CN104037327A - Stacked organic light emitting device and preparation method - Google Patents
Stacked organic light emitting device and preparation method Download PDFInfo
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- CN104037327A CN104037327A CN201310070596.8A CN201310070596A CN104037327A CN 104037327 A CN104037327 A CN 104037327A CN 201310070596 A CN201310070596 A CN 201310070596A CN 104037327 A CN104037327 A CN 104037327A
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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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
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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 a stacked organic light emitting device comprising 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 stacked sequentially. The charge generation layer comprises a first metal sulfide layer, a metal elemental layer and a second metal sulfide layer which are stacked sequentially. The work function of metal sulfide is moderate, which can improve the hole injection ability and the electron injection ability. Absorption in the range of visible light wavelength is small. The metal elemental substance has high light transmittance and conductivity and is suitable to be used as a middle layer of the charge generation layer. The structure can greatly improve the light transmission rate of the charge generation layer and reduce the resistance, and ensure the conductivity and light emitting uniformity of the device. 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 stacking gradually, 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 negative electrode, described charge generation layer comprises the first metal sulfide layer stacking gradually, metal simple-substance layer and the second metal sulfide layer, the structure of charge generation layer is metal sulfide/metal simple-substance/metal sulfide, in this structure, the work function of metal sulfide is more moderate, both can improve the injectability in hole, also can improve the injectability of electronics, there is larger energy gap, can guarantee to absorb within the scope of visible light wave range less, and metal simple-substance has very high photopermeability and conductivity, be suitable as the intermediate layer of charge generation layer, this structure can improve greatly the light transmission rate of charge generation layer and reduce resistance, guarantee the conductivity of device and send out uniformity of light, this laminated device can effectively improve luminous efficiency.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 stacking gradually, 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 negative electrode, described charge generation layer comprises the first metal sulfide layer stacking gradually, metal simple-substance layer and the second metal sulfide layer, the material of described the first metal sulfide layer and the second metal sulfide layer is zinc sulphide (ZnS), cadmium sulfide (CdS), calcium sulfide (CaS) or magnesium sulfide (MgS).
Preferably, the thickness of described the first metal sulfide layer and the second metal sulfide layer is 5～40nm.
Preferably, the material of described metal simple-substance layer is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
Preferably, the thickness of described metal simple-substance layer is 1～10nm.
Preferably, described anode substrate is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), more 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 30nm.
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 TAPC, and thickness is 40nm, 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 Bphen, and thickness is 80nm, and described the second electron transfer layer material is TPBI, and thickness is 180nm.
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 Cs
2cO
3, thickness is 2nm.
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 Al, and thickness is 150nm.
The invention discloses a kind of laminated organic electroluminescent device, in this device, charge generation layer comprises the first metal sulfide layer stacking gradually, metal simple-substance layer and the second metal sulfide layer, structure is metal sulfide/metal simple-substance/metal sulfide (brace "/" represents layer structure), the work function of the metal sulfide of this structure is-5.2～-4.8eV, more moderate, both can improve the injectability in hole, also can improve the injectability of electronics, there is larger energy gap, can guarantee to absorb within the scope of visible light wave range less, and metal simple-substance has very high photopermeability and conductivity, be suitable as the intermediate layer of charge generation layer, this structure can improve greatly the light transmission rate of charge generation layer and reduce device internal resistance, guarantee the conductivity of device and send out uniformity of light, 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 the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer stacking gradually, and the material of described the first metal sulfide layer and the second metal sulfide layer is zinc sulphide, cadmium sulfide, calcium sulfide or magnesium sulfide; The evaporation condition of described the first metal sulfide layer, the second metal sulfide layer and metal simple-substance layer is: evaporation pressure is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 1～10nm/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, the thickness of described the first metal sulfide layer and the second metal sulfide layer is 5～40nm.
Preferably, the material of described metal simple-substance layer is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
Preferably, the thickness of described metal simple-substance layer 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 30nm.
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 TAPC, and thickness is 40nm, 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 described electron transfer layer and the second electron transfer layer material are Bphen, TAZ or TPBI, and thickness is 40～200nm.
More preferably, described the first electron transfer layer is Bphen, and thickness is 80nm, and described the second electron transfer layer is TPBI, and thickness is 180nm.
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 preferably Cs
2cO
3, thickness is 2nm.
Preferably, described negative electrode is Ag, Al, Pt or Au, and thickness is 60～300nm.
More preferably, described negative electrode is Al, and thickness is 150nm.
The invention discloses a kind of laminated organic electroluminescent device, in this device, charge generation layer comprises the first metal sulfide layer stacking gradually, metal simple-substance layer and the second metal sulfide layer, charge generation layer structure is metal sulfide/metal simple-substance/metal sulfide, the work function of the metal sulfide of this structure is-5.2～-4.8eV, more moderate, both can improve the injectability in hole, also can improve the injectability of electronics, there is larger energy gap, can guarantee to absorb within the scope of visible light wave range less, and metal simple-substance has very high photopermeability and conductivity, be suitable as the intermediate layer of charge generation layer, this structure can improve greatly the light transmission rate of charge generation layer and reduce resistance, guarantee the conductivity of device and send out uniformity of light, 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 current density 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 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 30nm, evaporation pressure is 5 * 10
-3pa, evaporation speed is 1nm/s; The first hole transmission layer material is TAPC, and thickness is 40nm, and the material of the first luminescent layer is Alq
3, thickness is 10nm, and the first electron transfer layer material is Bphen, and thickness is 80nm, 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, evaporation ZnS on the first electron transfer layer first, obtaining thickness is the first metal sulfide layer of 10nm; Evaporation Ag on the first metal sulfide layer, obtaining thickness is 2nm metal simple-substance layer, evaporation ZnS on metal simple-substance layer, obtaining thickness is the second metal sulfide layer of 15nm; The evaporation condition of the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer is: evaporation pressure 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 the second metal sulfide layer, the second hole transmission layer material is TAPC, thickness is 50nm, same step (1) first luminescent layer of the second luminescent layer material and preparation method, the second electron transfer layer material is TPBI, thickness is 180nm, and electron injecting layer material is Cs
2cO
3, thickness is 2nm, 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 Al, and thickness is 150nm, 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 the first metal sulfide layer 61, metal simple-substance layer 62 and the second metal sulfide layer 63 stacking gradually.Concrete structure is expressed as: ito glass/MoO
3/ TAPC/Alq
3/ Bphen/ZnS/Ag/ZnS/TAPC/Alq
3/ TPBI/Cs
2cO
3/ Al, wherein, brace "/" represents layer structure, 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 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 2 * 10
-4pa, evaporation speed is 1nm/s;
(2) evaporation charge generation layer on the first electron transfer layer, evaporation CaS on the first electron transfer layer first, obtaining thickness is the first metal sulfide layer of 5nm; Evaporation Pt on the first metal oxide layer, obtaining thickness is the metal simple-substance layer of 1nm, evaporation CaS on metal simple-substance layer, obtaining thickness is the second metal sulfide layer of 40nm; The evaporation condition of the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer is: evaporation pressure is 2 * 10
-4pa, evaporation speed is 10nm/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 the second metal sulfide 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 TPBI, 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 the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer stacking gradually.Concrete structure is expressed as: AZO glass/V
2o
5/ NPB/ADN/TAZ/CaS/Pt/CaS/TAPC/BCzVBi/TPBI/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, evaporation CdS on the first electron transfer layer first, obtaining thickness is the first metal sulfide layer of 40nm; Evaporation Au on the first metal sulfide layer, obtaining thickness is the metal simple-substance layer of 10nm, evaporation CdS on metal simple-substance layer, obtaining thickness is the second metal sulfide layer of 5nm; The evaporation condition of the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer is: evaporation pressure is 1 * 10
-3pa, evaporation speed is 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 the second metal sulfide 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, thickness is 40nm, electron injecting layer material is CsF, thickness is 10nm, 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 Ag, 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 the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer stacking gradually.Concrete structure is expressed as: IZO glass/MoO
3/ TAPC/DCJTB/Bphen/CdS/Au/CdS/TCTA/DCJTB/Bphen/CsF/Ag.
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, evaporation MgS on the first electron transfer layer first, obtaining thickness is the first metal sulfide layer of 15nm; Evaporating Al on the first metal sulfide layer, obtaining thickness is the metal simple-substance layer of 7nm, evaporation MgS on metal simple-substance layer, obtaining thickness is the second metal sulfide layer of 15nm; The evaporation condition of the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer is: evaporation pressure is 1 * 10
-3pa, evaporation speed is 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 the second metal sulfide 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 the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer stacking gradually.Concrete structure is expressed as: IZO glass/WO
3/ NPB/ADN/TAZ/MgS/Al/MgS/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/ TAPC/Alq
3/ Bphen/Cs
2cO
3/ Al, the thickness of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode is respectively: 30nm, 40nm, 10nm, 80nm, 2nm and 150nm.
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 density 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 that the current density of the embodiment of the present invention 1 and comparative example's organic electroluminescence device is with the graph of a relation of change in voltage.
From Fig. 1, can find out, under different voltage, the current density of embodiment 1 is large than comparative example all, and when 6V, the current density of embodiment 1 is 101mA/cm
2, and that comparative example is only 72mA/cm
2this explanation, the structure of charge generation layer of the present invention is metal sulfide/metal simple-substance/metal sulfide, both can improve the injectability in hole, also can improve the injectability of electronics, can guarantee that charge generation layer absorbs within the scope of visible light wave range less, can improve greatly the transmitance of charge generation layer and reduce resistance, guarantee the conductivity of device and send out uniformity of light, effectively improving 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. 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 the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer stacking gradually, and the material of described the first metal sulfide layer and the second metal sulfide layer is zinc sulphide, cadmium sulfide, calcium sulfide or magnesium sulfide.
2. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, the thickness of described the first metal sulfide layer and the second metal sulfide layer is 5～40nm.
3. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, the material of described metal simple-substance layer is silver, aluminium, platinum or gold.
4. laminated organic electroluminescent device as claimed in claim 1, is characterized in that, the thickness of described metal simple-substance layer 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 the first metal sulfide layer, metal simple-substance layer and the second metal sulfide layer stacking gradually, and the material of described the first metal sulfide layer and the second metal sulfide layer is zinc sulphide, cadmium sulfide, calcium sulfide or magnesium sulfide; The evaporation condition of described the first metal sulfide layer, the second metal sulfide layer and metal simple-substance layer is: evaporation pressure is 2 * 10
-4～5 * 10
-3pa, evaporation speed is 1～10nm/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, 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.
7. 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.
8. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, the thickness of described the first metal sulfide layer and the second metal sulfide layer is 5～40nm.
9. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, the material of described metal simple-substance layer is silver, aluminium, platinum or gold.
10. the preparation method of laminated organic electroluminescent device as claimed in claim 5, is characterized in that, the thickness of described metal simple-substance layer is 1～10nm.
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| CN108183172A (en) * | 2016-12-08 | 2018-06-19 | 昆山国显光电有限公司 | Organic electroluminescence device and preparation method thereof, display device |
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| US20050051763A1 (en) * | 2003-09-05 | 2005-03-10 | Helicon Research, L.L.C. | Nanophase multilayer barrier and process |
| CN102723442A (en) * | 2011-03-30 | 2012-10-10 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
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