CN104124371A - Organic light-emitting device and preparation method thereof - Google Patents

Organic light-emitting device and preparation method thereof Download PDF

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Publication number
CN104124371A
CN104124371A CN201310143976.XA CN201310143976A CN104124371A CN 104124371 A CN104124371 A CN 104124371A CN 201310143976 A CN201310143976 A CN 201310143976A CN 104124371 A CN104124371 A CN 104124371A
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layer
evaporation
organic electroluminescence
electroluminescence device
thickness
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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

Abstract

The invention discloses an organic light-emitting device and a preparation method thereof. The organic light-emitting device comprises a conductive anode glass substrate, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a composite cathode, wherein the layers are successively laminated. The composite electrode includes a metallic oxide doping layer, a micromolecule organosilicone layer, and a conductive thin-film layer. The metallic oxide doping layer uses metallic oxide and a silicon compound to carry out doping; and the metallic oxide enables the electron injection capability to be improved and after preparation, the silicon compound forms a well-ordered microsphere structure, thereby carrying out light scattering. The micromolecule organosilicone layer can be crystallized at room temperature; and because of the crystal ordered structure after crystallization, the light scattering can be enhanced and the light based on side emission can be reduced. Because of the conductive thin-film material, the electron injection efficiency can be effectively improved; and the transmitted light can be reflected to the bottom of the device. Besides, because of the composite cathode, the luminous efficiency is effective enhanced.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic electroluminescent field, particularly 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).Under 10V, brightness reaches 1000cd/m 2, its luminous efficiency is 1.51lm/W, the life-span is 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 anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.
In traditional luminescent device, the light of device inside only has 18% left and right can be transmitted into outside to go, and other part can consume at device outside with other forms, (as the specific refractivity between glass and ITO, glass refraction is that 1.5, ITO is 1.8 between interface, refractive index poor, light arrives glass from ITO, will there is total reflection), caused the loss of total reflection, thereby it is lower to cause integral body to go out optical property.Therefore, be necessary to improve the luminous efficiency of OLED.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of organic electroluminescence device and preparation method thereof, described organic electroluminescence device, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the composite cathode that stack gradually, described composite cathode is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer, and the present invention has improved conductive capability and the luminous efficiency of device.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the composite cathode that stack gradually, described composite cathode is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer, described doped metallic oxide layer material is metal oxide and the silicon compound composite material that 1:0.2～1:0.5 is mixed to form in mass ratio, and described metal oxide is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in a kind of, described silicon compound is silicon monoxide (SiO), silicon dioxide (SiO 2) and sodium metasilicate (Na 2siO 3) in a kind of; The material of described little molecule silicone layer is diphenyl two (o-tolyl) silicon (UGH1), p-bis-(triphenyl silicon) benzene (UGH2), 1, a kind of in two (triphenyl silicon) benzene (UGH3) of 3-and p-pair of (triphenyl silicon) benzene (UGH4); The material of described conductive membrane layer is a kind of in indium tin oxide, aluminium zinc oxide and indium-zinc oxide.
Preferably, the thickness of described doped metallic oxide layer is 5～40nm.
Preferably, the thickness of described little molecule silicone layer is 50～200nm.
Preferably, the thickness of described conductive membrane layer is 200～400nm.
Preferably, described conductive anode substrate is a kind of in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO), more preferably ITO.
Preferably, the material of described hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) in a kind of, thickness is 20～80nm.More preferably, the material of described hole injection layer is MoO 3, thickness is 35nm.
Preferably, the material of described hole transmission layer is 1,1-, bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, a kind of in 4 '-benzidine (NPB), the thickness of described hole transmission layer is 20～60nm, more preferably, the material of described hole transmission layer is NPB, and thickness is 30nm.
Preferably, 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 (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and oxine aluminium (Alq 3) in a kind of, thickness is 5～40nm, more preferably, the material of described luminescent layer is Alq 3, thickness is 25nm.
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, a kind of in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI), thickness is 40～300nm, more preferably, the material of described electron transfer layer is TAZ, and thickness is 200nm.
Preferably, the material of described electron injecting layer is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) in a kind of, thickness is 0.5～10nm, more preferably, the material of described electron injecting layer is LiF, thickness is 1nm.
Described composite cathode is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer, the material of described doped metallic oxide layer is the composite material that metal oxide and silicon compound form, metal oxide has the performance of electronic injection, can improve the injectability of electronics, and silicon compound is microgranular, particle is larger, after preparation, at rete, forms and arranges orderly micro-sphere structure, this structure is carried out scattering to light again, improves effective emergent ray; Little molecule silicone layer material glass transition temperature is very low, at room temperature crystallizable, and the crystal ordered structure after crystallization can further be strengthened scattering of light, reduces the light of side emission; Conductive film material work function is between the HOMO(of organic material HOMO highest occupied molecular orbital) and LUMO(lowest unoccupied molecular orbital) between energy level, can increase the conductivity of composite cathode, and can reflect the light seeing through, make light reflect back into the bottom of device, this composite cathode can effectively improve device luminous efficiency.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises following operating procedure:
(1) provide the conductive anode substrate of glass of required size, dry after cleaning; In conductive anode substrate of glass, adopt the method for thermal resistance evaporation to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
(2) on electron injecting layer, prepare composite cathode, described composite cathode is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer;
By described metal oxide and silicon compound in mass ratio 1:0.2～1:0.5 be mixed to form composite material, electron beam evaporation plating composite material on electron injecting layer, obtains described doped metallic oxide layer, described metal oxide is MoO 3, WO 3and V 2o 5in a kind of, described silicon compound is SiO, SiO 2and Na 2siO 3in a kind of; The energy density of described electron beam evaporation plating is 10～l00W/cm 2;
On doped metallic oxide layer, adopt the method for thermal resistance evaporation to prepare little molecule silicone layer, the material of described little molecule silicone layer is a kind of in UGH1, UGH2, UGH3 and UGH4; Evaporation pressure is 5 * 10 -5pa～2 * 10 -3pa, evaporation speed is 0.1～1nm/s;
On little molecule silicone layer, adopt the method for magnetron sputtering to prepare conductive membrane layer, the material of described conductive membrane layer is a kind of in ITO, AZO and IZO, and the accelerating voltage of magnetron sputtering is 300～800V, and magnetic field is 50～200G, and power density is 1～40W/cm 2; Obtain described organic electroluminescence device.
Preferably, the thickness of described doped metallic oxide layer is 5～40nm.
Preferably, the thickness of described little molecule silicone layer is 50～200nm.
Preferably, the thickness of described conductive membrane layer is 200～400nm.
Preferably, the thermal resistance evaporation condition of described hole injection layer and electron injecting layer is: pressure is 5 * 10 -5pa～2 * 10 -3pa, evaporation speed is 1～10nm/s.
Preferably, the thermal resistance evaporation condition of described hole transmission layer, electron transfer layer and luminescent layer is: pressure is 5 * 10 -5pa～2 * 10 -3pa, evaporation speed is 0.1～1nm/s.
Preferably, described in the conductive anode substrate of glass of required size is provided, concrete operations are: conductive anode substrate of glass is carried out to photoetching treatment, be then cut into needed size.
Preferably, being operating as that described cleaning is dried afterwards used liquid detergent successively by conductive anode substrate of glass, deionized water, and acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface, cleans up rear air-dry.
Preferably, described conductive anode substrate is a kind of in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO), more preferably ITO.
Preferably, the material of described hole injection layer is MoO 3, WO 3and V 2o 5in a kind of, thickness is 20～80nm.More preferably, the material of described hole injection layer is MoO 3, thickness is 35nm.
Preferably, the material of described hole transmission layer is a kind of in TAPC, TCTA and NPB, and described hole transmission layer material thickness is 20～60nm, and more preferably, the material of described hole transmission layer is NPB, and thickness is 30nm.
Preferably, the material of described luminescent layer is DCJTB, ADN, BCzVBi and Alq 3in a kind of, thickness is 5～40nm, more preferably, the material of described luminescent layer is Alq 3, thickness is preferably 25nm.
Preferably, the material of described electron transfer layer is a kind of in Bphen, TAZ and TPBI, and thickness is 40～300nm, and more preferably, the material of described electron transfer layer is TAZ, and thickness is 200nm.
Preferably, the material of described electron injecting layer is Cs 2cO 3, CsF, CsN 3a kind of with in LiF, thickness is 0.5～10nm, and more preferably, the material of described electron injecting layer is LiF, and thickness is 1nm.
Described composite cathode is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer, the material of described doped metallic oxide layer is the composite material that metal oxide and silicon compound form, metal oxide has the performance of electronic injection, can improve the injectability of electronics, and silicon compound is microgranular, particle is larger, after preparation, at rete, forms and arranges orderly micro-sphere structure, this structure is carried out scattering to light again, improves effective emergent ray; Little molecule silicone layer material glass transition temperature is very low, at room temperature crystallizable, and the crystal ordered structure after crystallization can further be strengthened scattering of light, reduces the light of side emission; Conductive film material work function is between the HOMO(of organic material HOMO highest occupied molecular orbital) and LUMO(lowest unoccupied molecular orbital) between energy level, can increase the conductivity of composite cathode, and can reflect the light seeing through, make light reflect back into the bottom of device, this composite cathode can effectively improve device luminous efficiency.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) composite cathode provided by the invention is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer, has improved electric conductivity and the luminous efficiency of device;
(2) preparation method of composite cathode provided by the invention, technique is simple, and cost is low.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in execution mode be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structural representation of the organic electroluminescence device that provides of the embodiment of the present invention 1;
Fig. 2 is brightness and the luminous efficiency graph of a relation of the embodiment of the present invention 1 and comparative example's organic electroluminescence device.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Embodiment 1
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) first ito glass substrate is carried out to photoetching treatment, be then cut into 2 * 2cm 2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Then on anode, adopt the method for thermal resistance evaporation to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer; Wherein,
The material of hole injection layer is MoO 3, the pressure 8 * 10 adopting during evaporation -5pa, evaporation speed is 3nm/s, evaporation thickness is 35nm;
The material of hole transmission layer is NPB, and the pressure adopting during evaporation is 8 * 10 -5pa, evaporation speed is 0.2nm/s, evaporation thickness is 30nm;
The material of luminescent layer is Alq 3, the pressure adopting during evaporation is 8 * 10 -5pa, evaporation speed is 0.2nm/s, evaporation thickness is 25nm;
The material of electron transfer layer is TAZ, and the pressure adopting during evaporation is 8 * 10 -5pa, evaporation speed is 0.2nm/s, evaporation thickness is 200nm;
The material of electron injecting layer is LiF, and the pressure adopting during evaporation is 8 * 10 -5pa, evaporation speed is 3nm/s, evaporation thickness is 1nm;
(2) prepare composite cathode;
Electron beam evaporation plating MoO on electron injecting layer 3with SiO 2the composite material that 1:0.3 is mixed to form in mass ratio, obtaining thickness is the doped metallic oxide layer of 25nm, the energy density of electron beam evaporation plating is 25W/cm 2;
Thermal resistance evaporation UGH1 on doped metallic oxide layer, obtaining thickness is the little molecule silicone layer of 100nm, the pressure adopting during evaporation is 8 * 10 -5pa, evaporation speed is 0.2nm/s.
On little molecule silicone layer, adopt the method for magnetron sputtering to prepare ITO, obtain the conductive membrane layer that thickness is 250nm, the accelerating voltage of magnetron sputtering is 500V, and magnetic field is 150G, and power density is 20W/cm 2; Obtain organic electroluminescence device.
Fig. 1 is the structural representation of the organic electroluminescence device prepared of the present embodiment, as shown in Figure 1, organic electroluminescence device prepared by the present embodiment, comprise the conductive anode substrate of glass 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6 and the composite cathode 7 that stack gradually, composite cathode 7 is comprised of the doped metallic oxide layer 71 stacking gradually, little molecule silicone layer 72 and conductive membrane layer 73.Concrete structure is expressed as:
Ito glass/MoO 3/ NPB/Alq 3/ TAZ/LiF/MoO 3: SiO 2(1:0.3)/UGH1/ITO, wherein, slash "/" represents to stack gradually, MoO 3: SiO 2in colon ": " represent to mix, 1:0.3 represents the former and the latter's mass ratio, after each symbol represents in embodiment meaning identical.
Embodiment 2
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) first AZO substrate of glass is carried out to photoetching treatment, be then cut into 2 * 2cm 2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Then on anode, adopt the method for thermal resistance evaporation to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer; Wherein,
The material of hole injection layer is WO 3, the pressure adopting during evaporation is 2 * 10 -3pa, evaporation speed is 10nm/s, evaporation thickness is 80nm;
The material of hole transmission layer is NPB, and the pressure adopting during evaporation is 2 * 10 -3pa, evaporation speed is 0.1nm/s, evaporation thickness is 60nm;
The material of luminescent layer is ADN, and the pressure adopting during evaporation is 2 * 10 -3pa, evaporation speed is 0.1nm/s, evaporation thickness is 5nm;
The material of electron transfer layer is TPBi, and the pressure adopting during evaporation is 2 * 10 -3pa, evaporation speed is 10nm/s, evaporation thickness is 300nm;
The material of electron injecting layer is CsF, and the pressure adopting during evaporation is 2 * 10 -3pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm;
(2) prepare composite cathode;
Electron beam evaporation plating WO on electron injecting layer 3with the SiO composite material that 1:0.2 is mixed to form in mass ratio, obtaining thickness is the doped metallic oxide layer of 5nm, and the energy density of electron beam evaporation plating is 10W/cm 2;
Thermal resistance evaporation UGH2 on doped metallic oxide layer, obtaining thickness is the little molecule silicone layer of 50nm, the pressure adopting during evaporation is 2 * 10 -3pa, evaporation speed is 0.1nm/s.
On little molecule silicone layer, adopt the method for magnetron sputtering to prepare AZO, obtain the conductive membrane layer that thickness is 200nm, the accelerating voltage of magnetron sputtering is 300V, and magnetic field is 200G, and power density is 1W/cm 2; Obtain organic electroluminescence device.
Organic electroluminescence device prepared by the present embodiment, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the composite cathode that stack gradually, composite cathode is comprised of stacked doped metallic oxide layer, little molecule silicone layer and conductive membrane layer.Concrete structure is expressed as:
AZO glass/WO 3/ NPB/ADN/TPBi/CsF/WO 3: SiO (1:0.2)/UGH2/AZO.
Embodiment 3
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) first IZO substrate of glass is carried out to photoetching treatment, be then cut into 2 * 2cm 2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Then on anode, adopt the method for thermal resistance evaporation to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer; Wherein,
The material of hole injection layer is V 2o 5, the pressure adopting during evaporation is 5 * 10 -5pa, evaporation speed is 1nm/s, evaporation thickness is 20nm;
The material of hole transmission layer is TAPC, and the pressure adopting during evaporation is 5 * 10 -5pa, evaporation speed is 1nm/s, evaporation thickness is 20nm;
The material of luminescent layer is BCzVBi, and the pressure adopting during evaporation is 5 * 10 -5pa, evaporation speed is 1nm/s, evaporation thickness is 40nm;
The material of electron transfer layer is Bphen, and the pressure adopting during evaporation is 5 * 10 -5pa, evaporation speed is 1nm/s, evaporation thickness is 60nm;
The material of electron injecting layer is Cs 2cO 3, the pressure adopting during evaporation is 5 * 10 -5pa, evaporation speed is 1nm/s, evaporation thickness is 0.5nm;
(2) prepare composite cathode;
Electron beam evaporation plating V on electron injecting layer 2o 5with Na 2siO 3the composite material that 1:0.5 is mixed to form in mass ratio, obtaining thickness is the doped metallic oxide layer of 40nm, the energy density of electron beam evaporation plating is 100W/cm 2;
Thermal resistance evaporation UGH3 on doped metallic oxide layer, obtaining thickness is the little molecule silicone layer of 200nm, the pressure adopting during evaporation is 5 * 10 -5pa, evaporation speed is 1nm/s.
On little molecule silicone layer, adopt the method for magnetron sputtering to prepare IZO, obtain the conductive membrane layer that thickness is 400nm, the accelerating voltage of magnetron sputtering is 800V, and magnetic field is 50G, and power density is 40W/cm 2; Obtain organic electroluminescence device.
Organic electroluminescence device prepared by the present embodiment, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the composite cathode that stack gradually, composite cathode is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer.Concrete structure is expressed as:
IZO glass/V 2o 5/ TAPC/BCzVBi/Bphen/Cs 2cO 3/ V 2o 5: Na 2siO 3(1:0.5)/UGH3/IZO.
Embodiment 4
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) first IZO substrate of glass is carried out to photoetching treatment, be then cut into 2 * 2cm 2square dimensions, then use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, removes the organic pollution of glass surface, cleans up rear air-dry; Then on anode, adopt the method for thermal resistance evaporation to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer; Wherein,
The material of hole injection layer is WO 3, the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 5nm/s, evaporation thickness is 30nm;
The material of hole transmission layer is TCTA, and the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 0.2nm/s, evaporation thickness is 50nm;
The material of luminescent layer is DCJTB, and the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 0.2nm/s, evaporation thickness is 5nm;
The material of electron transfer layer is TPBi, and the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 0.2nm/s, evaporation thickness is 40nm;
The material of electron injecting layer is CsN 3, the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 5nm/s, evaporation thickness is 1nm;
(2) prepare composite cathode;
Electron beam evaporation plating MoO on electron injecting layer 3with the SiO composite material that 1:0.5 is mixed to form in mass ratio, obtaining thickness is the doped metallic oxide layer of 15nm, and the energy density of electron beam evaporation plating is 50W/cm 2;
Thermal resistance evaporation UGH4 on doped metallic oxide layer, obtaining thickness is the little molecule silicone layer of 150nm, the pressure adopting during evaporation is 5 * 10 -4pa, evaporation speed is 0.2nm/s;
On little molecule silicone layer, adopt the method for magnetron sputtering to prepare ITO, obtain the conductive membrane layer that thickness is 250nm, the accelerating voltage of magnetron sputtering is 350V, and magnetic field is 100G, and power density is 25W/cm 2; Obtain organic electroluminescence device.
Organic electroluminescence device prepared by the present embodiment, comprise the conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the composite cathode that stack gradually, composite cathode is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer.Concrete structure is expressed as:
IZO glass/WO 3/ TCTA/DCJTB/TPBi/CsN 3/ MoO 3: SiO (1:0.5)/UGH4/ITO.
Comparative example
For being presented as creativeness of the present invention, the present invention is also provided with comparative example, the difference of comparative example and embodiment 1 is that the negative electrode in comparative example is metal simple-substance silver (Ag), and thickness is 120nm, and the concrete structure of comparative example's organic electroluminescence device is ito glass/MoO 3/ NPB/Alq 3/ TAZ/LiF/Ag, respectively corresponding conductive anode substrate of glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Effect embodiment
Adopt the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the current-voltage tester Keithley2400 test electric property of U.S. Keithley company, CS-100A colorimeter test brightness and the colourity of Japan Konica Minolta company, obtain the luminous efficiency of organic electroluminescence device with the change curve of brightness, to investigate the luminous efficiency of device, tested object is organic electroluminescence device prepared by embodiment 1 and comparative example.Test result as shown in Figure 2.
Fig. 2 is the embodiment of the present invention 1 and the luminous efficiency of comparative example's organic electroluminescence device and the graph of a relation of brightness.As can be seen from Figure 2, under different brightness, the luminous efficiency of embodiment 1 is large than comparative example all, the maximum luminous efficiency of embodiment 1 is 7.97lm/W, and that comparative example is only 5.97lm/W, meanwhile, along with the increase of brightness, the ratio of the luminous efficiency decay of comparative example is very fast, and the decay of embodiment 1 is slower.This explanation, in embodiment 1 composite cathode, doped metallic oxide layer improves the injectability of electronics, form and arrange orderly micro-sphere structure, improve effective emergent ray, after the little molecular layer crystallization of organosilicon, can further strengthen scattering of light, conductive film layer material increases conductivity, makes light reflect back into the bottom of device, and this composite cathode can effectively improve device luminous efficiency.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (10)

1. an organic electroluminescence device, comprise the conductive anode substrate of glass stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and composite cathode, it is characterized in that, described composite cathode is by the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer form, the material of described doped metallic oxide layer is metal oxide and the silicon compound composite material that 1:0.2～1:0.5 is mixed to form in mass ratio, described metal oxide is molybdenum trioxide, a kind of in tungstic acid and vanadic oxide, described silicon compound is silicon monoxide, a kind of in silicon dioxide and sodium metasilicate, the material of described little molecule silicone layer is diphenyl two (o-tolyl) silicon, p-bis-(triphenyl silicon) benzene, 1, a kind of in two (triphenyl silicon) benzene of two (triphenyl silicon) benzene of 3-and p-, the material of described conductive membrane layer is a kind of in indium tin oxide, aluminium zinc oxide and indium-zinc oxide.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described doped metallic oxide layer is 5～40nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described little molecule silicone layer is 50～200nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described conductive membrane layer is 200～400nm.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises following operating procedure:
(1) provide the conductive anode substrate of glass of required size, dry after cleaning; In conductive anode substrate of glass, adopt the method for thermal resistance evaporation to prepare successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer;
(2) on electron injecting layer, prepare composite cathode, described composite cathode is comprised of the doped metallic oxide layer stacking gradually, little molecule silicone layer and conductive membrane layer;
By described metal oxide and silicon compound in mass ratio 1:0.2～1:0.5 be mixed to form composite material, electron beam evaporation plating composite material on electron injecting layer, obtain described doped metallic oxide layer, described metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide, and described silicon compound is a kind of in silicon monoxide, silicon dioxide and sodium metasilicate; The energy density of described electron beam evaporation plating is 10～l00W/cm 2;
On doped metallic oxide layer, adopt the method for thermal resistance evaporation to prepare little molecule silicone layer, the material of described little molecule silicone layer is diphenyl two (o-tolyl) silicon, p-bis-(triphenyl silicon) benzene, 1, a kind of in two (triphenyl silicon) benzene of two (triphenyl silicon) benzene of 3-and p-; Evaporation pressure is 5 * 10 -5pa～2 * 10 -3pa, evaporation speed is 0.1～1nm/s;
On little molecule silicone layer, adopt the method for magnetron sputtering to prepare conductive membrane layer, the material of described conductive membrane layer is a kind of in indium tin oxide, aluminium zinc oxide and indium-zinc oxide, the accelerating voltage of magnetron sputtering is 300～800V, magnetic field is 50～200G, and power density is 1～40W/cm 2; Obtain described organic electroluminescence device.
6. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described doped metallic oxide layer is 50～40nm.
7. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described little molecule silicone layer is 50～200nm.
8. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described conductive membrane layer is 200～400nm.
9. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thermal resistance evaporation condition of described hole injection layer and electron injecting layer is: pressure is 5 * 10 -5pa～2 * 10 -3pa, evaporation speed is 1～10nm/s.
10. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thermal resistance evaporation condition of described hole transmission layer, electron transfer layer and luminescent layer is: pressure is 5 * 10 -5pa～2 * 10 -3pa, evaporation speed is 0.1～1nm/s.
CN201310143976.XA 2013-04-24 2013-04-24 Organic light-emitting device and preparation method thereof Pending CN104124371A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101952990A (en) * 2007-11-27 2011-01-19 密执安州立大学董事会 Organic light emitting device having multiple separate emissive layers
US20110025224A1 (en) * 2009-05-07 2011-02-03 Massachusetts Institute Of Technology Light emitting device including semiconductor nanocrystals
CN102856504A (en) * 2011-06-28 2013-01-02 海洋王照明科技股份有限公司 Organic electroluminescence device and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101952990A (en) * 2007-11-27 2011-01-19 密执安州立大学董事会 Organic light emitting device having multiple separate emissive layers
US20110025224A1 (en) * 2009-05-07 2011-02-03 Massachusetts Institute Of Technology Light emitting device including semiconductor nanocrystals
CN102856504A (en) * 2011-06-28 2013-01-02 海洋王照明科技股份有限公司 Organic electroluminescence device and preparation method thereof

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Application publication date: 20141029