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition

Abstract

The invention relates to an organic electroluminescent device comprising an anode, a hole injection layer, a first hole transport layer, a first luminous layer, a first electron transfer layer, a charge generating layer, a second hole transport layer, a second luminous layer, a second electron transport layer, an electron injection layer and a cathode. The components are successively laminated. Materials employed by the charge generating layer includes metal, a hafnium compound, and metallic oxide, wherein the hafnium compound and the metallic oxide are doped in the metal, the mass ratio of the metallic oxide to the metal is 1:20 to 1:5, and the mass ratio of the hafnium compound to the metal is 1:100 to 1: 20. The luminous efficiency of the organic electroluminescent device is high. In addition, the invention also provides a preparation method of the organic electroluminescent 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
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.But the luminous efficiency of current organic electroluminescence device is lower.
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 stacked gradually, hole injection layer, first hole transmission layer, first luminescent layer, first electron transfer layer, charge generation layer, second hole transmission layer, second luminescent layer, second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer material comprises compound and the metal oxide of metal and doping hafnium in a metal, described metal is selected from silver, aluminium, at least one in platinum or gold, described metal oxide is selected from zinc oxide, zirconia, at least one in magnesium oxide or titanium dioxide, the compound of described hafnium is selected from least one in hafnium oxide or hafnium boride, wherein, the mass ratio of described metal oxide and described metal is 1:20 ~ 1:5, the compound of described hafnium and the mass ratio of described metal are 1:100 ~ 1:20.
The thickness of described charge generation layer is 5nm ~ 20nm.
The material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium.
The material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
The material of described first electron transfer layer and described second electron transfer layer is selected from least one in 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and N-aryl benzimidazole.
A preparation method for organic electroluminescence device, comprises the following steps:
Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer is prepared at anode surface successively evaporation;
Charge generation layer is prepared at described first electron transfer layer surface evaporation, described charge generation layer material comprises compound and the metal oxide of metal and doping hafnium in a metal, described metal is selected from silver, aluminium, at least one in platinum or gold, described metal oxide is selected from zinc oxide, zirconia, at least one in magnesium oxide or titanium dioxide, the compound of described hafnium is selected from least one in hafnium oxide or hafnium boride, wherein, the mass ratio of described metal oxide and described metal is 1:20 ~ 1:5, the compound of described hafnium and the mass ratio of described metal are 1:100 ~ 1:20, evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s, and
The second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode is formed on described charge generation layer surface successively evaporation.
The material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium.
The material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
The thickness of described charge generation layer is 5nm ~ 20nm.
Before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, 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 the compound of metal and doping hafnium in a metal and metal oxide, the chemical combination object height transmitted wave section of hafnium wide in 200nm ~ 10 μm through more than 70%, refractive index is greater than 2.0, there is the feature of broad-band gap and high-k, can make most light directly through, simultaneously, hafnium compound atomic radius is larger, can make to pile up between membrane-coating granules closely, improve rete density, the work function of metal is between the HOMO energy level and lumo energy of organic material, therefore, there is the effect of hole injection and electron injection simultaneously, improve the conductivity of charge generation layer simultaneously, high refractive index metal oxide can carry out scattering to light, the total reflection effect of abatement device second luminescent layer simultaneously, this charge generation layer effectively can improve the luminous efficiency of organic electroluminescence device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the flow chart of the preparation method of the organic electroluminescence device of an execution mode;
Fig. 3 is current density and the current efficiency graph of a relation of organic electroluminescence device prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is illustrated further.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the anode 10, hole injection layer 20, first hole transmission layer 32, first luminescent layer 34, first electron transfer layer 36, charge generation layer 40, second hole transmission layer 52, second luminescent layer 54, 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 surface.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.
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 '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) 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 50nm.
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 pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 10nm.
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 least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm ~ 300nm, is preferably 120nm.
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 compound and the metal oxide of metal and doping hafnium in a metal, and metal is selected from least one metal oxide materials in silver (Ag), aluminium (Al), platinum (Pt) or gold (Au) and comprises zinc oxide (ZnO), zirconia (ZrO 2), magnesium oxide (MgO) or titanium dioxide (TiO 2) at least one, the compound of hafnium comprises hafnium oxide (HfO 2) and hafnium boride (HfB 2); The mass ratio of described metal oxide and described metal is 1:20 ~ 1:5, and the compound of described hafnium and the mass ratio of described metal are 1:100 ~ 1:20.The thickness of charge generation layer 40 is 5nm ~ 20nm.
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 '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) 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 50nm.
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 pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 35nm.
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 least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TPBI.The thickness of the second electron transfer layer 56 is 40nm ~ 300nm, is preferably 80nm.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surface.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 Cs 2cO 3.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 2nm.
Negative electrode 70 is formed at electron injecting layer 60 surface.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 100nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is formed by the compound of metal and doping hafnium in a metal and metal oxide, the chemical combination object height transmitted wave section of hafnium wide in 200nm ~ 10 μm through more than 70%, refractive index is greater than 2.0, there is the feature of broad-band gap and high-k, can make most light directly through, simultaneously, hafnium compound atomic radius is larger, can make to pile up between membrane-coating granules closely, improve rete density, the work function of metal is between the HOMO energy level and lumo energy of organic material, therefore, there is the effect of hole injection and electron injection simultaneously, improve the conductivity of charge generation layer simultaneously, high refractive index metal oxide can carry out scattering to light, the total reflection effect of abatement device second luminescent layer simultaneously, this charge generation layer effectively can improve the luminous efficiency of organic electroluminescence device 100, organic electroluminescence device 100 has two luminescence units simultaneously, thus the brightness had at double and luminous efficiency.
Be appreciated that in this organic electroluminescence device 100 and also can other functional layers be set 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, first hole transmission layer 32, 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 surface forms hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surface.
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 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
First hole transmission layer 32 is formed at the surface of hole injection layer 20.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 '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) 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 50nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
First luminescent layer 34 is formed at the surface of the first hole transmission layer 32.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 pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 10nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5pa carries out, and evaporation rate is 0.1nm/s ~ 1nm/s.
First electron transfer layer 36 is formed at the surface of the first luminescent layer 32.First electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm ~ 300nm, is preferably 120nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate 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, charge generation layer 40 comprises compound and the metal oxide of metal and doping hafnium in a metal, and metal is selected from least one metal oxide materials in silver (Ag), aluminium (Al), platinum (Pt) or gold (Au) and comprises zinc oxide (ZnO), zirconia (ZrO 2), magnesium oxide (MgO) or titanium dioxide (TiO 2) at least one, the compound of hafnium comprises hafnium oxide (HfO 2) and hafnium boride (HfB 2); The mass ratio of described metal oxide and described metal is 1:20 ~ 1:5, and the compound of described hafnium and the mass ratio of described metal are 1:100 ~ 1:20.The thickness of charge generation layer 40 is 5nm ~ 20nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s.
Step S130, prepare the second hole transmission layer 52, second luminescent layer 54, second electron transfer layer 56, electron injecting layer 60 and negative electrode 70 on charge generation layer 40 surface successively evaporation.
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 '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) 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 50nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
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 pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 35nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
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 least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TPBI.The thickness of the second electron transfer layer 56 is 40nm ~ 300nm, is preferably 80nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surface.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 Cs 2cO 3.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 2nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Negative electrode 70 is formed at electron injecting layer 60 surface.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 100nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate 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 to organic electroluminescence device provided by the invention is described in detail.
The embodiment of the present invention and the preparation used by 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 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
Embodiment 1
Structure prepared by the present embodiment is ITO/MoO 3/ TCTA/Alq 3/ TAZ/HfO 2: ZnO:Ag/TCTA/Alq 3/ TPBI/Cs 2cO 3wherein, "/" presentation layer stack structure, ": " represents doping or mixing to the organic electroluminescence device of/Ag, and following examples are identical.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Evaporation hole injection layer, material is MoO3, and thickness is 40nm; Evaporation first hole transmission layer, material is TCTA, and thickness is 50nm; Evaporation first luminescent layer, material is Alq3, and thickness is 10nm; Evaporation first electron transfer layer, material is TAZ, and thickness is 120nm; Evaporation charge generation layer material is HfO2:ZnO:Ag, and the mass ratio of charge generation layer thickness to be the mass ratio of 10nm, ZnO and Ag be 1:10, HfO2 and Ag is 1:50; Evaporation second hole transmission layer, material is TCTA, and thickness is 50nm; Evaporation second luminescent layer, material is Alq3, and thickness is 35nm; Evaporation second electron transfer layer, material is TPBI, and thickness is 80nm; Evaporation electron injecting layer, material is Cs2CO3, and thickness is 2nm; Evaporation negative electrode, material is Ag, and thickness is 100nm.Finally obtain required electroluminescent device.Evaporation carries out under vacuum pressure is 8 × 10-5Pa, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s.
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/MoO 3/ TCTA/Alq 3/ TAZ/HfO 2: ZnO:Ag/TCTA/Alq 3/ TPBI/Cs 2cO 3structure prepared by organic electroluminescence device (curve 1) and the comparative example of/Ag is ito glass/MoO 3/ TAPC/Alq 3/ TPBi/Cs 2cO 3/ Ag(curve 2) current density and the relation of current efficiency.In organic electroluminescence device prepared by comparative example, each layer thickness is identical with each layer thickness in organic electroluminescence device prepared by embodiment 1.
Can see from figure, under different current density, the current efficiency of embodiment 1 is all larger than comparative example, the maximum current efficiency of organic electroluminescence device prepared by embodiment 1 is 8.0cd/A, and the current efficiency of organic electroluminescence device prepared by comparative example is only 4.2cd/A, this explanation, charge generation layer is formed by the compound of metal and doping hafnium in a metal and metal oxide, the chemical combination object height transmitted wave section of hafnium wide in 200nm ~ 10 μm through more than 70%, refractive index is greater than 2.0, there is the feature of broad-band gap and high-k, can make most light directly through, simultaneously, hafnium compound atomic radius is larger, can make to pile up between membrane-coating granules closely, improve rete density, the work function of metal is between the HOMO energy level and lumo energy of organic material, therefore, there is the effect of hole injection and electron injection simultaneously, improve the conductivity of charge generation layer simultaneously, high refractive index metal oxide can carry out scattering to light, the total reflection effect of abatement device second luminescent layer simultaneously, this charge generation layer effectively can improve the luminous efficiency of organic electroluminescence device.
The current efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/WO 3/ TCTA/ADN/TAZ/HfB 2: ZrO 2: Al/TAPC/ADN/TAZ/CsN 3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is WO 3, thickness is 80nm; Evaporation prepares the first hole transmission layer, and material is TCTA, and thickness is 60nm; Evaporation prepares the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation prepares the first electron transfer layer, and material is TAZ, and thickness is 200nm; Evaporation charge generation layer material is HfB 2: ZrO 2: Al, charge generation layer thickness is 5nm, ZrO 2be 1:5, HfB with the mass ratio of Al 2be 1:100 with the mass ratio of Al; Evaporation prepares the second hole transmission layer, and material is TAPC, and thickness is 20nm, the second luminescent layer, and material is ADN, and thickness is 7nm; Evaporation prepares the second electron transfer layer, and material is TAZ, and thickness is 40nm; Evaporation prepares electron injecting layer, and material is CsN 3, thickness is 10nm; Evaporation prepares negative electrode, and material is Pt, and thickness is 60nm, finally obtains required electroluminescent device.Evaporation is 2 × 10 at vacuum pressure -3carry out under Pa, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/MoO 3/ NPB/Alq 3/ TAZ/HfO 2: MgO:Pt/NPB/Alq 3the organic electroluminescence device of/Bphen/CsF/Ag.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is MoO 3, thickness is 20nm; Evaporation prepares the first hole transmission layer, and material is NPB, and thickness is 30nm; Evaporation prepares the first luminescent layer, and material is Alq 3, thickness is 40nm; Evaporation prepares the first electron transfer layer, and material is TAZ, and thickness is 200nm; It is HfO that evaporation prepares charge generation layer material 2: MgO:Pt, charge generation layer thickness is the mass ratio of 20nm, MgO and Pt is 1:20, HfB 2be 1:20 with the mass ratio of Pt; Evaporation prepares the second hole transmission layer, and material is NPB, and thickness is 60nm; Evaporation prepares the second luminescent layer, and material is Alq 3, thickness is 30nm; Evaporation prepares the second electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation prepares electron injecting layer, and material is LiF, and thickness is 0.5nm; Evaporation prepares negative electrode, and material is Ag, and thickness is 300nm, finally obtains required electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -5the evaporation rate carrying out organic material under Pa is 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/WO 3/ TAPC/DCJTB/TPBi/HfB 2: TiO 2: Au/TCTA/DCJTB/Bphen/Cs 2cO 3the organic electroluminescence device of/Au.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is WO 3, thickness is 30nm; Evaporation prepares the first hole transmission layer, and material is TAPC, and thickness is 40nm; Evaporation prepares the first luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation prepares the first electron transfer layer, and material is TPBi, and thickness is 40nm; It is HfB that evaporation prepares charge generation layer material 2: TiO 2: Au, charge generation layer thickness is 10nm, TiO 2be 3:20, HfO with the mass ratio of Au 2be 1:15 with the mass ratio of Au; Evaporation prepares the second hole transmission layer, and material is TCTA, and thickness is 50nm; Evaporation second luminescent layer, material is DCJTB, and thickness is 5nm, evaporation second electron transfer layer, and material is Bphen, and thickness is 80nm, and evaporation prepares electron injecting layer, and material is Cs 2cO 3, thickness is 2nm; Evaporation prepares negative electrode, and material is Au, and thickness is 100nm, finally obtains required electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -4carry out under Pa, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 stacked gradually, hole injection layer, first hole transmission layer, first luminescent layer, first electron transfer layer, charge generation layer, second hole transmission layer, second luminescent layer, second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer material comprises compound and the metal oxide of metal and doping hafnium in a metal, described metal is selected from silver, aluminium, at least one in platinum or gold, described metal oxide is selected from zinc oxide, zirconia, at least one in magnesium oxide or titanium dioxide, the compound of described hafnium is selected from least one in hafnium oxide or hafnium boride, wherein, the mass ratio of described metal oxide and described metal is 1:20 ~ 1:5, the compound of described hafnium and the mass ratio of described metal are 1:100 ~ 1:20.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described charge generation layer is 5nm ~ 20nm.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described first electron transfer layer and described second electron transfer layer is selected from 4,7-diphenyl-1, at least one in 10-phenanthroline, 1,2,4-triazole derivative and N-aryl benzimidazole.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer is prepared at anode surface successively evaporation;
Charge generation layer is prepared at described first electron transfer layer surface evaporation, described charge generation layer material comprises compound and the metal oxide of metal and doping hafnium in a metal, described metal is selected from silver, aluminium, at least one in platinum or gold, described metal oxide is selected from zinc oxide, zirconia, at least one in magnesium oxide or titanium dioxide, the compound of described hafnium is selected from least one in hafnium oxide or hafnium boride, wherein, the mass ratio of described metal oxide and described metal is 1:20 ~ 1:5, the compound of described hafnium and the mass ratio of described metal are 1:100 ~ 1:20, evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s, and
The second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode is formed 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 first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium.
8. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-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 5nm ~ 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 photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
CN201310261057.2A 2013-06-26 2013-06-26 Organic electroluminescent device and preparation method thereof Pending CN104253231A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310261057.2A CN104253231A (en) 2013-06-26 2013-06-26 Organic electroluminescent device and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310261057.2A CN104253231A (en) 2013-06-26 2013-06-26 Organic electroluminescent device and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104253231A true CN104253231A (en) 2014-12-31

Family

ID=52187945

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310261057.2A Pending CN104253231A (en) 2013-06-26 2013-06-26 Organic electroluminescent device and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104253231A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050264174A1 (en) * 2004-05-28 2005-12-01 Eastman Kodak Comany Tandem OLED having stable intermediate connectors
CN101006594A (en) * 2004-08-20 2007-07-25 伊斯曼柯达公司 White OLED having multiple white electroluminescent units
JP2008293895A (en) * 2007-05-28 2008-12-04 Panasonic Electric Works Co Ltd Organic electroluminescent element
CN101379884A (en) * 2006-02-07 2009-03-04 住友化学株式会社 Organic electroluminescent element
CN101444142A (en) * 2006-05-11 2009-05-27 出光兴产株式会社 organic electroluminescent element
CN102097598A (en) * 2010-12-06 2011-06-15 电子科技大学 Organic light-emitting device and production method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050264174A1 (en) * 2004-05-28 2005-12-01 Eastman Kodak Comany Tandem OLED having stable intermediate connectors
CN101006594A (en) * 2004-08-20 2007-07-25 伊斯曼柯达公司 White OLED having multiple white electroluminescent units
CN101379884A (en) * 2006-02-07 2009-03-04 住友化学株式会社 Organic electroluminescent element
CN101444142A (en) * 2006-05-11 2009-05-27 出光兴产株式会社 organic electroluminescent element
JP2008293895A (en) * 2007-05-28 2008-12-04 Panasonic Electric Works Co Ltd Organic electroluminescent element
CN102097598A (en) * 2010-12-06 2011-06-15 电子科技大学 Organic light-emitting device and production method thereof

Similar Documents

Publication Publication Date Title
CN103972413A (en) Organic light-emitting device and production method thereof
CN103972420A (en) Organic light-emitting device and method for manufacturing same
CN104183778A (en) Organic electroluminescent device and preparation method thereof
CN104183738A (en) Organic electroluminescent device and preparation method thereof
CN104037344A (en) Stacked organic light emitting device and preparation method thereof
CN104253228A (en) Organic light emitting diode and preparation method thereof
CN104253243A (en) Organic electroluminescent device and preparation method thereof
CN103972408A (en) Organic light-emitting device and method for manufacturing same
CN104183732A (en) Organic light emitting device and manufacturing method thereof
CN103972421A (en) Organic light-emitting device and production method thereof
CN104051641A (en) Laminated organic electroluminescent device and manufacturing method thereof
CN104253227A (en) Organic light emitting diode and preparation method thereof
CN104253231A (en) Organic electroluminescent device and preparation method thereof
CN103824956A (en) Organic electroluminescent device and preparation method thereof
CN103972409A (en) Organic light-emitting device and method for manufacturing same
CN104183740A (en) Organic electroluminescent device and preparation method thereof
CN104425724A (en) Organic electroluminescent device and preparation method thereof
CN104253229A (en) Organic light-emitting device and manufacturing method thereof
CN104425745A (en) Organic electroluminescent device and preparation method thereof
CN103972411A (en) Organic light-emitting device and production method thereof
CN103972410A (en) Organic light-emitting device and production method thereof
CN104183731A (en) Organic light emitting device and manufacturing method thereof
CN104078568A (en) Organic light-emitting diode and preparation method thereof
CN104183777A (en) Organic light emitting device and manufacturing method thereof
CN104183739A (en) Organic electroluminescent device and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20141231