CN101003909A - Electrochemical combined deposition method for preparing structure of composite membrane of Nano carbon tube - metal - Google Patents
Electrochemical combined deposition method for preparing structure of composite membrane of Nano carbon tube - metal Download PDFInfo
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Abstract
This invention discloses a method for preparing carbon nanotube-metal composite film structure by electrochemical-combined deposition. The method comprises: preparing electrophorectic solution of stably dispersed carbon nanotubes after purification, shearing and dispersion, applying a voltage onto the electrodes to deposit a uniform layer of carbon nanotube film onto the substrate, placing the film in the electroplating solution, and forming a metal conductive film within the intertube microstructure by electrochemical method. The electrophorectic solution comprises carbon nanotubes, electrophorectic dispersing agent and charge auxiliary salt for charge decoration. This invention reduces the contact resistance between metal and carbon nanotubes, thus can fulfill the excellent electricity and heat conductivity of carbon nanotubes, and can improve the bonding strength of carbon nanotubes and conductive substrate. This invention has good compatibility with fine processing, and has such advantages as simple process, large scale preparation, controllable operation, and high efficiency, and low cost.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of nano material, specifically, is the method that a kind of electrochemical combined deposition prepares structure of composite membrane of Nano carbon tube-metal.
Background technology
Carbon nanotube has excellent electrology characteristic, aspect enhancing conduction and the heat conductivility significant advantage being arranged, therefore, is having important and application prospects aspect the high-performance electronic device application especially.Yet, because carbon nanotube is a kind of nanostructure of accurate one dimension form, there is higher surface energy and is difficult for the dispersive problem, need it to be combined with existing device material and technology, thereby realize using effectively by special preparation method.In the application of many electron devices, carbon nanotube need be formed certain film or microstructure, but not form effective and reliable technology of preparing at present as yet, so the research of this respect also becomes the concentrated research of present various countries scholar focus.
The method that forms at present carbon nano-tube film mainly is divided into two big classes: become embrane method after direct growth method and the processing.The former mainly adopts the chemical vapor deposition (CVD) preparation method, has the producing apparatus costliness, and the growth temperature height can't obtain shortcomings such as the single high quality carbon of structure pipe.Handle the back become embrane method mainly to drip to be coated with, to revolve (spray) be coated with, soak draw, several different methods such as self-assembly, silk-screen, electrophoresis, composite plating, the characteristics of these methods are earlier through purification, shearing, dispersion treatment with isolating carbon pipe, add the other media material then, mix forming even carbon pipe solution, select aforesaid method to form the carbon nanotube membrane structure again.Handle the selection problem that the back deposition method has been avoided the problem of high growth temperature and solved the carbon tubular construction, but except that composite plating, the carbon pipe that additive method obtains is to be combined on the substrate by electrostatic adhesion, so the bonding force of film and substrate is relatively poor.Owing to utilize the electrochemical reaction sedimentation mechanism, sedimentary carbon pipe of composite plating and metal matrix on every side and the bonding force of substrate make moderate progress, but because the dispersion of carbon pipe in plating bath difficulty, problem such as cause carbon pipe in the composite membrane to distribute and concentration is wayward.Electrophoretic deposition is the more a kind of carbon pipe film that adopts at present, and patent all has report both at home and abroad.Though this technology preferably resolves the dispersion and the concentration control problem of carbon pipe, owing to the electrostatic absorption principle that remains that utilizes, so on the bonding force of film, there is certain problem.
Find through literature search prior art, Chinese patent application number is 200510053855.1, in the patent of invention of " improve with electrophoretic deposition and make the inhomogeneity method of CNT (carbon nano-tube) electron source " by name, a kind of method of improving the thin-film electro conduction has been proposed, specifically be in electrophoresis solution, to add metal-salts such as the indium chloride of conduction usefulness or indium nitrate, after the deposition with film at 400 ℃ of sintering temperatures, indium hydroxide is converted into Indium sesquioxide when forming when making electrophoretic deposition, because Indium sesquioxide has electroconductibility and forms around the carbon pipe, can play the effect of fixed carbon pipe and increase electroconductibility.The bonding force of film and electroconductibility are that method by high temperature sintering solves in this technology, have obviously introduced the circumscribed problem of high temperature and substrate again.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, proposed the method that a kind of electrochemical combined deposition prepares the carbon nanotube membrane structure.The present invention has concentrated the advantage of electrophoresis and electroplating deposition, has reduced the contact resistance of metal and carbon pipe effectively, carbon pipe good conductive, heat conductivility can be fully used, and the binding ability of carbon pipe film and conductive substrates is improved.
The present invention is achieved by the following technical solutions, the carbon nanotube of the present invention after with purified, shearing, dispersion treatment is mixed with the carbon nano-tube electrophoretic solution of stable dispersion, contains carbon nanotube, electrophoresis dispersion agent in the electrophoresis solution and is used for the charged auxiliary salt that electric charge is modified.On electrode, apply voltage, on substrate, deposit layer of even carbon pipe film earlier, then above-mentioned film is put into electroplate liquid, by forming metal conductive film in the microstructure of electrochemical method between the carbon pipe by electrophoresis method.The present invention is by adjusting the carbon pipe concentration in the electrophoresis, strength of electric field and depositing time, the carbon pipe concentration in can controlling carbon nanotube-metal composite film.Current density and depositing time when adjust electroplating can be controlled the thickness of metal conductive film.By adjusting the number of times of electrophoresis-plating combined deposition, can adjust total composite membrane of Nano carbon tube-metal thickness.
The carbon nanotube that uses among the present invention can be many walls or single-wall structure.
Electrochemical method among the present invention is to electroplate or chemical plating method, and sedimentary metal is Ni, Cu, Ag, Au, Zn, Sn, FeNi etc.
Electrophoresis method among the present invention and electrochemical method, these two kinds of method combined depositions can be single deposition or repeated deposition repeatedly.
The carbon periosteum structure that the electrophoresis method deposition obtains among the present invention can be continuous film or graphic films structure.Electrophoresis method deposition pattern membrane structure preferred methods is: select for use acetone as electrophoresis dispersion, the figure mask material is selected polyimide or negative photoresist for use.
The sedimentary basic parameter of electrophoresis method of the present invention is: the carbon nanotube weight percent concentration in the electrophoresis solution is: 0.05-1%, the electrophoresis dispersion agent is alcohols or ketone solution, being used for charged auxiliary salt can be magnesium nitrate, aluminum nitrate or magnesium chloride etc., preferably use magnesium nitrate, weight percent concentration is 0.1-0.5%, electrode cathode is a deposition substrate, and anode is a stainless steel sheet.Apply strength of electric field 5-20V/cm during electrophoretic deposition, the time is 2-10 minute.
Electrochemical method of the present invention, electroplate liquid can use conventional basic metal plating liquid, and the electroplating current density during deposition is 0.2A-2A/dm
2, the time is 2-5 minute.
The present invention combines the advantage of electrophoresis and electroplating deposition, remedied the deficiency of method separately, on substrate, alternately carry out electrophoresis and electroplating deposition, by the electrophoretic deposition carbon pipe film that at first formation is uniformly dispersed on substrate, concentration is controlled, then carry out electroplating deposition again, utilize and set up the metallic conduction connection in the microstructure of electrochemical reaction between the carbon pipe when electroplating, be embedded in the conductive metal film with making carbon pipe even compact.The sedimentary carbon pipe of the present invention film has that good dispersity, carbon pipe concentration are adjusted easily, gauge control is flexible, outstanding features such as tack is good, electroconductibility enhancing.The technology of the present invention and fine process have compatible preferably, can prepare various micrographics structures easily, have practicality characteristics such as apparatus and process is simple, controllability strong, large-area preparation, high efficiency, low cost, be suitable for high-performance electronic preparation of devices and application.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
1. cut-off directly is 40-60nm, and length is 5-10um, the multi-walled carbon nano-tubes 10mg after purification, shearing, dispersion treatment, magnesium nitrate 5mg, dehydrated alcohol 1266ml is mixed with carbon electrophoresis tube solution, then with ultrasonic 60 minutes of this solution, forms the aaerosol solution of favorable dispersity.
2. the negative electrode of the insulating substrate that adopts conductive metal thin plate or deposit conductive metal film during as deposition substrate material and electrophoretic deposition selects for use stainless steel substrates as the electrophoresis anode.Two electrodes are put into the container that fills electrophoresis liquid, and two electrode space 4cm apply the volts DS of 20V at the electrode two ends, and electrophoresis time is 10 minutes.
3. above-mentioned electrophoresis sample is taken out dry after, put into acidic copper electroplating solutions, still with deposition substrate as negative electrode, phosphorus copper plate is as anode, applying electroplating current density is 2A/dm
2, the time is 2 minutes.
By obtaining uniform carbon pipe/copper laminated film behind the aforesaid operations.Observe through field emission scanning electron microscope, the carbon pipe density in the film is higher, and the carbon pipe is evenly distributed in the deposition region, and interconnection formation reticulated structure, and carbon pipe and intermetallic do not have obvious hole, and the carbon pipe content in the X ray energy dispersion spectrum analysis film reaches 80%.
Embodiment 2
1. cut-off directly is 1-2nm, and length is 5-10um, the Single Walled Carbon Nanotube 5mg after purification, shearing, the dispersion treatment, magnesium nitrate 3mg, dehydrated alcohol 1266ml is mixed with carbon electrophoresis tube solution, then with ultrasonic 60 minutes of this solution, forms the aaerosol solution of favorable dispersity.
2. adopt silicon chip as base material, the surface sputtering depositing Ti by the chemical wet etching method, forms the Ti graphic structure as metal conducting layer.
With above-mentioned micrographics substrate as the electrophoresis negative electrode, stainless steel sheet is put into the container that fills electrophoresis liquid as anode with two electrodes, two electrode space 4cm apply the volts DS of 40V at the electrode two ends, electrophoresis time is 6 minutes.
4. after above-mentioned electrophoresis sample taking-up being dried, put into a watt nickel plating solution, as negative electrode, the nickel plate is as anode with the deposition substrate material, and applying electroplating current density is 1A/dm
2, the time is 3 minutes.
5. repeat 3,4 and can obtain carbon pipe and Ni compound micrographics structure after twice, field emission electron scanning electron microscopic observation, carbon pipe evenly are embedded in the Ni layer, and the carbon pipe content in X ray energy dispersion spectrum analysis film reaches 50%.
Embodiment 3
1. cut-off directly is 40-60nm, and length is 5-10um, the multi-walled carbon nano-tubes 5mg after purification, shearing, dispersion treatment, magnesium nitrate 5mg, acetone 1250ml is mixed with carbon electrophoresis tube solution, then with ultrasonic 60 minutes of this solution, forms the aaerosol solution of favorable dispersity.
2. adopt glass flake as the deposition substrate material, Cu/Ti is as metal conducting layer for the surface sputtering deposition.Spin-on polyimide forms the microstructure mask graph as the figure mask material behind the photoetching development on deposition substrate.
With above-mentioned micrographics substrate as the electrophoresis negative electrode, stainless steel sheet is put into the container that fills electrophoresis liquid as anode with two electrodes, two electrode space 4cm apply the volts DS of 80V at the electrode two ends, electrophoresis time is 3 minutes.
4. above-mentioned electrophoresis sample is taken out dry after, put into a watt nickel plating solution, still with the deposition substrate material as negative electrode, the nickel plate is as anode, applying electroplating current density is 0.2A/dm2, the time is 5 minutes.
5. repeat 3, can obtain carbon pipe/Ni micrographics structure after 4 three times, the field emission electron scanning electron microscopic observation, the micrographics surface coverage has uniform carbon pipe, part carbon pipe is embedded in the Ni layer, and part carbon pipe is exposed to micro-structure surface, analyzes through the energy dispersive spectrometer, carbon pipe content is 70% in the film, and this structure is applicable to field emission and animating electrode structure applications.
Claims (10)
1. an electrochemical combined deposition prepares the method for structure of composite membrane of Nano carbon tube-metal, it is characterized in that: the carbon nanotube after purified, shearing, the dispersion treatment is mixed with the carbon nano-tube electrophoretic solution of stable dispersion, contains carbon nanotube, electrophoresis dispersion agent in the electrophoresis solution and be used for the charged auxiliary salt that electric charge is modified; On electrode, apply voltage, on substrate, deposit layer of even carbon pipe film earlier, then above-mentioned film is put into electroplate liquid, by forming metal conductive film in the microstructure of electrochemical method between the carbon pipe by electrophoresis method.
2. electrochemical combined deposition as claimed in claim 1 prepares the method for carbon nanotube membrane structure, it is characterized in that: described carbon nanotube is single wall or multi-walled carbon nano-tubes.
3. electrochemical combined deposition as claimed in claim 1 prepares the method for carbon nanotube membrane structure, it is characterized in that: described electrophoresis method and electrochemical method, both combined depositions are single deposition or repeated deposition repeatedly.
4. prepare the method for carbon nanotube membrane structure as claim 1 or 3 described electrochemical combined depositions, it is characterized in that: described electrochemical method is to electroplate or chemical plating method, and sedimentary metal is a kind of among Ni, Cu, Ag, Au, Zn, Sn, the FeNi.
5. electrochemical combined deposition as claimed in claim 1 prepares the method for carbon nanotube membrane structure, it is characterized in that: described electrophoresis method, its sedimentary basic parameter is: the carbon nanotube weight percent concentration in the electrophoresis liquid is: 0.05-1%, being used for charged auxiliary salt is magnesium nitrate or magnesium chloride, and weight percent concentration is 0.1-0.5%; Electrophoresis applies strength of electric field 5-20V/cm, and the time is 3-10 minute.
6. electrochemical combined deposition as claimed in claim 5 prepares the method for carbon nanotube membrane structure, it is characterized in that: described to be used for charged auxiliary salt be magnesium nitrate.
7. electrochemical combined deposition as claimed in claim 1 prepares the method for carbon nanotube membrane structure, it is characterized in that: described electrophoresis dispersion agent is alcohols or ketone solution; Described electrode, its negative electrode are deposition substrate, and anode is a stainless steel sheet.
8. electrochemical combined deposition as claimed in claim 1 prepares the method for carbon nanotube membrane structure, it is characterized in that: described electrochemical method, its sedimentary processing parameter is: electroplate liquid uses conventional metal plating liquid, and the electroplating current density during deposition is 0.2A-2A/dm
2, the time is 2-5 minute.
9. electrochemical combined deposition as claimed in claim 1 prepares the method for carbon nanotube membrane structure, it is characterized in that: described by the sedimentary carbon pipe of electrophoresis method film, and be continuous film or graphic films structure.
10. electrochemical combined deposition as claimed in claim 9 prepares the method for carbon nanotube membrane structure, it is characterized in that: described electrophoresis method deposition pattern membrane structure, be specially: select for use acetone as electrophoresis dispersion, the figure mask material is selected polyimide or negative photoresist for use.
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| CN101255590B (en) * | 2008-04-03 | 2011-03-30 | 厦门大学 | Method for preparing carbon nano-tube/nano-platinum composite film |
| US8012585B2 (en) | 2008-02-01 | 2011-09-06 | Tsinghua University | Carbon nanotube composite film |
| CN102181912A (en) * | 2011-04-14 | 2011-09-14 | 上海交通大学 | Method for preparing nano polymer composite material based on electrophoretic deposition |
| US8158199B2 (en) | 2008-02-01 | 2012-04-17 | Tsinghua University | Method for making individually coated and twisted carbon nanotube wire-like structure |
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