CN104124380A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN104124380A CN104124380A CN201310145216.2A CN201310145216A CN104124380A CN 104124380 A CN104124380 A CN 104124380A CN 201310145216 A CN201310145216 A CN 201310145216A CN 104124380 A CN104124380 A CN 104124380A
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- H10K50/00—Organic light-emitting devices
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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
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- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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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 phthalocyanines metal compound layer and a conductive thin film layer which are stacked in sequence. The silicon compound doped layer of the organic electroluminescent device is made of a mixture mixed by a silicon compound and a metal sulfide having a refractive index of 1.8 to 2.0 according to a mass ratio of 5:1 to 20:1. 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, the metal sulfide is higher in transmittance in a visible light range, and the light transmittance can be improved. Compared with a conventional organic electroluminescent device, the organic electroluminescent device is higher in light emitting efficiency. The invention further discloses a preparation method of the organic electroluminescent device.
Description
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 Eastman Kodak company of the U.S. 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 other part can consume in device outside with other forms, (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), cause the loss of total reflection, thereby cause overall 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, phthalocyanines metal compound layer and the conductive membrane layer that stack gradually, described silicon compound doped layer, phthalocyanines metal compound layer and conductive membrane layer composition cathode composite layer;
The material of described silicon compound doped layer is that the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 is mixed to get according to mass ratio;
The material of described phthalocyanines metal compound layer is phthalocyanines metallic compound;
The material of described conductive membrane layer is conducting metal oxide.
In one embodiment, described silicon compound is silicon monoxide, silicon dioxide or sodium metasilicate;
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 silicon compound doped layer is 10nm～40nm.
In one embodiment, described phthalocyanines metallic compound is CuPc, Phthalocyanine Zinc, phthalocyanine vanadium or magnesium phthalocyanine;
The thickness of described phthalocyanines metal compound layer is 5nm～60nm.
In one embodiment, described conducting metal oxide is indium tin oxide, aluminium zinc oxide or indium-zinc oxide;
The thickness of described conductive membrane layer is 100nm～250nm.
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, 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-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 the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 is mixed to get according to mass ratio, and the energy density of described electron beam evaporation plating is 10W/cm
2～100W/cm
2;
On described silicon compound doped layer, evaporation forms phthalocyanines metal compound layer, and wherein, the material of described phthalocyanines metal compound layer is phthalocyanines metallic compound;
On described phthalocyanines metal compound layer, magnetron sputtering forms conductive membrane layer, obtain described organic electroluminescence device, described silicon compound doped layer, phthalocyanines metal compound layer and conductive membrane layer composition cathode composite layer, wherein, the material of described conductive membrane layer is conducting metal oxide, the accelerating voltage of described magnetron sputtering is 300V～800V, and magnetic field is 50G～200G, and power density is 1W/cm
2～40W/cm
2.
The material of the silicon compound doped layer of this organic electroluminescence device is that the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 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, thereby light is encountered this microspheroidal and can be formed scattering and make to get back in the middle of device to the light scattering of both sides transmittings, improve light extraction efficiency, metal sulfide transmitance in visible-range is higher, can improve the transmitance of light, with respect to traditional organic electroluminescence device, luminous efficiency is higher.
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 the current density of organic electroluminescence device and the graph of a relation of luminous 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 are 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, and therefore 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, phthalocyanines metal compound layer 80 and conductive membrane layer 90.
Silicon compound doped layer 70, phthalocyanines metal compound layer 80 and conductive membrane 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 molybdenum trioxide (MoO
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 50nm.
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), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-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 18nm.
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 100nm.
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 1nm.
The material of silicon compound doped layer 70 is that the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 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).
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 silicon compound doped layer 70 can be 10nm～40nm.
Phthalocyanines metal compound layer 80 materials are phthalocyanines metallic compound.
Phthalocyanines metallic compound can be CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) or magnesium phthalocyanine (MgPc).
The thickness of phthalocyanines metal compound layer 80 can be 5nm～60nm.
The material of conductive membrane layer 90 is conducting metal oxide.Conducting metal oxide can be indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).
The thickness of conductive membrane layer 90 can be 100nm～250nm.
The material of the silicon compound doped layer 70 of this organic electroluminescence device is that the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 is mixed to get according to mass ratio,
Phthalocyanines metal compound layer 80 materials are phthalocyanines metallic compound, 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 the metallic element of conductive membrane layer (parallel free electron can lose with vertical photon coupling), improve photon utilance.
Conductive membrane layer 90 improves conductivity, and under certain thickness, can make reflection of light strengthen, and effectively 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 ultrasonic cleaning 15min respectively, 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 molybdenum trioxide (MoO
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 50nm.
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), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-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 18nm.
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 100nm.
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 1nm.
S30, on electron injecting layer 60, electron beam evaporation plating forms silicon compound doped layer 70.
The energy density of electron beam evaporation plating is 10W/cm
2～100W/cm
2.
The material of silicon compound doped layer 70 is that the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 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).
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 silicon compound doped layer 70 can be 10nm～40nm.
S40, on silicon compound doped layer 70, evaporation forms phthalocyanines metal compound layer 80.
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.
Phthalocyanines metal compound layer 80 materials are phthalocyanines metallic compound.
Phthalocyanines metallic compound can be CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine vanadium (VPc) or magnesium phthalocyanine (MgPc).
The thickness of phthalocyanines metal compound layer 80 can be 5nm～60nm.
S50, on phthalocyanines metal compound layer 80 magnetron sputtering form conductive membrane layer 90, obtain organic electroluminescence device.
In magnetron sputtering process, accelerating voltage is 300V～800V, and magnetic field is 50G～200G, and power density is 1W/cm
2～40W/cm
2.
Silicon compound doped layer 70, phthalocyanines metal compound layer 80 and conductive membrane layer 90 form cathode composite layer.
The material of conductive membrane layer 90 is conducting metal oxide.Conducting metal oxide can be indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).
Conductive membrane layer 90 can pass through indium-tin oxide target material (ITO), aluminium zinc oxide target (AZO) or indium-zinc oxide target (IZO), adopts the method preparation of magnetron sputtering.
The thickness of conductive membrane layer 90 can be 100nm～250nm.
The material of the silicon compound doped layer 70 of this organic electroluminescence device is that the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 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, thereby light is encountered this microspheroidal and can be formed scattering and make to get back in the middle of device to the light scattering of both sides transmittings, improve light extraction efficiency, metal sulfide transmitance in visible-range higher (in visible-range, transmitance reaches 80%～90%), can improve the transmitance of light.
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 Keithley company of the U.S.), 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, phthalocyanines metal compound layer and the metallic compound doped layer that stack gradually, concrete structure is expressed as: ito glass/MoO
3/ NPB/Alq
3/ TAZ/LiF/SiO
2: ZnS(7:1)/CuPc/ITO.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.
Be 8 × 10 in operating pressure
-5under the condition of Pa, be 0.2nm/s according to the evaporation speed of organic material, 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 MoO
3, thickness is 30nm.The material of hole transmission layer is NPB, and thickness is 50nm.The material of luminescent layer is Alq
3, thickness is 18nm.The material of electron transfer layer is TAZ, and thickness is 100nm.The material of electron injecting layer is LiF, and thickness is 1nm.
Then be 50W/cm in the energy density of electron beam evaporation plating
2condition under, on electron injecting layer, electron beam evaporation plating is prepared silicon compound doped layer.The material SiO of silicon compound doped layer
2be that the mixture that 7:1 is mixed to get (can be expressed as SiO with ZnS according to mass ratio
2: ZnS), thickness is 15nm.
Then be 8 × 10 in operating pressure
-5under the condition of Pa, be 0.2nm/s according to the evaporation speed of organic material, the evaporation speed of metal and metallic compound is 3nm/s, and on silicon compound doped layer, evaporation is prepared phthalocyanines metal compound layer.The material of phthalocyanines metal compound layer is CuPc, and thickness is 25nm.
On phthalocyanines metal compound layer, magnetron sputtering is prepared conductive membrane layer, obtains organic electroluminescence device.In magnetron sputtering process, accelerating voltage is 500V, and magnetic field is 100G, and power density is 25W/cm
2.The material of conductive membrane layer is ITO, and thickness is 150nm.
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, phthalocyanines metal compound layer and the metallic compound doped layer that stack gradually, concrete structure is expressed as: AZO glass/MoO
3/ TCTA/ADN/TAZ/CsF/SiO:CdS(5:1)/ZnPc/AZO.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.
Be 2 × 10 in operating pressure
-3under the condition of Pa, be 0.1nm/s according to the evaporation speed of organic material, the evaporation speed of metal and metallic compound is 10nm/s, prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer at AZO evaporation successively on glass.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 be 10W/cm in the energy density of electron beam evaporation plating
2condition under, on electron injecting layer, electron beam evaporation plating is prepared silicon compound doped layer.The material SiO of silicon compound doped layer and CdS are the mixture (can be expressed as SiO:CdS) that 5:1 is mixed to get according to mass ratio, and thickness is 40nm.
Then be 2 × 10 in operating pressure
-3under the condition of Pa, be 0.1nm/s according to the evaporation speed of organic material, the evaporation speed of metal and metallic compound is 10nm/s, and on silicon compound doped layer, evaporation is prepared phthalocyanines metal compound layer.The material of phthalocyanines metal compound layer is ZnPc, and thickness is 60nm.
On phthalocyanines metal compound layer, magnetron sputtering is prepared conductive membrane layer, obtains organic electroluminescence device.In magnetron sputtering process, accelerating voltage is 300V, and magnetic field is 200G, and power density is 1W/cm
2.The material of conductive membrane layer is AZO, and thickness is 100nm.
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, phthalocyanines metal compound layer 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: MgS(10:1)/VPc(2:1)/IZO.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.
Be 5 × 10 in operating pressure
-5under the condition of Pa, be 1nm/s according to the evaporation speed of organic material, the evaporation speed of metal and metallic compound is 1nm/s, prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer at IZO evaporation successively on glass.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 be 100W/cm in the energy density of electron beam evaporation plating
2condition under, on electron injecting layer, electron beam evaporation plating is prepared silicon compound doped layer.The material Na of silicon compound doped layer
2siO
3be that the mixture that 10:1 is mixed to get (can be expressed as Na with MgS according to mass ratio
2siO
3: MgS), thickness is 10nm.
Then be 5 × 10 in operating pressure
-5under the condition of Pa, be 1nm/s according to the evaporation speed of organic material, the evaporation speed of metal and metallic compound is 1nm/s, and on silicon compound doped layer, evaporation is prepared phthalocyanines metal compound layer.The material of phthalocyanines metal compound layer is VPc, and thickness is 5nm.
On phthalocyanines metal compound layer, magnetron sputtering is prepared conductive membrane layer, obtains organic electroluminescence device.In magnetron sputtering process, accelerating voltage is 800V, and magnetic field is 50G, and power density is 40W/cm
2.The material of conductive membrane layer is IZO, and thickness is 250nm.
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, phthalocyanines metal compound layer and the metallic compound doped layer that stack gradually, concrete structure is expressed as: IZO glass/WO
3/ TAPC/DCJTB/Bphen/CsN
3/ ITO/MgPc:TiO
2(1.5:1)/Au:CuS(15:1).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.
Be 5 × 10 in operating pressure
-4under the condition of Pa, be 0.2nm/s according to the evaporation speed of organic material, the evaporation speed of metal and metallic compound is 5nm/s, prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer at IZO evaporation successively on glass.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 be 30W/cm in the energy density of electron beam evaporation plating
2condition under, on electron injecting layer, electron beam evaporation plating is prepared silicon compound doped layer.The material SiO of silicon compound doped layer
2be that the mixture that 8:1 is mixed to get (can be expressed as SiO with CuS according to mass ratio
2: CuS), thickness is 30nm.
Then be 5 × 10 in operating pressure
-4under the condition of Pa, be 0.2nm/s according to the evaporation speed of organic material, the evaporation speed of metal and metallic compound is 5nm/s, and on silicon compound doped layer, evaporation is prepared phthalocyanines metal compound layer.The material of phthalocyanines metal compound layer is MgPc, and thickness is 40nm.
On phthalocyanines metal compound layer, magnetron sputtering is prepared conductive membrane layer, obtains organic electroluminescence device.In magnetron sputtering process, accelerating voltage is 400V, and magnetic field is 150G, and power density is 30W/cm
2.The material of conductive membrane layer is ITO, and thickness is 200nm.
Comparative example
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, phthalocyanines metal compound layer and the metallic compound doped layer that stack gradually, concrete structure is expressed as: ito glass/MoO
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.
Be 8 × 10 in operating pressure
-5under the condition of Pa, be 0.2nm/s according to the evaporation speed of organic material, 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 MoO
3, thickness is 30nm.The material of hole transmission layer is NPB, and thickness is 50nm.The material of luminescent layer is Alq
3, thickness is 18nm.The material of electron transfer layer is TAZ, and thickness is 100nm.The material of electron injecting layer is LiF, and thickness is 1nm.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 luminous efficiency that embodiment 1 and comparative example prepare, and curve 1 shows the current density of organic electroluminescence device and the relation of luminous efficiency prepared by embodiment 1; The current density of organic electroluminescence device and the relation of luminous 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 luminous efficiency of the organic electroluminescence device that embodiment 1 prepares all prepares than comparative example large, the maximum luminous efficiency of embodiment 1 is 9.68lm/W, and that comparative example is only 7.19lm/W.Meanwhile, along with the raising of current density, the luminous efficiency decay of organic electroluminescence device prepared by embodiment 1 is slower.The silicon compound particle of the silicon compound doped layer of the organic electroluminescence device that this explanation embodiment 1 prepares is larger, be microspheroidal, preparation makes inner formation of rete arrange orderly micro-sphere structure after getting on, thereby light is encountered this microspheroidal and can be formed scattering and make to get back in the middle of device to the light scattering of both sides transmittings, improve light extraction efficiency, metal sulfide transmitance in visible-range higher (in visible-range, transmitance reaches 80%～90%), can improve the transmitance of light, the phthalocyanines metallic compound of phthalocyanines metal compound layer, 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 the metallic element of conductive membrane layer (parallel free electron can lose with vertical photon coupling), improve photon utilance, conductive membrane layer improves conductivity, and under certain thickness, can make reflection of light strengthen, effectively improve luminous efficiency.This composite cathode being made up of silicon compound doped layer, phthalocyanines metal compound layer and conductive membrane layer can effectively improve light extraction 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, phthalocyanines metal compound layer and the conductive membrane layer that stack gradually, described silicon compound doped layer, phthalocyanines metal compound layer and conductive membrane layer composition cathode composite layer;
The material of described silicon compound doped layer is that the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 is mixed to get according to mass ratio;
The material of described phthalocyanines metal compound layer is phthalocyanines metallic compound;
The material of described conductive membrane layer is conducting metal oxide.
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 refractive index is that 1.8～2.0 metal sulfide is zinc sulphide, cadmium sulfide, magnesium sulfide or copper sulfide;
The thickness of described silicon compound doped layer is 10nm～40nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, described phthalocyanines metallic compound is CuPc, Phthalocyanine Zinc, phthalocyanine vanadium or magnesium phthalocyanine;
The thickness of described phthalocyanines metal compound layer is 5nm～60nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described conducting metal oxide is indium tin oxide, aluminium zinc oxide or indium-zinc oxide;
The thickness of described conductive membrane layer is 100nm～250nm.
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, 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-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 the metal sulfide that silicon compound and refractive index are 1.8～2.0 is the mixture that 5:1～10:1 is mixed to get according to mass ratio, and the energy density of described electron beam evaporation plating is 10W/cm
2～100W/cm
2;
On described silicon compound doped layer, evaporation forms phthalocyanines metal compound layer, and wherein, the material of described phthalocyanines metal compound layer is phthalocyanines metallic compound;
On described phthalocyanines metal compound layer, magnetron sputtering forms conductive membrane layer, obtain described organic electroluminescence device, described silicon compound doped layer, phthalocyanines metal compound layer and conductive membrane layer composition cathode composite layer, wherein, the material of described conductive membrane layer is conducting metal oxide, the accelerating voltage of described magnetron sputtering is 300V～800V, and magnetic field is 50G～200G, and power density is 1W/cm
2～40W/cm
2.
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| JP2020532042A (en) * | 2017-08-25 | 2020-11-05 | 京東方科技集團股▲ふん▼有限公司Ｂｏｅ Ｔｅｃｈｎｏｌｏｇｙ Ｇｒｏｕｐ Ｃｏ．，Ｌｔｄ． | Display panels and their manufacturing methods, electroluminescence devices and display devices |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1334967A (en) * | 1998-12-16 | 2002-02-06 | 剑桥显示技术有限公司 | Organic light-emitting device |
| EP1394870A2 (en) * | 1997-10-09 | 2004-03-03 | The Trustees of Princeton University | Organic light emitting device |
| CN102956830A (en) * | 2011-08-29 | 2013-03-06 | 海洋王照明科技股份有限公司 | Bottom-emitting organic electroluminescence device and preparation method thereof |
-
2013
- 2013-04-24 CN CN201310145216.2A patent/CN104124380A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1394870A2 (en) * | 1997-10-09 | 2004-03-03 | The Trustees of Princeton University | Organic light emitting device |
| CN1334967A (en) * | 1998-12-16 | 2002-02-06 | 剑桥显示技术有限公司 | Organic light-emitting device |
| CN102956830A (en) * | 2011-08-29 | 2013-03-06 | 海洋王照明科技股份有限公司 | Bottom-emitting organic electroluminescence device and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020532042A (en) * | 2017-08-25 | 2020-11-05 | 京東方科技集團股▲ふん▼有限公司Ｂｏｅ Ｔｅｃｈｎｏｌｏｇｙ Ｇｒｏｕｐ Ｃｏ．，Ｌｔｄ． | Display panels and their manufacturing methods, electroluminescence devices and display devices |
| JP7201442B2 (en) | 2017-08-25 | 2023-01-10 | 京東方科技集團股▲ふん▼有限公司 | Display panel and its manufacturing method, electroluminescence device and display device |
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