CN104124384A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104124384A
CN104124384A CN201310156409.8A CN201310156409A CN104124384A CN 104124384 A CN104124384 A CN 104124384A CN 201310156409 A CN201310156409 A CN 201310156409A CN 104124384 A CN104124384 A CN 104124384A
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layer
thickness
oxide
organic
zinc oxide
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周明杰
冯小明
张娟娟
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Priority to CN201310156409.8A priority Critical patent/CN104124384A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • 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]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • 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
    • 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
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3031—Two-side emission, e.g. transparent OLEDs [TOLED]
    • 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
    • H10K2102/301—Details of OLEDs
    • H10K2102/321—Inverted OLED, i.e. having cathode between substrate and anode

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses an organic electroluminescent device comprising a transparent substrate, cathode sequentially stacked, low work function metal layer, a first light-emitting unit, a charge generating layer, a second light-emitting unit and the anode, the cathode material for transparent conductive oxide, the work function of the low work function metal layer material is 2.7eV ~ 3.0eV, the charge generating layer comprises a laminated to the first light-emitting unit surface metal oxide layer and N type doping layer laminated on the metal oxide layer on surface, the metal oxide layer material selected from the group consisting of molybdenum trioxide, tungsten trioxide and five oxygen at least a two V, the N type doping layer material including lithium carbonate organic materials and doping in the organic material, the quality of the lithium carbonate and the organic material ratio of 15: 100, the anode material for transparent conductive oxide. The organic electroluminescent device has advantages of simple structure and double light. The invention also provides an organic electroluminescent device preparation method.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
The principle of luminosity of organic electroluminescence device (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.
Existing OLED major part can only go out light from a side-draw of anode or negative electrode, make end transmitting or top transmitting OLED device.The OLED device that double-side shows adopts two organic electroluminescence devices to fit together back-to-back simultaneously, such structure more complicated that becomes.
Summary of the invention
Based on this, be necessary to provide comparatively simple organic electroluminescence device of a kind of double-side and structure and preparation method thereof.
A kind of organic electroluminescence device, comprise the light-transparent substrate stacking gradually, negative electrode, low workfunction metal layer, the first luminescence unit, charge generation layer, the second luminescence unit and anode, the material of described negative electrode is transparent conductive oxide, the work function of the material of described low workfunction metal layer is, described charge generation layer comprises the N-shaped doped layer that is laminated in the metal oxide layer on described the first luminescence unit surface and is laminated in described metal oxide layer surface, the material of described metal oxide layer is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, the material of described N-shaped doped layer comprises organic material and is entrained in the lithium carbonate in described organic material, described organic material is selected from 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, at least one in 10-phenanthrolene and oxine aluminium, the mass ratio of described lithium carbonate and described organic material is 15:100, the material of described anode is transparent conductive oxide.
In an embodiment, the material of described negative electrode is selected from least one in indium and tin oxide film, indium-zinc oxide, aluminium zinc oxide and gallium zinc oxide therein, and the thickness of described negative electrode is 70nm～200nm.
In an embodiment, the material of described low workfunction metal layer is selected from least one in lithium, calcium and magnesium therein, and the thickness of described low workfunction metal layer is 5nm～15nm.
In an embodiment, the thickness of described metal oxide layer is 5nm～10nm therein, and the thickness of described N-shaped doped layer is 5nm～15nm.
In an embodiment, the material of described anode is selected from least one in indium and tin oxide film, indium-zinc oxide, aluminium zinc oxide and gallium zinc oxide therein, and the thickness of described anode is 40nm～80nm.
A preparation method for organic electroluminescence device, comprises the following steps:
At light-transparent substrate surface vacuum sputter, prepare negative electrode, the material of described negative electrode is transparent conductive oxide;
At described cathode surface evaporation, prepare low workfunction metal layer, the work function of the material of described low workfunction metal layer is 2.7eV～3.0eV;
On the surface of described low workfunction metal layer, prepare the first luminescence unit;
Surperficial evaporation at described the first luminescence unit is prepared metal oxide layer, and the material of described metal oxide layer is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide;
On described metal oxide layer surface, evaporation is prepared N-shaped doped layer, the material of described N-shaped doped layer comprises organic material and is entrained in the lithium carbonate in described organic material, described organic material is selected from 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene and oxine aluminium, the mass ratio of described lithium carbonate and described organic material is 15:100;
On the surface of described N-shaped doped layer, prepare the second luminescence unit; And
Surface vacuum sputter at described the second luminescence unit is prepared anode, and the material of described anode is transparent conductive oxide.
In an embodiment, the material of described negative electrode is selected from least one in indium and tin oxide film, indium-zinc oxide, aluminium zinc oxide and gallium zinc oxide therein, and the thickness of described negative electrode is 70nm～200nm.
In an embodiment, the material of described low workfunction metal layer is selected from least one in lithium, calcium and magnesium therein, and the thickness of described low workfunction metal layer is 5nm～15nm.
In an embodiment, the thickness of described metal oxide layer is 5nm～10nm therein, and the thickness of described N-shaped doped layer is 5nm～15nm.
In an embodiment, the material of described anode is selected from least one in indium and tin oxide film, indium-zinc oxide, aluminium zinc oxide and gallium zinc oxide therein, and the thickness of described anode is 40nm～80nm.
Above-mentioned organic electroluminescence device and preparation method thereof, adopts inverted structure, and the first luminescence unit and the second luminescence unit are coupled together by charge generation layer, and double-side and structure are comparatively simple; The material of negative electrode and anode is transparent conductive oxide, thereby makes the bright dipping Strength retention of both direction consistent; Low workfunction metal layer can improve the injectability of electronics, thereby makes electronics easily from negative electrode, inject the first luminescence unit; The first luminescence unit and the second luminescence unit couple together by charge generation layer, under electric field action, electronics occurs separated with hole in charge generation layer, hole and electronics are injected into respectively in two luminescence units, two luminescence units are because luminous separately separately, do not exist energy to shift and the unbalanced problem of carrier transport, thereby organic electroluminescence device is more efficient, stable.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's the flow chart of the organic electroluminescence device of an execution mode.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises light-transparent substrate 10, negative electrode 20, low workfunction metal layer 30, the first luminescence unit 40, charge generation layer 50, the second luminescence unit 60 and the anode 70 stacking gradually.
The material of light-transparent substrate 10 is glass.
Negative electrode 20 is formed at the surface of light-transparent substrate 10.The material of negative electrode 20 is transparent conductive oxide.Concrete, the material of negative electrode 20 is selected from least one in indium and tin oxide film (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) and gallium zinc oxide (GZO).The thickness of negative electrode 20 is 70nm～200nm.
Low workfunction metal layer 30 is formed at the surface of negative electrode 20.The work function of the material of low workfunction metal layer 30 is 2.7eV～3.0eV.Preferably, the material of low workfunction metal layer 30 is selected from least one in lithium (Li), calcium (Ca) and magnesium (Mg).The thickness of low workfunction metal layer 30 is 5nm～15nm.
The first luminescence unit 40 comprises the first electron injecting layer 41, the first electron transfer layer 42, the first luminescent layer 43, the first hole transmission layer 44 and the first hole injection layer 45 stacking gradually.
The first electron injecting layer 41 is formed at low workfunction metal layer 30 surface.The material of the first electron injecting layer 41 is selected from least one in cesium fluoride (CsF) and lithium fluoride (LiF).The thickness of the first electron injecting layer 41 is 0.5nm～1nm.
The first electron transfer layer 42 is formed at the first electron injecting layer 41 surfaces.Be selected from-(4-xenyl)-5-(4-tert-butyl group of the material of the first electron transfer layer 42) phenyl-1,3,4-oxadiazole (PBD), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) and 1, at least one in 2,4-triazole derivative (TAZ).The thickness of the first electron transfer layer 42 is 20nm～60nm.
The first luminescent layer 43 is formed at the first electron transfer layer 42 surfaces.
The first hole transmission layer 44 is formed at the surface of the first luminescent layer 43.The material of the first hole transmission layer 44 is selected from 4,4 ', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N; N '-diphenyl-N; N '-bis-(1-naphthyl)-1; 1 '-biphenyl-4; 4 '-diamines (NPB), (4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD) and 4,4 ', 4 " at least one in tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of the first hole transmission layer 44 is 10nm～60nm.
The first hole injection layer 45 is formed at the first hole transmission layer 44 surfaces.The material of the first hole injection layer 45 is selected from CuPc (CuPc), Phthalocyanine Zinc (ZnPc), molybdenum trioxide (MoO 3), vanadic oxide (V 2o 5) and tungstic acid (WO 3) at least one.The thickness of the first hole injection layer 45 is 10nm～80nm.
Charge generation layer 50 is formed at the surface of the first hole injection layer 45.Charge generation layer 50 comprises the N-shaped doped layer 54 that is laminated in the metal oxide layer 52 on the first hole injection layer 45 surfaces and is laminated in metal oxide layer 52 surfaces.
The material of metal oxide layer 52 is selected from molybdenum trioxide (MoO 3), vanadic oxide (V 2o 5) and tungstic acid (WO 3) at least one.The thickness of metal oxide layer 52 is 5nm～10nm.
The material of N-shaped doped layer 54 comprises organic material and is entrained in the lithium carbonate (Li in organic material 2cO 3).Organic material is selected from 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene (BCP) and oxine aluminium (Alq3).In N-shaped doped layer 54, the mass ratio of lithium carbonate and organic material is 15:100.The thickness of N-shaped doped layer 54 is 5nm～15nm.
The second luminescence unit 60 comprises the second electron transfer layer 62, the second luminescent layer 63, the second hole transmission layer 64 and the second hole injection layer 65 stacking gradually.
The second electron transfer layer 62 is formed at N-shaped doped layer 54 surfaces.Be selected from-(4-xenyl)-5-(4-tert-butyl group of the material of the second electron transfer layer 62) phenyl-1,3,4-oxadiazole (PBD), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) and 1, at least one in 2,4-triazole derivative (TAZ).The thickness of the second electron transfer layer 62 is 20nm～60nm.
The second luminescent layer 63 is formed at the second electron transfer layer 62 surfaces.
The second hole transmission layer 64 is formed at the surface of the second luminescent layer 63.The material of the second hole transmission layer 64 is selected from 4,4 ', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N; N '-diphenyl-N; N '-bis-(1-naphthyl)-1; 1 '-biphenyl-4; 4 '-diamines (NPB), (4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD) and 4,4 ', 4 " at least one in tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of the second hole transmission layer 64 is 10nm～60nm.
The second hole injection layer 65 is formed at the second hole transmission layer 64 surfaces.The material of the second hole injection layer 65 is selected from CuPc (CuPc), Phthalocyanine Zinc (ZnPc), molybdenum trioxide (MoO 3), vanadic oxide (V 2o 5) and tungstic acid (WO 3) at least one.The thickness of the second hole injection layer 65 is 10nm～80nm.
One in the first luminescent layer 43 and the second luminescent layer 63 is blue light-emitting layer, and another is red light emitting layer.
The material of blue light-emitting layer is mixture or the fluorescent material that material of main part and phosphor material doping form.Material of main part is selected from least one in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and 4,4 '-bis-(9-carbazole) biphenyl (CBP).Phosphor material is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls and closes iridium (FIrpic) and two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid and close a kind of in iridium (FIr6).The mass ratio of phosphor material and material of main part is 2:100～10:100.Fluorescent material is selected from 4,4 '-bis-(2,2-diphenylethyllene)-1,1 '-biphenyl (DPVBi) and 4,4 '-bis-[4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi).The thickness of blue light-emitting layer is 5nm～20nm.
The material of red light emitting layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB) is entrained in mixture, two (2-(benzo [b] thiophene-2-yl) pyridine forming in oxine aluminium (Alq3)) (acetylacetone,2,4-pentanedione) close iridium (Ir (btp) 2 (acac)) and be entrained in 4, the mixture or the guest materials that in 4 '-bis-(9-carbazole) biphenyl (CBP), form are entrained in N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the mixture forming in 4 '-diamines (NPB).Guest materials is selected from (acetylacetone,2,4-pentanedione) and closes iridium (Ir (MDQ) 2 (acac)) and three (1-phenyl-isoquinolin) close at least one in iridium (Ir (piq) 3).4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl) mass ratio of-4H-pyrans (DCJTB) oxine aluminium (Alq3) is 1:100～10:100.Two (2-(benzo [b] thiophene-2-yl) pyridine) (acetylacetone,2,4-pentanedione) to close the mass ratio of iridium (Ir (btp) 2 (acac)) and 4,4 '-bis-(9-carbazole) biphenyl (CBP) be 1:100～10:100.Guest materials and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the mass ratio of 4 '-diamines (NPB) is 1:100～10:100.The thickness of red light emitting layer is 5nm～20nm.
It should be noted that, the material of the first electron transfer layer 42 and the second electron transfer layer 62, the first hole transmission layer 44 and the second hole transmission layer 64, the second hole injection layer 45 and the second hole injection layer 65 can be the same or different.
Anode 70 is formed at the second hole injection layer 65 surfaces.The material of anode 70 is transparent conductive oxide.Concrete, the material of anode 70 is selected from least one in indium and tin oxide film (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) and gallium zinc oxide (GZO).The thickness of anode 70 is 40nm～80nm.
Be appreciated that in this organic electroluminescence device 100 and also other functional layers can be set as required.
Above-mentioned organic electroluminescence device 100, adopts inverted structure, and the first luminescence unit 40 and the second luminescence unit 60 are coupled together by charge generation layer 50, and double-side and structure are comparatively simple; The material of negative electrode 20 and anode 70 is transparent conductive oxide, thereby makes the bright dipping Strength retention of both direction consistent; Low workfunction metal layer 30 can improve the injectability of electronics, thereby makes electronics easily from negative electrode, inject the first luminescence unit; The first luminescence unit 40 and the second luminescence unit 60 couple together by charge generation layer 50, under electric field action, electronics occurs separated with hole in charge generation layer, hole and electronics are injected into respectively in two luminescence units, one in the first luminescence unit 40 and the second luminescence unit 60 is blue light emitting unit, another is red light-emitting unit, and two luminescence units are launched jointly, forms white light; Two luminescence units, because luminous separately separately, do not exist energy to shift and the unbalanced problem of carrier transport, thereby organic electroluminescence device 100 are more efficient, stable; In organic electroluminescence device 100, each assembly is transparent material, therefore, cold time, presents transparent state, can also use as Transparent Parts.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an execution mode, it comprises the following steps:
Step S110, at light-transparent substrate 10 surface vacuum sputters, prepare negative electrode 20, the material of negative electrode 20 is transparent conductive oxide.
Vacuum splashing and plating is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out.
The material of light-transparent substrate 10 is glass.
In present embodiment, before forming negative electrode 20, light-transparent substrate 10 surfaces first light-transparent substrate 10 is carried out to pre-treatment, pre-treatment comprises: light-transparent substrate 10 is placed on and in the deionized water that contains washing agent, carries out ultrasonic cleaning, after cleaning up, use successively isopropyl alcohol, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Preferably, the material of negative electrode 20 is selected from least one in indium and tin oxide film (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) and gallium zinc oxide (GZO).The thickness of negative electrode 20 is 70nm～200nm.
Step S120, at the surperficial evaporation of negative electrode 20, prepare low workfunction metal layer 30, the work function of the material of low workfunction metal layer 30 is 2.0eV～3.7eV.
In present embodiment, evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Preferably, the material of low workfunction metal layer 30 is selected from least one in lithium (Li), calcium (Ca) and magnesium (Mg).The thickness of low workfunction metal layer 30 is 5nm～15nm.
Step S130, on the surface of low workfunction metal layer 30, prepare the first luminescence unit 40.
The first luminescence unit 40 comprises the first electron injecting layer 41, the first electron transfer layer 42, the first luminescent layer 43, the first hole transmission layer 44 and the first hole injection layer 45 stacking gradually.The first luminescence unit 40 is prepared by evaporation.
The first electron injecting layer 41 is formed at low workfunction metal layer 30 surface.The material of the first electron injecting layer 41 is selected from least one in cesium fluoride (CsF) and lithium fluoride (LiF).The thickness of the first electron injecting layer 41 is 0.5nm～1nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The first electron transfer layer 42 is formed at the first electron injecting layer 41 surfaces.Be selected from-(4-xenyl)-5-(4-tert-butyl group of the material of the first electron transfer layer 42) phenyl-1,3,4-oxadiazole (PBD), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) and 1, at least one in 2,4-triazole derivative (TAZ).The thickness of the first electron transfer layer 42 is 20nm～60nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The first luminescent layer 43 is formed at the first electron transfer layer 42 surfaces.The first luminescent layer 43 is a kind of in blue light-emitting layer and red light emitting layer.
The material of blue light-emitting layer is mixture or the fluorescent material that material of main part and phosphor material doping form.Material of main part is selected from least one in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and 4,4 '-bis-(9-carbazole) biphenyl (CBP).Phosphor material is selected from two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls and closes iridium (FIrpic) and two (4,6-difluorophenyl pyridines)-tetra-(1-pyrazolyl) boric acid and close a kind of in iridium (FIr6).The mass ratio of phosphor material and material of main part is 2:100～10:100.Fluorescent material is selected from 4,4 '-bis-(2,2-diphenylethyllene)-1,1 '-biphenyl (DPVBi) and 4,4 '-bis-[4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi).The thickness of blue light-emitting layer is 5nm～20nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The material of red light emitting layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB) is entrained in mixture, two (2-(benzo [b] thiophene-2-yl) pyridine forming in oxine aluminium (Alq3)) (acetylacetone,2,4-pentanedione) close iridium (Ir (btp) 2 (acac)) and be entrained in 4, the mixture or the guest materials that in 4 '-bis-(9-carbazole) biphenyl (CBP), form are entrained in N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the mixture forming in 4 '-diamines (NPB).Guest materials is selected from (acetylacetone,2,4-pentanedione) and closes iridium (Ir (MDQ) 2 (acac)) and three (1-phenyl-isoquinolin) close at least one in iridium (Ir (piq) 3).4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl) mass ratio of-4H-pyrans (DCJTB) oxine aluminium (Alq3) is 1:100～10:100.Two (2-(benzo [b] thiophene-2-yl) pyridine) (acetylacetone,2,4-pentanedione) to close the mass ratio of iridium (Ir (btp) 2 (acac)) and 4,4 '-bis-(9-carbazole) biphenyl (CBP) be 1:100～10:100.Guest materials and N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4, the mass ratio of 4 '-diamines (NPB) is 1:100～10:100.The thickness of red light emitting layer is 5nm～20nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The first hole transmission layer 44 is formed at the surface of the first luminescent layer 43.The material of the first hole transmission layer 44 is selected from 4,4 ', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N; N '-diphenyl-N; N '-bis-(1-naphthyl)-1; 1 '-biphenyl-4; 4 '-diamines (NPB), (4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD) and 4,4 ', 4 " at least one in tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of the first hole transmission layer 44 is 10nm～60nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The first hole injection layer 45 is formed at the first hole transmission layer 44 surfaces.The material of the first hole injection layer 45 is selected from CuPc (CuPc), Phthalocyanine Zinc (ZnPc), molybdenum trioxide (MoO 3), vanadic oxide (V 2o 5) and tungstic acid (WO 3) at least one.The thickness of the first hole injection layer 45 is 10nm～80nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Step S140, at the surperficial evaporation of the first hole injection layer 45, prepare metal oxide layer 52.
The material of metal oxide layer 52 is selected from molybdenum trioxide (MoO 3), vanadic oxide (V 2o 5) and tungstic acid (WO 3) at least one.The thickness of metal oxide layer 52 is 5nm～10nm.
In present embodiment, evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Step S150, at the surperficial evaporation of metal oxide layer 52, prepare N-shaped doped layer 54.
The material of N-shaped doped layer 54 comprises organic material and is entrained in the lithium carbonate (Li in organic material 2cO 3).Organic material is selected from 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene (BCP) and oxine aluminium (Alq3).In N-shaped doped layer 54, the mass ratio of lithium carbonate and organic material is 15:100.The thickness of N-shaped doped layer 54 is 5nm～15nm.
During evaporation, lithium carbonate and organic material evaporate respectively in two evaporation boats, and evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, the evaporation speed of lithium carbonate is 0.1nm/s～1nm/s, and the evaporation speed of organic material is 0.1nm/s～1nm/s.
Step S160, on the surface of N-shaped doped layer 54, prepare the second luminescence unit.
The second luminescence unit 60 comprises the second electron transfer layer 62, the second luminescent layer 63, the second hole transmission layer 64 and the second hole injection layer 65 stacking gradually.The second luminescence unit 60 is prepared by evaporation.
The second electron transfer layer 62 is formed at N-shaped doped layer 54 surfaces.Be selected from-(4-xenyl)-5-(4-tert-butyl group of the material of the second electron transfer layer 62) phenyl-1,3,4-oxadiazole (PBD), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) and 1, at least one in 2,4-triazole derivative (TAZ).The thickness of the second electron transfer layer 62 is 20nm～60nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The second luminescent layer 63 is formed at the second electron transfer layer 62 surfaces.One in the first luminescent layer 43 and the second luminescent layer 63 is blue light-emitting layer, and another is red light emitting layer.
The second hole transmission layer 64 is formed at the surface of the second luminescent layer 63.The material of the second hole transmission layer 64 is selected from 4,4 ', 4 " tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N; N '-diphenyl-N; N '-bis-(1-naphthyl)-1; 1 '-biphenyl-4; 4 '-diamines (NPB), (4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines (TPD) and 4,4 ', 4 " at least one in tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of the second hole transmission layer 64 is 10nm～60nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The second hole injection layer 65 is formed at the second hole transmission layer 64 surfaces.The material of the second hole injection layer 65 is selected from CuPc (CuPc), Phthalocyanine Zinc (ZnPc), molybdenum trioxide (MoO 3), vanadic oxide (V 2o 5) and tungstic acid (WO 3) at least one.The thickness of the second hole injection layer 65 is 10nm～80nm.Evaporation is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Step S170, at the surface vacuum sputter of the second hole injection layer 65, prepare anode 70.
The material of anode 70 is transparent conductive oxide.Concrete, the material of anode 70 is selected from least one in indium and tin oxide film (ITO), indium-zinc oxide (IZO), aluminium zinc oxide (AZO) and gallium zinc oxide (GZO).The thickness of anode 70 is 40nm～80nm.
In present embodiment, vacuum splashing and plating is 1 * 10 at vacuum pressure -3～1 * 10 -5under Pa, carry out.
Above-mentioned organic electroluminescence device preparation method, technique is simple.
Below in conjunction with specific embodiment, the preparation method of organic electroluminescence device provided by the invention is elaborated.
The preparation used of the embodiment of the present invention and comparative example and tester are: test is high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd) with Preparation equipment, the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 test electric property of U.S. Keithley company, CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
Structure prepared by the present embodiment is glass light-transparent substrate/ITO/Li/LiF/Bphen/DCJTB:Alq 3/ NPB/CuPc/MoO 3/ Li 2cO 3: the organic electroluminescence device of BCP/Bphen/FIrpic:TPBi/NPB/CuPc/ITO.
The manufacture method of this Organnic electroluminescent device, comprises following step:
Step 1, provide light-transparent substrate, light-transparent substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Step 2, in vacuum degree, be 5 * 10 -4in the vacuum coating system of Pa, at light-transparent substrate surface sputtering, prepare negative electrode, material is that ITO thickness is 100nm; Then being transferred to vacuum degree is 5 * 10 -4in the hot deposition system of Pa, at cathode surface evaporation, prepare low work function metal layer, material is Li, and thickness is 5nm, and evaporation speed is 0.1nm/s;
Step 3, in vacuum degree, be 5 * 10 -4in the vacuum coating system of Pa, on low work function metal layer surface, by thermal evaporation techniques, prepare the first organic light-emitting units.The first organic light-emitting units comprises the first electron injecting layer, the first electron transfer layer, the first luminescent layer, the first hole transmission layer and the first hole injection layer stacking gradually.The material of the first electron injecting layer is LiF, and thickness is 0.5nm, and evaporation speed is 0.1nm/s; The first electric transmission layer material is Bphen, and thickness is 20nm, and evaporation speed is 0.1nm/s; The material of the first luminescent layer comprises Alq 3and be entrained in Alq 3in DCJTB, DCJTB and Alq 3mass ratio be 1:100, thickness is 10nm, the evaporation speed of DCJTB is 0.1nm/s, Alq 3evaporation speed be 1nm/s; The material of the first hole transmission layer is NPB, and thickness is 30nm, and evaporation speed is 0.1nm/s; The material of the first hole injection layer is CuPc, and thickness is 10nm, and evaporation speed is 0.1nm/s.
Step 4, in vacuum degree, be 5 * 10 -4in the vacuum coating system of Pa, by thermal evaporation technique, continue to prepare charge generation layer, charge generation layer 50 comprises the N-shaped doped layer that is laminated in the metal oxide layer on the first hole injection layer surface and is laminated in metal oxide layer surface.The material of metal oxide layer is MoO 3, thickness is 5nm, evaporation speed is 0.1nm/s; The material of N-shaped doped layer comprises BCP and is entrained in the Li of middle BCP 2cO 3, Li 2cO 3with the mass ratio of BCP be 15:100, thickness is 5nm, Li 2cO 3evaporation speed be 0.1nm/s, the evaporation speed of BCP is 1nm/s.
Step 5, in vacuum degree, be 5 * 10 -4in the vacuum coating system of Pa, on N-shaped doped layer surface, continue preparation the second organic light-emitting units.The second luminescence unit comprises the second electron transfer layer, the second luminescent layer, the second hole transmission layer and the second hole injection layer stacking gradually.The material of the second electron transfer layer is Bphen, and thickness is that 60nm evaporation speed is 0.1nm/s; The material of the second luminescent layer comprises TPBi and is entrained in the FIrpic in TPBi, and the mass ratio of FIrpic and TPBi is 1:10, and thickness is 20nm, and the evaporation speed of TPBi is 1nm/s, and the evaporation speed of FIrpic is 0.1nm/s; The material of the second hole transmission layer is NPB, and thickness is 10nm, and evaporation speed is 0.1nm/s; The material of the second hole injection layer is CuPc, and thickness is 80nm, and evaporation speed is 0.1nm/s.
Step 6, in vacuum degree, be 5 * 10 -4in the magnetic control sputtering system of Pa, on the second organic light-emitting units surface, prepare anode, material is ITO, and thickness is 40nm.
Embodiment 2
Structure prepared by the present embodiment is glass light-transparent substrate/AZO/Ca/LiF/BCP/DPVBi/2-TNATA/ZnPc/WO 3/ Li 2cO 3: Alq 3/ TPBi/Ir (piq) 3: CBP/NPB/WO 3the organic electroluminescence device of/AZO.
The manufacture method of this Organnic electroluminescent device, comprises following step:
Step 1, provide light-transparent substrate, light-transparent substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Step 2, in vacuum degree, be 1 * 10 -3in the vacuum coating system of Pa, at light-transparent substrate surface sputtering, prepare negative electrode, material is that AZO thickness is 70nm; Then being transferred to vacuum degree is 1 * 10 -3in the hot deposition system of Pa, at cathode surface evaporation, prepare low work function metal layer, material is Ca, and thickness is 10nm, and evaporation speed is 0.2nm/s;
Step 3, in vacuum degree, be 1 * 10 -3in the vacuum coating system of Pa, on low work function metal layer surface, by thermal evaporation techniques, prepare the first organic light-emitting units.The first organic light-emitting units comprises the first electron injecting layer, the first electron transfer layer, the first luminescent layer, the first hole transmission layer and the first hole injection layer stacking gradually.The material of the first electron injecting layer is LiF, and thickness is 0.5nm, and evaporation speed is 0.1nm/s; The first electric transmission layer material is BCP, and thickness is 60nm, and evaporation speed is 1nm/s; The material of the first luminescent layer is DPVBi, and thickness is 10nm, and evaporation speed is 0.2nm/s; The material of the first hole transmission layer is 2-TNATA, and thickness is 60nm, and evaporation speed is 1nm/s; The material of the first hole injection layer is ZnPc, and thickness is 10nm, and evaporation speed is 0.2nm/s.
Step 4, in vacuum degree, be 1 * 10 -3in the vacuum coating system of Pa, by thermal evaporation technique, continue to prepare charge generation layer, charge generation layer 50 comprises the N-shaped doped layer that is laminated in the metal oxide layer on the first hole injection layer surface and is laminated in metal oxide layer surface.The material of metal oxide layer is WO 3, thickness is 10nm, evaporation speed is 0.1nm/s; The material of N-shaped doped layer comprises Alq 3and be entrained in middle Alq 3li 2cO 3, Li 2cO 3with Alq 3mass ratio be 15:100, thickness is 15nm, Li 2cO 3evaporation speed be 0.15nm/s, Alq 3evaporation speed be 1nm/s.
Step 5, in vacuum degree, be 1 * 10 -3in the vacuum coating system of Pa, on N-shaped doped layer surface, continue preparation the second organic light-emitting units.The second luminescence unit comprises the second electron transfer layer, the second luminescent layer, the second hole transmission layer and the second hole injection layer stacking gradually.The material of the second electron transfer layer is TPBi, and thickness is that 60nm evaporation speed is 1nm/s; The material of the second luminescent layer comprises CBP and is entrained in the Ir (piq) in CBP 3, Ir (piq) 3with the mass ratio of CBP be 1:10, thickness is 12nm, the evaporation speed of CBP is 1nm/s, Ir (piq) 3evaporation speed be 0.1nm/s; The material of the second hole transmission layer is NPB, and thickness is 40nm, and evaporation speed is 0.2nm/s; The material of the second hole injection layer is WO 3, thickness is 30nm, evaporation speed is 0.2nm/s.
Step 6, in vacuum degree, be 1 * 10 -3in the magnetic control sputtering system of Pa, on the second organic light-emitting units surface, prepare anode, material is AZO, and thickness is 80nm.
Embodiment 3
Structure prepared by the present embodiment is glass substrate/GZO/Mg/LiF/TAZ/FIr6:CBP/m-MTDATA/ZnPc/V 2o 5/ Li 2cO 3: TPBi/BPhen/Ir (btp) 2 (acac): CBP/m-MTDATA/V 2o 5the organic electroluminescence device of/GZO.
The manufacture method of this Organnic electroluminescent device, comprises following step:
Step 1, provide light-transparent substrate, light-transparent substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Step 2, in vacuum degree, be 1 * 10 -5in the vacuum coating system of Pa, at light-transparent substrate surface sputtering, prepare negative electrode, material is GZO, and thickness is 200nm; Then being transferred to vacuum degree is 1 * 10 -5in the hot deposition system of Pa, at cathode surface evaporation, prepare low work function metal layer, material is Mg, and thickness is 15nm, and evaporation speed is 0.2nm/s;
Step 3, in vacuum degree, be 1 * 10 -5in the vacuum coating system of Pa, on low work function metal layer surface, by thermal evaporation techniques, prepare the first organic light-emitting units.The first organic light-emitting units comprises the first electron injecting layer, the first electron transfer layer, the first luminescent layer, the first hole transmission layer and the first hole injection layer stacking gradually.The material of the first electron injecting layer is LiF, and thickness is 1nm, and evaporation speed is 0.1nm/s; The first electric transmission layer material is TAZ, and thickness is 30nm, and evaporation speed is 0.2nm/s; The material of the first luminescent layer comprises the FIr6 of CBP in CBP and doping, and the mass ratio of FIr6 and CBP is 2:100, and thickness is 5nm, and the evaporation speed of FIr6 is 0.1nm/s, and the evaporation speed of CBP is 1nm/s; The material of the first hole transmission layer is m-MTDATA, and thickness is 30nm, and evaporation speed is 0.1nm/s; The material of the first hole injection layer is ZnPc, and thickness is 10nm, and evaporation speed is 0.1nm/s.
Step 4, in vacuum degree, be 1 * 10 -5in the vacuum coating system of Pa, by thermal evaporation technique, continue to prepare charge generation layer, charge generation layer 50 comprises the N-shaped doped layer that is laminated in the metal oxide layer on the first hole injection layer surface and is laminated in metal oxide layer surface.The material of metal oxide layer is V 2o 5, thickness is 8nm, evaporation speed is 0.1nm/s; The material of N-shaped doped layer comprises TPBi and is entrained in the Li of middle TPBi 2cO 3, Li 2cO 3with the mass ratio of TPBi be 15:100, thickness is 10nm, Li 2cO 3evaporation speed be 0.15nm/s, the evaporation speed of TPBi is 1nm/s.
Step 5, in vacuum degree, be 1 * 10 -5in the vacuum coating system of Pa, on N-shaped doped layer surface, continue preparation the second organic light-emitting units.The second luminescence unit comprises the second electron transfer layer, the second luminescent layer, the second hole transmission layer and the second hole injection layer stacking gradually.The material of the second electron transfer layer is Bphen, and thickness is 30nm, and evaporation speed is 0.2nm/s; The material of the second luminescent layer comprises CBP and is entrained in the Ir (btp) 2 (acac) in CBP, Ir (btp) 2 (acac) is 1:10 with the mass ratio of CBP, thickness is 5nm, the evaporation speed of CBP is 1nm/s, and the evaporation speed of Ir (btp) 2 (acac) is 0.1nm/s; The material of the second hole transmission layer is m-MTDATA, and thickness is 30nm, and evaporation speed is 0.2nm/s; The material of the second hole injection layer is V 2o 5, thickness is 30nm, evaporation speed is 0.5nm/s.
Step 6, in vacuum degree, be 1 * 10 -5in the magnetic control sputtering system of Pa, on the second organic light-emitting units surface, prepare anode, material is GZO, and thickness is 60nm.
Embodiment 4
Structure prepared by the present embodiment be glass substrate/IZO (100nm)/Ca (15nm)/LiF (1nm)/BCP (40nm)/Ir (MDQ) 2 (acac): NPB (8%, 20nm)/m-MTDATA (40nm)/ZnPc (20nm)/MoO 3(5nm)/Li 2cO 3: BCP(15%, 10nm) organic electroluminescence device of/Bphen (40nm)/DPAVBi (15nm)/NPB (20nm)/ZnPc (60nm)/IZO (40nm).
The manufacture method of this Organnic electroluminescent device, comprises following step:
Step 1, provide light-transparent substrate, light-transparent substrate is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Step 2, in vacuum degree, be 1 * 10 -4in the vacuum coating system of Pa, at light-transparent substrate surface sputtering, prepare negative electrode, material is IZO, and thickness is 100nm; Then being transferred to vacuum degree is 1 * 10 -4in the hot deposition system of Pa, at cathode surface evaporation, prepare low work function metal layer, material is Ca, and thickness is 15nm, and evaporation speed is 0.2nm/s;
Step 3, in vacuum degree, be 1 * 10 -4in the vacuum coating system of Pa, on low work function metal layer surface, by thermal evaporation techniques, prepare the first organic light-emitting units.The first organic light-emitting units comprises the first electron injecting layer, the first electron transfer layer, the first luminescent layer, the first hole transmission layer and the first hole injection layer stacking gradually.The material of the first electron injecting layer is LiF, and thickness is 1nm, and evaporation speed is 0.1nm/s; The first electric transmission layer material is BCP, and thickness is 40nm, and evaporation speed is 0.2nm/s; The material of the first luminescent layer comprises the Ir (MDQ) 2 (acac) of NPB in NPB and doping, Ir (MDQ) 2 (acac) is 8:100 with the mass ratio of NPB, thickness is 20nm, the evaporation speed of Ir (MDQ) 2 (acac) is 0.1nm/s, and the evaporation speed of NPB is 1nm/s; The material of the first hole transmission layer is m-MTDATA, and thickness is 40nm, and evaporation speed is 0.5nm/s; The material of the first hole injection layer is ZnPc, and thickness is 20nm, and evaporation speed is 0.2nm/s.
Step 4, in vacuum degree, be 1 * 10 -4in the vacuum coating system of Pa, by thermal evaporation technique, continue to prepare charge generation layer, charge generation layer 50 comprises the N-shaped doped layer that is laminated in the metal oxide layer on the first hole injection layer surface and is laminated in metal oxide layer surface.The material of metal oxide layer is MoO 3, thickness is 5nm, evaporation speed is 0.1nm/s; The material of N-shaped doped layer comprises BCP and is entrained in the Li of middle BCP 2cO 3, Li 2cO 3with the mass ratio of BCP be 15:100, thickness is 10nm, Li 2cO 3evaporation speed be 0.15nm/s, the evaporation speed of BCP is 1nm/s.
Step 5, in vacuum degree, be 1 * 10 -4in the vacuum coating system of Pa, on N-shaped doped layer surface, continue preparation the second organic light-emitting units.The second luminescence unit comprises the second electron transfer layer, the second luminescent layer, the second hole transmission layer and the second hole injection layer stacking gradually.The material of the second electron transfer layer is Bphen, and thickness is 40nm, and evaporation speed is 0.5nm/s; The material of the second luminescent layer is DPAVBi, and thickness is 15nm, and evaporation speed is 0.2nm/s; The material of the second hole transmission layer is NPB, and thickness is 20nm, and evaporation speed is 0.2nm/s; The material of the second hole injection layer is ZnPc, and thickness is 60nm, and evaporation speed is 1nm/s.
Step 6, in vacuum degree, be 1 * 10 -4in the magnetic control sputtering system of Pa, on the second organic light-emitting units surface, prepare anode, material is ITO, and thickness is 40nm.
Table 1
Refer to table 1, table 1 is embodiment 1,2, the luminescent properties data of 3,4 devices of making, luminous efficiency is that test obtains under the driving voltage of 8V, as can be seen from Table 1, the Organnic electroluminescent device that method provided by the invention is made has higher luminous efficiency, in addition, and because the present invention is by red, blue two luminescent layers are separately arranged, make redly, each self-luminous of blue luminescent layer is not subject to that energy shifts and the unbalanced impact of carrier transport, so luminous efficiency also can be improved.And its chromaticity coordinates value more approaches white-light emitting point.
Under the driving voltage of 8V, the negative electrode of luminescent device and anode both sides are tested respectively to the luminosity of each face direction, and test result shows, more approaching at the luminosity of two faces, the luminous flux that both direction is described is consistent, thereby can realize the uniformly light-emitting on two sides.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, it is characterized in that, comprise the light-transparent substrate stacking gradually, negative electrode, low workfunction metal layer, the first luminescence unit, charge generation layer, the second luminescence unit and anode, the material of described negative electrode is transparent conductive oxide, the work function of the material of described low workfunction metal layer is 2.7eV～3.0eV, described charge generation layer comprises the N-shaped doped layer that is laminated in the metal oxide layer on described the first luminescence unit surface and is laminated in described metal oxide layer surface, the material of described metal oxide layer is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, the material of described N-shaped doped layer comprises organic material and is entrained in the lithium carbonate in described organic material, described organic material is selected from 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, at least one in 10-phenanthrolene and oxine aluminium, the mass ratio of described lithium carbonate and described organic material is 15:100, the material of described anode is transparent conductive oxide.
2. organic electroluminescence device according to claim 1, is characterized in that, the material of described negative electrode is selected from least one in indium and tin oxide film, indium-zinc oxide, aluminium zinc oxide and gallium zinc oxide, and the thickness of described negative electrode is 70nm～200nm.
3. organic electroluminescence device according to claim 1, is characterized in that, the material of described low workfunction metal layer is selected from least one in lithium, calcium and magnesium, and the thickness of described low workfunction metal layer is 5nm～15nm.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described metal oxide layer is 5nm～10nm, and the thickness of described N-shaped doped layer is 5nm～15nm.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described anode is selected from least one in indium and tin oxide film, indium-zinc oxide, aluminium zinc oxide and gallium zinc oxide, and the thickness of described anode is 40nm～80nm.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
At light-transparent substrate surface vacuum sputter, prepare negative electrode, the material of described negative electrode is transparent conductive oxide;
At described cathode surface evaporation, prepare low workfunction metal layer, the work function of the material of described low workfunction metal layer is 2.7eV～3.0eV;
On the surface of described low workfunction metal layer, prepare the first luminescence unit;
Surperficial evaporation at described the first luminescence unit is prepared metal oxide layer, and the material of described metal oxide layer is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide;
On described metal oxide layer surface, evaporation is prepared N-shaped doped layer, the material of described N-shaped doped layer comprises organic material and is entrained in the lithium carbonate in described organic material, described organic material is selected from 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene and oxine aluminium, the mass ratio of described lithium carbonate and described organic material is 15:100;
On the surface of described N-shaped doped layer, prepare the second luminescence unit; And
Surface vacuum sputter at described the second luminescence unit is prepared anode, and the material of described anode is transparent conductive oxide.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: the material of described negative electrode is selected from least one in indium and tin oxide film, indium-zinc oxide, aluminium zinc oxide and gallium zinc oxide, the thickness of described negative electrode is 70nm～200nm.
8. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the material of described low workfunction metal layer is selected from least one in lithium, calcium and magnesium, and the thickness of described low workfunction metal layer is 5nm～15nm.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the thickness of described metal oxide layer is 5nm～10nm, and the thickness of described N-shaped doped layer is 5nm～15nm.
10. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: the material of described anode is selected from least one in indium and tin oxide film, indium-zinc oxide, aluminium zinc oxide and gallium zinc oxide, the thickness of described anode is 40nm～80nm.
CN201310156409.8A 2013-04-28 2013-04-28 Organic electroluminescent device and preparation method thereof Pending CN104124384A (en)

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Application publication date: 20141029