CN102315391B - Organic electroluminescent device and production method thereof - Google Patents
Organic electroluminescent device and production method thereof Download PDFInfo
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- CN102315391B CN102315391B CN201110223728.7A CN201110223728A CN102315391B CN 102315391 B CN102315391 B CN 102315391B CN 201110223728 A CN201110223728 A CN 201110223728A CN 102315391 B CN102315391 B CN 102315391B
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Abstract
The invention is applied to the field of electroluminescent devices, which provides an organic electroluminescent device and a production method thereof. The electroluminescent device comprises an anode, a cathode, and a light-emitting layer positioned between the anode and the cathode; and a hole injection layer, a hole transmission layer and an exciton separating layer are arranged between the anode and the light-emitting layer. According to the organic electroluminescent device disclosed by the invention, the exciton separating layer and the hole transmission layer are arranged on the hole injection layer, thus the hole transmission function is achieved; and meanwhile, electrons can enter the interior of the light-emitting layer again and the light-emitting efficiency is greatly improved. The production method for the organic electroluminescent device, which is disclosed by the invention, has the advantages of simpleness in operation, low cost and high production benefit; and the production method is especially suitable for industrial production.
Description
Technical field
The invention belongs to electroluminescent device technical field, relate in particular to a kind of organic electroluminescence device and preparation method thereof.
Background technology
OLED device adopts sandwich structure conventionally, be between negative electrode and anode, to press from both sides organic layer structure, current multilayer organic layer structure is generally: hole injection layer/hole transmission layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer, and in the interface of organic layer and motor, can introduce resilient coating and improve carrier injection ability.The luminosity of OLED device with from the two poles of the earth injected holes, electronic carrier quantity, the two is compounded to form exciton situation, the luminous situation of exciton relaxation is relevant, luminous efficiency is relevant to the degree of balance of hole in luminescent layer and electron amount.In conventional this structure, hole is majority carrier, and electronics is minority carrier.In existing device, electron amount is on the low side, affects device luminous efficiency.
Summary of the invention
In view of this, the embodiment of the present invention provides a kind of organic electroluminescence device, solves the not high technical problem of device luminous efficiency in prior art; And, this organic electroluminescence device preparation method is provided.
The present invention is achieved in that
A kind of organic electroluminescence device, comprises anode, negative electrode, the luminescent layer between this anode and negative electrode; Between this anode and luminescent layer, be provided with hole injection layer, hole transmission layer and exciton dissociation layer, this hole injection layer comprises that being positioned at the first hole on anode injects part and be positioned at the second hole injection part in this first hole injection part; This hole transmission layer is positioned at the first hole and injects part above, divides adjacent arrangement with this second hole injection unit; This exciton dissociation layer is positioned at the second hole and injects in part; This hole transmission layer upper surface and exciton dissociation layer upper surface are in same level; The material that part is injected in this second hole is phthalocyanine metal complex compound.
And,
A kind of organic electroluminescence device preparation method, comprises the steps:
By vacuum evaporation or be spin-coated on a substrate and form anode, obtain the substrate containing anode;
By vacuum evaporation or be spin-coated on and prepare the first hole on anode and inject part, by vacuum evaporation or be spin-coated on this first hole and inject the upper preparation of part second hole and inject part, by vacuum evaporation or be spin-coated on this second hole and inject the upper preparation of part exciton dissociation layer;
By vacuum evaporation or be spin-coated on and inject preparation in part in the first hole and form hole transmission layer, make this hole transmission layer and the second hole injection unit divide adjacent arrangement, make this hole transmission layer upper surface and exciton dissociation layer upper surface in same level;
By vacuum evaporation or be spin-coated on this luminescent layer and form negative electrode, obtain organic electroluminescence device.
Embodiment of the present invention organic electroluminescence device, by exciton dissociation layer and hole transmission layer are arranged on hole injection layer, has both realized hole transport function; Simultaneously, hole injection layer adopts light absorbent, in the device course of work, hole injection layer absorbs visible ray and produces hole-electron pair, this hole-electron pair enters exciton dissociation layer, be separated into hole and electronics, electronics can reenter luminescent layer and again be utilized, and luminous efficiency is increased greatly.Embodiment of the present invention organic electroluminescence device preparation method, simple to operate, with low cost, productivity effect is high, is very suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention one organic electroluminescence device structure chart;
Fig. 2 is the embodiment of the present invention two organic electroluminescence device structure charts;
Fig. 3 is the embodiment of the present invention three organic electroluminescence device structure charts;
Fig. 4 is the embodiment of the present invention four organic electroluminescence device structure charts.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, 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.
Refer to Fig. 1, Fig. 1 shows embodiment of the present invention organic electroluminescence device structure chart, comprises anode 1, negative electrode 2, the luminescent layer 3 between this anode 1 and negative electrode 2; Between this anode 1 and luminescent layer 3, be provided with hole injection layer 4, hole transmission layer 5 and exciton dissociation layer 6, this hole injection layer 4 comprises that being positioned at the first hole on anode 1 injects part 41 and be positioned at the second hole injection part 42 in this first hole injection part 41; This hole transmission layer 5 is positioned at the first hole and injects in part 41, injects the adjacent arrangement of part 42 with this second hole; This exciton dissociation layer 6 is positioned at the second hole and injects in part 42, and these hole transmission layer 5 upper surfaces and exciton dissociation layer 6 upper surface are in same level; The material that part 42 is injected in this second hole is phthalocyanine metal complex compound.
Particularly, embodiment of the present invention organic electroluminescence device, by exciton dissociation layer 6 and hole transmission layer 5 are arranged on hole injection layer 4, had both realized hole transport function; Simultaneously, hole injection layer 4 adopts light absorbent, in the device course of work, hole injection layer 4 absorbs visible ray and produces hole-electron pair, this hole-electron pair enters exciton dissociation layer 6, be separated into hole and electronics, electronics can reenter luminescent layer 3 and again be utilized, and luminous efficiency is increased greatly.
Particularly, this anode 1 comprises substrate 11 and conducting film 12.
Particularly, this hole injection layer 4 is positioned on anode 1.This hole injection layer 4 comprises that part 41 is injected in the first hole and part 42 is injected in the second hole, part 41 is injected in this first hole and the second hole injection part 42 is listed between anode 1 and negative electrode 2, this first hole is injected part 41 and is positioned on anode 1, this second hole is injected part 42 and is positioned in this first hole injection part 41, and the Area Ratio that part 41 and the second hole injection part 42 are injected in this first hole is 2-4: 1;
Particularly, this hole transmission layer 5 is positioned at the first hole and injects in part 41, this exciton dissociation layer 6 is positioned at the second hole and injects in part 42, and the upper surface of the upper surface of this hole transmission layer 5 and exciton dissociation layer 6 is in same level, and the thickness of this exciton dissociation layer 6 is 1-5 nanometer.
Further, embodiment of the present invention organic electroluminescence device also comprises electron transfer layer 7, and this electron transfer layer 7 is between negative electrode 2 and luminescent layer 3;
Further, embodiment of the present invention organic electroluminescence device also comprises electron injecting layer 8, and this electron injecting layer 8 is between electron transfer layer 7 and negative electrode 2;
Further, embodiment of the present invention organic electroluminescence device also comprises hole blocking layer 9, and this hole blocking layer 9 is between electron transfer layer 8 and luminescent layer 3.
The structure of embodiment of the present invention electroluminescent device can be selected from following kind:
1. glass/ITO/ hole injection layer/hole transport+exciton dissociation layer/luminescent layer/cathode layer
2. glass/ITO/ hole injection layer/hole transport+exciton dissociation layer/luminescent layer/electron transfer layer/cathode layer
3. glass/ITO/ hole injection layer/hole transport+exciton dissociation layer/luminescent layer/electron transfer layer/electron injecting layer/cathode layer
4. glass/ITO/ hole injection layer/hole transport+exciton dissociation layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/cathode layer
5. glass/conducting polymer/hole injection layer/hole transport+exciton dissociation layer/luminescent layer/cathode layer
6. glass/conducting polymer/hole injection layer/hole transport+exciton dissociation layer/luminescent layer/electron transfer layer/cathode layer
7. glass/conducting polymer/hole injection layer/hole transport+exciton dissociation layer/luminescent layer/electron transfer layer/electron injecting layer/cathode layer
8. glass/conducting polymer/hole injection layer/hole transport+exciton dissociation layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/cathode layer
9. flexible substrate/ITO/ hole injection layer/hole transport+exciton dissociation layer/luminescent layer/cathode layer
10. flexible substrate/ITO/ hole injection layer/hole transport+exciton dissociation layer/luminescent layer/electron transfer layer/cathode layer
11. flexible substrate/ITO/ hole injection layer/hole transport+exciton dissociation layer/luminescent layer/electron transfer layer/electron injecting layer/cathode layer
12. flexible substrate/ITO/ hole injection layer/hole transport+exciton dissociation layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/cathode layer
Particularly, this anode comprises substrate and conducting film, the material of this substrate is selected from glass flake, sheet metal, or flexible substrate (petchem, poly-phthalimide compound etc.), the material of this conducting film is selected from metal, metal oxide, or organic conductive polymer, this metal can be the higher metals of work function such as gold, copper, silver; This metal oxide can be tin indium oxide (ITO), zinc oxide or zinc tin oxide, and organic conductive polymer can be 3,4-ethylene dioxythiophene mixing poly styrene sulfonate (PEDOT:PSS) or polyaniline (PANI).Also, this conducting film is selected from the metallic film that work function is higher, such as gold thin film, silver-colored film, copper film etc.; This metal-oxide film for example, ito thin film or zinc-oxide film or zinc tin oxide film etc.; The material of this anode can also be selected from 3,4-ethylene dioxythiophene mixing poly styrene sulfonate (PEDOT:PSS) or polyaniline (PANI) class organic conductive polymer.
Particularly, this negative electrode comprises resilient coating and metal level, this resilient coating is between luminescent layer and metal level, and the material of this resilient coating is inorganic molecules compound or the organic compound with high unoccupied energy level (LUMO), for example LiF, MgFZ, LiZO, CsF; The material of this metal level is metal or its oxide that work function is lower, for example, and lithium, magnesium, calcium, strontium, aluminium, indium etc.; Or, lithia, magnesium oxide, calcium oxide, strontium oxide strontia, alundum (Al2O3), indium oxide etc.; Or, above-mentioned metal and gold or silver-colored alloy, for example gold and lithium alloy, gold and magnesium alloy, silver-colored and aluminium alloy, silver and indium alloy etc.
Particularly, the material of this exciton dissociation layer is exciton dissociation material, has the material that electron hole pair is separated into the ability of electronics and holoe carrier, for example, be selected from fullerene (C
60) or derivatives thereof (PCBM), Si Suo Ji perylene derivative (PV).
Particularly, the material of this hole transmission layer is selected from aromatic diamine compounds or star triphenyl amine compound;
Particularly, the material of this luminescent layer is selected from fluorescence luminescent material or phosphorescent light-emitting materials, does not specifically limit;
Particularly, the material of this hole blocking layer is selected from one or more in 1,10-phenanthroline derivative (BCP), two (2-methyl-8-quinoline acid group closes) tri-phenyl-silane aluminium alcoholates (III), two (2-methyl-8-quinoline acid group closes) 4-phenol aluminium (III) or two (2-methyl-8-quinoline acid group closes) 4-phenylphenol aluminium (III);
Particularly, the material of this electron injecting layer and electron transfer layer is all selected from metal complex, oxadiazole electron-like transferring material or imidazoles electron transport material, does not specifically limit;
Particularly, the material of this first hole injection layer is selected from TiO
2, one or several in m-MTDATA, F4TCNQ, TCNQ, PPDN, CuPc, TiOPc, mCP, TcTA, TCP, CBP or PEDOT-PSS;
Particularly, the material of this second hole injection layer is selected from has visible absorption material, be preferably phthalocyanine metal complex compound, for example CuPc (CuPc, this CuPc is as sulfonated copper phthalocyanine, phthalimide methyl copper phthalocyanine, chloromethylation copper phthalocyanine, nitration copper phthalocyanine and amination copper phthalocyanine), TiOPc (TiOPc); Also can be formed with the doping system of other hole-injecting materials by the blue or green series of phthalein, for example:
CuPc：m-MTDATA、CuPc：TiO2、CuPc：F4TCNQ、CuPc：TCNQ、CuPc：PPDN、CuPc：mCP、CuPc：TCP、CuPc：TcTa、CuPc：CBP；
TiOPc：m-MTDATA、TiOPc：TiO2、TiOPc：F4TCNQ、TiOPc：TCNQ、TiOPc：PPDN、TiOPc：mCP、TiOPc：TCP、TiOPc：TcTa、TiOPc：CBP。
The adjacent setting of exciton dissociation layer and hole transmission layer in the present invention, forms a kind of compound organic layer, and during device additional power source driving element, hole is injected in from anode to hole injection layer, then sets out in photosphere through hole transmission layer transmission; Electronics injects from negative electrode simultaneously, can pass through electron injecting layer, and in electron transfer layer and hole blocking layer, one or more layers enters in luminescent layer; Also can luminescent layer take into account the effect of electron transfer layer, electronics is directly injected in luminescent layer from negative electrode; Electronics and hole are combined into exciton in luminescent layer, and exciton relaxation produces light transmitting.Hole injection layer (particularly part is injected in the second hole) material used absorbs the light of transmitting, produce hole-electron pair, hole-electron pair enters exciton dissociation layer, be separated into hole and electronics, electrons re-injects sets out in photosphere, be compounded to form again exciton with the hole in luminescent layer, after exciton relaxation, produce light transmitting.
The embodiment of the present invention further provides above-mentioned organic electroluminescence device preparation method, comprises the steps:
Step S01, prepares anode
By vacuum evaporation or be spin-coated on substrate and form anode, obtain the substrate containing anode;
Step S02, part is injected in preparation the first hole, part and exciton dissociation layer are injected in the second hole
By vacuum evaporation or be spin-coated on and prepare the first hole on anode and inject part, by vacuum evaporation or be spin-coated on this first hole and inject the upper preparation of part second hole and inject part, by vacuum evaporation or be spin-coated on this second hole and inject the upper preparation of part exciton dissociation layer;
Step S03, prepares hole transmission layer
By vacuum evaporation or be spin-coated on and inject preparation in part in the first hole and form hole transmission layer, make this hole transmission layer and the second hole injection unit divide adjacent arrangement, make this hole transmission layer upper surface and exciton dissociation layer upper surface in same level;
Step S04, prepares luminescent layer
By vacuum evaporation or be spin-coated on this exciton dissociation layer and hole transmission layer upper surface form luminescent layer;
Step S05, prepares negative electrode
By vacuum evaporation or be spin-coated on this luminescent layer and form negative electrode, obtain organic electroluminescence device.
Particularly, before step S01, also comprise substrate cleaning step, be specially:
Substrate is used respectively to ethanol, acetone and deionized water ultrasonic cleaning, after cleaning, with drying nitrogen, dry up.
Particularly, before step S02, also comprise following anode pre-treatment step:
The substrate of this anode is not used to ethanol, acetone and deionized water ultrasonic cleaning, after cleaning, with drying nitrogen, dry up, then be placed in vacuum chamber, under the oxygen pressure ring border that is 20Pa at air pressure, ito glass is carried out to oxygen plasma bombardment preliminary treatment 10 minutes;
Particularly, in step S02, first on this anode, by vacuum evaporation or sputter, form the first hole and inject part, then by the part that baffle plate injects part upper surface by this first hole, cover that (this covers part is 1-3 with not covering part Area Ratio: 1), in the part not covered at this hole injection layer upper surface, continue evaporation or sputter, form the second hole and inject part, therefore realized hole injection layer stepped on the whole; Then, by vacuum evaporation or be spin-coated on this second hole and inject the upper preparation of part and form exciton dissociation layer; This exciton dissociation layer thickness is 1-5 nanometer;
Particularly, in step S03, exciton dissociation layer is covered with baffle plate, remove the first hole and inject the baffle plate in part, in the first hole, inject in the part not covered in part and form hole transmission layer by vacuum evaporation or sputter, make this hole transmission layer and the second hole injection unit divide adjacent arrangement; Make this hole transmission layer upper surface and exciton dissociation layer upper surface in same level simultaneously;
The Area Ratio of this exciton dissociation layer and hole transmission layer is 1: 1-3, is preferably 1: 1-2.
Further, embodiment of the present invention organic electroluminescence device preparation method, also comprises the step of preparing electron injecting layer, electron transfer layer or hole blocking layer, adopts vacuum evaporation or sputtering method preparation, does not specifically limit.
Embodiment of the present invention organic electroluminescence device preparation method, simple to operate, with low cost, productivity effect is high, is very suitable for suitability for industrialized production.
Below in conjunction with specific embodiment, above-mentioned organic electroluminescence device and preparation method thereof is described in detail.
Embodiment mono-
Refer to Fig. 1, Fig. 1 shows the embodiment of the present invention one organic electroluminescence device structure chart, comprises anode 1, negative electrode 2, the luminescent layer 3 between this anode 1 and negative electrode 2; Between this anode 1 and luminescent layer 3, also comprise hole injection layer 4, hole transmission layer 5 and exciton dissociation layer 6; This hole injection layer 4 comprises the second hole injection part 42 that is positioned at the first hole injection part 41 on anode 1 and is positioned at this first hole injection part 41, part 41 is injected in this first hole and the second hole injection part 42 Area Ratios are 2: 1, this hole transmission layer 5 is positioned at the first hole and injects in part 41, inject the adjacent arrangement of part 42 with the second hole, thickness is 20 nanometers, this exciton dissociation layer 6 is positioned at the second hole and injects in part 42, thickness is 1 nanometer, and this hole transmission layer 5 and exciton dissociation layer 6 upper surface are in same level; This luminescent layer 3 is positioned on this hole transmission layer 5 and exciton dissociation layer 6.
The embodiment of the present invention one organic electroluminescence device preparation method, comprises the steps:
Utilize ethanol, acetone and deionized water ultrasonic cleaning glass respectively, after cleaning, with drying nitrogen, dry up, be placed in vacuum chamber, at this ito thin film of preparing on glass as anode;
Ito glass is used to the ultrasonic cleaning respectively of ethanol, acetone and deionized water, after cleaning, with drying nitrogen, dry up, be placed in vacuum chamber, under the oxygen pressure ring border that is 20Pa at air pressure, ito glass is carried out to oxygen plasma bombardment preliminary treatment 10 minutes;
The complete ito glass of preliminary treatment moves in high vacuum chamber, and part is injected in the first hole that is 20nm by CuPc evaporation formation thickness;
Then place mask plate a part for this first hole injection part upper surface is covered, making the first hole injection part upper surface be covered the area of part is 1: 1 with the Area Ratio that is not covered part; In the first hole not covered, inject on part upper surface, part is injected in the second hole that CuPc evaporation is formed to 19nm, then on the hole injection layer forming for the second time by C
60evaporation forms the exciton dissociation layer of 1nm;
This exciton dissociation layer is covered with mask plate, remove the first hole and inject the mask plate in part, in the part not covered at the first hole injection part upper surface, NPB evaporation is formed to the hole transmission layer of 20nm;
On this hole transmission layer and exciton dissociation layer by Alq
3evaporation forms luminescent layer, and thickness is 50nm;
The Mg that is 10: 1 by mass ratio on this luminescent layer: Ag alloy evaporation forms negative electrode, and thickness is 100nm, obtains organic electroluminescence device.
In embodiment of the present invention organic electroluminescence device preparation method, the evaporation speed of functional layer is 0.1nm/s, and the evaporation speed of negative electrode is 1nm/s, and the thickness of each layer and evaporation speed have film thickness gauge monitoring; The organic electroluminescence device preparing is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
Embodiment bis-
Refer to Fig. 2, Fig. 2 shows the embodiment of the present invention two organic electroluminescence device structure charts, comprises anode 1, negative electrode 2, the luminescent layer 3 between this anode 1 and negative electrode 2; Between this anode 1 and luminescent layer 3, also comprise hole injection layer 4, hole transmission layer 5 and exciton dissociation layer 6; Between this luminescent layer 3 and negative electrode 2, also comprise electron transfer layer 7; This hole injection layer 4 comprises the second hole injection part 42 that is positioned at the first hole injection part 41 on anode 1 and is positioned at this first hole injection part 41, part 41 is injected in this first hole and the second hole injection part 42 Area Ratios are 3: 1, this hole transmission layer 5 is positioned at the first hole and injects in part 41, inject the adjacent arrangement of part 42 with the second hole, thickness is 20 nanometers, this exciton dissociation layer 6 is positioned at the second hole and injects in part 42, thickness is 2 nanometers, and this hole transmission layer 5 and exciton dissociation layer 6 upper surface are in same level; This luminescent layer 3 is positioned on this hole transmission layer 5 and exciton dissociation layer 6.
The embodiment of the present invention one organic electroluminescence device preparation method, comprises the steps:
Utilize ethanol, acetone and deionized water ultrasonic cleaning glass respectively, after cleaning, with drying nitrogen, dry up, be placed in vacuum chamber, at this ito thin film of preparing on glass as anode;
Ito glass is used to the ultrasonic cleaning respectively of ethanol, acetone and deionized water, after cleaning, with drying nitrogen, dry up, be placed in vacuum chamber, under the oxygen pressure ring border that is 20Pa at air pressure, ito glass is carried out to oxygen plasma bombardment preliminary treatment 10 minutes;
The complete ito glass of preliminary treatment moves in high vacuum chamber, and part is injected in the first hole that is 20nm by CuPc evaporation formation thickness;
Then place mask plate a part for this first hole injection part upper surface is covered, making the first hole injection part upper surface be covered the area of part is 2: 1 with the Area Ratio that is not covered part; In the first hole not covered, inject on part upper surface, part is injected in the second hole that CuPc evaporation is formed to 18nm, then on the hole injection layer forming for the second time by C
60evaporation forms the exciton dissociation layer of 2nm;
This exciton dissociation layer is covered with mask plate, remove the first hole and inject the mask plate in part, in the part not covered at the first hole injection part upper surface, NPB evaporation is formed to the hole transmission layer of 20nm;
The Alq that is 20: 1 by mass ratio on this hole transmission layer and exciton dissociation layer
3and Rubrene (rubrene) mixture evaporation formation luminescent layer, thickness is 30nm;
On this luminescent layer by Alq
3evaporation forms the electron transfer layer that thickness is 20nm;
The Mg that is 10: 1 by mass ratio on this electron transfer layer: Ag alloy evaporation forms negative electrode, and thickness is 100nm, obtains organic electroluminescence device.
In embodiment of the present invention organic electroluminescence device preparation method, the evaporation speed of functional layer is 0.1nm/s, and the evaporation speed of negative electrode is 1nm/s, and the thickness of each layer and evaporation speed have film thickness gauge monitoring; The organic electroluminescence device preparing is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
Embodiment tri-
Refer to Fig. 3, Fig. 3 shows the embodiment of the present invention three organic electroluminescence device structure charts, comprises anode 1, negative electrode 2, the luminescent layer 3 between this anode 1 and negative electrode 2; Between this anode 1 and luminescent layer 3, also comprise hole injection layer 4, hole transmission layer 5 and exciton dissociation layer 6; Between this luminescent layer 3 and negative electrode 2, also comprise electron transfer layer 7; Between this electron transfer layer 7 and negative electrode 2, also comprise electron injecting layer 8; This hole injection layer 4 comprises the second hole injection part 42 that is positioned at the first hole injection part 41 on anode 1 and is positioned at this first hole injection part 41, part 41 is injected in this first hole and the second hole injection part 42 Area Ratios are 4: 1, this hole transmission layer 5 is positioned at the first hole and injects in part 41, inject the adjacent arrangement of part 42 with the second hole, thickness is 20 nanometers, this exciton dissociation layer 6 is positioned at the second hole and injects in part 42, thickness is 3 nanometers, and this hole transmission layer 5 and exciton dissociation layer 6 upper surface are in same level; This luminescent layer 3 is positioned on this hole transmission layer 5 and exciton dissociation layer 6.
The embodiment of the present invention one organic electroluminescence device preparation method, comprises the steps:
Utilize ethanol, acetone and deionized water ultrasonic cleaning glass respectively, after cleaning, with drying nitrogen, dry up, be placed in vacuum chamber, at this ito thin film of preparing on glass as anode;
Ito glass is used to the ultrasonic cleaning respectively of ethanol, acetone and deionized water, after cleaning, with drying nitrogen, dry up, be placed in vacuum chamber, under the oxygen pressure ring border that is 20Pa at air pressure, ito glass is carried out to oxygen plasma bombardment preliminary treatment 10 minutes;
The complete ito glass of preliminary treatment moves in high vacuum chamber, and part is injected in the first hole that is 20nm by CuPc evaporation formation thickness;
Then place mask plate a part for this first hole injection part upper surface is covered, making the first hole injection part upper surface be covered the area of part is 3: 1 with the Area Ratio that is not covered part; In the first hole not covered, inject on part upper surface, part is injected in the second hole that CuPc evaporation is formed to 17nm, then on the hole injection layer forming for the second time by C
60evaporation forms the exciton dissociation layer of 3nm;
This exciton dissociation layer is covered with mask plate, remove the first hole and inject the mask plate in part, in the part not covered at the first hole injection part upper surface, NPB evaporation is formed to the hole transmission layer of 20nm;
The Alq that is 20: 1 by mass ratio on this hole transmission layer and exciton dissociation layer
3form luminescent layer with Rubrene mixture evaporation, thickness is 30nm;
On this luminescent layer by Alq
3evaporation forms the electron transfer layer that thickness is 20nm;
On this electron transfer layer, LiF evaporation is formed to electron injecting layer;
On this electron injecting layer, Al evaporation is formed to negative electrode, thickness is 100nm, obtains organic electroluminescence device.
In embodiment of the present invention organic electroluminescence device preparation method, the evaporation speed of functional layer is 0.1nm/s, Alq
3with the evaporation speed ratio of Rubrene be 20: 1, the evaporation speed of negative electrode is 1nm/s, the thickness of each layer and evaporation speed have film thickness gauge monitoring; The organic electroluminescence device preparing is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
Embodiment tetra-
Refer to Fig. 4, Fig. 4 shows the embodiment of the present invention four organic electroluminescence device structure charts, comprises anode 1, negative electrode 2, the luminescent layer 3 between this anode 1 and negative electrode 2; Between this anode 1 and luminescent layer 3, also comprise hole injection layer 4, hole transmission layer 5 and exciton dissociation layer 6; Between this luminescent layer 3 and negative electrode 2, also comprise electron transfer layer 7; Between this electron transfer layer 7 and negative electrode 2, also comprise electron injecting layer 8; Between this electron transfer layer 7 and anode 1, also comprise hole blocking layer 9; This hole injection layer 4 comprises the second hole injection part 42 that is positioned at the first hole injection part 41 on anode 1 and is positioned at this first hole injection part 41, part 41 is injected in this first hole and the second hole injection part 42 Area Ratios are 2.5: 1, this hole transmission layer 5 is positioned at the first hole and injects in part 41, inject the adjacent arrangement of part 42 with the second hole, thickness is 25 nanometers, this exciton dissociation layer 6 is positioned at the second hole and injects in part 42, thickness is 5 nanometers, and this hole transmission layer 5 and exciton dissociation layer 6 upper surface are in same level; This luminescent layer 3 is positioned on this hole transmission layer 5 and exciton dissociation layer 6.
The embodiment of the present invention one organic electroluminescence device preparation method, comprises the steps:
Utilize ethanol, acetone and deionized water ultrasonic cleaning glass respectively, after cleaning, with drying nitrogen, dry up, be placed in vacuum chamber, at this ito thin film of preparing on glass as anode;
Ito glass is used to the ultrasonic cleaning respectively of ethanol, acetone and deionized water, after cleaning, with drying nitrogen, dry up, be placed in vacuum chamber, under the oxygen pressure ring border that is 20Pa at air pressure, ito glass is carried out to oxygen plasma bombardment preliminary treatment 10 minutes;
The complete ito glass of preliminary treatment moves in high vacuum chamber, and part is injected in the first hole that is 20nm by CuPc evaporation formation thickness;
Then place mask plate a part for this first hole injection part upper surface is covered, making the first hole injection part upper surface be covered the area of part is 1.5: 1 with the Area Ratio that is not covered part; In the first hole not covered, inject on part upper surface, part is injected in the second hole that CuPc evaporation is formed to 20nm, then on the hole injection layer forming for the second time by C
60evaporation forms the exciton dissociation layer of 5nm;
This exciton dissociation layer is covered with mask plate, remove the first hole and inject the mask plate in part, in the part not covered at the first hole injection part upper surface, NPB evaporation is formed to the hole transmission layer of 25nm;
The Alq that is 20: 1 by mass ratio on this hole transmission layer and exciton dissociation layer
3and Rubrene (rubrene) mixture evaporation formation luminescent layer, thickness is 25nm;
On this luminescent layer, BCP evaporation being formed to thickness is the hole blocking layer of 5 nanometers;
On this hole blocking layer by Alq
3evaporation forms the electron transfer layer that thickness is 20nm;
On this electron transfer layer, LiF evaporation is formed to electron injecting layer;
On this electron injecting layer, Al evaporation is formed to negative electrode, thickness is 100nm, obtains organic electroluminescence device.
In embodiment of the present invention organic electroluminescence device preparation method, the evaporation speed of functional layer is 0.1nm/s, Alq
3with the evaporation speed ratio of Rubrene be 20: 1, the evaporation speed of negative electrode is 1nm/s, the thickness of each layer and evaporation speed have film thickness gauge monitoring; The organic electroluminescence device preparing is sent to glove box and encapsulates, glove box is 99.9% nitrogen atmosphere.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. an organic electroluminescence device, comprises anode, negative electrode, the luminescent layer between described anode and negative electrode; Between described anode and luminescent layer, be provided with hole injection layer, hole transmission layer and exciton dissociation layer, it is characterized in that, described hole injection layer comprises the first hole injection part being positioned on anode and the second hole injection part being positioned in described the first hole injection part; Described hole transmission layer is positioned at the first hole and injects part above, divides adjacent arrangement with described the second hole injection unit; Described exciton dissociation layer is positioned at the second hole and injects in part; Described hole transmission layer upper surface and exciton dissociation layer upper surface are in same level; The material that part is injected in described the second hole is phthalocyanine metal complex compound.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, surface area described exciton dissociation layer and the surface area stacked combination of described luminescent layer and hole transmission layer and the stacked combination of described luminescent layer is than being 1:1-1:3.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, what part was injected in described the first hole divides the surface area of stacked combination than being 2-4:1 with part is injected in the surface area of the stacked combination of described anode and the second hole with described the first hole injection unit.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the material that part is injected in described the first hole is selected from TiO
2, m-MTDATA, F4TCNQ, TCNQ, PPDN, CuPc, TiOPc, mCP, TcTA, TCP, CBP or PEDOT-PSS.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described exciton dissociation layer is 1-5 nanometer.
6. organic electroluminescence device as claimed in claim 1, is characterized in that, the material that part is injected in described the second hole is CuPc or TiOPc.
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| CN101386630A (en) * | 2007-09-14 | 2009-03-18 | 富士胶片株式会社 | Organic electroluminescence device |
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