CN104009175A - Organic electroluminescent device and preparation method - Google Patents
Organic electroluminescent device and preparation method Download PDFInfo
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- CN104009175A CN104009175A CN201310059130.8A CN201310059130A CN104009175A CN 104009175 A CN104009175 A CN 104009175A CN 201310059130 A CN201310059130 A CN 201310059130A CN 104009175 A CN104009175 A CN 104009175A
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- praseodymium
- evaporation
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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
- H10K50/81—Anodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Abstract
The invention discloses an organic electroluminescent device which comprises a glass substrate, an anode layer, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode which are successively laminated. The anode layer is composed of a hafnium-containing compound layer, a conductive single metal layer and a praseodymium oxide layer which are successively laminated. The hafnium-containing compound has high refractive index and high light transmittance, thus reducing refractive index difference between an anode and the glass substrate, avoiding total reflection and effectively enhancing light extraction efficiency. The conductive single metal plays a role in electric conduction, thus raising carrier transmission efficiency, reducing interior energy consumption of the device and making energy to be used more in light extraction. The highest occupied molecular orbital energy of the praseodymium oxide is high, thus guaranteeing hole injection. The invention also discloses a preparation method of the organic electroluminescent 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 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, all generally to take anode glass substrate as exiting surface, in this structure, the outgoing meeting of light is first reflected through the absorption of anode conducting material, carry out again subvitreous absorption and a reflection, finally just can shine in air, but between glass and anodic interface, there is the specific refractivity between poor (as glass and the ITO(tin indium oxide) of refractive index, glass refraction is 1.5, ITO is 1.8), light arrives glass from ITO, and total reflection will occur, caused the loss of total reflection, thereby it is lower to cause integral body to go out optical property.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of organic electroluminescence device, comprise the substrate of glass, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described anode layer is comprised of the oxide skin(coating) containing hafnium compound layer, conducting metal simple substance layer and praseodymium stacking gradually.By prepare anode layer on substrate of glass exiting surface, avoid total reflection phenomenon, effectively strengthen light exitance, meanwhile, improved the transmission rate of charge carrier; The present invention also provides the preparation method of this organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the substrate of glass, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described anode layer is comprised of the oxide skin(coating) containing hafnium compound layer, conducting metal simple substance layer and praseodymium stacking gradually.
Preferably, described is hafnium oxide (HfO containing hafnium compound layer material
2) or hafnium boride (HfB
x), described is 20～100nm containing hafnium compound layer thickness.
Preferably, described conducting metal simple substance layer material is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and described conducting metal simple substance layer thickness is 10～30nm.
Preferably, the oxide skin(coating) of described praseodymium is titanium dioxide praseodymium (PrO
2) or praseodymium sesquioxide (Pr
2o
3), the oxide skin(coating) thickness of described praseodymium is 1～10nm.
Preferably, described substrate of glass refractive index is 1.8～2.2, at the light transmission rate of 400nm, is 90%～96%.
More preferably, described substrate of glass is selected from the glass that the trade mark is N-LAF36, N-LASF31A, N-LASF41 or N-LASF44, and described substrate of glass refractive index is 1.8～1.9.
It is 1.8～2.2 that the present invention adopts refractive index, the glass that is 90%～96% at the light transmission rate of 400nm is as the substrate of device, can make the more light of device incide on substrate, described is transmission wide waveband (μ m light transmission rate is 70%～85% in 200nm～10) containing hafnium compound layer, high index of refraction (refractive index is 2.0～2.3) material forms, containing hafnium compound layer transmission wide waveband, can guarantee the light transmission rate in visible-range, play anti-reflection effect; High containing hafnium compound layer refractive index, can guarantee to arrive anode from the luminous energy of device inside transmitting, containing hafnium compound layer and high index of refraction substrate refractive index comparison match, can dwindle refringence between the two simultaneously, avoid total reflection phenomenon, effectively strengthen light exitance; Described conducting metal simple substance layer plays electric action, can improve the transmission rate of charge carrier, and the energy that device inside consumes is reduced, and makes energy more for the outgoing of light; The oxide skin(coating) of described praseodymium is high work function (work function is-7.2eV～-6.5eV) material, contributes to the injection in hole, improves the hole injection efficiency of device, and meanwhile, the oxide skin(coating) material of praseodymium is more stable, is difficult for and airborne oxygen reaction; Therefore, the light extraction efficiency of organic electroluminescence device of the present invention is high.
Preferably, the material of described hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5), the thickness of described hole injection layer is 20～80nm, more preferably, described hole injection layer material is V
2o
5, thickness is 25nm.
Preferably, described hole transmission layer material is 1,1-, bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4 " described hole transmission layer material thickness is 20～60nm, more preferably; described hole transmission layer material is NPB for tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N; N '-diphenyl-4; 4 '-benzidine (NPB), and thickness is 30nm.
Preferably, described luminescent layer material 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) or oxine aluminium (Alq
3), thickness is 5～40nm, more preferably, described luminescent layer material is Alq
3, thickness is preferably 20nm.
Preferably, described electron transfer layer material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or N-aryl benzimidazole (TPBI), thickness is 40～250nm, more preferably, described electron transfer layer material is Bphen, and thickness is 80nm.
Preferably, described electron injecting layer material is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF), thickness is 0.5～10nm, and more preferably, described electron injecting layer material is CsF, and thickness is 1nm.
Preferably, described negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and thickness is 80～250nm, and more preferably, described negative electrode is Al, and thickness is 150nm.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise following operating procedure:
Corresponding substrate of glass is provided, dry after cleaning;
On substrate of glass exiting surface, prepare anode layer, described anode layer is comprised of the oxide skin(coating) containing hafnium compound layer, conducting metal simple substance layer and praseodymium stacking gradually;
Preparation method is: first on substrate of glass exiting surface, adopt the method preparation of electron beam evaporation plating described containing hafnium compound layer, the energy density of described electron beam evaporation plating is 10～100W/cm
2;
Then containing on hafnium compound layer, adopting thermal resistance vapour deposition method to prepare successively the oxide skin(coating) of described conducting metal simple substance layer and praseodymium, described thermal resistance evaporation pressure is 5 * 10
-5~ 2 * 10
-3pa, evaporation speed is 1 ~ 10nm/s;
On the oxide skin(coating) of praseodymium, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, finally obtains described organic electroluminescence device.
Preferably, described is HfO containing hafnium compound layer material
2or HfB
2, described is 20～100nm containing hafnium compound layer thickness.
Preferably, described conducting metal simple substance layer material is Ag, Al, Pt or Au, and described conducting metal simple substance layer thickness is 10～30nm.
Preferably, the oxide skin(coating) material of described praseodymium is PrO
2or Pr
2o
3, the oxide skin(coating) thickness of described praseodymium is 1～10nm.
Preferably, the thermal resistance evaporation condition of described hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is: evaporation pressure is 5 * 10
-5~ 2 * 10
-3pa, evaporation speed is 0.1 ~ 1nm/s, the thermal resistance evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 5 * 10
-5~ 2 * 10
-3pa, evaporation speed is 1 ~ 10nm/s.
Preferably, described substrate of glass refractive index is 1.8～2.2, at the light transmission rate of 400nm, is 90%～96%.
More preferably, described substrate of glass is selected from the glass that the trade mark is N-LAF36, N-LASF31A, N-LASF41 or N-LASF44, and described substrate of glass refractive index is 1.8～1.9.
Preferably, after described cleaning, be dried as after glass substrate being used successively distilled water, alcohol flushing totally, be placed in isopropyl alcohol and soak an evening, clean up rear air-dry.
Preferably, the material of described hole injection layer is MoO
3, WO
3or V
2o
5, the thickness of described hole injection layer is 20～80nm, more preferably, described hole injection layer material is V
2o
5, thickness is 25nm.
Preferably, described hole transmission layer material is TAPC, TCTA or NPB, and described hole transmission layer material thickness is 20～60nm, and more preferably, described hole transmission layer material is NPB, and thickness is 30nm.
Preferably, described luminescent layer material is DCJTB, ADN, BCzVBi or Alq
3, thickness is 5～40nm, more preferably, described luminescent layer material is Alq
3, thickness is preferably 20nm.
Preferably, described electron transfer layer material is Bphen, TAZ or TPBI, and thickness is 40～250nm, and more preferably, described electron transfer layer material is Bphen, and thickness is 80nm.
Preferably, described electron injecting layer material is Cs
2cO
3, CsF, CsN
3or LiF, thickness is 0.5～10nm, and more preferably, described electron injecting layer material is CsF, and thickness is 1nm.
Preferably, described negative electrode is Ag, Al, Pt or Au, and thickness is 80～250nm, and more preferably, described negative electrode is Al, and thickness is 150nm.
It is 1.8～2.2 that the present invention adopts refractive index, the glass that is 90%～96% at the light transmission rate of 400nm is as the substrate of device, can make the more light of device incide on substrate, described is transmission wide waveband (μ m light transmission rate is 70%～85% in 200nm～10) containing hafnium compound layer, high index of refraction (refractive index is 2.0～2.3) material forms, containing hafnium compound layer transmission wide waveband, can guarantee the light transmission rate in visible-range, play anti-reflection effect; High containing hafnium compound layer refractive index, can guarantee to arrive anode from the luminous energy of device inside transmitting, containing hafnium compound layer and high index of refraction substrate refractive index comparison match, can dwindle refringence between the two simultaneously, avoid total reflection phenomenon, effectively strengthen light exitance; Described conducting metal simple substance layer plays electric action, can improve the transmission rate of charge carrier, and the energy that device inside consumes is reduced, and makes more energy for the outgoing of light; The oxide skin(coating) of described praseodymium is high work function (work function is-7.2eV～-6.5eV) material, contributes to the injection in hole, improves the hole injection efficiency of device, and meanwhile, the oxide skin(coating) material of praseodymium is more stable, is difficult for and airborne oxygen reaction; Therefore, the light extraction efficiency of organic electroluminescence device of the present invention is high.
Implement the embodiment of the present invention, there is following beneficial effect:
The present invention eliminates the total reflection between glass and anode, more light is incided in substrate, containing hafnium compound layer, can guarantee the light transmission rate in visible-range, dwindle the refringence between glass and anode, avoid total reflection phenomenon, effectively strengthen light exitance, conducting metal simple substance layer has improved the transmission rate of charge carrier, and the oxide skin(coating) HOMO highest occupied molecular orbital energy level of the praseodymium of high work function is larger, can guarantee the injection in hole, effectively improve the light extraction efficiency of device.
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 organic electroluminescence device of the present invention;
Fig. 2 is voltage 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) selecting the trade mark is that (refractive index is 1.8 for the glass of N-LASF44, light transmission rate at 400nm is 96%) as substrate of glass 1, after using successively distilled water, alcohol flushing totally substrate of glass 1, be placed in isopropyl alcohol and soak an evening, clean up rear air-dry.
(2) on substrate of glass exiting surface, preparing anode layer 2, first adopt the method for electron beam evaporation plating on substrate of glass 1 exiting surface, to prepare containing hafnium compound layer 21, is HfO containing hafnium compound layer 21 material
2, thickness is 60nm, the energy density of electron beam evaporation plating is 30W/cm
2, then containing on hafnium compound layer 21, adopting thermal resistance vapour deposition method to prepare successively the oxide skin(coating) 23 of conducting metal simple substance layer 22 and praseodymium, conducting metal simple substance layer 22 material are Ag, and thickness is 20nm, and oxide skin(coating) 23 materials of praseodymium are PrO
2, thickness is 2nm, the oxide skin(coating) 23 evaporation pressure of conducting metal simple substance layer 22 and praseodymium are 8 * 10
-4pa, evaporation speed is 2nm/s.
(3) on anode, adopt successively thermal resistance evaporation to prepare hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and negative electrode 8, obtain organic electroluminescence device, wherein,
Hole injection layer 3 materials are V
2o
5, the pressure adopting during evaporation is 8 * 10
-4pa, evaporation speed is 2nm/s, evaporation thickness is 25nm;
Hole transmission layer 4 materials are NPB, and the pressure adopting during evaporation is 8 * 10
-4pa, evaporation speed is 0.2nm/s, evaporation thickness is 30nm;
Luminescent layer 5 materials are Alq
3, the pressure adopting during evaporation is 8 * 10
-4pa, evaporation speed is 0.2nm/s, evaporation thickness is 20nm;
The material of electron transfer layer 6 is Bphen, and the pressure adopting during evaporation is 8 * 10
-4pa, evaporation speed is 0.2nm/s, evaporation thickness is 80nm;
The material of electron injecting layer 7 is CsF, and the pressure adopting during evaporation is 8 * 10
-4pa, evaporation speed is 0.2nm/s, evaporation thickness is 1nm;
The material of negative electrode 8 is Al, and the pressure adopting during evaporation is 8 * 10
-4pa, evaporation speed is 2nm/s, evaporation thickness is 150nm.
Fig. 1 is the structural representation of the organic electroluminescence device prepared of the present embodiment, organic electroluminescence device prepared by the present embodiment, comprise the substrate of glass 1, anode layer 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and the negative electrode 8 that stack gradually, anode layer 2 comprises the oxide skin(coating) 23 containing hafnium compound layer 21, conducting metal simple substance layer 22 and praseodymium stacking gradually.Concrete structure is expressed as:
Substrate of glass/HfO
2/ Ag/PrO
2/ V
2o
5/ NPB/Alq
3/ Bphen/CsF/Al.
Embodiment 2
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) select the trade mark be the glass (refractive index is 1.8, is 95% at the light transmission rate of 400nm) of N-LAF36 as substrate of glass, after using successively distilled water, alcohol flushing clean substrate of glass, be placed in isopropyl alcohol and soak an evening, clean up rear air-dry.
(2) on substrate of glass exiting surface, preparing anode layer, first adopt the method for electron beam evaporation plating on substrate of glass exiting surface, to prepare containing hafnium compound layer, is HfB containing hafnium compound layer material
2, thickness is 20nm, the energy density of electron beam evaporation plating is 10W/cm
2, then containing on hafnium compound layer, adopting thermal resistance vapour deposition method to prepare successively the oxide skin(coating) of conducting metal simple substance layer and praseodymium, conducting metal simple substance layer material is Al, and thickness is 10nm, and the oxide skin(coating) material of praseodymium is Pr
2o
3, thickness is 1nm, the oxide skin(coating) thermal resistance evaporation pressure of conducting metal simple substance layer and praseodymium is 2 * 10
-3pa, evaporation speed is 10nm/s.
(3) on anode, adopt successively thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, obtain organic electroluminescence device, wherein,
Hole injection layer material is MoO
3, the pressure adopting during evaporation is 2 * 10
-3pa, evaporation speed is 10nm/s, evaporation thickness is 40nm;
Hole transmission layer material is TAPC, and the pressure adopting during evaporation is 2 * 10
-3pa, evaporation speed is 1nm/s, evaporation thickness is 45nm;
Luminescent layer material is DCJTB, and the pressure adopting during evaporation is 2 * 10
-3pa, evaporation speed is 1nm/s, evaporation thickness is 8nm;
The material of electron transfer layer is TAZ, and the pressure adopting during evaporation is 2 * 10
-3pa, evaporation speed is 1nm/s, evaporation thickness is 65nm;
The material of electron injecting layer is Cs
2cO
3, the pressure adopting during evaporation is 2 * 10
-3pa, evaporation speed is 1nm/s, evaporation thickness is 10nm;
The material of negative electrode is Pt, and the pressure adopting during evaporation is 2 * 10
-3pa, evaporation speed is 10nm/s, evaporation thickness is 80nm.
Organic electroluminescence device prepared by the present embodiment, comprise the substrate of glass, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, anode layer comprises the oxide skin(coating) containing hafnium compound layer, conducting metal simple substance layer and praseodymium stacking gradually.Concrete structure is expressed as:
Substrate of glass/HfB
2/ Al/Pr
2o
3/ MoO
3/ TAPC/DCJTB/TAZn/Cs
2cO
3/ Pt.
Embodiment 3
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) selecting the trade mark is that (refractive index is 1.9 for the glass of N-LASF31A, light transmission rate at 400nm is 92%) as substrate of glass, after using successively distilled water, alcohol flushing totally substrate of glass, be placed in isopropyl alcohol and soak an evening, clean up rear air-dry.
(2) on substrate of glass exiting surface, preparing anode layer, first adopt the method for electron beam evaporation plating on substrate of glass exiting surface, to prepare containing hafnium compound layer, is HfO containing hafnium compound layer material
2, thickness is 100nm, the energy density of electron beam evaporation plating is 100W/cm
2, then containing on hafnium compound layer, adopting thermal resistance vapour deposition method to prepare successively the oxide skin(coating) of conducting metal simple substance layer and praseodymium, conducting metal simple substance layer material is Pt, and thickness is 30nm, and the oxide skin(coating) material of praseodymium is PrO
2, thickness is 10nm, the oxide skin(coating) evaporation pressure of conducting metal simple substance layer and praseodymium is 5 * 10
-5pa, evaporation speed is 1nm/s.
(3) on anode, adopt successively thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, obtain organic electroluminescence device, wherein,
Hole injection layer material is MoO
3, the pressure adopting during evaporation is 5 * 10
-5pa, evaporation speed is 1nm/s, evaporation thickness is 20nm;
Hole transmission layer material is TCTA, and the pressure adopting during evaporation is 5 * 10
-5pa, evaporation speed is 0.1nm/s, evaporation thickness is 60nm;
Luminescent layer material is ADN, and the pressure adopting during evaporation is 5 * 10
-5pa, evaporation speed is 0.1nm/s, evaporation thickness is 10nm;
The material of electron transfer layer is TPBI, and the pressure adopting during evaporation is 5 * 10
-5pa, evaporation speed is 0.1nm/s, evaporation thickness is 200nm;
The material of electron injecting layer is LiF, and the pressure adopting during evaporation is 5 * 10
-5pa, evaporation speed is 0.1nm/s, evaporation thickness is 0.5nm;
The material of negative electrode is Ag, and the pressure adopting during evaporation is 5 * 10
-5pa, evaporation speed is 1nm/s, evaporation thickness is 100nm.
Organic electroluminescence device prepared by the present embodiment, comprise the substrate of glass, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, anode layer comprises the oxide skin(coating) containing hafnium compound layer, conducting metal simple substance layer and praseodymium stacking gradually.Concrete structure is expressed as:
Substrate of glass/HfO
2/ Pt/PrO
2/ MoO
3/ TCTA/ADN/TPBI/LiF/Ag.
Embodiment 4
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) selecting the trade mark is that (refractive index is 1.83 for the glass of N-LASF41, light transmission rate at 400nm is 90%) as substrate of glass, after using successively distilled water, alcohol flushing totally substrate of glass, be placed in isopropyl alcohol and soak an evening, clean up rear air-dry.
(2) on substrate of glass exiting surface, preparing anode layer, first adopt the method for electron beam evaporation plating on substrate of glass exiting surface, to prepare containing hafnium compound layer, is HfO containing hafnium compound layer material
2, thickness is 25nm, the energy density of electron beam evaporation plating is 80W/cm
2, then containing on hafnium compound layer, adopting thermal resistance vapour deposition method to prepare successively the oxide skin(coating) of conducting metal simple substance layer and praseodymium, conducting metal simple substance layer material is Au, and thickness is 20nm, and the oxide skin(coating) material of praseodymium is PrO
2, thickness is 1nm, the oxide skin(coating) evaporation pressure of conducting metal simple substance layer and praseodymium is 2 * 10
-4pa, evaporation speed is 6nm/s.
(3) on anode, adopt successively thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, obtain organic electroluminescence device, wherein,
Hole injection layer material is WO
3, the pressure adopting during evaporation is 2 * 10
-4pa, evaporation speed is 6nm/s, evaporation thickness is 80nm;
Hole transmission layer material is NPB, and the pressure adopting during evaporation is 2 * 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 60nm;
Luminescent layer material is BCzVBi, and the pressure adopting during evaporation is 2 * 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 40nm;
The material of electron transfer layer is TAZ, and the pressure adopting during evaporation is 2 * 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 35nm;
The material of electron injecting layer is CsN
3, the pressure adopting during evaporation is 2 * 10
-4pa, evaporation speed is 0.5nm/s, evaporation thickness is 3nm;
The material of negative electrode is Au, and the pressure adopting during evaporation is 2 * 10
-4pa, evaporation speed is 6nm/s, evaporation thickness is 250nm.
Organic electroluminescence device prepared by the present embodiment, comprise the substrate of glass, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, anode layer comprises the oxide skin(coating) containing hafnium compound layer, conducting metal simple substance layer and praseodymium stacking gradually.Concrete structure is expressed as:
Substrate of glass/HfO
2/ Au/PrO
2/ WO
3/ NPB/BCzVBi/TAZ/CsN
3/ Au.
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 anode in comparative example is indium tin oxide glass (ITO), thickness is 120nm, and the concrete structure of comparative example's organic electroluminescence device is: substrate of glass/ITO/V
2o
5/ NPB/Alq
3/ Bphen/CsF/Al.
Effect embodiment
Adopt fiber spectrometer (U.S. marine optics Ocean Optics company, model: USB4000), current-voltage tester (U.S. Keithly company, 2400), colorimeter (Japanese Konica Minolta company model:, model: CS-100A) current efficiency of test organic electroluminescence device is with pressure change curve, to investigate the luminous efficiency of device, tested object is embodiment 1 and comparative example's organic electroluminescence device.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 pressure.
As can be seen from Figure 2, from 2V, raising along with voltage, the current efficiency of embodiment 1 is large than comparative example all, when 4V, the current efficiency of embodiment 1 is 1.7cd/A, and that comparative example is only 1.0cd/A, this explanation, adopting refractive index is 1.8～2.2, the glass that is 90%～96% at the light transmission rate of 400nm is as the substrate of device, in substrate of glass, prepare anode layer, can eliminate the total reflection between glass and anode layer, guarantee the light transmission rate of device in visible-range, dwindle refringence between the two, avoid total reflection phenomenon, effectively strengthen light exitance, and the metal oxide that the oxide skin(coating) of praseodymium in anode layer is high work function, can guarantee the injection in hole, effectively improve the light extraction 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, it is characterized in that, comprise the substrate of glass, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described anode layer is comprised of the oxide skin(coating) containing hafnium compound layer, conducting metal simple substance layer and praseodymium stacking gradually.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described is hafnium oxide or hafnium boride containing hafnium compound layer material, and described is 20～100nm containing hafnium compound layer thickness.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, described conducting metal simple substance layer material is silver, aluminium, platinum or gold, and described conducting metal simple substance layer thickness is 10～30nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the oxide skin(coating) of described praseodymium is titanium dioxide praseodymium or praseodymium sesquioxide, and the oxide skin(coating) thickness of described praseodymium is 1～10nm.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, described substrate of glass refractive index is 1.8～2.2, at the light transmission rate of 400nm, is 90%～96%.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises following operating procedure:
Corresponding substrate of glass is provided, dry after cleaning;
On substrate of glass exiting surface, prepare anode layer, described anode layer is comprised of the oxide skin(coating) containing hafnium compound layer, conducting metal simple substance layer and praseodymium stacking gradually;
Preparation method is: first on substrate of glass exiting surface, adopt the method preparation of electron beam evaporation plating described containing hafnium compound layer, the energy density of described electron beam evaporation plating is 10 ~ l00W/cm
2;
Then containing on hafnium compound layer, adopting thermal resistance vapour deposition method to prepare successively the oxide skin(coating) of described conducting metal simple substance layer and praseodymium, described thermal resistance evaporation pressure is 5 * 10
-5~ 2 * 10
-3pa, evaporation speed is 1 ~ 10nm/s;
On the oxide skin(coating) of praseodymium, adopt successively thermal resistance evaporation to prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, finally obtain described organic electroluminescence device.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described is hafnium oxide or hafnium boride containing hafnium compound layer material, and described is 20～100nm containing hafnium compound layer thickness.
8. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described conducting metal simple substance layer material is silver, aluminium, platinum or gold, and described conducting metal simple substance layer thickness is 10～30nm.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the oxide skin(coating) material of described praseodymium is titanium dioxide praseodymium or praseodymium sesquioxide, and the oxide skin(coating) thickness of described praseodymium is 1～10nm.
10. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, the thermal resistance evaporation condition of described hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is: evaporation pressure is 5 * 10
-5~ 2 * 10
-3pa, evaporation speed is 0.1 ~ 1nm/s, the thermal resistance evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 5 * 10
-5~ 2 * 10
-3pa, evaporation speed is 1 ~ 10nm/s.
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Application publication date: 20140827 |