CN104037344A - Stacked organic light emitting device and preparation method thereof - Google Patents
Stacked organic light emitting device and preparation method thereof Download PDFInfo
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- CN104037344A CN104037344A CN201310071195.4A CN201310071195A CN104037344A CN 104037344 A CN104037344 A CN 104037344A CN 201310071195 A CN201310071195 A CN 201310071195A CN 104037344 A CN104037344 A CN 104037344A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H—ELECTRICITY
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Abstract
The invention discloses a stacked organic light emitting device and a preparation method thereof. The stacked organic light emitting device comprises an anode, a hole injection layer, a first hole transport layer, a first light emitting layer, a first electron transport layer, a charge generation layer, a second hole transport layer, a second light emitting layer, a second electron transport layer, an electron injection layer and a cathode which are sequentially stacked. The charge generation layer comprises a metal oxide layer, an n-type doped layer and a metal oxide doped layer which are sequentially stacked. The metal oxide layer can improve the electron transport rate. The n-type doped layer can provide electrons and holes at the same time, and improves the stability and light scattering effect of the charge generation layer. The metal oxide doped layer improves the hole transport rate, and meanwhile, the metal oxide is of an amorphous structure which can inhibit crystallization of polycrystalline hole transport materials and avoid the presence of electron traps. The invention further provides a preparation method of the stacked organic light emitting device.
Description
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of laminated organic electroluminescent 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.At present, in order to improve luminosity and luminous efficiency, increasing research is to take laminated device as main, this structure is normally together in series several luminescence units as articulamentum with charge generation layer, compare with unit component, multilayer devices often has current efficiency and luminosity at double, at present research many be utilize two or more to have that hole is injected or material of electronic injection as charge generating layers (as Cs:BCP/V
2o
5), or N-shaped and p-type doped layer as charge generation layer (as N-shaped (Alq
3: Li) and p-type (NPB:FeCl
3)) or Al-WO
3-Au etc. are linked in sequence a plurality of luminescence units and form, but this device light transmission rate and luminous efficiency are all lower, are unfavorable for the further application of laminated organic electroluminescent device.Meanwhile, the preparation of this charge generation layer at least needs to carry out more than twice operation, to preparation, brings certain complexity.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of laminated organic electroluminescent device, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually, and described metal oxide layer can improve electric transmission speed.Described N-shaped doped layer can improve stability and the light scattering effect of charge generation layer, meanwhile, not only electronics can be provided but also hole can be provided, and has improved greatly the power of regeneration of electric charge; Described doped metallic oxide layer is when improving hole transport speed, and because this metal oxide is impalpable structure, this form can suppress the crystallization of the hole mobile material of polycrystalline, avoids the existence of electron trap; Meanwhile, the present invention also provides a kind of preparation method of above-mentioned laminated organic electroluminescent device.
First aspect, the invention provides a kind of laminated organic electroluminescent device, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually; Described metal oxide layer material is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5); The material of described N-shaped doped layer is that metal simple-substance and N-shaped metal oxide are the composite material of the ratio formation of 0.05:1～0.2:1 in mass ratio, and described N-shaped metal oxide is zinc oxide (ZnO), magnesium oxide (MgO) or zirconia (ZrO
2); Described doped metallic oxide layer material is the composite material that organic hole transferring material and metal oxide form for 0.2:1～0.6:1 in mass ratio; Described metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5); Described organic hole transferring material is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB) or N, N '-diphenyl-N, N '-(3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD).
Preferably, described metal oxide layer thickness is 5～20nm.
Preferably, the metal simple-substance in described N-shaped doped layer is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and the thickness of described N-shaped doped layer is 5～20nm.
Preferably, described doped metallic oxide layer thickness is 1～10nm.
Preferably, described anode substrate is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Preferably, described hole injection layer material is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5), thickness is 20～80nm;
More preferably, described hole injection layer material is MoO
3, thickness is 40nm.
Preferably, described the first hole transmission layer and the second hole transmission layer material are 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), thickness is 20～60nm.
More preferably, the first hole transmission layer material is NPB, and thickness is 30nm, and the second hole transmission layer material is TAPC, and thickness is 50nm.
Preferably, described the first luminescent layer and the second luminescent layer material are 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 the first luminescent layer and the second luminescent layer material are Alq
3, thickness is 10nm.
Preferably, described the first electron transfer layer and the second electron transfer layer material are 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 40～200nm.
More preferably, described the first electron transfer layer material is TAZ, and thickness is 180nm, and described the second electron transfer layer material is TPBI, 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;
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 60～300nm.
More preferably, described negative electrode is Ag, and thickness is 120nm.
The invention discloses a kind of laminated organic electroluminescent device, in this device, charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually; Described metal oxide layer can improve electric transmission speed; Described N-shaped doped layer material is metal simple-substance (work function is 4.0～6.0eV) and the composite material that N-shaped metal oxide forms, and electronics and hole can be provided simultaneously, improves greatly the power of regeneration in electronics and hole; Because N-shaped burning properties is unstable, add metal simple-substance, can improve the stability of charge generation layer, the light scattering effect that the existence of N-shaped metal oxide can improve device simultaneously; Described doped metallic oxide layer material is the composite material that organic hole transferring material and metal oxide form, and reduced the operating voltage of device, improves hole transport speed; The easy crystallization of organic hole transferring material, in crystallization process because impurity exists and the problem of technique when preparation, relatively be difficult to form smooth film, therefore, increased the probability that electron trap produces, the existence of electron trap falls into into electronics and hole, carry out compoundly with the room of rete, cause and bury in oblivion, because this metal oxide is impalpable structure, this form can suppress the crystallization of the hole mobile material of polycrystalline, avoids the existence of electron trap; Therefore, this laminated device can effectively improve luminous efficiency.
Second aspect, the invention provides a kind of preparation method of laminated organic electroluminescent device, comprises following operating procedure:
Required size anode is provided, dry after cleaning;
At described anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and charge generation layer; Described charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually; Described metal oxide is MoO
3, WO
3or V
2o
5; The material of described N-shaped doped layer is that metal simple-substance and N-shaped metal oxide are the composite material of the ratio formation of 0.05:1～0.2:1 in mass ratio, and described N-shaped metal oxide is ZnO, MgO or ZrO
2; Described doped metallic oxide layer material is the composite material that organic hole transferring material and metal oxide form for 0.2:1～0.6:1 in mass ratio; Described metal oxide is MoO
3, WO
3or V
2o
5; Described organic hole transferring material is TAPC, NPB or TPD; The evaporation condition of described metal oxide layer and N-shaped doped layer is: evaporation pressure is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 1～10nm/s; The evaporation pressure of described doped metallic oxide layer is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 0.1～1nm/s;
Evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on charge generation layer, finally obtain laminated organic electroluminescent device.
Preferably, described metal oxide layer thickness is 5～20nm.
Preferably, the metal simple-substance in described N-shaped doped layer is Ag, Al, Pt or Au, and the thickness of described N-shaped doped layer is 5～20nm.
Preferably, described doped metallic oxide layer thickness is 1～10nm.
Preferably, the evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 1～10nm/s.
Preferably, described the first hole transmission layer, the first luminescent layer, the first electron transfer layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 0.1～1nm/s.
Preferably, described anode substrate is ITO, AZO or IZO, more preferably ITO.
Preferably, described in the anode of required size is provided, concrete operations are: anode substrate 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 anode, 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 hole injection layer material is molybdenum trioxide MoO
3, WO
3or V
2o
5, thickness is 20～80nm;
More preferably, hole injection layer material is MoO
3, thickness is 40nm.
Preferably, the first described hole transmission layer and the second hole transmission layer material are TAPC, TCTA or NPB, and thickness is 20～60nm.
More preferably, the first hole transmission layer material is for being NPB, and thickness is 30nm, and the second hole transmission layer material is TAPC, and thickness is 50nm.
Preferably, described the first luminescent layer and the second luminescent layer material are DCJTB, ADN, BCzVBi or Alq
3, thickness is 5～40nm.
More preferably, described the first luminescent layer and the second luminescent layer material are Alq
3, thickness is 10nm.
Preferably, the first and second described electron transfer layer materials are Bphen, TAZ or TPBI, and thickness is 40～200nm.
More preferably, described the first electron transfer layer is TAZ, and thickness is 180nm, and described the second electron transfer layer is TPBI, and thickness is 80nm.
Preferably, described electron injecting layer material is Cs
2cO
3, CsF, CsN
3or LiF, thickness is 0.5～10nm;
More preferably, described electron injecting layer is CsF, and thickness is 1nm.
Preferably, described negative electrode is Ag, Al, Pt or Au, and thickness is 60～300nm.
More preferably, described negative electrode is Ag, and thickness is 120nm.
The invention discloses a kind of laminated organic electroluminescent device, in this device, charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually; Described metal oxide layer can improve electric transmission speed.Described N-shaped doped layer material is the composite material that metal simple-substance (work function is 4.0～6.0eV) and N-shaped metal oxide form, can improve the stability of charge generation layer, the existence of N-shaped metal oxide can improve light scattering effect, simultaneously, this layer not only can provide electronics but also hole can be provided, and improves greatly the power of regeneration of device, described doped metallic oxide layer material is the composite material that organic hole transferring material and metal oxide form, the easy crystallization of hole mobile material, in crystallization process due to impurity exists and when preparation due to the problem of technique, relatively be difficult to form smooth film, therefore, strengthened the probability that electron trap produces, the existence of electron trap falls into into hole, carry out compound with the room of rete, cause and bury in oblivion, because this metal oxide is impalpable structure, this form can suppress the crystallization of the hole mobile material of polycrystalline, avoided the existence of electron trap, improved the hole transport speed of device, this laminated device can effectively improve luminous efficiency.Meanwhile, the present invention prepares the method preparation that charge generation layer is only used evaporation, and method is simple.
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 embodiment of the present invention 1 laminated organic electroluminescent device;
Fig. 2 is voltage and the brightness relationship figure 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 laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected ito glass, first anode is carried out to photoetching treatment, is cut into 2 * 2cm
2square, 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; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is MoO
3, thickness is 40nm, evaporation pressure is 5 * 10
-3pa, evaporation speed is 1nm/s; The first hole transmission layer material is NPB, and thickness is 30nm, and the material of the first luminescent layer is Alq
3, thickness is 10nm, and the first electron transfer layer material is TAZ, and thickness is 180nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 5 * 10
-3pa, evaporation speed is 0.1nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation WO on the first electron transfer layer
3, obtain the metal oxide layer that thickness is 7nm; On metal oxide layer, evaporation Ag and ZnO are the composite material of the ratio formation of 0.1:1 in mass ratio, and obtaining thickness is the N-shaped doped layer of 10nm, evaporation NPB and MoO on N-shaped doped layer
3the composite material forming for 0.4:1 in mass ratio, obtaining thickness is the doped metallic oxide layer of 5nm, the evaporation condition of metal oxide layer and N-shaped doped layer is: evaporation pressure is 5 * 10
-3pa, evaporation speed is 1nm/s; The evaporation pressure of doped metallic oxide layer is 5 * 10
-3pa, evaporation speed is 0.1nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on doped metallic oxide layer, the second hole transmission layer material is NPB, thickness is 50nm, the second electron transfer layer material is TPBI, thickness is 80nm, electron injecting layer material is CsF, and thickness is 1nm, and the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 5 * 10
-3pa, evaporation speed is 0.1nm/s; The material of negative electrode is Ag, and thickness is 120nm, and evaporation pressure is 5 * 10
-3pa, evaporation speed is 1nm/s.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, organic electroluminescence device prepared by the present embodiment, comprise the anode 1, hole injection layer 2, the first hole transmission layer 3, the first luminescent layer 4, the first electron transfer layer 5, charge generation layer 6, the second hole transmission layer 7, the second luminescent layer 8, the second electron transfer layer 9, electron injecting layer 10 and the negative electrode 11 that stack gradually, charge generation layer comprises metal oxide layer 61, N-shaped doped layer 62 and the doped metallic oxide layer 63 stacking gradually.Concrete structure is expressed as:
Ito glass/MoO
3/ NPB/Alq
3/ TAZ/WO
3/ ZnO:Ag/MoO
3: NPB/TAPC/Alq
3/ TPBI/CsF/Ag, wherein, brace "/" represents layer structure, ZnO:Ag and MoO
3: the colon ": " in NPB represents to mix, lower same.
Embodiment 2
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected AZO glass, first anode is carried out to photoetching treatment, is then cut into 2 * 2cm
2square, 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; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is V
2o
5, thickness is 80nm, evaporation pressure is 2 * 10
-4pa, evaporation speed is 10nm/s; The first hole transmission layer material is NPB, and thickness is 60nm, and the material of the first luminescent layer is ADN, thickness is 5nm, the first electron transfer layer material is TPBI, and thickness is 40nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 2 * 10
-4pa, evaporation speed is 1nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation V on the first electron transfer layer
2o
5, obtain the metal oxide layer that thickness is 5nm; Evaporating Al and ZrO on metal oxide layer
2be the composite material of the ratio formation of 0.2:1 in mass ratio, obtaining thickness is the N-shaped doped layer of 20nm, evaporation TPD and WO on N-shaped doped layer
3the composite material forming for 0.2:1 in mass ratio, obtaining thickness is the doped metallic oxide layer of 10nm, the evaporation condition of metal oxide layer and N-shaped doped layer is: evaporation pressure is 5 * 10
-3pa, evaporation speed is 10nm/s; The evaporation pressure of doped metallic oxide layer is 5 * 10
-3pa, evaporation speed is 1nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on doped metallic oxide layer, the second hole transmission layer material is TAPC, thickness is 20nm, the second luminescent layer material is BCzVBi, thickness is 40nm, the second electron transfer layer material is TAZ, and thickness is 200nm, and electron injecting layer material is CsN
3, thickness is 0.5nm, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 2 * 10
-4pa, evaporation speed is 1nm/s; The material of negative electrode is Pt, and thickness is 60nm, and evaporation pressure is 2 * 10
-4pa, evaporation speed is 10nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually.Concrete structure is expressed as:
AZO glass/V
2o
5/ NPB/ADN/TPBI/V
2o
5/ ZrO
2: Al/WO
3: TPD/TAPC/BCzVBi/TAZ/CsN
3/ Pt.
Embodiment 3
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected IZO glass, first anode is carried out to photoetching treatment, is cut into 2 * 2cm
2square, 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; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is MoO
3, thickness is 20nm, evaporation pressure is 1 * 10
-3pa, evaporation speed is 5nm/s; The first hole transmission layer material is TAPC, thickness is 30nm, the material of the first luminescent layer is DCJTB, thickness is 10nm, the first electron transfer layer material is Bphen, thickness is 200nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 1 * 10
-3pa, evaporation speed is 0.5nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation WO on the first electron transfer layer
3, obtain the metal oxide layer that thickness is 20nm; On metal oxide layer, evaporation Pt and MgO are the composite material of the ratio formation of 0.05:1 in mass ratio, and obtaining thickness is the N-shaped doped layer of 5nm, evaporation TAPC and V on N-shaped doped layer
2o
5the composite material forming for 0.6:1 in mass ratio, obtaining thickness is the doped metallic oxide layer of 1nm, the evaporation condition of metal oxide layer and N-shaped doped layer is: evaporation pressure is 1 * 10
-3pa, evaporation speed is 5nm/s; The evaporation pressure of doped metallic oxide layer is 1 * 10
-3pa, evaporation speed is 0.5nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on doped metallic oxide layer, the second hole transmission layer material is TCTA, thickness is 60nm, the second luminescent layer material is DCJTB, thickness is 5nm, the second electron transfer layer material is Bphen, and thickness is 40nm, and electron injecting layer material is Cs
2cO
3, thickness is 10nm, the second hole transmission layer, luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 1 * 10
-3pa, evaporation speed is 1nm/s; The material of negative electrode is Al, and thickness is 300nm, and evaporation pressure is 1 * 10
-3pa, evaporation speed is 5nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually.Concrete structure is expressed as:
IZO glass/MoO
3/ TAPC/DCJTB/Bphen/WO
3/ MgO:Pt/V
2o
5: TAPC/TCTA/DCJTB/Bphen/Cs
2cO
3/ Al.
Embodiment 4
A preparation method for laminated organic electroluminescent device, comprises following operating procedure:
(1) anode is selected IZO glass, first anode is carried out to photoetching treatment, is cut into 2 * 2cm
2square, 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; Evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer successively on anode, hole injection layer material is WO
3, thickness is 30nm, evaporation pressure is 1 * 10
-3pa, evaporation speed is 5nm/s; The first hole transmission layer material is NPB, and thickness is 50nm, and the material of the first luminescent layer is ADN, thickness is 8nm, the first electron transfer layer material is TAZ, and thickness is 40nm, and the first hole transmission layer, the first luminescent layer and the first electron transfer layer evaporation condition are: evaporation pressure is 1 * 10
-3pa, evaporation speed is 0.5nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, first evaporation MoO on the first electron transfer layer
3, obtain the metal oxide layer that thickness is 15nm; On metal oxide layer, evaporation Au and ZnO are the composite material of the ratio formation of 0.08:1 in mass ratio, and obtaining thickness is the N-shaped doped layer of 18nm, evaporation NPB and WO on N-shaped doped layer
3the composite material forming for 0.35:1 in mass ratio, obtaining thickness is the doped metallic oxide layer of 8nm, the evaporation condition of metal oxide layer and N-shaped doped layer is: evaporation pressure is 1 * 10
-3pa, evaporation speed is 5nm/s; The evaporation pressure of doped metallic oxide layer is 1 * 10
-3pa, evaporation speed is 0.5nm/s;
(3) evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on doped metallic oxide layer, the second hole transmission layer material is NPB, thickness is 50nm, the second luminescent layer material is ADN, thickness is 7nm, the second electron transfer layer material is Bphen, thickness is 100nm, electron injecting layer material is LiF, thickness is 2nm, and the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 1 * 10
-3pa, evaporation speed is 1nm/s; The material of negative electrode is Au, and thickness is 180nm, and evaporation pressure is 1 * 10
-3pa, evaporation speed is 10nm/s.
Organic electroluminescence device prepared by the present embodiment, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually.Concrete structure is expressed as:
IZO glass/WO
3/ NPB/ADN/TAZ/MoO
3/ ZnO:Au/WO
3: NPB/NPB/ADN/Bphen/LiF/Au.
Comparative example
For being presented as creativeness of the present invention, the present invention is also provided with comparative example, comparative example is existing organic electroluminescence device, comprise the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, the concrete structure of comparative example's organic electroluminescence device is: ito glass/MoO
3/ NPB/Alq
3/ TPBI/CsF/Ag, the thickness of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode is respectively: 40nm, 30nm, 10nm, 180nm, 1nm and 120nm.
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) brightness of test organic electroluminescence device is with change in voltage 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 brightness of comparative example's organic electroluminescence device and the graph of a relation of voltage.
From Fig. 2, can find out, under different voltage, the brightness of embodiment 1 is large than comparative example all, and when 8V, the brightness of embodiment 1 is 1074cd/m
2, and that comparative example is only 674cd/m
2, this explanation, a kind of laminated organic electroluminescent device charge generation layer provided by the invention, has effectively improved 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. a laminated organic electroluminescent device, it is characterized in that, comprise the anode, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually; Described metal oxide layer material is molybdenum trioxide, tungstic acid or vanadic oxide; The material of described N-shaped doped layer is that metal simple-substance and N-shaped metal oxide are the composite material of the ratio formation of 0.05:1～0.2:1 in mass ratio, and described N-shaped metal oxide is zinc oxide, magnesium oxide or zirconia; Described doped metallic oxide layer material is the composite material that organic hole transferring material and metal oxide form for 0.2:1～0.6:1 in mass ratio; Described metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide; Described organic hole transferring material is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine or N, N '-diphenyl-N, N '-(3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines.
2. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, described metal oxide layer thickness is 5～20nm.
3. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, the metal simple-substance in described N-shaped doped layer is silver, aluminium, platinum or gold, and the thickness of described N-shaped doped layer is 5～20nm.
4. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, described doped metallic oxide layer thickness is 1～10nm.
5. a preparation method for laminated organic electroluminescent device, is characterized in that, comprises following operating procedure:
Required size anode is provided, dry after cleaning;
At described anode surface successively evaporation hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer and charge generation layer; Described charge generation layer comprises metal oxide layer, N-shaped doped layer and the doped metallic oxide layer stacking gradually; Described metal oxide layer material is molybdenum trioxide, tungstic acid or vanadic oxide; The material of described N-shaped doped layer is that metal simple-substance and N-shaped metal oxide are the composite material of the ratio formation of 0.05:1～0.2:1 in mass ratio, and described N-shaped metal oxide is zinc oxide, magnesium oxide or zirconia; Described doped metallic oxide layer material is the composite material that organic hole transferring material and metal oxide form for 0.2:1～0.6:1 in mass ratio; Described metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide; Described organic hole transferring material is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine or N, N '-diphenyl-N, N '-(3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines; The evaporation condition of described metal oxide layer and N-shaped doped layer is: evaporation pressure is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 1～10nm/s; The evaporation pressure of described doped metallic oxide layer is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 0.1～1nm/s;
Evaporation the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode successively on charge generation layer, finally obtain laminated organic electroluminescent device.
6. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, described metal oxide layer thickness is 5～20nm.
7. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, the metal simple-substance in described N-shaped doped layer is silver, aluminium, platinum or gold, and the thickness of described N-shaped doped layer is 5～20nm.
8. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, described doped metallic oxide layer thickness is 1～10nm.
9. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, the evaporation condition of described hole injection layer and negative electrode is: evaporation pressure is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 1～10nm/s.
10. the preparation method of laminated organic electroluminescent device as claimed in claim 5, it is characterized in that, described the first hole transmission layer, the first luminescent layer, the first electron transfer layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer evaporation condition are: evaporation pressure is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 0.1～1nm/s.
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| CN113611805A (en) * | 2020-08-14 | 2021-11-05 | 广东聚华印刷显示技术有限公司 | Light emitting device, method of manufacturing the same, and light emitting apparatus |
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