CN108598288A - A kind of composite multifunction OLED electrodes and preparation method thereof - Google Patents

A kind of composite multifunction OLED electrodes and preparation method thereof Download PDF

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Publication number
CN108598288A
CN108598288A CN201810752287.1A CN201810752287A CN108598288A CN 108598288 A CN108598288 A CN 108598288A CN 201810752287 A CN201810752287 A CN 201810752287A CN 108598288 A CN108598288 A CN 108598288A
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nanometer line
metal nanometer
composite multifunction
oled electrodes
preparation
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Inventor
唐振宇
陈旻彧
赵艺
凌志天
杨佳丽
魏斌
李春亚
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/805Electrodes
    • H10K50/81Anodes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/805Electrodes
    • H10K50/82Cathodes
    • H10K50/828Transparent cathodes, e.g. comprising thin metal layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60Forming conductive regions or layers, e.g. electrodes

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses a kind of composite multifunction OLED electrodes and preparation method thereof, composite multifunction OLED electrodes include the metal nanometer line Optoelectronic polymers mixed layer of flexible base board and growth on flexible substrates, metal nanometer line Optoelectronic polymers mixed layer includes metal nanometer line and Optoelectronic polymers material, one layer of Optoelectronic polymers material of spin coating on metal nanometer line so that Optoelectronic polymers material is filled in the gap of metal nanometer line.The present invention makes that metal nanometer line insertion is soft, is constituted in sticky Optoelectronic polymers material and has interface smooth and the composite multifunction OLED electrodes of good electrically conducting transparent characteristic and hole/electron injection ability by pressure, the translucency and electric conductivity for solving the problems, such as metal nanometer line prepared by conventional method are difficult to take into account, and using the method for antivacuum preparation, the manufacturing cost of current OLED electrodes can be substantially reduced.

Description

A kind of composite multifunction OLED electrodes and preparation method thereof
Technical field
The present invention relates to transparent conductive electrode technical fields, more particularly to a kind of to be based on metal nanometer line and Optoelectronic polymers Composite multifunction OLED electrodes of material and preparation method thereof.
Background technology
Metal is prepared to electrode extensively due to its high conductivity, is used as in organic electronic and opto-electronic device, But blocky or film metal is typically opaque, the use which has limited metal as transparent conductive electrode.To understand The certainly opaque problem of metallic film, researchers have found to solve using metal mesh structure and metal nano wire grid above-mentioned Problem.Metal grill is typically two-dimensional grid or the form of hexagonal mesh, is deposited by thermal evaporation, by photoetching technique into Row patterning or printing.Since the cavity in metalolic network is almost 100% transparent, so the coverage rate by changing metal (i.e. the line width of metal nano net) can easily tune the transmissivity of metal grill flexible and transparent conductive electrode.Theoretically, The metal grill of perfect condition with optimization line width is than the ITO with identical square resistance with higher transmissivity.For example, Theoretically the square resistance of 90% optical transmittance and 0.8 Ω/nm may be implemented in the Ag films electrode of nano-patterning, practical The metal grid electrode of preparation can generally also reach about 80% light transmission.
Metal nano wire grid also has other than metal grill has the advantage that and passes through solwution method from liquid dispersion The remarkable advantage of Direct precipitation.So far, most widely used metal nanometer line is nano silver wire (AgNWs), can be equal It is even to be dispersed in alcohol solvent to form the solution of high quality, have benefited from the intrinsic metalline of nano silver wire and height in length and breadth Than the ultra-thin random nano wire grid being grown in plastic supporting base has very high mechanical flexibility, high conductivity and transparency. But metal nano wire grid and metal grill all have there are one apply upper problem, that is, from the metal gate of substrate protrusion Lattice (micron order) are relatively thicker than ultra-film organic layer (nanoscale), are easy to cause the short circuit of device so that this flexible and transparent is led Electrode is not suitable for directly applying to actual organic optoelectronic device.
At present in this field, there are many kinds of the effective technologies for preparing flexible transparent electrode using metal nanometer line, than Such as nano silver wire is embedded in flexible base board to reduce its surface roughness, or in nano silver wire surface spin coating conducting polymer Material PEDOT:PSS(PEDOT:PSS is a kind of aqueous solution of high molecular polymer, is made of two kinds of substances of PEDOT and PSS. PEDOT is the polymer of EDOT (3,4-rthylene dioxythiophene monomer), PSS is poly styrene sulfonate) fill up nano silver wire The out-of-flatness of film surface is to avoid short circuit, or sacrifices its partially flexible and combined nano silver wire with ITO to obtain preferably Electric conductivity also has in addition by directly by applying the method for external force, film prepared by nano silver wire being flattened to reduce surface Roughness.Although the above method has certain achievement, many disadvantages are still had:1, existing technology has and is difficult to take into account The shortcomings that translucency and electric conductivity:If increasing the concentration of nano silver wire in nano silver wire solution, the film resistor of preparation is smaller, But translucency is poor;If reducing the concentration of nano silver wire, the electric conductivity of its film can be corresponding while translucency is promoted Decline.2, the technology of the existing out-of-flatness for solving nano silver wire film surface is incomplete, is such as directly embedded in nano silver wire Although in the high molecular material of insulation the flatness of film surface can improve, its electric conductivity can be also limited;Or directly exist Nano silver wire surface spin coating conducting polymer PEDOT:PSS, although reducing the coarse of nano wire film surface to a certain extent Degree, but its PEDOT:The surfaces PSS are still out-of-flatness, are unfavorable for subsequently preparing device.3, the cost of the prior art is higher.
Invention content
The purpose of the present invention is to propose to a kind of composite multifunction based on metal nanometer line Yu Optoelectronic polymers material OLED electrodes and preparation method thereof make to constitute in metal nanometer line insertion softness, sticky Optoelectronic polymers material by pressure Composite multifunction OLED electrodes, composite multifunction OLED electrodes not only have smooth interface, good electrically conducting transparent characteristic and Hole/electron injection ability, can also realize single electrode shine or OLED (Chinese is organic electroluminescent LED, Hereinafter referred to as OLED) color conversion.The present invention solves the translucency of the metal nanometer line of conventional method preparation and electric conductivity is difficult to The problem of taking into account, and using the method for antivacuum preparation, the manufacturing cost of current OLED electrodes can be substantially reduced.
To achieve the above object, the present invention provides following schemes:
A kind of composite multifunction OLED electrodes, the composite multifunction OLED electrodes include flexible base board and are grown in institute State metal nanometer line-Optoelectronic polymers mixed layer on flexible base board;
The metal nanometer line-Optoelectronic polymers mixed layer includes metal nanometer line and Optoelectronic polymers material;Described One layer of the spin coating Optoelectronic polymers material on metal nanometer line so that the Optoelectronic polymers material is filled in the metal and receives In the gap of rice noodles.
Optionally, the metal nanometer line is nano silver wire.
Optionally, the nano silver wire is grain size 80nm, the nano silver wire that 5 μm of length.
Optionally, the Optoelectronic polymers material is poly- 2- (2- ethyls oxygroup) -5- Methoxy-phenylacetylene solution.
Optionally, the flexible base board is PEI flexible base boards or PI flexible base boards.
The present invention also provides a kind of preparation method of composite multifunction OLED electrodes, the preparation method includes:
It uses solwution method to cover one layer of metal nanometer line solution on flexible substrates, forms metal nanometer line layer;The gold Belong to nano-solution to be formed by metal nanometer line is dispersed in ethanol solution;
One layer of Optoelectronic polymers material of spin coating on the metal nanometer line layer, and the photoelectricity is made using heating and pressurizing method High molecular material is inserted in the gap of the metal nanometer line, is formed metal nanometer line-Optoelectronic polymers mixed layer, is made compound Multi-functional OLED electrodes.
Optionally, the thickness of the metal nanometer line layer is 150~250nm.
Optionally, the thickness of the metal nanometer line-Optoelectronic polymers mixed layer is 150~250nm.
Optionally, heating temperature is 100 degree in the heating and pressurizing method, and pressurization air pressure is in 0.6Mpa or more.
Optionally, the solwution method be spin-coating method, spray coating method or print process, the heating and pressurizing method be nano-imprint method or Pneumatic process.
According to specific embodiment provided by the invention, the invention discloses following technique effects:
The present invention provides a kind of composite multifunction OLED electrodes and preparation method thereof, composite multifunction OLED electrode packets Metal nanometer line-Optoelectronic polymers the mixed layer of flexible base board and growth on flexible substrates is included, metal nanometer line-photoelectricity is high Molecular mixing layer includes metal nanometer line and Optoelectronic polymers material, one layer of Optoelectronic polymers material of spin coating on metal nanometer line Material so that Optoelectronic polymers material is filled in the gap of metal nanometer line.The present invention makes metal nanometer line be embedded in by pressure Being constituted in soft, sticky Optoelectronic polymers material has smooth interface and good electrically conducting transparent characteristic and hole/electronics The composite multifunction OLED electrodes of injectability, translucency and the electric conductivity for solving the metal nanometer line of conventional method preparation are difficult The problem of to take into account, and using the method for antivacuum preparation, the manufacturing cost of current OLED electrodes can be substantially reduced.
Description of the drawings
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the present invention Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings Obtain other attached drawings.
Fig. 1 is the structural schematic diagram of composite multifunction OLED electrodes of the embodiment of the present invention;
Fig. 2 is the flow diagram of composite multifunction OLED electrode preparation methods of the embodiment of the present invention;
Fig. 3 is combination electrode of the embodiment of the present invention based on nano silver wire electrode and Optoelectronic polymers material MEH-PPV Preparation process schematic diagram.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
The purpose of the present invention is to propose to a kind of composite multifunction based on metal nanometer line Yu Optoelectronic polymers material OLED electrodes and preparation method thereof, composite multifunction OLED electrodes not only with good electrically conducting transparent characteristic and hole/ Electron injection ability can also be realized and shine and the conversion of OLED colors, solve the translucency of the nano silver wire of conventional method preparation The problem of being difficult to take into account with electric conductivity, and using the method for antivacuum preparation, the system of current OLED electrodes can be substantially reduced Cause this.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings and specific real Applying mode, the present invention is described in further detail.
Embodiment one
Fig. 1 is the structural schematic diagram of composite multifunction OLED electrodes of the embodiment of the present invention,
As shown in Figure 1, composite multifunction OLED electrodes provided in an embodiment of the present invention include flexible base board 1 and are grown in Metal nanometer line-Optoelectronic polymers mixed layer 2 on the flexible base board;The metal nanometer line-Optoelectronic polymers mixed layer Including metal nanometer line 21 and Optoelectronic polymers material 22;One layer of Optoelectronic polymers of spin coating on the metal nanometer line 21 Material 22 so that the Optoelectronic polymers material 22 is filled in the gap of the metal nanometer line 21.
Preferably, the metal nanometer line 21 is grain size 80nm, the nano silver wire that 5 μm of length.The Optoelectronic polymers material Material 22 is poly- 2- (2- ethyls oxygroup) -5- Methoxy-phenylacetylene solution, English abbreviation MEH-PPV solution, the photoelectricity high score Sub- material 22 has many advantages, such as to inject hole, shine.The flexible base board 1 is PEI flexible base boards or PI flexible base boards.
Fig. 2 is the flow diagram of composite multifunction OLED electrode preparation methods of the embodiment of the present invention, as shown in Fig. 2, this The preparation method of a kind of composite multifunction OLED electrodes that inventive embodiments provide includes:
Step 101:It uses solwution method to cover one layer of metal nanometer line solution on flexible substrates, forms metal nanometer line Layer;The metal nano solution is formed by metal nanometer line is dispersed in ethanol solution.
Step 102:One layer of Optoelectronic polymers material of spin coating on the metal nanometer line layer, and made using heating and pressurizing method The Optoelectronic polymers material is inserted in the gap of the metal nanometer line, and metal nanometer line-Optoelectronic polymers mixed layer is formed, Composite multifunction OLED electrodes are made.
Wherein, the thickness of the metal nanometer line layer is 150~250nm.
The thickness of the metal nanometer line-Optoelectronic polymers mixed layer is 150~250nm.
Heating temperature is 100 degree in the heating and pressurizing method, and pressurization air pressure is in 0.6Mpa or more.
The solwution method includes spin-coating method, spray coating method, print process etc., and the heating and pressurizing method includes nano-imprint method, gas Platen press etc..
Embodiment three:
Fig. 3 is combination electrode of the embodiment of the present invention based on nano silver wire electrode and Optoelectronic polymers material MEH-PPV Preparation process schematic diagram, as shown in figure 3, an embodiment of the present invention provides based on nano silver wire electrode and Optoelectronic polymers material The preparation method of the combination electrode of MEH-PPV includes:
First, using grain size 80nm, the nano silver wire that 50 μm of length will be dispersed in ethanol solution, and it is molten to form nano silver wire Liquid, the mass fraction 1wt% of ethanol solution.
Secondly, nano silver wire solution is spun on flexible pet substrate, average film thickness is controlled in 200nm or so, then 100 DEG C are annealed 20 minutes.
Furthermore the spin coating MEH-PPV solution in silver nanowire film, solvent use toluene, control film thickness in 200m or so, and Optoelectronic polymers material MEH-PPV solution is set to be filled into the gap of nano silver wire using heating and pressurizing method, to be made flexible, thoroughly The small combination electrode of bright, good conductivity, roughness, and ensure the planarization at interface.
The present invention is combined the high molecular material that can be shone with the advantage of metal nanometer line, be made can shine or color convert Multifunctional combination electrode.Compared with prior art, the present invention has the advantage that:
1, the Multifunctional combination electrode prepared by the present invention not only realizes flexible, transparent, conductive function, but also interface Roughness is very low, and the performance of compatible topmost thin film is good.
2, shining for electrode may be implemented in the multi-functional recombination luminescence electrode prepared by the present invention, can be with lower cost The light spectrum of modulation device, it is easy to accomplish large area produces.
Principle and implementation of the present invention are described for specific case used herein, and above example is said The bright method and its core concept for being merely used to help understand the present invention;Meanwhile for those of ordinary skill in the art, foundation The thought of the present invention, there will be changes in the specific implementation manner and application range.In conclusion the content of the present specification is not It is interpreted as limitation of the present invention.

Claims (10)

1. a kind of composite multifunction OLED electrodes, which is characterized in that the composite multifunction OLED electrodes include flexible base board with And it is grown in metal nanometer line-Optoelectronic polymers mixed layer on the flexible base board;
The metal nanometer line-Optoelectronic polymers mixed layer includes metal nanometer line and Optoelectronic polymers material;In the metal One layer of the spin coating Optoelectronic polymers material on nano wire so that the Optoelectronic polymers material is filled in the metal nanometer line Gap in.
2. composite multifunction OLED electrodes according to claim 1, which is characterized in that the metal nanometer line is silver nanoparticle Line.
3. composite multifunction OLED electrodes according to claim 2, which is characterized in that the nano silver wire is grain size 80nm, the nano silver wire that 5 μm of length.
4. composite multifunction OLED electrodes according to claim 1, which is characterized in that the Optoelectronic polymers material is poly- 2- (2- ethyls oxygroup) -5- Methoxy-phenylacetylene solution.
5. composite multifunction OLED electrodes according to claim 1, which is characterized in that the flexible base board is PEI flexible Substrate or PI flexible base boards.
6. a kind of preparation method of composite multifunction OLED electrodes, which is characterized in that the preparation method includes:
It uses solwution method to cover one layer of metal nanometer line solution on flexible substrates, forms metal nanometer line layer;The metal is received Rice solution is formed by metal nanometer line is dispersed in ethanol solution;
One layer of Optoelectronic polymers material of spin coating on the metal nanometer line layer, and the photoelectricity high score is made using heating and pressurizing method Sub- material is inserted in the gap of the metal nanometer line, forms metal nanometer line-Optoelectronic polymers mixed layer, compound more work(are made It can OLED electrodes.
7. the preparation method of composite multifunction OLED electrodes according to claim 6, which is characterized in that the metal nano The thickness of line layer is 150~250nm.
8. the preparation method of composite multifunction OLED electrodes according to claim 6, which is characterized in that the metal nano The thickness of line-Optoelectronic polymers mixed layer is 150~250nm.
9. the preparation method of composite multifunction OLED electrodes according to claim 6, which is characterized in that the heating pressurization Heating temperature is 100 degree in method, and pressurization air pressure is in 0.6Mpa or more.
10. the preparation method of composite multifunction OLED electrodes according to claim 6, which is characterized in that the solwution method For spin-coating method, spray coating method or print process, the heating and pressurizing method is nano-imprint method or pneumatic process.
CN201810752287.1A 2018-07-10 2018-07-10 A kind of composite multifunction OLED electrodes and preparation method thereof Pending CN108598288A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931641A (en) * 2019-11-22 2020-03-27 徐州吴瑞信息科技有限公司 Silicon-based organic-inorganic hybrid solar cell and preparation method thereof
CN110993794A (en) * 2019-11-22 2020-04-10 徐州吴瑞信息科技有限公司 Heterojunction solar cell and preparation method thereof
WO2021073608A1 (en) * 2019-10-16 2021-04-22 The University Of Hong Kong Integration of metal nanowire network into conducting polymers

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CN101689568A (en) * 2007-04-20 2010-03-31 凯博瑞奥斯技术公司 Composite transparent conductors and methods of forming the same
CN103959500A (en) * 2011-07-05 2014-07-30 哈钦森公司 Transparent conductive multilayer electrode and associated manufacturing process
CN104094365A (en) * 2012-02-16 2014-10-08 大仓工业株式会社 Method for manufacturing transparent conductive base material, and transparent conductive base material
CN105632652A (en) * 2016-02-05 2016-06-01 华中科技大学 Preparation method of high-performance refined transparent conductive electrode

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN101292362A (en) * 2005-08-12 2008-10-22 凯博瑞奥斯技术公司 Nanowires-based transparent conductors
CN101689568A (en) * 2007-04-20 2010-03-31 凯博瑞奥斯技术公司 Composite transparent conductors and methods of forming the same
CN103959500A (en) * 2011-07-05 2014-07-30 哈钦森公司 Transparent conductive multilayer electrode and associated manufacturing process
CN104094365A (en) * 2012-02-16 2014-10-08 大仓工业株式会社 Method for manufacturing transparent conductive base material, and transparent conductive base material
CN105632652A (en) * 2016-02-05 2016-06-01 华中科技大学 Preparation method of high-performance refined transparent conductive electrode

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021073608A1 (en) * 2019-10-16 2021-04-22 The University Of Hong Kong Integration of metal nanowire network into conducting polymers
CN110931641A (en) * 2019-11-22 2020-03-27 徐州吴瑞信息科技有限公司 Silicon-based organic-inorganic hybrid solar cell and preparation method thereof
CN110993794A (en) * 2019-11-22 2020-04-10 徐州吴瑞信息科技有限公司 Heterojunction solar cell and preparation method thereof
CN110993794B (en) * 2019-11-22 2023-09-05 江苏海钜星新能源科技有限公司 Heterojunction solar cell and preparation method thereof
CN110931641B (en) * 2019-11-22 2024-01-02 山西晋开电力科技有限公司 Silicon-based organic-inorganic hybrid solar cell and preparation method thereof

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Application publication date: 20180928