CN104616728B - A kind of nano-cable transparent conductive film with copper as inner core and preparation method thereof - Google Patents
A kind of nano-cable transparent conductive film with copper as inner core and preparation method thereof Download PDFInfo
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- CN104616728B CN104616728B CN201510036928.XA CN201510036928A CN104616728B CN 104616728 B CN104616728 B CN 104616728B CN 201510036928 A CN201510036928 A CN 201510036928A CN 104616728 B CN104616728 B CN 104616728B
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Abstract
A kind of nano-cable transparent conductive film with copper as inner core and preparation method thereof, belongs to new material technology field.Copper nano-wire is utilized bar coating process to form one layer of transparent conductive film with copper nano-wire as conductive network at transparent glass surface by the present invention.Then, with corresponding nickel, zinc sheet metal as anode, with copper nano-wire transparent conductive film as negative electrode, in the electroplate liquid containing respective metal ion, make metal ion be deposited on the surface of copper nano-wire with the form of metal simple-substance, thus form the copper nickel of " nucleocapsid " structure, copper-zinc nano cable transparent conductive film.The thickness of sedimentary can be controlled by controlling electrodeposition condition during electro-deposition.Such deposition layer is possible not only to be greatly improved corrosion resistance and the electric conductivity of metal nanometer line based conductive film, and it can be made still to have the light transmittance compared favourably with ITO, FTO electro-conductive glass.
Description
Technical field
The invention belongs to new material technology field, be specifically related to a kind of nano-cable electrically conducting transparent being cable inner core with copper
Thin film and preparation method thereof.
Background technology
Traditional FTO or ITO electro-conductive glass, owing to needing expensive vacuum coating equipment when producing, causes the one-tenth of product
This is higher.In order to reduce the cost of electro-conductive glass, researchers find to be uniformly coated in substrate of glass copper nano-wire, can
The copper nano-wire conductive film that can compare favourably with FTO or ITO electro-conductive glass with acquisition light transmittance and electric conductivity.This is due to copper
Nano wire is mutually linked togather formation conductive network at glass surface, and light can pass from the hole of " net ".Metallic copper is received
Rice noodle conductive film, owing to need not the equipment of costliness, can use spin coating, spray or the technology of the multiple maturation such as printing is large quantities of
Amount ground produces, so its cost is expected to significantly less than FTO or ITO electro-conductive glass.Can be as a kind of cheap high-performance
Transparency electrode substitutes traditional FTO or ITO electro-conductive glass and is applied in the multiple electronic device such as photovoltaic cell, display, has
Well application prospect.But, the Metal Substrate transparent conducting glass of this low cost has some more serious shortcomings of ratio, that is,
Its corrosion resistance in certain environments is less desirable, and electric conductivity need to improve.
Summary of the invention
It is an object of the invention to provide a kind of with copper be cable inner core nano-cable transparent conductive film and preparation side
Method.
Based on above-mentioned purpose, this invention takes following technical scheme:
The preparation method of a kind of nano-cable transparent conductive film with copper as inner core, comprises the steps: that (1) synthesizes copper
Nano wire transparent conductive film: by diameter 60-100nm, the copper nano-wire of length 5-20 μm be dispersed in dehydrated alcohol formed dense
Degree is 2-8mg/mL copper nano-wire alcohol suspension, alcohol suspension warp rod coating method (Rathmell A R, Wiley B
J. The synthesis and coating of long, thin copper nanowires to make flexible,
transparent conducting films on plastic substrates. Advanced Materials, 2011,
23 (41): 4798-4803) being coated in the surface of transparent substrates, be dried, hydrogen stream processes, and obtains with copper nano-wire as conductive network
Transparent conductive film；
(2) at copper core surface plated metal outer shell: with corresponding metal or graphite as anode, lead so that copper nano-wire is transparent
Conductive film is negative electrode, with the aqueous solution of corresponding metal sulfate as electroplate liquid, utilizes electro-deposition method to carry out electroplating and get final product.
In described step (2), described metal shell layer is nickel dam or zinc layers.
During electroless nickel layer, the process of step (2) is: with metallic nickel or graphite as anode, thin with copper nano-wire electrically conducting transparent
Film is negative electrode, with containing 10-240g/L six hydration nickel sulfate, 2-3g/L sodium chloride, 0.05-0.2g/L lauryl sulphate acid
Sodium, 10-20g/L boron aqueous acid are electroplate liquid, utilize electro-deposition method to carry out electroplating and get final product；During electro-galvanized layer, step (2)
Process be: with zinc sheet metal or graphite as anode, with copper nano-wire transparent conductive film as negative electrode, with containing 20-180g/L
Zinc sulfate, 2-3g/L sodium chloride, 0.05-0.2g/L sodium lauryl sulphate, 10-20g/L boron aqueous acid are electroplate liquid,
Electro-deposition method is utilized to carry out electroplating and get final product.
In described step (1), transparent substrates is silicate glasses, quartz glass, pottery or plastics.
Described electro-deposition method is direct current constant potential electro-deposition, direct current constant current electro-deposition, pulse electrodeposition or circulation
Volt-ampere electro-deposition.
The nano-cable transparent conductive film with copper as inner core that above-mentioned preparation method prepares.
The thickness of nickel dam or zinc layers is between 10-2000nm.
Copper nano-wire is utilized bar coating process to form one on clear glass (or flexible transparent plastic) surface by the present invention
The layer transparent conductive film with copper nano-wire as conductive network.Then, with corresponding nickel, zinc sheet metal as anode, with copper nanometer
Line transparent conductive film is negative electrode, in the electroplate liquid containing respective metal ion, makes metal ion with the form of metal simple-substance
It is deposited on the surface of copper nano-wire, thus forms the copper-nickel of " core-shell structure copolymer " structure, copper-zinc nano-cable transparent conductive film.Electricity
The thickness of sedimentary can be controlled by controlling electrodeposition condition during deposition.Such deposition layer is possible not only to significantly
Improve corrosion resistance and the electric conductivity of metal nanometer line based conductive film, it can be made still to have and ITO, FTO electro-conductive glass phase
The light transmittance matched in excellence or beauty.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of analogue copper nano wire substrates nickel dam；
Fig. 2 is transmission electron microscope (left) and the distribution diagram of element (right) of copper-nickel nano-cable transparent conductive film.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in further detail, but the protection model of the present invention
Enclose and be not limited thereto.
The preparation of embodiment 1 bronze medal-nickel (core-shell structure copolymer) nano-cable transparent membrane
The first step, synthesizes copper nano-wire transparent conductive film: will (diameter 100 nanometer, length 5-20 is micro-containing copper nano-wire
Rice) concentration be 3mg/mL alcohol suspension warp rod coating method (Rathmell A R, Wiley B J. The
synthesis and coating of long, thin copper nanowires to make flexible,
transparent conducting films on plastic substrates. Advanced Materials, 2011,
23 (41): 4798-4803) transparent substrates (quartz glass, 2 millimeters thick, 5 × 5cm it are coated in2) surface, form one layer and receive with copper
Rice noodle is the transparent conductive film of conductive network；By the above-mentioned transparent conductive film drying at room temperature with copper nano-wire as conductive network
Put into after 30 minutes in tube furnace, process 30 minutes at a temperature of 200 DEG C in the hydrogen gas stream, take when temperature is down to room temperature
Go out, i.e. obtain copper nano-wire transparent conductive film；The light transmittance of prepared copper nano-wire transparent conductive film is 60-95%, side
Block resistance is less than 800 ohm.
Second step, copper nano-wire substrates cable jacket (nickel dam): with metal nickel sheet as anode, transparent with copper nano-wire
Conductive film is negative electrode, with containing 60g/L six hydration nickel sulfate, 3g/L sodium chloride, 0.1g/L sodium lauryl sulphate, 20g/
L boron aqueous acid is electroplate liquid, utilize constant potential electrodeposition process under the driving of the DC source of 4 volts, through the electricity of 3 seconds
Deposition, at the compact metal nickel shell of one layer of 30 nanometer thickness of surface electro-deposition of copper nano-wire, thus can obtain high-quality Cu-
Ni(core-shell structure copolymer) nano-cable thin film, the thickness of cable jacket can be regulated and controled by the length adjusting electrodeposition time, and Fig. 1 is for being somebody's turn to do
The simulation schematic diagram of step, Fig. 2 is transmission electron microscope (left) and the distribution diagram of element (right) of product, as shown in Figure 2, obtained
A diameter of 160 nanometers of copper-nickel (core-shell structure copolymer) nano-cable, wherein a diameter of 100 nanometers of copper inner core, the thickness of nickel shell is
30 nanometers.
Embodiment 2 Cu-Zn(core-shell structure copolymer) preparation of nano-cable transparent membrane
The first step, synthesizes copper nano-wire transparent conductive film: will (diameter 100 nanometer, length 5-20 is micro-containing copper nano-wire
Rice) concentration be 3mg/mL alcohol suspension warp rod coating technology be coated in transparent substrates (quartz glass, 2 millimeters thick, 5 ×
5cm2) surface, form one layer of transparent conductive film with copper nano-wire as conductive network；By above-mentioned with copper nano-wire for conduction
The transparent conductive film drying at room temperature of network was put in tube furnace after 30 minutes, processed in the hydrogen gas stream at a temperature of 200 DEG C
30 minutes, take out when temperature is down to room temperature, i.e. obtain copper nano-wire transparent conductive film；Prepared copper nano-wire is transparent
The light transmittance of conductive film is 60-95%, and square resistance is less than 800 ohm.
Second step, copper nano-wire substrates cable jacket (zinc layers): with metal zinc metal sheet as anode, transparent with copper nano-wire
Conductive film is negative electrode, utilize constant potential electrodeposition process under the effect of the DC source that voltage is 3.8 volts, containing 50g/L
Zinc sulfate, in 2g/L sodium chloride, 0.1g/L sodium lauryl sulphate, 12g/L boron aqueous acid, sinks through the electricity of 15 seconds
Long-pending, form layer of metal zinc can on the surface of metal nanometer line, thus obtain Cu-Zn(core-shell structure copolymer) nano-cable thin film, cable
The thickness of shell can be controlled by the length adjusting electrodeposition time.
By said method, light transmittance can be obtained more than 65%, square resistance copper-nickel less than 30 ohm, copper-zinc (core-
Shell) nano-cable transparent conductive film material.Owing to metallic nickel, zinc have good corrosion resistance, so the copper obtained-
Nickel, the nickel of copper-zinc (core-shell structure copolymer) nano-cable, zinc can play good corrosion resistant effect.
Claims (8)
1. the preparation method of the nano-cable transparent conductive film with copper as inner core, it is characterised in that comprise the steps:
(1) synthesis copper nano-wire transparent conductive film: by diameter 60-100nm, the copper nano-wire of length 5-20 μm is dispersed in dehydrated alcohol
Middle formation copper nano-wire alcohol suspension, alcohol suspension warp rod coating method is coated in the surface of transparent substrates, is dried, hydrogen
Stream processes, and obtains copper nano-wire transparent conductive film；
(2) at copper core surface plated metal outer shell: with corresponding metal or graphite as anode, thin with copper nano-wire electrically conducting transparent
Film is negative electrode, with the aqueous solution of corresponding metal sulfate as electroplate liquid, utilizes electro-deposition method to carry out electroplating and get final product.
The preparation method of the nano-cable transparent conductive film with copper as inner core the most according to claim 1, its feature exists
In, in step (2), described metal shell layer is nickel dam or zinc layers.
The preparation method of the nano-cable transparent conductive film with copper as inner core the most according to claim 2, its feature exists
In, during electroless nickel layer, the process of step (2) is: with metallic nickel or graphite as anode, with copper nano-wire transparent conductive film as the moon
Pole, with containing 10-240g/L six hydration nickel sulfate, 2-3g/L sodium chloride, 0.05-0.2g/L sodium lauryl sulphate, 10-
20g/L boron aqueous acid is electroplate liquid, utilizes electro-deposition method to carry out electroplating and get final product；During electro-galvanized layer, the process of step (2)
For: with zinc sheet metal or graphite as anode, with copper nano-wire transparent conductive film as negative electrode, with containing 20-180g/L zinc sulfate,
2-3g/L sodium chloride, 0.05-0.2g/L sodium lauryl sulphate, 10-20g/L boron aqueous acid are electroplate liquid, utilize electricity
Deposition process carries out electroplating and get final product.
The preparation method of the nano-cable transparent conductive film with copper as inner core the most according to claim 1, its feature exists
In, in described step (1), the concentration of copper nano-wire alcohol suspension is 2-8mg/mL.
The preparation method of the nano-cable transparent conductive film with copper as inner core the most according to claim 1, its feature exists
In, in described step (1), transparent substrates is silicate glasses, quartz glass, pottery or plastics.
The preparation method of the nano-cable transparent conductive film with copper as inner core the most according to claim 1, its feature exists
In, described electro-deposition method is direct current constant potential electro-deposition, direct current constant current electro-deposition, pulse electrodeposition or cyclic voltammetric electricity
Deposition.
7. the nano-cable electrically conducting transparent with copper as inner core utilizing the arbitrary described preparation method of claim 1 to 6 to prepare is thin
Film.
Nano-cable transparent conductive film with copper as inner core the most according to claim 7, it is characterised in that metal shell
The thickness of layer is between 10-2000nm.
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Families Citing this family (5)
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| CN105483795B (en) * | 2016-01-21 | 2017-12-05 | 广州中国科学院先进技术研究所 | A kind of method that compound copper nano-wire is prepared using underpotential deposition technology |
| CN108206069B (en) * | 2017-06-22 | 2019-07-30 | 中国科学院福建物质结构研究所 | A kind of transparent conductive film and preparation method thereof prepared using tin net as template |
| CN109961871B (en) * | 2018-08-15 | 2020-09-15 | 浙江光达电子科技有限公司 | Slurry for forming transparent conductor by silk-screen sintering and application |
| CN110824804B (en) * | 2019-12-16 | 2022-08-02 | 哈尔滨工业大学 | Flexible electrochromic film and preparation method thereof |
| CN112992422B (en) * | 2021-02-07 | 2022-07-26 | 哈尔滨工业大学 | Preparation method of copper-gold alloy nanowire flexible transparent conductive film |
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| CN1966779A (en) * | 2005-11-17 | 2007-05-23 | 中国科学院兰州化学物理研究所 | Process for making Ni-Cu-Ag multilayer film |
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| EP2704156A1 (en) * | 2011-04-28 | 2014-03-05 | Fujifilm Corporation | Dispersion liquid containing metal nanowires, and conductive film |
| CN103878384A (en) * | 2014-02-28 | 2014-06-25 | 江苏大学 | Core-shell structure Cu-based nanowire of composite Ni and Co and preparation method of core-shell structure Cu-based nanowire |
| CN104134484A (en) * | 2014-07-31 | 2014-11-05 | 中国电子科技集团公司第五十五研究所 | Flexible transparent conductive film based on silver nanowires and preparation method |
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| CN1966779A (en) * | 2005-11-17 | 2007-05-23 | 中国科学院兰州化学物理研究所 | Process for making Ni-Cu-Ag multilayer film |
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| EP2704156A1 (en) * | 2011-04-28 | 2014-03-05 | Fujifilm Corporation | Dispersion liquid containing metal nanowires, and conductive film |
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