CN108374187A - A kind of high current-carrying compound wire of carbon nano tube/copper and preparation method thereof - Google Patents
A kind of high current-carrying compound wire of carbon nano tube/copper and preparation method thereof Download PDFInfo
- Publication number
- CN108374187A CN108374187A CN201810290246.5A CN201810290246A CN108374187A CN 108374187 A CN108374187 A CN 108374187A CN 201810290246 A CN201810290246 A CN 201810290246A CN 108374187 A CN108374187 A CN 108374187A
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- Prior art keywords
- carbon nano
- copper
- nano tube
- high current
- preparation
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4885—Wire-like parts or pins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/49—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions wire-like arrangements or pins or rods
Abstract
The present invention relates to high current-carrying compound wire of a kind of carbon nano tube/copper and preparation method thereof, which includes mainly the carbon nano-tube film electroplating technology based on vacuum aided, and electroplating technology is subdivided into two steps of seed layer and conventional plating；Uniform, fine and close and non-oxidation copper carbon nano tube/copper composite material can be prepared using this technique, the advantages that conducting wire being prepared into based on this composite processing is conductive good, and current-carrying capability is high.
Description
Technical field
The present invention relates to high current-carrying compound wires of a kind of carbon nano tube/copper and preparation method thereof, and in particular to a kind of big electricity
The nano combined conducting wire and preparation method thereof for flowing the copper and carbon nanotube composition of current-carrying capability, belongs to field of nanometer material technology.
Background technology
In recent decades, with the progress of semi-conductor industry process technique, the size of transistor is smaller and smaller, unit area
The transistor size integrated on chip is more and more, causes the power demand of chip higher and higher.High-power chip power supply mesh
Preceding to be mainly powered by copper conductor, when transistor size reduces, the size of copper conductor is also gradually reducing, and limits core
The lasting promotion of piece power.Foreign study mechanism is proposed carbon nanotube and copper being prepared into uniform composite material, be received by carbon
Mitron limits the electromigration on copper atom crystal boundary and surface in polycrystalline copper conductor, makes 106 Acm-2s of its current-carrying capability from fine copper
6.3 × 108 Acm-2 are promoted to, up to 100 times of current-carrying capability is promoted, and conductivity is expected to be used as not close to fine copper
Carry out high-power die power supply candidate material.It is compound that foreign study personnel mainly obtain above-mentioned carbon nano tube/copper using two-step method
Conducting wire：First, carbon nanotube is prepared into film and is soaked in the organic solution of copper and form seed layer.Secondly, by above-mentioned place
The carbon nano tube/copper seed thin film managed carries out plating until copper is stuffed entirely with carbon nano-tube film in water phase using low current
Gap form uniform compound phase.However, studies in China personnel but often fail when repeating the above results, main cause exists
In being difficult to form uniform seed layer in carbon nano-tube film, and with the progress of electroplating technology, carbon is received by soaking technology
Hole inside mitron/copper compound phase is gradually reduced, and is caused electroplate liquid to enter inside carbon nano tube/copper compound phase and is become difficult,
To be mainly electroplated on its surface.
Invention content
The purpose of the present invention is to provide high current-carrying compound wire of a kind of carbon nano tube/copper and preparation method thereof, this method
Be so that copper ion is formed uniform seed layer in carbon nano tube/copper film under vacuum aided, and
Ensure that electroplate liquid can easily overcome the resistance into carbon nano tube/copper internal void in follow-up low current electroplating process, into
Enter carbon nano tube/copper laminated film internal void, eventually forms uniform carbon nano tube/copper compound wire, show high current
Current-carrying capability, relative to technology path disclosed in tradition, technical solution provided by the invention is more stable and reliable.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of the high current-carrying compound wire of carbon nano tube/copper, it is characterised in that steps are as follows：
Step 1, carbon nano-tube film is placed in acetone and isopropanol and removes degreasing, catalyst granules, juxtaposition are removed in diluted acid
It is dried in baking oven；
Step 2, by step 1, treated that carbon nano-tube film is cut into suitable shape, is positioned over and is connected with the flat of vacuum pump
Bottom funnel bottom, and so that it is fitted closely with hopper base holding using ethanol in proper amount；
Step 3, vacuum pump is opened, the Buchner filter in step 2 is added in the acetonitrile solution containing copper ion, is made containing copper ion
Acetonitrile solution under vacuum penetrate carbon nano-tube film, add the organic solution containing copper ion as needed, keep
It filters；
Step 4, after the organic solvent in step 3 is drained completely, vacuum pump is continued on, the cathode of electroplating device is received with carbon
Mitron film connects, and the anode of electroplating device is connect with pure copper sheet, and is added in Buchner filter and contains the aqueous electricity of copper ion
Plating solution completes the electroplating technology of copper, forms carbon nano tube/copper laminated film；
Step 5, it by the carbon nano tube/copper laminated film in step 4, is initially positioned under inert atmosphere and handles, be placed in containing hydrogen
Environment in reduction treatment；
Step 6, the carbon nano tube/copper laminated film in step 5 is processed into the conducting wire of width suitable by focused ion beam.
In step 1, the growth of floating method may be used in the carbon nano-tube film, includes the carbon nanotube for growth of floating
Self-supporting film, vacuum filtration obtain carbon nano-tube film or can spinning carbon nano pipe array prepare carbon nano-tube film.
In step 1, the diluted acid can be arbitrary group of dilute hydrochloric acid, dilute sulfuric acid, dust technology or these three diluted acids
It closes.
In step 3, a concentration of 1-10mM of copper ion acetonitrile solution.
In step 3, the vacuum degree remains 10-20 KPa；During subsequent suction filtration, when needing to keep filtering
A length of 30-60min.
In step 4, it is 50 KPa-100 KPa that pressure is kept after vacuum pump is opened；In subsequent electroplating process, protect
It is 1-5 mAcm-2 to hold electroplating current.
In steps of 5, the inert atmosphere can be nitrogen or argon gas.
In steps of 5, selection is handled under the conditions of 200-300 DEG C in inert gas, and handling duration is 2-4 hours；
In subsequent reduction treatment process, the temperature of atmosphere of hydrogen is 200-250 DEG C, and the density of hydrogen is 100-250 sccm.
The carbon nano tube/copper compound wire prepared using the present invention, the wherein content of copper are the 40-60% of mass fraction.
Beneficial effects of the present invention are as follows：
The preparation method of the present invention is the pressure generated using vacuum aided, allows the solution containing copper ion more easily
Into the inside of carbon nano-tube film, empty nucleating layer evenly is formed, while being electroplated using the low current of vacuum aided, it can be with
Make the compound phase of carbon nano tube/copper formation evenly；The compound wire being prepared using the present invention, compound phase is uniform, fine and close,
With the current carrying capability with the analogous conductivity of copper and an order of magnitude higher than copper.
Description of the drawings
Fig. 1 is the device and assembling schematic diagram of carbon nano-tube film nucleation stage used by the embodiment of the present invention 1.
Fig. 2 is the device and assembling schematic diagram of low current electroplating technology used by the embodiment of the present invention 1.
In figure：1 is Buchner filter, and 2 be copper ion acetonitrile solution, and 3 be vacuum buffer equipment, and 4 connect for vacuum pump, and 5 are
Carbon nano-tube film, 6 be electroplating cathode, and 7 be galvanic anode, and 9 be copper ion aqueous solution.
Specific implementation mode
The present invention is described in detail in conjunction with specific embodiments.The experimental method for the actual conditions being not specified in example, usually
According to the condition described in normal condition and handbook, or according to the condition proposed by manufacturing firm's specification.
Embodiment 1
A kind of specific embodiment of the preparation method of the high current-carrying compound wire of carbon nano tube/copper, carries out in accordance with the following steps：
It is big to be cut into 2 inches of Buchner filters by the first step for the carbon nano-tube film that Suzhou Creative-carbon Nanotechnology Co., Ltd. produces
Film is placed in analytically pure acetone and impregnates and heat 50 DEG C by small area, keeps 30 min, takes out.It is subsequently placed at analysis
It is impregnated in pure ethyl alcohol and heats 80 DEG C, 30 min of holding take out, and using baking oven in 75 DEG C of drying.Film after drying is set
It is heated to 75 DEG C in the dilute hydrochloric acid of a concentration of 0.2 M, and keeps 60 min.It repeats dilute hydrochloric acid process 3 times, is put into after taking-up true
Empty baking oven is dried for standby in 80 DEG C.
Above-mentioned processed carbon nano-tube film is placed in 2 inches of Buchner filter by second step, to keep the two close
Fitting infiltrates carbon nano-tube film using a small amount of ethyl alcohol.
Third walks, using device as shown in Figure 1 and assembly method, by the second containing a concentration of 2.75 mM of copper acetate
Nitrile solution pours into Buchner filter, and it is 10-20 KPa to open vacuum pump and keep pressure, and solution is made to be completed through carbon nano-tube film
The acetonitrile solution of copper acetate is added in nucleation process as needed during paying attention to, keep 45 min of suction filtration process.
4th step, according to fig. 2 shown in device and assembly method, the copper sulfate solution of a concentration of 5 mM is added, and
It uses current density to complete electroplating process for the electroplating technology of 2 mAcm-2, pays attention to mending copper-bath in electroplating process.
5th step, the film that completion is electroplated are dried under 80 DEG C of vacuum drying oven, the tubular type being placed under the conditions of pure argon
It is handled 3 hours for 250 DEG C in stove, the hydrogen that 150 sccm are then passed through under the conditions of 200 carries out reduction treatment.
6th step, film cut into the conducting wire that sectional dimension is 10 μm of 50 μ m using focused ion beam and are used to test.
Claims (10)
1. a kind of preparation method of the high current-carrying compound wire of carbon nano tube/copper, it is characterised in that steps are as follows：
Step 1, carbon nano-tube film is placed in acetone and isopropanol and removes degreasing, remove catalyst granules in diluted acid, and dry
It is dry；
Step 2, by step 1 treated carbon nano-tube film（5）It is cut into suitable shape, is positioned over and is connected with vacuum pump
（4）Buchner filter（1）Bottom, and so that it is fitted closely with hopper base holding using ethyl alcohol, while connecting vacuum buffer equipment
（3）；
Step 3, vacuum pump is opened（4）, by the acetonitrile solution containing copper ion（2）The Buchner filter described in step 2 is added
（1）, make the acetonitrile solution containing copper ion（2）Carbon nano-tube film is penetrated under vacuum（5）, add as needed containing
The organic solution of copper ion keeps filtering；
Step 4, after the organic solvent in step 3 is drained completely, vacuum pump is continued on（4）, by the cathode of electroplating device（6）
With carbon nano-tube film（5）Connection, by the anode of electroplating device（7）With pure copper sheet（8）Connection, and in Buchner filter（1）In plus
Enter containing copper ion Aqueous plating baths（9）, the electroplating technology of copper is completed, carbon nano tube/copper laminated film is formed；
Step 5, it by the carbon nano tube/copper laminated film in step 4, is initially positioned under inert atmosphere and handles, be placed in containing hydrogen
Environment in reduction treatment；
Step 6, the carbon nano tube/copper laminated film after reduction treatment in step 5 is processed into conducting wire by focused ion beam.
2. the preparation method of the high current-carrying compound wire of carbon nano tube/copper according to claim 1, it is characterised in that：In step
In rapid 1, the carbon nano-tube film includes float the carbon nanotube self-supporting film grown, the carbon nanometer of vacuum filtration acquisition
Pipe film or can spinning carbon nano pipe array prepare carbon nano-tube film.
3. the preparation method of the high current-carrying compound wire of carbon nano tube/copper according to claim 1, it is characterised in that：It is described
Diluted acid be dilute hydrochloric acid or dilute sulfuric acid or dust technology or the arbitrary combination of these three diluted acids.
4. the preparation method of the high current-carrying compound wire of carbon nano tube/copper according to claim 1, it is characterised in that：In step
In rapid 3, a concentration of 1-10 mM of the copper ion acetonitrile solution.
5. the preparation method of the high current-carrying compound wire of carbon nano tube/copper according to claim 1, it is characterised in that：In step
In rapid 3, the vacuum degree remains 10-20 KPa；During subsequent suction filtration, a length of 30- when needing to keep filtering
60min。
6. the preparation method of the high current-carrying compound wire of carbon nano tube/copper according to claim 1, it is characterised in that：In step
In rapid 4, vacuum pump keeps pressure after opening be 50 KPa-100 KPa；In subsequent electroplating process, holding electroplating current is
1-5 mA·cm-2。
7. the preparation method of the high current-carrying compound wire of carbon nano tube/copper according to claim 1, it is characterised in that：In step
In rapid 5, the inert atmosphere is nitrogen or argon gas.
8. the preparation method of the high current-carrying compound wire of carbon nano tube/copper according to claim 1, it is characterised in that：In step
It in rapid 5, selects under the conditions of 200-300 DEG C, is handled in inert gas, handling duration is 2-4 hours.
9. the preparation method of the high current-carrying compound wire of carbon nano tube/copper according to claim 1, it is characterised in that：In step
In rapid 5, in reduction treatment process, the temperature of atmosphere of hydrogen is 200-250 DEG C, and the density of hydrogen is 100-250
sccm。
10. according to the high current-carrying composite guide of carbon nano tube/copper that preparation method is prepared described in claim 1-9 any one
Line, it is characterised in that：In the high current-carrying compound wire of carbon nano tube/copper, the content of copper is the 40-60% of mass fraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810290246.5A CN108374187A (en) | 2018-03-30 | 2018-03-30 | A kind of high current-carrying compound wire of carbon nano tube/copper and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810290246.5A CN108374187A (en) | 2018-03-30 | 2018-03-30 | A kind of high current-carrying compound wire of carbon nano tube/copper and preparation method thereof |
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| CN108374187A true CN108374187A (en) | 2018-08-07 |
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| CN201810290246.5A Pending CN108374187A (en) | 2018-03-30 | 2018-03-30 | A kind of high current-carrying compound wire of carbon nano tube/copper and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109136986A (en) * | 2018-10-29 | 2019-01-04 | 河南工程学院 | A kind of preparation method of nano nickel/array carbon nano tube composite material |
| CN112301394A (en) * | 2020-10-30 | 2021-02-02 | 西北工业大学 | Plating cavity capable of improving uniformity of electroplated layer on inner surface of ring-shaped piece |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101976594A (en) * | 2010-08-31 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite conductor application of carbon nano tube fiber and preparation method thereof |
| CN102140668A (en) * | 2011-03-10 | 2011-08-03 | 上海交通大学 | Optimization method for carbon nanotube and metal copper composite electroplating process |
| CN105913972A (en) * | 2016-06-13 | 2016-08-31 | 苏州捷迪纳米科技有限公司 | Preparation method of carbon nanotube composite wire |
-
2018
- 2018-03-30 CN CN201810290246.5A patent/CN108374187A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101976594A (en) * | 2010-08-31 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite conductor application of carbon nano tube fiber and preparation method thereof |
| CN102140668A (en) * | 2011-03-10 | 2011-08-03 | 上海交通大学 | Optimization method for carbon nanotube and metal copper composite electroplating process |
| CN105913972A (en) * | 2016-06-13 | 2016-08-31 | 苏州捷迪纳米科技有限公司 | Preparation method of carbon nanotube composite wire |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109136986A (en) * | 2018-10-29 | 2019-01-04 | 河南工程学院 | A kind of preparation method of nano nickel/array carbon nano tube composite material |
| CN109136986B (en) * | 2018-10-29 | 2020-05-22 | 高彪峰 | Preparation method of nano nickel/array carbon nanotube composite material |
| CN112301394A (en) * | 2020-10-30 | 2021-02-02 | 西北工业大学 | Plating cavity capable of improving uniformity of electroplated layer on inner surface of ring-shaped piece |
| CN112301394B (en) * | 2020-10-30 | 2022-05-24 | 西北工业大学 | Plating cavity capable of improving uniformity of electroplated layer on inner surface of ring-shaped element |
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Application publication date: 20180807 |