CN104124375A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104124375A CN104124375A CN201310143986.3A CN201310143986A CN104124375A CN 104124375 A CN104124375 A CN 104124375A CN 201310143986 A CN201310143986 A CN 201310143986A CN 104124375 A CN104124375 A CN 104124375A
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- H10K50/00—Organic light-emitting devices
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- 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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- H—ELECTRICITY
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- H10K50/856—Arrangements for extracting light from the devices comprising reflective means
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Abstract
The invention discloses an organic light-emitting device and a preparation method thereof. The organic light-emitting device is composed of 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 anode includes a metal doping layer, a conductive thin-film layer, and a titanium dioxide layer, wherein the layers are successively laminated. The metal doping layer is made of a mixing material formed by an elemental metal and anatase structure-based titanium dioxide; the titanium dioxide with large particle has the crystal structure, so that the film layer can form particle-shaped micro lens structure and thus the light scattering can be carried out beneficially and the light extraction efficiency can be improved; and the elemental metal has the conducting effect, so that the conductivity of the device can be improved. The conductive thin-film layer material has the high film-forming property and the film layer can be modified, so that the roughness of the film layer can be reduced; and the light transmittance is high and the light absorption is low. The titanium dioxide layer reflect the transmitted light to the bottom of the device; and because of the composite cathode, the luminous efficiency can be effectively improved.
Description
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 metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually, 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 metal-doped layer stacking gradually, conductive membrane layer and titanium dioxide layer, and the material of described metal-doped layer is a kind of in silver, aluminium, platinum and gold and composite material that anatase structured titanium dioxide is mixed to form with mass ratio 4:1～2:1; 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 metal-doped layer is 20～50nm.
Preferably, the thickness of described conductive membrane layer is 50～100nm.
Preferably, in described titanium dioxide layer, titanium dioxide particle diameter is 20～200nm, and the thickness of described titanium dioxide layer is 100～400nm.
Preferably, in described titanium dioxide layer, titanium dioxide source is not limit.
Preferably, described conductive anode substrate of glass 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 70nm.
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), described hole transmission layer material thickness is 20～60nm, more preferably, the material of described hole transmission layer is TAPC, and thickness is 55nm.
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 BCzVBi, thickness is 10nm.
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 Bphen, and thickness is 60nm.
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 0.7nm.
Composite cathode in organic electroluminescence device of the present invention is comprised of the metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually; A kind of and the anatase structured titania additive of metal-doped layer in silver, aluminium, platinum and gold forms, titanium dioxide granule is large and have an anatase crystal structure, can make rete form granular microlens structure, form array, be conducive to light and carry out scattering, reduce to the light of both sides transmitting, improve light and take out efficiency, and metal simple-substance has electric action, can improve the conductive capability of device; On metal-doped layer, prepare layer of conductive film layer, can modify rete, rete roughness is reduced, and this material filming is good, technical maturity, and transmitance is higher, lower to light absorption, finally on conductive membrane layer, prepare layer of titanium dioxide layer, titanium dioxide layer reflects the light seeing through, get back to the bottom of device, this composite cathode can effectively improve the luminous efficiency of device.
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, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively;
(2) on electron injecting layer, prepare composite cathode, described composite cathode is comprised of the metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually;
The titanium dioxide of getting particle diameter and be 20～200nm will be placed in Muffle furnace, at 400～600 ℃, calcine 20～60min, then take out and will dry, and fully grind; Then the titanium dioxide after a kind of and calcining in silver, aluminium, platinum and gold is mixed to form to composite material with mass ratio 4:1～2:1, then electron beam evaporation plating composite material on electron injecting layer, obtain described metal-doped layer, in described metal-doped layer, titanium dioxide is anatase structured, and the energy density of described electron beam evaporation plating is 10～l00W/cm
2;
On metal-doped 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 (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO); The accelerating voltage of magnetron sputtering is 300～800V, and magnetic field is 50～200G, and power density is 1～40W/cm
2;
On conductive membrane layer, adopt the method for electron beam evaporation plating to prepare titanium dioxide layer; The energy density of electron beam evaporation plating is 10～l00W/cm
2; Obtain described organic electroluminescence device.
Preferably, the thickness of described metal-doped layer is 20～50nm.
When the metal-doped layer of preparation, in order to improve specific area and the hole diameter enlargement of titanium dioxide, by calcining, titanium dioxide is changed into anatase structured.
Preferably, the thickness of described conductive membrane layer is 50～100nm.
Preferably, the titanium dioxide in described titanium dioxide layer is that particle diameter is 20～200nm, and the thickness of described titanium dioxide layer is 100～400nm.
Preferably, in described titanium dioxide layer, titanium dioxide source is not limit.
Preferably, described hole injection layer and electron injecting layer thermal resistance evaporation condition are: pressure is 5 * 10
-5pa～2 * 10
-3, 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
-3, 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 of glass 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 70nm.
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 TAPC, and thickness is 55nm.
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 BCzVBi, thickness is preferably 10nm.
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 Bphen, and thickness is 60nm.
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 0.7nm.
Composite cathode in organic electroluminescence device of the present invention is comprised of the metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually; A kind of and the anatase structured titania additive of metal-doped layer in silver, aluminium, platinum and gold forms, titanium dioxide granule is large and have an anatase crystal structure, can make rete form granular microlens structure, form array, be conducive to light and carry out scattering, reduce to the light of both sides transmitting, improve light and take out efficiency, and metal simple-substance has electric action, can improve the conductive capability of device; On metal-doped layer, prepare layer of conductive film layer, can modify rete, rete roughness is reduced, and this material filming is good, technical maturity, and transmitance is higher, lower to light absorption, finally on conductive membrane layer, prepare layer of titanium dioxide layer, titanium dioxide layer reflects the light seeing through, get back to the bottom of device, this composite cathode can effectively improve the luminous efficiency of device.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) composite cathode provided by the invention is comprised of the metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually, 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, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; 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 70nm;
The material of hole transmission layer is TAPC, and the pressure adopting during evaporation is 8 * 10
-5pa, evaporation speed is 0.2nm/s, evaporation thickness is 55nm;
The material of luminescent layer is BCzVBi, and the pressure adopting during evaporation is 8 * 10
-5pa, evaporation speed is 0.2nm/s, evaporation thickness is 10nm;
The material of electron transfer layer is Bphen, and the pressure adopting during evaporation is 8 * 10
-5pa, evaporation speed is 0.2nm/s, evaporation thickness is 60nm;
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 0.7nm;
(2) prepare composite cathode;
The commercially available TiO that is 50nm by particle diameter
2put into Muffle furnace, at 450 ℃, calcine 30min, then take out and dry, fully grind, standby.Then by TiO after Ag and calcining
2with mass ratio, 3:1 is mixed to form composite material, electron beam evaporation plating composite material on electron injecting layer, and obtaining thickness is the metal-doped layer of 30nm; In metal-doped layer, titanium dioxide is anatase structured, and the energy density of electron beam evaporation plating is 25W/cm
2;
On metal-doped layer, adopt the method for magnetron sputtering to prepare the ito thin film layer that thickness is 80nm, the accelerating voltage of magnetron sputtering is 400V, and magnetic field is 150G, and power density is 25W/cm
2;
On ito thin film layer, adopt the method for electron beam evaporation plating to prepare the titanium dioxide layer that thickness is 250nm, titanium dioxide granule is that particle diameter is the commercially available TiO of 100nm
2, the energy density of electron beam evaporation plating is 25W/cm
2;
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 metal-doped layer 71, conductive membrane layer 72 and the titanium dioxide layer 73 that stack gradually.Concrete structure is expressed as:
Ito glass/MoO
3/ TAPC/BCzVBi/Bphen/LiF/Ag:TiO
2(3:1)/ITO/TiO
2, wherein, slash "/" represents to stack gradually, Ag:TiO
2in colon ": " represent to mix, 3:1 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, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; 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 Bphen, 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 CsN
3, the pressure adopting during evaporation is 2 * 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm;
(2) prepare composite cathode;
The commercially available TiO that is 20nm by particle diameter
2put into Muffle furnace, at 400 ℃, calcine 60min, then take out and dry, fully grind, standby.Then by TiO after Al and calcining
2with mass ratio, 2:1 is mixed to form composite material, electron beam evaporation plating composite material on electron injecting layer, and obtaining thickness is the metal-doped layer of 20nm; In metal-doped layer, titanium dioxide is anatase structured, and the energy density of electron beam evaporation plating is 10W/cm
2;
On metal-doped layer, adopt the method for magnetron sputtering to prepare the AZO thin layer that thickness is 100nm, the accelerating voltage of magnetron sputtering is 800V, and magnetic field is 50G, and power density is 1W/cm
2;
On AZO thin layer, adopt the method for electron beam evaporation plating to prepare the titanium dioxide layer that thickness is 100nm, titanium dioxide granule is that particle diameter is the commercially available TiO of 20nm
2, the energy density of electron beam evaporation plating is 10W/cm
2;
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 metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually.Concrete structure is expressed as:
AZO glass/WO
3/ NPB/ADN/Bphen/CsN
3/ Al:TiO
2(2:1)/AZO/TiO
2.
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, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; Wherein,
The material of hole injection layer is MoO
3, 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 TCTA, 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 Alq
3, 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 TAZ, 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 CsF, and the pressure adopting during evaporation is 5 * 10
-5pa, evaporation speed is 1nm/s, evaporation thickness is 0.5nm;
(2) prepare composite cathode;
The commercially available TiO that is 200nm by particle diameter
2put into Muffle furnace, at 600 ℃, calcine 20min, then take out and dry, fully grind, standby.Then by TiO after Pt and calcining
2with mass ratio, 4:1 is mixed to form composite material, electron beam evaporation plating composite material on electron injecting layer, and obtaining thickness is the metal-doped layer of 50nm; In metal-doped layer, titanium dioxide is anatase structured, and the energy density of electron beam evaporation plating is 100W/cm
2;
On metal-doped layer, adopt the method for magnetron sputtering to prepare the IZO thin layer that thickness is 50nm, the accelerating voltage of magnetron sputtering is 300V, and magnetic field is 200G, and power density is 40W/cm
2;
On IZO thin layer, adopt the method for electron beam evaporation plating to prepare the titanium dioxide layer that thickness is 400nm, titanium dioxide granule is that particle diameter is the commercially available TiO of 200nm
2, the energy density of electron beam evaporation plating is 100W/cm
2;
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 metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually.Concrete structure is expressed as:
IZO glass/MoO
3/ TCTA/Alq
3/ TAZ/CsF/Pt:TiO
2(4:1)/IZO/TiO
2.
Embodiment 4
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, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; Wherein,
The material of hole injection layer is V
2o
5, 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 TAPC, 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 Cs
2cO
3, the pressure adopting during evaporation is 5 * 10
-4pa, evaporation speed is 5nm/s, evaporation thickness is 1nm;
(2) prepare composite cathode;
The commercially available TiO that is 40nm by particle diameter
2put into Muffle furnace, at 500 ℃, calcine 40min, then take out and dry, fully grind, standby.Then by TiO after Au and calcining
2with mass ratio, 2.5:1 is mixed to form composite material, electron beam evaporation plating composite material on electron injecting layer, and obtaining thickness is the metal-doped layer of 25nm; In metal-doped layer, titanium dioxide is anatase structured, and the energy density of electron beam evaporation plating is 50W/cm
2;
On metal-doped layer, adopt the method for magnetron sputtering to prepare the ito thin film layer that thickness is 60nm, the accelerating voltage of magnetron sputtering is 400V, and magnetic field is 180G, and power density is 35W/cm
2;
On ito thin film layer, adopt the method for electron beam evaporation plating to prepare the titanium dioxide layer that thickness is 300nm, titanium dioxide granule is that particle diameter is the commercially available TiO of 40nm
2, the energy density of electron beam evaporation plating is 50W/cm
2;
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 metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually.Concrete structure is expressed as:
IZO glass/V
2o
5/ TAPC/DCJTB/TPBi/Cs
2cO
3/ Au:TiO
2(2.5:1)/ITO/TiO
2.
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 150nm, and the concrete structure of comparative example's organic electroluminescence device is: ito glass/MoO
3/ TAPC/BCzVBi/Bphen/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 brightness change curve, 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.From accompanying drawing 2, can see, under different brightness, the luminous efficiency of embodiment 1 is large than comparative example all, the maximum luminous efficiency of embodiment 1 is 10.44lm/W, and that comparative example is only 6.72lm/W, simultaneously, increase along with brightness, the luminous efficiency of comparative example is faster than the decline of embodiment 1, this explanation, rete in metal-doped layer in composite cathode in embodiment 1 forms granular microlens structure, be conducive to light and carry out scattering, and metal simple-substance improves the conductive capability of device, conductive membrane layer reduces rete roughness, titanium dioxide layer reflects light, this composite cathode can effectively improve the luminous efficiency of device.
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, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the composite cathode that stack gradually, it is characterized in that, described composite cathode is comprised of the metal-doped layer stacking gradually, conductive membrane layer and titanium dioxide layer, and the material of described metal-doped layer is a kind of in silver, aluminium, platinum and gold and composite material that anatase structured titanium dioxide is mixed to form with mass ratio 4:1～2:1; 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 metal-doped layer is 20～50nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described conductive membrane layer is 50～100nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, in described titanium dioxide layer, the particle diameter of titanium dioxide granule is 20～200nm, and the thickness of described titanium dioxide layer is 100～400nm.
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, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively;
(2) on electron injecting layer, prepare composite cathode, described composite cathode is comprised of the metal-doped layer, conductive membrane layer and the titanium dioxide layer that stack gradually;
The titanium dioxide of getting particle diameter and be 20～200nm will be placed in Muffle furnace, at 400～600 ℃, calcine 20～60min, then take out and will dry, and fully grind, standby; Titanium dioxide after a kind of and calcining in silver, aluminium, platinum and gold is mixed to form to composite material with mass ratio 4:1～2:1, then electron beam evaporation plating composite material on electron injecting layer, obtain described metal-doped layer, in described metal-doped layer, titanium dioxide is anatase structured, and the energy density of described electron beam evaporation plating is 10～l00W/cm
2;
On metal-doped 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, and magnetic field is 50～200G, and power density is 1～40W/cm
2;
On conductive membrane layer, adopt the method for electron beam evaporation plating to prepare titanium dioxide layer; The energy density of described electron beam evaporation plating is 10～l00W/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 metal-doped layer is 20～50nm.
7. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described conductive membrane layer is 50～100nm.
8. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, in described titanium dioxide layer, titanium dioxide particle diameter is 20～200nm, and the thickness of described titanium dioxide layer is 100～400nm.
9. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, described hole injection layer and electron injecting layer thermal resistance evaporation condition are: 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.
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| US7268369B2 (en) * | 2004-07-06 | 2007-09-11 | Fujifilm Corporation | Functional device and method for producing the same |
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