CN103545451A - Organic electroluminescence device and manufacturing method thereof - Google Patents

Organic electroluminescence device and manufacturing method thereof Download PDF

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Publication number
CN103545451A
CN103545451A CN201210243329.1A CN201210243329A CN103545451A CN 103545451 A CN103545451 A CN 103545451A CN 201210243329 A CN201210243329 A CN 201210243329A CN 103545451 A CN103545451 A CN 103545451A
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layer
hole
evaporation
electroluminescent device
organnic electroluminescent
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周明杰
王平
冯小明
张振华
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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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    • 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
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • 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]
    • H10K50/18—Carrier blocking layers
    • 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

Abstract

The invention discloses an organic electroluminescence device and a manufacturing method thereof. The organic electroluminescence device comprises a substrate, an anode layer, a hole transfer layer, a luminous layer, an electronic transfer layer and a cathode layer which are successively stacked, wherein the electronic transfer layer has a doping structure and comprises an electronic transfer matrix material and alkali metal doping agents which form the structure; and a hole barrier layer which limits alkali metal ions to move into the luminous layer is also arranged between the luminous layer and the electronic transfer layer. The manufacturing method of the organic electroluminescence device comprises the following steps of manufacturing the anode layer on the surface of the substrate by using a sputtering method; and successively manufacturing the hole transfer layer, the luminous layer, the hole barrier layer, the electronic transfer layer and the cathode layer on the surface of the anode layer by using a thermal evaporation method. In the organic electroluminescence device, the alkali metal doping agents can effectively reduce driving current of the organic electroluminescence device, and the integral lighting effect can be improved; the hole barrier layer which is arranged additionally can effectively stop the alkali metal doping agents from spreading to the luminous layer, and the service life of the organic electroluminescence device can be obviously prolonged; and the organic electroluminescence device is simple in preparation technology and convenient to implement.

Description

A kind of Organnic electroluminescent device and manufacture method thereof
Technical field
The invention belongs to organic electroluminescence device technical field, and relate to a kind of Organnic electroluminescent device and manufacture method thereof.More specifically, the present invention relates to a kind of long-life Organnic electroluminescent device and manufacture method thereof.
Background technology
Organnic electroluminescent device (as organic electroluminescent LED) is a kind of structure of similar sandwich, it is respectively negative electrode and anode up and down, and between two electrodes, clip the organic material functional layer of single or multiple lift different materials kind and different structure, for example, can be successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer.Organic electroluminescence device is carrier injection type luminescent device, at anode and negative electrode, add after operating voltage, hole is injected into respectively the organic material layer of device work from negative electrode from anode, electronics, it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and light sends from electrode one side subsequently.
Up to the present, be effectively to improve the combination property of above-mentioned organic electroluminescence device, the scientific research personnel of various countries, the whole world aspect the material selection of organic material functional layer and the appropriate design aspect of device architecture carried out more research.For example, adopt PN doping process to prepare starting resistor that transport layer can reduce the type luminescent device to improve light efficiency.In prior art, for the N doping of electron transfer layer, conventionally adopt alkali metal compound as the dopant of electron transfer layer; This is because alkali metal work content is low, easily realizes N doping effect.But, because alkali metal ion volume is little and diffusivity is strong, its diffusion length in the electron transfer layer of organic material is longer, in being entrained in electron transfer layer, alkali metal ion also may diffuse in luminescent layer, directly cause the cancellation of exciton, affect light efficiency and the life-span of luminescent device.
Summary of the invention
The technical problem to be solved in the present invention is, for diffusing in luminescent layer as the alkali metal ion of electron transfer layer dopant in prior art and then cause exciton quencher and affect the light efficiency of luminescent device and the defect in life-span, thus provide a kind of stop alkali metal ion to luminescent layer diffusion improve luminescent device useful life, and improve Organnic electroluminescent device and the manufacture method thereof of lighting device light efficiency simultaneously.
The technical problem to be solved in the present invention is achieved by the following technical programs: a kind of Organnic electroluminescent device is provided, comprise the substrate, anode layer, hole transmission layer, luminescent layer, electron transfer layer and the cathode layer that stack gradually, described electron transfer layer comprises electric transmission host material and alkali-metal-doped agent, described electric transmission host material and alkali-metal-doped agent form doped structure, be also provided with restriction alkali metal ion and move to the hole blocking layer in described luminescent layer between described luminescent layer and electron transfer layer.
In above-mentioned Organnic electroluminescent device, described hole blocking layer consists of inorganic, metal oxide.
In above-mentioned Organnic electroluminescent device, at least one that described inorganic, metal oxide is following compound: antimonous oxide, vanadic oxide, molybdenum oxide, tungsten oxide, bismuth oxide and rheium oxide.
In above-mentioned Organnic electroluminescent device, the thickness of described hole blocking layer is 3～10nm.
In above-mentioned Organnic electroluminescent device, described electric transmission host material is (oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, described alkali-metal-doped agent is lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate or cesium fluoride.
In above-mentioned Organnic electroluminescent device, described hole transmission layer comprises hole dopant and hole transport host material, and described hole dopant and hole transport host material form doped structure;
Described hole dopant is 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes, 1,3,4,5,7, and 8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones or 2,2 '-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) two malononitrile; Described hole transport host material is Phthalocyanine Zinc, CuPc, 4,4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,4 '; 4 "-tri-(2-naphthyl phenyl amino) triphenylamine, N, N '-diphenyl-N, N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines or (N, N, N ', N '-tetramethoxy phenyl)-benzidine.
In above-mentioned Organnic electroluminescent device, between described hole transmission layer and luminescent layer, be also provided with electronic barrier layer.
According to a further aspect in the invention, provide a kind of manufacture method of Organnic electroluminescent device, said method comprising the steps of:
S1, will after substrate preliminary treatment, put into magnetic control sputtering system, in pretreated substrate surface sputter, prepare anode layer;
S2, in vacuum coating system, adopt anode layer surface that hot evaporation coating method prepares in described step S1 successively evaporation prepare hole transmission layer and luminescent layer;
S3, the surperficial evaporation of the luminescent layer that adopts hot evaporation coating method to prepare in described step S2 are prepared hole blocking layer;
S4, the hole blocking layer surface evaporation preparing in described step S3 are prepared electron transfer layer: alkali-metal-doped agent and electric transmission host material are placed in respectively to two independently evaporation sources, control respectively the evaporation rate of described alkali-metal-doped agent and electric transmission host material, on described hole blocking layer surface, evaporation is prepared electron transfer layer; And
S5, the electron transfer layer surface evaporation preparing in described step S4 are prepared cathode layer.
In the manufacture method of above-mentioned Organnic electroluminescent device, in described step S3, the evaporation rate of described hole blocking layer is 0.1～1nm/s, and the thickness of the hole blocking layer preparing is 3～10nm.
In the manufacture method of above-mentioned Organnic electroluminescent device, described step S2 specifically comprises the following steps:
S21, prepare hole transmission layer: hole dopant and hole transport host material are placed in respectively to two independently evaporation sources, control respectively the evaporation rate of described hole dopant and hole transport host material, on described anode layer surface, evaporation is prepared hole transmission layer;
S22, prepare electronic barrier layer: adopt the hole transmission layer surface evaporation that hot evaporation coating method prepares in described step S21 to prepare electronic barrier layer; And
S23, prepare luminescent layer: adopt the electronic barrier layer surface evaporation that hot evaporation coating method prepares in described step S22 to prepare luminescent layer.
In the manufacture method of above-mentioned Organnic electroluminescent device, in described step S1, pre-processed substrate comprises that described substrate is placed in to the deionized water that contains washing agent carries out ultrasonic cleaning, after cleaning up, described substrate is entered successively in isopropyl alcohol and acetone and carries out ultrasonic processing, then with nitrogen, dry up.
In the manufacture method of above-mentioned Organnic electroluminescent device, described step S1 has also been included in and the substrate containing described anode layer has been placed in to plasma processing chamber after the preparation of described anode layer and carries out plasma treatment.This treatment step can improve anode layer work content, reduces the injection barrier in hole.
In the manufacture method of above-mentioned Organnic electroluminescent device, described method encapsulates Organnic electroluminescent device after being also included in step S5: adopt glass cover-plate to encapsulate described Organnic electroluminescent device, form encapsulated layer.
The inorganic, metal oxide of the formation hole blocking layer adopting in the present invention is 5 * 10 in vacuum degree -4under the pressure of Pa, be fusing point lower than the chemical substance of 1000 ℃, therefore can adopt vacuum thermal evaporation technique to complete the preparation of this structure sheaf, preparation process is simple and be easy to realize and control.
Implement the present invention and can obtain following beneficial effect: the alkali-metal-doped agent that the work content of adulterating in electron transfer layer is low can effectively reduce the drive current of light-emitting device, improve the whole light efficiency of Organnic electroluminescent device (being designated hereinafter simply as light-emitting device); The hole blocking layer arranging between electron transfer layer and luminescent layer can effectively stop that alkali metal ion spreads to luminescent layer, and the alkali metal ion of stopping to exist in prior art causes the problem of exciton quencher, thereby significantly improves the useful life of light-emitting device; Light-emitting device provided by the present invention can adopt the preparation of traditional sputtering technology and hot evaporation process, and technique is simple and be easy to realize; The light-emitting device stability preparing is good, can use for a long time.
Accompanying drawing explanation
Below with reference to the drawings and specific embodiments, the present invention is described in further details.In accompanying drawing:
Fig. 1 a is according to the structural representation of the Organnic electroluminescent device of the embodiment of the present invention 1;
Fig. 1 b is according to the flow chart of the manufacture Organnic electroluminescent device of the embodiment of the present invention 1;
Fig. 2 a is according to the structural representation of the Organnic electroluminescent device of the embodiment of the present invention 2;
Fig. 2 b is according to the flow chart of the manufacture Organnic electroluminescent device of the embodiment of the present invention 2; And
Fig. 3 is the comparison diagram in useful life of the Organnic electroluminescent device of embodiment of the present invention 2-7 and the Organnic electroluminescent device of comparative example 1-2.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of high light efficiency and long-life Organnic electroluminescent device, the electron transfer layer of this light-emitting device is the doped structure that contains alkali-metal-doped agent, can improve the whole light efficiency of light-emitting device; Between the electron transfer layer of this light-emitting device and luminescent layer, be provided with hole blocking layer, can stop that the alkali metal ion from alkali-metal-doped agent diffuses to luminescent layer, improve the terminal life of light-emitting device.Hole blocking layer of the present invention can adopt inorganic, metal oxide; Preferably adopt 5 * 10 -4under Pa pressure, fusing point is at the inorganic, metal oxide below 1000 ℃, and preferably in this light-emitting device, forms the hole blocking layer of 3-10nm.
In order to realize good illumination effect, embodiment provided by the present invention preferably adopts following material:
(1) substrate can adopt transparent glass material;
(2) anode can adopt indium doped stannum oxide film (ITO);
(3) hole dopant of hole transmission layer can select 2, 3, 5, 6-tetrafluoro-7, 7', 8, 8 '-tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1, 3, 4, 5, 7, 8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones (F6-TNAP) or 2, 2'-(2, 5-dicyano-3, 6-difluoro cyclohexane-2, 5-diene-1, 4-bis-subunits) two malononitrile (F2-HCNQ), the hole transport host material of hole transmission layer can be selected Phthalocyanine Zinc (ZnPc), CuPc (CuPc), 4, 4 ', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 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) or (N, N, N ', N '-tetramethoxy phenyl)-benzidine (MeO-TPD),
(4) electronic barrier layer can adopt 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA);
(5) luminescent layer can adopt (oxine)-aluminium (Alq 3);
(6) hole blocking layer can adopt at least one of following compound: antimonous oxide (Sb 2o 3), vanadic oxide (V 2o 5), molybdenum oxide (MoO 3), tungsten oxide (WO 3), bismuth oxide (Bi 2o 3) and rheium oxide (ReO 3); Except tungsten oxide, above-mentioned inorganic, metal oxide is fusing point lower than the inorganic, metal oxide of 1000 ℃, and its fusing point is respectively 656 ℃, 690 ℃, 795 ℃, 820 ℃ and 300 ℃; Although it should be noted that WO here 3fusing point under an atmospheric pressure is higher than 1000 ℃ (being specially 1473 ℃), but is 5 * 10 in vacuum degree -4under the pressure of Pa, its fusing point is equally lower than 1000 ℃;
(7) the alkali-metal-doped agent of electron transfer layer can be selected lithium carbonate (Li 2cO 3), Lithium Azide (LiN 3), lithium fluoride (LiF), cesium azide (CsN 3), cesium carbonate (Cs 2cO 3) or cesium fluoride (CsF), the electric transmission host material of electron transfer layer can be selected (oxine)-aluminium (Alq 3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), two (2-methyl-oxine-N1, O8)-(1,1 '-biphenyl-4-hydroxyl) aluminium (BAlq) or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP);
(8) negative electrode can adopt argent (Ag).
Below in conjunction with specific embodiment, Organnic electroluminescent device of the present invention is further explained in detail.
Embodiment 1:
A kind of Organnic electroluminescent device (referring to Fig. 1 a), this light-emitting device consists of the substrate 101 stacking gradually, anode layer 102, hole transmission layer 103, luminescent layer 105, hole blocking layer 106, electron transfer layer 107 and cathode layer 108, wherein, substrate 101 is glass substrate, the ITO that anode layer 102 is 100nm, the CuPc that hole transmission layer 103 is 50nm, the Alq that luminescent layer 105 is 20nm 3, the ReO that hole blocking layer 106 is 3nm 3, the Cs that electron transfer layer 107 is 50nm 2cO 3: Bphen doped structure (Cs 2cO 3: the doping mass ratio of Bphen is 1: 5, wherein, and Cs 2cO 3: Bphen is expressed as doping composite material, and following statement is similar), the Ag that cathode layer 108 is 100nm.The manufacture method of this light-emitting device comprises the following steps (Fig. 1 b):
Step 11, glass substrate is placed in to the deionized water that contains washing agent carries out ultrasonic cleaning, after cleaning up, glass substrate is entered successively in isopropyl alcohol and acetone and carries out ultrasonic processing, then with nitrogen, dry up.The glass substrate subsequently preliminary treatment being completed is put into magnetic control sputtering system, prepares the ITO of 100nm at its surface sputtering;
Step 12, in vacuum degree, be 5 * 10 -4vacuum coating system in, adopt hot evaporation coating method respectively with the speed of 0.4nm/s and 0.5nm/s at the ITO surface successively CuPc of evaporation 50nm and the Alq of 20nm 3;
Step 3 13, adopt hot evaporation coating method with the speed of 0.1nm/s at Alq 3the luminescent layer surface evaporation ReO forming 3, the thickness of the hole blocking layer preparing in this step is 3nm;
Step 14, by Cs 2cO 3be placed in respectively two independently evaporation sources with Bphen, make alkali-metal-doped agent Cs 2cO 3with the evaporation rate ratio of electric transmission host material Bphen be 1: 4, particularly, control and to make Cs 2cO 3evaporation rate be 0.1nm/s, to make the evaporation rate of Bphen be 0.4nm/s, forms the Cs of 50nm at hole blocking layer surface evaporation 2cO 3: Bphen doped structure; And
Step 15, the Ag with the speed of 0.5nm/s at the electron transfer layer surface evaporation 100nm preparing, form cathode layer.
After completing the manufacture process of Organnic electroluminescent device, light-emitting device is encapsulated so that test.Packaging technology adopts glass cover-plate encapsulation, forms the encapsulated layer 109 shown in Fig. 1 a.
Embodiment 2:
A kind of Organnic electroluminescent device (referring to Fig. 2 a), this light-emitting device consists of the substrate 201 stacking gradually, anode layer 202, hole transmission layer 203, electronic barrier layer 204, luminescent layer 205, hole blocking layer 206, electron transfer layer 207 and cathode layer 208, wherein, substrate 201 is glass substrate, the ITO that anode layer 202 is 100nm, hole transmission layer 203 is the F4-TCNQ of 50nm: CuPc doped structure (the doping mass ratio of F4-TCNQ: CuPc is 1: 20), the TCTA that electronic barrier layer 204 is 10nm, the Alq that luminescent layer 205 is 20nm 3, the ReO that hole blocking layer 206 is 3nm 3, the Cs that electron transfer layer 207 is 50nm 2cO 3: Bphen doped structure (Cs 2cO 3: the doping mass ratio of Bphen is 1: 5), the Ag that cathode layer 208 is 100nm.The manufacture method of this light-emitting device comprises the following steps (Fig. 2 b):
Step 21, glass substrate is placed in to the deionized water that contains washing agent carries out ultrasonic cleaning, after cleaning up, glass substrate is entered successively in isopropyl alcohol and acetone and carries out ultrasonic processing, then with nitrogen, dry up.The glass substrate subsequently preliminary treatment being completed is put into magnetic control sputtering system, prepares the ITO of 100nm at its surface sputtering;
Step 22, in vacuum degree, be 5 * 10 -4vacuum coating system in, F4-TCNQ and CuPc are placed in respectively to two independently evaporation sources, making hole dopant F4-TCNQ and the evaporation rate ratio of hole transport host material CuPc is 1: 20, particularly, it is 0.02nm/s that control makes the evaporation rate of F4-TCNQ, make the evaporation rate of CuPc is 0.4nm/s, forms the F4-TCNQ of 50nm: CuPc doped structure at ITO surface evaporation;
Step 23, adopt hot evaporation coating method with the speed of 0.5nm/s the successively successively TCTA of evaporation 10nm and the Alq of 20nm on the hole transmission layer surface of doped structure 3;
Step 24, adopt hot evaporation coating method with the speed of 0.1nm/s at Alq 3the luminescent layer surface evaporation ReO forming 3, the thickness of the hole blocking layer preparing in this step is 3nm;
Step 25, by Cs 2cO 3be placed in respectively two independently evaporation sources with Bphen, make alkali-metal-doped agent Cs 2cO 3with the evaporation rate ratio of electric transmission host material Bphen be 1: 4, particularly, control and to make Cs 2cO 3evaporation rate be 0.1nm/s, to make the evaporation rate of Bphen be 0.4nm/s, forms the Cs of 50nm at hole blocking layer surface evaporation 2cO 3: Bphen doped structure; And
Step 26, the Ag with the speed of 0.5nm/s at the electron transfer layer surface evaporation 100nm preparing, form cathode layer.
After completing the manufacture process of Organnic electroluminescent device, light-emitting device is encapsulated so that test.Packaging technology adopts glass cover-plate encapsulation, forms the encapsulated layer 209 shown in Fig. 2 a.
Embodiment 3:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the F4-TCNQ of 50nm: m-MTDATA doped structure (the doping mass ratio of F4-TCNQ: m-MTDATA is 1: 20), the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the WO that hole blocking layer is 5nm 3, the LiN that electron transfer layer is 50nm 3: Alq 3doped structure (LiN 3: Alq 3doping mass ratio be 1: 5), the Ag that cathode layer is 100nm.In the manufacture process of this light-emitting device, except prepare hole blocking layer with 0.5nm/s evaporation rate, other operating procedures are with embodiment 2, at this repeated description no longer.
Embodiment 4:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the F2-HCNQ of 50nm: ZnPc doped structure (the doping mass ratio of F2-HANQ: ZnPc is 1: 20), the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the V that hole blocking layer is 3nm 2o 5, the LiN that electron transfer layer is 50nm 3: Alq 3doped structure (CsN 3: the doping mass ratio of BCP is 1: 5), the Ag that cathode layer is 100nm.The manufacture method of this light-emitting device is with embodiment 2, at this repeated description no longer.
Embodiment 5:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the F2-HANQ of 50nm: MeO-TPD doped structure (the doping mass ratio of F2-HCNQ: MeO-TPD is 1: 20), the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the Sb that hole blocking layer is 6nm 2o 3, the Li that electron transfer layer is 50nm 2cO 3: BAlq doped structure (Li 2cO 3: the doping mass ratio of BAlq is 1: 5), the Ag that cathode layer is 100nm.The manufacture method of this light-emitting device is with embodiment 2, at this repeated description no longer.
Embodiment 6:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the F6-TNAP of 50nm: 2-TNATA doped structure (the doping mass ratio of F6-TNAP: 2-TNATA is 1: 20), the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the Bi that hole blocking layer is 3nm 2o 3, the LiF that electron transfer layer is 50nm: TPBi doped structure (the doping mass ratio of LiF: TPBi is 1: 5), the Ag that cathode layer is 100nm.In the manufacture method of the light-emitting device of this embodiment, after step 21 completes, also the glass substrate containing anode layer is placed in to plasma processing chamber and carries out plasma treatment.This treatment step can improve anode layer work content, reduces the injection barrier in hole.All the other manufacturing steps are with embodiment 2, at this repeated description no longer.
Embodiment 7:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the F4-TCNQ of 50nm: NPB doped structure (the doping mass ratio of F4-TCNQ: NPB is 1: 20), the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the MoO that hole blocking layer is 10nm 3, the CsF that electron transfer layer is 50nm: TPBi doped structure (the doping mass ratio of CsF: TPBi is 1: 5), the Ag that cathode layer is 100nm.In the manufacture process of this light-emitting device, except prepare hole blocking layer with 1.0nm/s evaporation rate, other operating procedures are with embodiment 2, at this repeated description no longer.
Embodiment 8:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the F2-HCNQ of 50nm: CuPc doped structure (the doping mass ratio of F2-HCNQ: CuPc is 1: 20), the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the MoO that hole blocking layer is 5nm 3and V 2o 5mixture, the CsF that electron transfer layer is 50nm: TPBi doped structure (the doping mass ratio of CsF: TPBi is 1: 5), the Ag that cathode layer is 100nm.The manufacture process of light-emitting device is with embodiment 2, at this repeated description no longer.
Embodiment 9:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the F4-TCNQ of 50nm: CuPc doped structure (the doping mass ratio of F4-TCNQ: CuPc is 1: 20), the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, hole blocking layer is followed successively by the ReO of 2nm 3, 2nm Bi 2o 3wO with 2nm 3, the LiF that electron transfer layer is 50nm: BCP doped structure (the doping mass ratio of LiF: BCP is 1: 5), the Ag that cathode layer is 100nm.The manufacture process of light-emitting device is with embodiment 2, at this repeated description no longer.
Embodiment 10:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the CuPc of 50nm, the Alq that luminescent layer is 20nm 3, the MoO that hole blocking layer is 10nm 3, the CsF that electron transfer layer is 50nm: TPBi doped structure (the doping mass ratio of CsF: TPBi is 1: 5), the Ag that cathode layer is 100nm.The manufacture method of this light-emitting device is with embodiment 1, at this repeated description no longer.
Embodiment 11:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the MeO-TPD of 50nm, the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the Sb that hole blocking layer is 6nm 2o 3, the Li that electron transfer layer is 50nm 2cO 3: BAlq doped structure (Li 2cO 3: the doping mass ratio of BAlq is 1: 5), the Ag that cathode layer is 100nm.The manufacture method of this light-emitting device is with embodiment 1, at this repeated description no longer.
For further absolutely proving that Organnic electroluminescent device of the present invention, in the marked improvement aspect light efficiency and useful life, provides following comparative example.
Comparative example 1:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole transmission layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the F4-TCNQ of 50nm: CuPc doped structure (the doping mass ratio of F4-TCNQ: CuPc is 1: 20), the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the Cs that electron transfer layer is 50nm 2cO 3: Bphen doped structure (Cs 2cO 3: the doping mass ratio of Bphen is 1: 5), the Ag that cathode layer is 100nm.In comparative example 1, the manufacture method of light-emitting device is with embodiment 1.
Comparative example 2:
A kind of Organnic electroluminescent device, this light-emitting device consists of the substrate stacking gradually, anode layer, hole transmission layer, electronic barrier layer, luminescent layer, hole transmission layer and cathode layer, wherein, substrate is glass substrate, anode layer is the ITO of 100nm, hole transmission layer is the CuPc of 50nm, the TCTA that electronic barrier layer is 10nm, the Alq that luminescent layer is 20nm 3, the Bphen that electron transfer layer is 50nm, the Ag that cathode layer is 100nm.In comparative example 1, the manufacture method of light-emitting device is with embodiment 1.
The luminescent properties data of Organnic electroluminescent device in table 1 embodiment 2-7 and comparative example 1-2
T 70Life-span (h) Light efficiency (1m/W)
Embodiment 2 1600 20.3
Embodiment 3 1800 19.7
Embodiment 4 1700 21.8
Embodiment 5 1700 22.4
Embodiment 6 1600 18.8
Embodiment 7 1700 20.1
Comparative example 1 900 20.5
Comparative example 2 700 13.1
Table 1 is the luminescent properties data of the light-emitting device of manufacturing in embodiment 2-7 and comparative example 1-2.As can be seen from the table, because embodiment 2-7 and comparative example 1 are the luminescent devices with doping transport layer, in it, the injection efficiency in electronics and hole is improved, so light efficiency is better than common luminescent device comparative example 2.Table 1 has also shown that the light-emitting device of embodiment 2-7 and comparative example 1-2 is 1000cd/m in initial brightness 2under, the useful life of brightness decay to 70% time.The light-emitting device adopting due to the present invention has the transport layer structure (hole transmission layer and electron transfer layer) of doping, makes the required drive current of light-emitting device less; Simultaneously owing to having adopted the diffusion process of alkali-metal-doped agent in hole blocking layer block electrons transport layer, thereby can obtain longer useful life.Under identical initial brightness, when brightness decay is to 70% time, embodiment 2-7 has all obtained the useful life that surpasses 1600 hours, and comparative example 1-2 only has respectively the useful life of 900 and 700 hours.
Fig. 3 is that the light-emitting device of embodiment 2-7 and comparative example 1-2 is 1000cd/m in initial brightness 2under brightness-life-span attenuation curve, the concrete outcome in useful life is listed in table 1.From figure, each attenuation curve can be found out the low Decay Rate of Organnic electroluminescent device of the present invention more intuitively, under equal service condition, can obtain longer useful life.
In sum, in Organnic electroluminescent device of the present invention, the alkali-metal-doped agent that the work content of adulterating in electron transfer layer is low can effectively reduce the drive current of light-emitting device, improves its whole light efficiency; The hole blocking layer consisting of inorganic, metal oxide can effectively stop that alkali metal ion spreads to luminescent layer, the exciton quencher problem of avoiding alkali metal ion to cause, thus significantly improve useful life of light-emitting device; Light-emitting device provided by the present invention can adopt the preparation of traditional sputtering technology and hot evaporation process, and technique is simple and be easy to realize; The light-emitting device stability preparing is good, can use for a long time.
Should be noted that, the doping ratio of the transport layer that the Organnic electroluminescent device of long-life provided by the present invention and high light efficiency is not limited to provide in above-described embodiment (hole transmission layer and electron transfer layer), the concrete evaporation rate providing in above-described embodiment is also provided its preparation process equally.
The foregoing is only the preferred embodiments of the present invention, not in order to limit the present invention, all any modifications of doing in the spirit and principles in the present invention, be equal to and replace or improvement etc., all should be included in protection scope of the present invention.

Claims (10)

1. an Organnic electroluminescent device, comprise the substrate, anode layer, hole transmission layer, luminescent layer, electron transfer layer and the cathode layer that stack gradually, it is characterized in that, described electron transfer layer comprises electric transmission host material and alkali-metal-doped agent, described electric transmission host material and alkali-metal-doped agent form doped structure, be also provided with restriction alkali metal ion and move to the hole blocking layer in described luminescent layer between described luminescent layer and electron transfer layer.
2. Organnic electroluminescent device according to claim 1, is characterized in that, described hole blocking layer consists of inorganic, metal oxide.
3. Organnic electroluminescent device according to claim 2, is characterized in that, at least one that described inorganic, metal oxide is following compound: antimonous oxide, vanadic oxide, molybdenum oxide, tungsten oxide, bismuth oxide and rheium oxide.
4. Organnic electroluminescent device according to claim 1 and 2, is characterized in that, the thickness of described hole blocking layer is 3 ~ 10nm.
5. Organnic electroluminescent device according to claim 1, it is characterized in that, described electric transmission host material is (oxine)-aluminium, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, described alkali-metal-doped agent is lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate or cesium fluoride.
6. Organnic electroluminescent device according to claim 1, is characterized in that, described hole transmission layer comprises hole dopant and hole transport host material, and described hole dopant and hole transport host material form doped structure;
Described hole dopant is 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes, 1,3,4,5,7, and 8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones or 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit), two malononitrile; Described hole transport host material is Phthalocyanine Zinc, CuPc, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,4', 4''-tri-(2-naphthyl phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines or (N, N, N', N '-tetramethoxy phenyl)-benzidine.
7. according to the Organnic electroluminescent device described in claim 1 or 6, it is characterized in that, between described hole transmission layer and luminescent layer, be also provided with electronic barrier layer.
8. a manufacture method for Organnic electroluminescent device, is characterized in that, said method comprising the steps of:
S1, will after substrate preliminary treatment, put into magnetic control sputtering system, in pretreated substrate surface sputter, prepare anode layer;
S2, in vacuum coating system, adopt anode layer surface that hot evaporation coating method prepares in described step S1 successively evaporation prepare hole transmission layer and luminescent layer;
S3, the surperficial evaporation of the luminescent layer that adopts hot evaporation coating method to prepare in described step S2 are prepared hole blocking layer;
S4, the hole blocking layer surface evaporation preparing in described step S3 are prepared electron transfer layer: alkali-metal-doped agent and electric transmission host material are placed in respectively to two independently evaporation sources, control respectively the evaporation rate of described alkali-metal-doped agent and electric transmission host material, on described hole blocking layer surface, evaporation is prepared electron transfer layer; And
S5, the electron transfer layer surface evaporation preparing in described step S4 are prepared cathode layer.
9. the manufacture method of Organnic electroluminescent device according to claim 8, is characterized in that, described step S2 specifically comprises the following steps:
S21, prepare hole transmission layer: hole dopant and hole transport host material are placed in respectively to two independently evaporation sources, control respectively the evaporation rate of described hole dopant and hole transport host material, on described anode layer surface, evaporation is prepared hole transmission layer;
S22, prepare electronic barrier layer: adopt the hole transmission layer surface evaporation that hot evaporation coating method prepares in described step S21 to prepare electronic barrier layer; And
S23, prepare luminescent layer: adopt the electronic barrier layer surface evaporation that hot evaporation coating method prepares in described step S22 to prepare luminescent layer.
10. the manufacture method of Organnic electroluminescent device according to claim 8 or claim 9, is characterized in that, in described step S3, the evaporation rate of described hole blocking layer is 0.1 ~ 1nm/s, and the thickness of the hole blocking layer preparing is 3 ~ 10nm.
CN201210243329.1A 2012-07-13 2012-07-13 Organic electroluminescence device and manufacturing method thereof Pending CN103545451A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104651941A (en) * 2015-02-03 2015-05-27 湖北大学 Potassium-doped phenanthrene molecular crystal and preparation method thereof
CN106531769A (en) * 2016-12-16 2017-03-22 上海天马有机发光显示技术有限公司 Organic light-emitting display panel, electronic equipment and manufacturing method thereof
CN112095077A (en) * 2020-08-26 2020-12-18 四川阿格瑞新材料有限公司 OLED device and evaporation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104651941A (en) * 2015-02-03 2015-05-27 湖北大学 Potassium-doped phenanthrene molecular crystal and preparation method thereof
CN106531769A (en) * 2016-12-16 2017-03-22 上海天马有机发光显示技术有限公司 Organic light-emitting display panel, electronic equipment and manufacturing method thereof
CN106531769B (en) * 2016-12-16 2019-06-25 上海天马有机发光显示技术有限公司 A kind of organic light emitting display panel, electronic equipment and preparation method thereof
CN112095077A (en) * 2020-08-26 2020-12-18 四川阿格瑞新材料有限公司 OLED device and evaporation method thereof

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Application publication date: 20140129