CN104124345A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104124345A
CN104124345A CN201310145684.XA CN201310145684A CN104124345A CN 104124345 A CN104124345 A CN 104124345A CN 201310145684 A CN201310145684 A CN 201310145684A CN 104124345 A CN104124345 A CN 104124345A
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layer
silicon compound
thickness
doped layer
compound doped
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周明杰
黄辉
张振华
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/826—Multilayers, e.g. opaque multilayers
    • 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
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • 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
    • H10K50/856—Arrangements for extracting light from the devices comprising reflective means

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

Abstract

The invention discloses an organic electroluminescent device comprising a conductive anode substrate, a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injection layer, a silicon compound doped layer, a metal layer and a metal compound doped layer which are stacked in sequence. The silicon compound doped layer is made of a mixture mixed by a silicon compound and a phthalocyanines metal compound according to a mass ratio of 0.02:1 to 0.15:1. The silicon compound doped layer of the organic electroluminescent device is made of a mixture mixed by a silicon compound and a phthalocyanines metal compound according to a mass ratio of 0.02:1 to 0.15:1. Particles of the silicon compound are very large and in the shape of microspheres, after preparation, microspherical structures arranged in sequence are formed in a film layer, light encountering the shape of microspheres would be scattered so that light transmitted from two sides can be scattered back to the center of the device, the light exit efficiency is improved, and thus the light emitting efficiency is higher. The invention further discloses a preparation method of the organic electroluminescent device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic electroluminescent field, relate in particular to a kind of organic electroluminescence device and preparation method thereof.
Background technology
1987, the C.W.Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in organic electroluminescent research.Utilize ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, under 10V, brightness reaches 1000cd/m2, and its luminous efficiency is 1.51lm/W, life-span to be greater than 100 hours.
The principle of luminosity of OLED is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from conductive anode substrate.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.
In traditional organic electroluminescence device, the light of device inside only has 18% left and right can be transmitted into outside to go, and that other part can consume at device with other forms is outside, (as the specific refractivity between glass and ITO, glass refraction is 1.5 between interface, refractive index poor, ITO is 1.8, light arrives glass from ITO, and total reflection will occur), caused the loss of total reflection, thereby cause whole bright dipping lower, thereby cause the luminous efficiency of device lower.
Summary of the invention
Based on this, be necessary the organic electroluminescence device that provides a kind of luminous efficiency higher.
A kind of organic electroluminescence device, comprise the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, silicon compound doped layer, metal level and the metallic compound doped layer that stack gradually, described silicon compound doped layer, metal level and metallic compound doped layer form cathode composite layer;
The material of described silicon compound doped layer is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio;
The material of described metal level is that work function is-metal of 2.0eV～-3.5eV;
The material of described metallic compound doped layer is that the metal sulfide that bipolarity metal oxide and refractive index are 1.8～2.0 is the mixture that 1:1～1:2 is mixed to get according to mass ratio.
In one embodiment, described silicon compound is silicon monoxide, silicon dioxide or sodium metasilicate;
Described phthalocyanines metallic compound is CuPc, Phthalocyanine Zinc, phthalocyanine vanadium or magnesium phthalocyanine;
The thickness of described silicon compound doped layer is 10nm～30nm.
In one embodiment, the material of described metal level is magnesium, strontium, calcium or ytterbium;
The thickness of described metal level is 5nm～10nm.
In one embodiment, described bipolarity metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide;
Described refractive index is that 1.8～2.0 metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide;
The thickness of described metallic compound doped layer is 200nm～400nm.
In one embodiment, the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide, and the thickness of described hole injection layer is 20nm～80nm.
In one embodiment, the material of described hole transmission layer is 1,1-, bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; The thickness of described hole transmission layer is 20nm～60nm.
In one embodiment, the material of described luminescent layer is 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'-, 1'-biphenyl or oxine aluminium, the thickness of described luminescent layer is 5nm～40nm.
In one embodiment, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2, and 4-triazole derivative or N-aryl benzimidazole, the thickness of described electron transfer layer is 40nm～300nm.
In one embodiment, the material of described electron injecting layer is cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride, and the thickness of described electron injecting layer is 0.5nm～10nm.
A preparation method for organic electroluminescence device, comprises the steps:
Conductive anode substrate is carried out to surface preparation;
In described conductive anode substrate, evaporation forms hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively;
On described electron injecting layer, electron beam evaporation plating forms silicon compound doped layer, wherein, the material of described silicon compound doped layer is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio, and the energy density of described electron beam evaporation plating is 10W/cm 2～l00W/cm 2;
On described silicon compound doped layer, evaporation forms metal level and metallic compound doped layer successively, obtain described organic electroluminescence device, described silicon compound doped layer, metal level and metallic compound doped layer form cathode composite layer, wherein, the material of described metal level is that work function is-metal of 2.0eV～-3.5eV, and the material of described metallic compound doped layer is that the metal sulfide that bipolarity metal oxide and refractive index are 1.8～2.0 is the mixture that 1:1～1:2 is mixed to get according to mass ratio.
The material of the silicon compound doped layer of this organic electroluminescence device is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio, silicon compound particle is larger, be microspheroidal, preparation makes inner formation of rete arrange orderly micro-sphere structure after getting on, light is encountered this microspheroidal and can be formed in the middle of thereby scattering makes to get back to device to the light scattering of both sides transmittings, improve light extraction efficiency, thereby luminous efficiency is higher.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's the flow chart of the organic electroluminescence device of an execution mode;
Fig. 3 is the current density of organic electroluminescence device and the graph of a relation of current efficiency that embodiment 1 and comparative example prepare.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
The organic electroluminescence device of an execution mode as shown in Figure 1, it is characterized in that, comprise conductive anode substrate 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60, silicon compound doped layer 70, metal level 80 and metallic compound doped layer 90.
Silicon compound doped layer 70, metal level 80 and metallic compound doped layer 90 form cathode composite layer.
Conductive anode substrate 10 can be indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).At one, preferably in embodiment, conductive anode substrate 10 is indium tin oxide glass (ITO).
The thickness of the conductive layer of anode conducting substrate 10 can be 80nm～150nm.
The material of hole injection layer 20 can be molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5).The thickness of hole injection layer 20 can be 20nm～80nm.At one, preferably in embodiment, the material of hole injection layer 20 is tungstic acid (WO 3), the thickness of hole injection layer 20 is 30nm.
The material of hole transmission layer 30 can be 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB).The thickness of hole transmission layer 30 can be 20nm～60nm.At one, preferably in embodiment, the material of hole transmission layer 30 is N, N'-(1-naphthyl)-N, and N'-diphenyl-4,4'-benzidine (NPB), the thickness of hole transmission layer 30 is 40nm.
The material of luminescent layer 40 can be 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) or oxine aluminium (Alq 3).The thickness of luminescent layer 40 can be 5nm～40nm.At one, preferably in embodiment, the material of luminescent layer 40 is oxine aluminium (Alq 3), the thickness of luminescent layer 40 is 22nm.
The material of electron transfer layer 50 can be 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (TAZ) or N-aryl benzimidazole (TPBI).The thickness of electron transfer layer 50 can be 40nm～300nm.At one, preferably in embodiment, the material of electron transfer layer 50 is TAZ, and the thickness of electron transfer layer 50 is 120nm.
The material of electron injecting layer 60 can be cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) or lithium fluoride (LiF).The thickness of electron injecting layer 60 can be 0.5nm～10nm.At one, preferably in embodiment, the material of electron injecting layer 60 is LiF, and the thickness of electron injecting layer 60 is 0.7nm.
The material of silicon compound doped layer 70 is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio.
Silicon compound can be silicon monoxide (SiO), silicon dioxide (SiO 2) or sodium metasilicate (Na 2siO 3).
Phthalocyanines metallic compound can be CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) or magnesium phthalocyanine (MgPc).
The thickness of silicon compound doped layer 70 can be 10nm～30nm.
The material of metal level 80 is that work function is-metal of 2.0eV～-3.5eV.Concrete, the material of metal level 80 can be magnesium (Mg), strontium (Sr), calcium (Ca) or ytterbium (Yb).
The thickness of metal level 80 can be 5nm～10nm.
The material of metallic compound doped layer 90 is that the metal sulfide that bipolarity metal oxide and refractive index are 1.8～2.0 is the mixture that 1:1～1:2 is mixed to get according to mass ratio.
Bipolarity metal oxide can be molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5).
Refractive index is that 1.8～2.0 metal sulfide can be zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) or copper sulfide (CuS).
The thickness of metallic compound doped layer 90 is 200nm～400nm.
The material of the silicon compound doped layer 70 of this organic electroluminescence device is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio, silicon compound particle is larger, be microspheroidal, preparation makes inner formation of rete arrange orderly micro-sphere structure after getting on, light is encountered this microspheroidal and can be formed in the middle of thereby scattering makes to get back to device to the light scattering of both sides transmittings, improve light extraction efficiency, thereby luminous efficiency is higher.
Simultaneously, after the crystallization of phthalocyanines metallic compound, make segment marshalling, make film surface form wave structure, make the light scattering of Vertical Launch, no longer vertical, thereby can not be coupled with the free electron of metal level (parallel free electron can lose with vertical photon coupling), improve photon utilance.
The material of metal level 80 is that work function is-metal of 2.0eV～-3.5eV, is conducive to the injection of electronics, improves the injection efficiency of electronics.
The material of metallic compound doped layer 90 is that the metal sulfide that bipolarity metal oxide and refractive index are 1.8～2.0 is the mixture that 1:1～1:2 is mixed to get according to mass ratio, bipolarity metal oxide can transmission electronic, improve the injection efficiency of electronics, metal sulfide can reflect light, make to reflect back into bottom to the light process of top-emission, improve light extraction efficiency, thereby effectively improve luminous efficiency.
In addition, silicon compound is more stable in air, can improve the stability of metal level after doping.The material of metal level 80 is that work function is-metal of 2.0eV～-3.5eV, is conducive to reduce the injection barrier of electronics, improves electron injection efficiency.Electron transfer layer 50 can improve the electron density of cathode composite layer, thereby improves carrier transport speed, simultaneously, electron transfer layer 50 can also improve the evenness of cathode composite layer film forming, smooth surface, reduces the existence of inner electron trap, thereby improves luminous efficiency.
The preparation method of above-mentioned organic electroluminescence device as shown in Figure 2, comprises the steps:
S10, conductive anode substrate 10 is carried out to surface preparation.
Conductive anode substrate 10 can be indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).At one, preferably in embodiment, conductive anode substrate 10 is indium tin oxide glass (ITO).
The thickness of the conductive layer of anode conducting substrate 10 can be 80nm～150nm.
The operation of surface preparation can be: first conductive anode substrate 10 is carried out to photoetching treatment, be cut into needed size, with liquid detergent, deionized water, acetone, ethanol and isopropyl alcohol difference ultrasonic cleaning 15min, remove the organic pollution on conductive anode substrate 10 surfaces successively.
S20, in conductive anode substrate 10, evaporation forms hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50 and electron injecting layer 60 successively.
In evaporate process, operating pressure is 2 * 10 -3～5 * 10 -5pa, the evaporation speed of organic material is 0.1～1nm/s, the evaporation speed of metal and metallic compound is 1～10nm/s.
The material of hole injection layer 20 can be molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5).The thickness of hole injection layer 20 can be 20nm～80nm.At one, preferably in embodiment, the material of hole injection layer 20 is tungstic acid (WO 3), the thickness of hole injection layer 20 is 30nm.
The material of hole transmission layer 30 can be 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB).The thickness of hole transmission layer 30 can be 20nm～60nm.At one, preferably in embodiment, the material of hole transmission layer 30 is N, N'-(1-naphthyl)-N, and N'-diphenyl-4,4'-benzidine (NPB), the thickness of hole transmission layer 30 is 40nm.
The material of luminescent layer 40 can be 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) or oxine aluminium (Alq 3).The thickness of luminescent layer 40 can be 5nm～40nm.At one, preferably in embodiment, the material of luminescent layer 40 is oxine aluminium (Alq 3), the thickness of luminescent layer 40 is 22nm.
The material of electron transfer layer 50 can be electron transport material.The thickness of electron transfer layer 50 can be 40nm～300nm.Electric transmission layer material can be 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (TAZ) or N-aryl benzimidazole (TPBI).At one, preferably in embodiment, the material of electron transfer layer 50 is TAZ, and the thickness of electron transfer layer 50 is 120nm.
The material of electron injecting layer 60 can be cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) or lithium fluoride (LiF).The thickness of electron injecting layer 60 can be 0.5nm～10nm.At one, preferably in embodiment, the material of electron injecting layer 60 is LiF, and the thickness of electron injecting layer 60 is 0.7nm.
S30, on electron injecting layer 60, electron beam evaporation plating forms silicon compound doped layer 70.
In electron beam evaporation plating process, operating pressure is 2 * 10 -3～5 * 10 -5pa.The energy density of electron beam evaporation plating is 10W/cm 2～l00W/cm 2.
The material of silicon compound doped layer 70 is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio.
Silicon compound can be silicon monoxide (SiO), silicon dioxide (SiO 2) or sodium metasilicate (Na 2siO 3).
Phthalocyanines metallic compound can be CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) or magnesium phthalocyanine (MgPc).
The thickness of silicon compound doped layer 70 can be 10nm～30nm.
S40, on silicon compound doped layer 70, evaporation forms metal level 80 and metallic compound doped layer 90 successively, obtains organic electroluminescence device.
Silicon compound doped layer 70, metal level 80 and metallic compound doped layer 90 form cathode composite layer.
In evaporate process, operating pressure is 2 * 10 -3～5 * 10 -5pa, the evaporation speed of organic material is 0.1～1nm/s, the evaporation speed of metal and metallic compound is 1～10nm/s.
The material of metal level 80 is that work function is-metal of 2.0eV～-3.5eV.Concrete, the material of metal level 80 can be magnesium (Mg), strontium (Sr), calcium (Ca) or ytterbium (Yb).
The thickness of metal level 80 can be 5nm～10nm.
The material of metallic compound doped layer 90 is that the metal sulfide that bipolarity metal oxide and refractive index are 1.8～2.0 is the mixture that 1:1～1:2 is mixed to get according to mass ratio.
Bipolarity metal oxide can be molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5).
Refractive index is that 1.8～2.0 metal sulfide can be zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) or copper sulfide (CuS).
The thickness of metallic compound doped layer 90 is 200nm～400nm.
The material of the silicon compound doped layer 70 of the organic electroluminescence device that this organic electroluminescence device preparation method prepares is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio, silicon compound particle is larger, be microspheroidal, preparation makes inner formation of rete arrange orderly micro-sphere structure after getting on, light is encountered this microspheroidal and can be formed in the middle of thereby scattering makes to get back to device to the light scattering of both sides transmittings, improve light extraction efficiency, thereby luminous efficiency is higher.
Be below specific embodiment and comparative example part, the test and the Preparation equipment that in embodiment, use comprise: the high vacuum coating system (evaporation) of 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 U.S. Keithley company), the CS-100A colorimeter (test brightness and colourity) of Japanese Konica Minolta company.
In specific embodiment and comparative example part, "/" represents stacked, and ": " represents that the former with the latter mixes, and m:n represents the former and the latter's mass ratio.
Embodiment 1
A kind of organic electroluminescence device, comprise the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, silicon compound doped layer, metal level and the metallic compound doped layer that stack gradually, concrete structure is expressed as: ito glass/WO 3/ NPB/Alq 3/ TAZ/LiF/SiO:CuPc(0.1:1)/Mg/MoO 3: ZnS(1:1.2).Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and with liquid detergent and deionized water, ito glass is carried out to ultrasonic cleaning 15min successively, removes the organic pollution of glass surface.
In operating pressure, be 8 * 10 -5under the condition of Pa, according to the evaporation speed of organic material, be 0.2nm/s, the evaporation speed of metal and metallic compound is 3nm/s, and on ito glass, evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively.The material of hole injection layer is WO 3, thickness is 30nm.The material of hole transmission layer is NPB, and thickness is 40nm.The material of luminescent layer is Alq 3, thickness is 22nm.The material of electron transfer layer is TAZ, and thickness is 120nm.The material of electron injecting layer is LiF, and thickness is 0.7nm.
Then the energy density at electron beam evaporation plating is 50W/cm 2condition under, on electron injecting layer, electron beam evaporation plating is prepared silicon compound doped layer.The material of silicon compound doped layer is that SiO and CuPc are the mixture (can be expressed as SiO:CuPc) that 0.1:1 is mixed to get according to mass ratio, and thickness is 20nm.
In operating pressure, be 8 * 10 -5under the condition of Pa, according to the evaporation speed of organic material, be 0.2nm/s, the evaporation speed of metal and metallic compound is 3nm/s, and on silicon compound doped layer, evaporation forms metal level and metallic compound doped layer successively, obtains organic electroluminescence device.The material of metal level is Mg, and thickness is 7nm.The material of metallic compound doped layer is MoO 3according to mass ratio, be that the mixture that 1:1.2 is mixed to get (can be expressed as MoO with ZnS 3: ZnS), thickness is 250nm.
Embodiment 2
A kind of organic electroluminescence device, comprise the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, silicon compound doped layer, metal level and the metallic compound doped layer that stack gradually, concrete structure is expressed as: AZO glass/MoO 3/ TCTA/ADN/TAZ/CsF/SiO 2: ZnPc(0.01:1)/Sr/WO 3: CdS(1:1).Preparation process is:
It is the AZO glass of 80nm that conductive layer thickness is provided, and with liquid detergent and deionized water, AZO glass is carried out to ultrasonic cleaning 15min successively, removes the organic pollution of glass surface.
In operating pressure, be 2 * 10 -3under the condition of Pa, according to the evaporation speed of organic material, be 0.1nm/s, the evaporation speed of metal and metallic compound is 10nm/s, at AZO evaporation successively on glass, prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer.The material of hole injection layer is MoO 3, thickness is 80nm.The material of hole transmission layer is TCTA, and thickness is 60nm.The material of luminescent layer is ADN, and thickness is 5nm.The material of electron transfer layer is TAZ, and thickness is 200nm.The material of electron injecting layer is CsF, and thickness is 10nm.
Then the energy density at electron beam evaporation plating is 10W/cm 2condition under, on electron injecting layer, electron beam evaporation plating is prepared silicon compound doped layer.The material of silicon compound doped layer is SiO 2according to mass ratio, be that the mixture that 0.01:1 is mixed to get (can be expressed as SiO with ZnPc 2: ZnPc), thickness is 10nm.
In operating pressure, be 2 * 10 -3under the condition of Pa, according to the evaporation speed of organic material, be 0.1nm/s, the evaporation speed of metal and metallic compound is 10nm/s, and on silicon compound doped layer, evaporation forms metal level and metallic compound doped layer successively, obtains organic electroluminescence device.The material of metal level is Sr, and thickness is 5nm.The material of metallic compound doped layer is WO 3according to mass ratio, be that the mixture that 1:1 is mixed to get (can be expressed as WO with CdS 3: CdS), thickness is 400nm.
Embodiment 3
A kind of organic electroluminescence device, comprise the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, silicon compound doped layer, metal level and the metallic compound doped layer that stack gradually, concrete structure is expressed as: IZO glass/V 2o 5/ TCTA/BCzVBi/TPBi/Cs 2cO 3/ Na 2siO 3: VPc(0.15:1)/Ca/V 2o 5: MgS(1:2).Preparation process is:
It is the IZO glass of 120nm that conductive layer thickness is provided, and with liquid detergent and deionized water, IZO glass is carried out to ultrasonic cleaning 15min successively, removes the organic pollution of glass surface.
In operating pressure, be 5 * 10 -5under the condition of Pa, according to the evaporation speed of organic material, be 1nm/s, the evaporation speed of metal and metallic compound is 1nm/s, at IZO evaporation successively on glass, prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer.The material of hole injection layer is V 2o 5, thickness is 20nm.The material of hole transmission layer is TCTA, and thickness is 30nm.The material of luminescent layer is BCzVBi, and thickness is 40nm.The material of electron transfer layer is TPBi, and thickness is 60nm.The material of electron injecting layer is Cs 2cO 3, thickness is 0.5nm.
Then the energy density at electron beam evaporation plating is 100W/cm 2condition under, on electron injecting layer, electron beam evaporation plating is prepared silicon compound doped layer.The material of silicon compound doped layer is Na 2siO 3according to mass ratio, be that the mixture that 0.15:1 is mixed to get (can be expressed as Na with VPc 2siO 3: VPc), thickness is 30nm.
In operating pressure, be 5 * 10 -5under the condition of Pa, according to the evaporation speed of organic material, be 1nm/s, the evaporation speed of metal and metallic compound is 1nm/s, and on silicon compound doped layer, evaporation forms metal level and metallic compound doped layer successively, obtains organic electroluminescence device.The material of metal level is Ca, and thickness is 5nm.The material of metallic compound doped layer is V 2o 5according to mass ratio, be that the mixture that 1:2 is mixed to get (can be expressed as V with MgS 2o 5: MgS), thickness is 200nm.
Embodiment 4
A kind of organic electroluminescence device, comprise the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, silicon compound doped layer, metal level and the metallic compound doped layer that stack gradually, concrete structure is expressed as: IZO glass/WO 3/ TAPC/DCJTB/Bphen/CsN 3/ SiO 2: MgPc(0.12:1)/Yb/MoO 3: CuS(1:1.1).Preparation process is:
It is the IZO glass of 150nm that conductive layer thickness is provided, and with liquid detergent and deionized water, IZO glass is carried out to ultrasonic cleaning 15min successively, removes the organic pollution of glass surface.
In operating pressure, be 5 * 10 -4under the condition of Pa, according to the evaporation speed of organic material, be 0.2nm/s, the evaporation speed of metal and metallic compound is 5nm/s, at IZO evaporation successively on glass, prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer.The material of hole injection layer is WO 3, thickness is 30nm.The material of hole transmission layer is TAPC, and thickness is 50nm.The material of luminescent layer is DCJTB, and thickness is 5nm.The material of electron transfer layer is Bphen, and thickness is 40nm.The material of electron injecting layer is CsN 3, thickness is 1nm.
Then the energy density at electron beam evaporation plating is 30W/cm 2condition under, on electron injecting layer, electron beam evaporation plating is prepared silicon compound doped layer.The material of silicon compound doped layer is SiO 2according to mass ratio, be that the mixture that 0.12:1 is mixed to get (can be expressed as SiO with MgPc 2: MgPc), thickness is 18nm.
In operating pressure, be 5 * 10 -4under the condition of Pa, according to the evaporation speed of organic material, be 0.2nm/s, the evaporation speed of metal and metallic compound is 5nm/s, and on silicon compound doped layer, evaporation forms metal level and metallic compound doped layer successively, obtains organic electroluminescence device.The material of metal level is Yb, and thickness is 6nm.The material of metallic compound doped layer is MoO 3according to mass ratio, be that the mixture that 1:1.1 is mixed to get (can be expressed as MoO with CuS 3: CuS), thickness is 350nm.
Comparative example
An organic electroluminescence device, comprises the conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and concrete structure is expressed as: ito glass/WO 3/ NPB/Alq 3/ TAZ/LiF/Ag.Preparation process is:
It is the ito glass of 100nm that conductive layer thickness is provided, and with liquid detergent and deionized water, ito glass is carried out to ultrasonic cleaning 15min successively, removes the organic pollution of glass surface.
In operating pressure, be 8 * 10 -5under the condition of Pa, according to the evaporation speed of organic material, be 0.2nm/s, the evaporation speed of metal and metallic compound is 3nm/s, and on ito glass, evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively.The material of hole injection layer is WO 3, thickness is 30nm.The material of hole transmission layer is NPB, and thickness is 40nm.The material of luminescent layer is Alq 3, thickness is 22nm.The material of electron transfer layer is TAZ, and thickness is 120nm.The material of electron injecting layer is LiF, and thickness is 0.7nm.The materials A g of negative electrode, thickness is 200nm.
Fig. 3 is the current density of organic electroluminescence device and the graph of a relation of current efficiency that embodiment 1 and comparative example prepare, and curve 1 shows the current density of organic electroluminescence device and the relation of current efficiency of embodiment 1 preparation; The current density of organic electroluminescence device and the relation of current efficiency of curve 2 display comparison example preparations.As can be seen from Figure 3, under different current densities, the organic electroluminescence device that the current efficiency of the organic electroluminescence device that embodiment 1 prepares all prepares than comparative example large, the maximum current efficiency of embodiment 1 is 12.72cd/A, and that comparative example is only 10.45cd/A.
The inner formation of rete that make of the silicon compound doped layer of the organic electroluminescence device that embodiment 1 prepares, metal level and metallic compound doped layer arranged orderly micro-sphere structure, make film surface form wave structure, improve photon utilance, improve the injection efficiency of electronics, transmission electronic, make to reflect back into bottom to the light process of top-emission, improve light extraction efficiency, this composite cathode being comprised of silicon compound doped layer, metal level and metallic compound doped layer can effectively improve luminous efficiency.
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 conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, silicon compound doped layer, metal level and the metallic compound doped layer that stack gradually, described silicon compound doped layer, metal level and metallic compound doped layer form cathode composite layer;
The material of described silicon compound doped layer is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio;
The material of described metal level is that work function is-metal of 2.0eV～-3.5eV;
The material of described metallic compound doped layer is that the metal sulfide that bipolarity metal oxide and refractive index are 1.8～2.0 is the mixture that 1:1～1:2 is mixed to get according to mass ratio.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described silicon compound is silicon monoxide, silicon dioxide or sodium metasilicate;
Described phthalocyanines metallic compound is CuPc, Phthalocyanine Zinc, phthalocyanine vanadium or magnesium phthalocyanine;
The thickness of described silicon compound doped layer is 10nm～30nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described metal level is magnesium, strontium, calcium or ytterbium;
The thickness of described metal level is 5nm～10nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described bipolarity metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide;
Described refractive index is that 1.8～2.0 metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide;
The thickness of described metallic compound doped layer is 200nm～400nm.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide, and the thickness of described hole injection layer is 20nm～80nm.
6. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine; The thickness of described hole transmission layer is 20nm～60nm.
7. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described luminescent layer is 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'-, 1'-biphenyl or oxine aluminium, the thickness of described luminescent layer is 5nm～40nm.
8. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, the thickness of described electron transfer layer is 40nm～300nm.
9. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described electron injecting layer is cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride, and the thickness of described electron injecting layer is 0.5nm～10nm.
10. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Conductive anode substrate is carried out to surface preparation;
In described conductive anode substrate, evaporation forms hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively;
On described electron injecting layer, electron beam evaporation plating forms silicon compound doped layer, wherein, the material of described silicon compound doped layer is that silicon compound and phthalocyanines metallic compound are the mixture that 0.02:1～0.15:1 is mixed to get according to mass ratio, and the energy density of described electron beam evaporation plating is 10W/cm 2～l00W/cm 2;
On described silicon compound doped layer, evaporation forms metal level and metallic compound doped layer successively, obtain described organic electroluminescence device, described silicon compound doped layer, metal level and metallic compound doped layer form cathode composite layer, wherein, the material of described metal level is that work function is-metal of 2.0eV～-3.5eV, and the material of described metallic compound doped layer is that the metal sulfide that bipolarity metal oxide and refractive index are 1.8～2.0 is the mixture that 1:1～1:2 is mixed to get according to mass ratio.
CN201310145684.XA 2013-04-24 2013-04-24 Organic electroluminescent device and preparation method thereof Pending CN104124345A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020036297A1 (en) * 2000-02-04 2002-03-28 Karl Pichler Low absorption sputter protection layer for OLED structure
CN1596048A (en) * 2004-05-07 2005-03-16 友达光电股份有限公司 Organic luminous display, cathode composite layer and method for manufacturing same
CN1825662A (en) * 2006-02-09 2006-08-30 友达光电股份有限公司 Organic electroluminescent device
CN101710612A (en) * 2009-11-13 2010-05-19 清华大学 Organic electroluminescent device
CN101859879A (en) * 2010-05-26 2010-10-13 上海大学 White organic electroluminescent device and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020036297A1 (en) * 2000-02-04 2002-03-28 Karl Pichler Low absorption sputter protection layer for OLED structure
CN1596048A (en) * 2004-05-07 2005-03-16 友达光电股份有限公司 Organic luminous display, cathode composite layer and method for manufacturing same
CN1825662A (en) * 2006-02-09 2006-08-30 友达光电股份有限公司 Organic electroluminescent device
CN101710612A (en) * 2009-11-13 2010-05-19 清华大学 Organic electroluminescent device
CN101859879A (en) * 2010-05-26 2010-10-13 上海大学 White organic electroluminescent device and preparation method thereof

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