CN104124352A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN104124352A CN104124352A CN201310143702.0A CN201310143702A CN104124352A CN 104124352 A CN104124352 A CN 104124352A CN 201310143702 A CN201310143702 A CN 201310143702A CN 104124352 A CN104124352 A CN 104124352A
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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
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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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
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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
- H10K50/85—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 includes a conductive anode glass substrate, a hole injection layer, a hole transmission layer, a light-emitting layer, an electronic transmission layer, an electronic injection layer and a composite cathode, which are sequentially laminated. The composite cathode is formed by a metal oxide doping layer, a fullerene derivative layer and a conductive film layer, which are sequentially laminated. The refractive index of the material of the metal oxide doping layer is a mixed material formed by a low-refractive-index metal oxide with a refractive index of 1.7-2.0 and a high-refractive-index metal oxide with a refractive index of 2.0-2.5. The metal oxide doping layer is capable of preventing total-reflection loss of the device. The fullerene derivative is a micromolecule material and easy to form a film so that film quality is improved. At the same time, light is enabled to be reflected back to a bottom part so that light loss is prevented. The material of the conductive film is capable of effectively improving the injection efficiency of electrons and enabling the light to be reflected back to the bottom part of the device. The composite cathode is capable of effectively improving the light-emitting efficiency of the device.
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 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).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 in 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 entirety 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 made up of the doped metallic oxide layer stacking gradually, fullerene derivate 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 stacking gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and composite cathode, described composite cathode is by the doped metallic oxide layer stacking gradually, fullerene derivate layer and conductive membrane layer composition, described doped metallic oxide layer material is that refractive index is the high refractive index metal oxide composite material that 1:1～1:3 is mixed to form in mass ratio that 1.7～2.0 low-refraction metal oxide and refractive index are 2.0～2.5, described low-refraction metal oxide is magnesium oxide (MgO), zirconia (ZrO
2) and calcium oxide (CaO) in one, described high refractive index metal oxide is zinc oxide (ZnO), titanium dioxide (TiO
2) and cupric oxide (CuO) in one, described fullerene derivate layer material is football alkene (C60), carbon 70(C70), one in [6,6]-phenyl-C61-methyl butyrate (PC61BM) and [6,6]-phenyl-C71-methyl butyrate (P71BM), the material of described conductive membrane layer is the one in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO).
Preferably, the thickness of described doped metallic oxide layer is 50～200nm.
Preferably, the thickness of described fullerene derivate layer is 1～5nm.
Preferably, the thickness of described conductive membrane layer is 200～400nm.
Preferably, described conductive anode substrate of glass is the one 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 one, thickness is 20～80nm.More preferably, the material of described hole injection layer is MoO
3, thickness is 30nm.
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, one in 4 '-benzidine (NPB), the thickness of described hole transmission layer is 20～60nm, more preferably, described hole transmission layer material is NPB, and thickness is 50nm.
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'-, the one in 1'-biphenyl (BCzVBi) and oxine aluminium (Alq3), thickness is 5～40nm, more preferably, the material of described luminescent layer is Alq3, and 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, the one 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 250nm.
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 one, thickness is 0.5～10nm, more preferably, the material of described electron injecting layer is LiF, thickness is 1nm.
Described composite cathode is by the doped metallic oxide layer stacking gradually, fullerene derivate layer and conductive membrane layer composition, doped metallic oxide layer material is that refractive index is the composite material that metal oxide (high refractive index metal oxide) that 1.7～2.0 metal oxide (low-refraction metal oxide) and refractive index are 2.0～2.5 forms, the refractive index of low-refraction metal and organic layer is more or less the same, can avoid the total reflection loss of device, simultaneously, high refractive index metal oxide absorbs less in visible-range, can make light transmission, simultaneously, the nanometer diameter of metal oxide particle is larger, it is micro-spherical particle, can make rete keep arranging orderly micro-sphere structure, light is carried out to scattering, fullerene derivate is small molecule material, therefore, easily film forming, can reduce the roughness of doped metallic oxide layer, improves the quality of film, simultaneously, fullerene derivate layer refractive index ratio high index of refraction metallic compound is low, when light transmitting, can form total reflection, make light reflection get back to bottom, avoid light loss, conductive film layer 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 effectively improve the injection efficiency of electronics, increase conductivity simultaneously, 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 made up of the doped metallic oxide layer stacking gradually, fullerene derivate layer and conductive membrane layer;
On electron injecting layer, adopt the method for electron beam evaporation plating to prepare doped metallic oxide layer, the material of described doped metallic oxide layer is that refractive index is the high refractive index metal oxide composite material that 1:1～1:3 is mixed to form in mass ratio that 1.7～2.0 low-refraction metal oxide and refractive index are 2.0～2.5, and described low-refraction metal oxide is MgO, ZrO
2with the one in CaO, described high refractive index metal oxide is ZnO, TiO
2with the one in CuO; 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 fullerene derivate layer, the material of described fullerene derivate layer is the one in C60, C70, PC61BM and P71BM; Evaporation pressure is 5 × 10
-5pa～2 × 10
-3pa, evaporation speed is 0.1～1nm/s;
On fullerene derivate layer, adopt the method for magnetron sputtering to prepare conductive membrane layer, the material of described conductive membrane layer is the one 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 50～200nm.
Preferably, the thickness of described fullerene derivate layer is 1～5nm.
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, conductive anode substrate of glass is used successively liquid detergent by being operating as that described cleaning is dried afterwards, deionized water, and acetone, ethanol, the 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 the one 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 one, thickness is 20～80nm.More preferably, the material of described hole injection layer is MoO
3, thickness is 30nm.
Preferably, the material of described hole transmission layer is the one 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 50nm.
Preferably, the material of described luminescent layer is the one in DCJTB, ADN, BCzVBi and Alq3, and thickness is 5～40nm, and more preferably, the material of described luminescent layer is Alq3, and thickness is preferably 25nm.
Preferably, the material of described electron transfer layer is the one 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 250nm.
Preferably, the material of described electron injecting layer is Cs
2cO
3, CsF, CsN
3with the one 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 by the doped metallic oxide layer stacking gradually, fullerene derivate layer and conductive membrane layer composition, doped metallic oxide layer is that refractive index is the composite material that metal oxide (high refractive index metal oxide) that 1.7～2.0 metal oxide (low-refraction metal oxide) and refractive index are 2.0～2.5 forms, the refractive index of low-refraction metal and organic layer is more or less the same, can avoid the total reflection loss of device, simultaneously, high refractive index metal oxide absorbs less in visible-range, can make light transmission, simultaneously, the nanometer diameter of metal oxide particle is larger, it is micro-spherical particle, can make rete keep arranging orderly micro-sphere structure, light is carried out to scattering, fullerene derivate is small molecule material, therefore, easily film forming, can reduce the roughness of doped metallic oxide layer, improves the quality of film, simultaneously, fullerene derivate layer refractive index ratio high index of refraction metallic compound is low, when light transmitting, can form total reflection, make light reflection get back to bottom, avoid light loss, conductive film layer material work function is between the HOMO(of organic material HOMO highest occupied molecular orbital) and LUMO(lowest unoccupied molecular orbital) between energy level, preparation is when composite cathode on one side, can effectively improve the injection efficiency of electronics, increase conductivity simultaneously, 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 made up of the doped metallic oxide layer stacking gradually, fullerene derivate 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.
Brief description of the drawings
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 skill in the art, 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 current density and the current 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, the 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 when evaporation
-5pa, evaporation speed is 3nm/s, evaporation thickness is 30nm;
The material of hole transmission layer is NPB, and the pressure adopting when evaporation is 8 × 10
-5pa, evaporation speed is 0.2nm/s, evaporation thickness is 50nm;
The material of luminescent layer is Alq3, and the pressure adopting when evaporation is 8 × 10
-5pa, evaporation speed is 0.2nm/s, evaporation thickness is 25nm;
The material of electron transfer layer is Bphen, and the pressure adopting when evaporation is 8 × 10
-5pa, evaporation speed is 0.2nm/s, evaporation thickness is 250nm;
The material of electron injecting layer is LiF, and the pressure adopting when evaporation is 8 × 10
-5pa, evaporation speed is 3nm/s, evaporation thickness is 1nm;
(2) prepare composite cathode;
On electron injecting layer, electron beam evaporation plating is prepared MgO and the ZnO composite material that 1:1.5 is mixed to form in mass ratio, and obtaining thickness is the doped metallic oxide layer of 100nm, and the energy density of electron beam evaporation plating is 25W/cm
2;
Thermal resistance evaporation PC61BM on doped metallic oxide layer, obtaining thickness is the fullerene derivate layer of 2nm, the pressure adopting when evaporation is 8 × 10
-5pa, evaporation speed is 0.2nm/s.
On fullerene derivate layer, adopt the method for magnetron sputtering to prepare ITO, obtain the conductive membrane layer that thickness is 300nm, 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 made up of the doped metallic oxide layer 71 stacking gradually, fullerene derivate layer 72 and conductive membrane layer 73.Concrete structure is expressed as:
Ito glass/MoO
3/ NPB/Alq
3/ Bphen/LiF/MgO:ZnO(1:1.5)/PC61BM/ITO, wherein, slash "/" represents to stack gradually, and the colon ": " in MgO:ZnO represents to mix, 1:1.5 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, the 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 when 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 when 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 when 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 when 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 when evaporation is 2 × 10
-3pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm;
(2) prepare composite cathode;
On electron injecting layer, electron beam evaporation plating is prepared ZrO
2and TiO
2the composite material that 1:1 is mixed to form in mass ratio, obtaining thickness is the doped metallic oxide layer of 50nm, the energy density of electron beam evaporation plating is 10W/cm
2;
Thermal resistance evaporation C60 on doped metallic oxide layer, obtaining thickness is the fullerene derivate layer of 1nm, the pressure adopting when evaporation is 2 × 10
-3pa, evaporation speed is 0.1nm/s.
On fullerene derivate 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 made up of stacked doped metallic oxide layer, fullerene derivate layer and conductive membrane layer.Concrete structure is expressed as:
AZO glass/WO
3/ NPB/ADN/TPBi/CsF/ZrO
2: TiO
2(1:1)/C60/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, the 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 when 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 when 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 when 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 when 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 when evaporation is 5 × 10
-5pa, evaporation speed is 1nm/s, evaporation thickness is 0.5nm;
(2) prepare composite cathode;
On electron injecting layer, electron beam evaporation plating is prepared CaO and the CuO composite material that 1:3 is mixed to form in mass ratio, and obtaining thickness is the doped metallic oxide layer of 200nm, and the energy density of electron beam evaporation plating is 100W/cm
2;
Thermal resistance evaporation C70 on doped metallic oxide layer, obtaining thickness is the fullerene derivate layer of 5nm, the pressure adopting when evaporation is 5 × 10
-5pa, evaporation speed is 1nm/s.
On fullerene derivate 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 made up of the doped metallic oxide layer stacking gradually, fullerene derivate layer and conductive membrane layer.Concrete structure is expressed as:
IZO glass/V
2o
5/ TAPC/BCzVBi/Bphen/Cs
2cO
3/ CaO:CuO(1:3)/C70/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, the 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 when 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 when 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 when evaporation is 5 × 10
-4pa, evaporation speed is 0.2nm/s, evaporation thickness is 5nm;
The material of electron transfer layer is TAZ, and the pressure adopting when 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 when evaporation is 5 × 10
-4pa, evaporation speed is 5nm/s, evaporation thickness is 1nm;
(2) prepare composite cathode;
On electron injecting layer, electron beam evaporation plating is prepared MgO and TiO
2the composite material that 1:1.5 is mixed to form in mass ratio, obtaining thickness is the doped metallic oxide layer of 150nm, the energy density of electron beam evaporation plating is 25W/cm
2;
Thermal resistance evaporation PC61BM on doped metallic oxide layer, obtaining thickness is the fullerene derivate layer of 5nm, the pressure adopting when evaporation is 5 × 10
-4pa, evaporation speed is 0.2nm/s;
On fullerene derivate layer, adopt the method for magnetron sputtering to prepare ITO, obtain the conductive membrane layer that thickness is 280nm, 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 made up of the doped metallic oxide layer stacking gradually, fullerene derivate layer and conductive membrane layer.Concrete structure is expressed as:
IZO glass/WO
3/ TCTA/DCJTB/TAZ/CsN
3/ MgO:TiO
2(1:1.5)/P71BM/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/ 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 Keithley company of the U.S., CS-100A colorimeter test brightness and the colourity of Konica Minolta company of Japan, obtain the current efficiency of organic electroluminescence device with current density 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 current efficiency of comparative example's organic electroluminescence device and the graph of a relation of current density.As can be seen from Figure 2, under different current densities, all large than comparative example of the current efficiency of embodiment 1, the maximum current efficiency of embodiment 1 is 8.38cd/A, and that comparative example is only 6.27cd/A, this explanation, composite cathode of the present invention utilizes high refractive index metal oxide and low-refraction metal oxide to adulterate, can avoid the total reflection loss of device, make rete keep arranging orderly micro-sphere structure, light is carried out to scattering, fullerene derivate reduces the roughness of doped metallic oxide layer, improve the quality of film, conductive film layer material effectively improves the injection efficiency of electronics, increase conductivity simultaneously, and can reflect light, make light reflect back into the bottom of device, 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, fullerene derivate layer and conductive membrane layer composition, the material of described doped metallic oxide layer is that refractive index is the high refractive index metal oxide composite material that 1:1～1:3 is mixed to form in mass ratio that 1.7～2.0 low-refraction metal oxide and refractive index are 2.0～2.5, described low-refraction metal oxide is magnesium oxide, one in zirconia and calcium oxide, described high refractive index metal oxide is zinc oxide, one in titanium dioxide and cupric oxide, the material of described fullerene derivate layer is the one in football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6]-phenyl-C71-methyl butyrate, the material of described conductive membrane layer is the one 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 50～200nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described fullerene derivate layer is 1～5nm.
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 made up of the doped metallic oxide layer stacking gradually, fullerene derivate layer and conductive membrane layer;
On electron injecting layer, adopt the method for electron beam evaporation plating to prepare doped metallic oxide layer, the material of described doped metallic oxide layer is that refractive index is the high refractive index metal oxide composite material that 1:1～1:3 is mixed to form in mass ratio that 1.7～2.0 low-refraction metal oxide and refractive index are 2.0～2.5, described low-refraction metal oxide is the one in magnesium oxide, zirconia and calcium oxide, and described high refractive index metal oxide is the one in zinc oxide, titanium dioxide and cupric oxide; 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 fullerene derivate layer, the material of described fullerene derivate layer is the one in football alkene, carbon 70, [6,6]-phenyl-C61-methyl butyrate and [6,6]-phenyl-C71-methyl butyrate; Evaporation pressure is 5 × 10
-5pa～2 × 10
-3pa, evaporation speed is 0.1～1nm/s;
On fullerene derivate layer, adopt the method for magnetron sputtering to prepare conductive membrane layer, the material of described conductive membrane layer is the one 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 50～200nm.
7. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described fullerene derivate layer is 1～5nm.
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.
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| CN109935731A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | Composite membrane and its preparation method and application |
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