CN102251278A - Controllable preparation method of monocrystal copper nanowires - Google Patents
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Abstract
The invention relates to a preparation method of copper nanowires and in particular relates to a controllable preparation method of high-yield monocrystal copper nanowires in a liquid-phase reduction manner. The controllable preparation method comprises the steps: firstly, mixing a divalent metal copper salt solution and ethylenediamine, and heating in a water bath to form a single and stable copper ion chelate compound; mixing a strong base solution with hydrazine hydrate, and preparing a reducing agent in the water bath at the same temperature; then transferring the two mixture solutions into a reaction vessel, fully stirring to reach a uniform state, covering well, and placing in the water bath at the same temperature for heating reaction to prepare the copper nanowires; and fishing out flaky copper nanowires floating on the upper layer of the solution, washing the flaky copper nanowires with deionized water and absolute ethyl alcohol in sequence three times, and drying at room temperature under an Ar gas protection condition to prepare the copper nanowires. The controllable preparation method provided by the invention has the advantages of simple process, low cost and high yield, and the prepared copper nanowires are of monocrystal structures, and have relatively smooth surfaces, uniform radial thickness, and controllable and more uniform length and diameter.
Description
Technical field
The present invention relates to the preparation method of copper nano-wire, the controlled method for preparing high yield single crystal Cu nano wire of especially a kind of liquid-phase reduction.
Background technology
As a kind of typical quasi-one-dimensional nanometer material, nano wire is because self small-size effect and structural anisotropy show many physics, chemical property that are different from the conventional blocks material; In the middle of numerous nano wires, metal nanometer line because of its metal properties as little/receive the construction unit of device and the aspects such as connection material between the unit and have potential application foreground, because copper has than better electroconductibility of aluminium and deelectric transferred performance, be beneficial to running frequency that improves device and the electric current that allows bigger density by (referring to document: 1. Hwang S T, Shim I, Lee K O, et al. J Mater Res, 1996,11:1051-1060; 2. Whitman C, Moslehi M N, Paranjpe A, et al. J Vac Sci Technol A, 1999,17:1893-1897; 3. Xia Y N, Yang P D, Sun Y G, et al. Adv Mater, 2003,15:353-389), thereby copper nano-wire has caused the extensive concern of industry; At present, the preparation method of copper nano-wire mainly contains vacuum vapor deposition (referring to document: 1. Liu Z W, Bando Y. Adv Mater, 2003,15:303-305), based on the solid phase reduction method of gas-solid reaction growth mechanism (referring to document: 1. Yen M Y, Chui C W, Hsia C H, et al. Adv Mater, 2003,15:235-237), template is (referring to document: 1. Motoyama M, Fukunaka Y, Tetsuo S, et al. J Electroanal Chem, 2005,584:84-91; 2. Gao T, Meng G W, Zhang J, et al. Appl Phys A:Mater Sci Process, 2001,73:251-254) and liquid phase reduction (referring to document: 1. Chang Y, Lye M L, Zeng H C. Langmuir, 2005,21:3746-3748; 2. Rathmell A R, Bergin S M, Hua Y L, et al. Adv Mater, 2010,22:3558-3563); Wherein, the mechanism of vacuum vapor deposition and solid phase reduction method is generally comparatively complicated, the condition harshness, and cost is higher, is not suitable for large-scale production; The template complex process need be removed template with thermal treatment or dissolution with solvents way usually, and easily established nanostructure be destroyed to some extent when removing template framework.
And liquid phase reduction generally flexibly, effectively and can the large-scale production copper nano-wire; Chang etc. (referring to document: 1. Chang Y, Lye M L, Zeng H C. Langmuir, 2005,21:3746-3748) introduced and a kind ofly (comprised NaOH solution, Cu (NO by regulating various materials
3)
2Solution, quadrol (EDA), hydrazine (H
2NNH
2)) concentration and volume, and parameters such as bath temperature, reaction times are reduced preparation copper nano-wire (about 40～50 μ m of length, the method for diameter about 90～120nm) in the aqueous solution; Rathmell etc. are (referring to document: 1. Rathmell A R, Bergin S M, Hua Y L, et al. Adv Mater, 2010,22:3558-3563) further adopt the method for Chang etc. to prepare an end and have particulate copper nano-wire (about 10 ± 3 μ m of length, diameter about 90 ± 10nm); Their preparation method's cost is lower, but mass production, but all come with some shortcomings, for the former, because processing parameter more (about 10), wayward and complex operation, and, change the wherein volume of any one material, to cause the variation that mixes other material actual concentration of back, and make above-mentioned processing parameter lose reference value, and cause the preparation process of copper nano-wire and form mechanism research complicated, in other words, the concentration of various materials and volume seemed inadvisable even unreliable as the way of processing parameter before their this handle mixed; For the latter, because the copper nano-wire radially general inhomogeneous and end of thickness has the copper particle, the popularization of its potential application is restricted, and, on the method that changes copper nano-wire length, Rathmell etc. adopt and reduce the reaction times, but this method is generally owing to reaction does not cause productive rate lower as yet fully, product also is not easy to separate from solution, in addition, in preparation process, just place water-bath to heat after Chang etc. and Rathmell etc. just simply will above-mentioned several materials mix and prepare copper nano-wire, this way may cause existing in the mixing solutions the various title complexs of cupric ion, as [Cu (OH)
4]
2-, [Cu (EDA) (OH)
2], [Cu (EDA)
2]
2+Deng (referring to document: 1. Chang Y; Lye M L, Zeng H C. Langmuir, 2005; 21:3746-3748), and finally cause occurring in the reduzate copper nano-wire that a copper particle or an end have copper particulate copper nano-wire or length, diameter inequality.
Summary of the invention
The objective of the invention is to solve present copper nano-wire preparation cost height, productive rate is low, complex process, homogeneity and poor controllability, and the copper nano-wire pattern is non-linear and be shortcoming such as polycrystalline structure, thereby provides that a kind of low cost, high yield, technology are simple, the preparation method of single crystal Cu nano wire that length and diameter are more even and controlled.
Technical scheme of the present invention is that single, the stable cupric ion inner complex that forms with divalent metal copper salt solution and quadrol Hybrid Heating is a presoma, mixed solution with highly basic and hydrazine hydrate is a reductive agent, mix parameters such as the concentration of the various materials in back and bath temperature by suitable adjusting, thus controlled preparation high yield single crystal Cu nano wire.
The preparation method of high yield single crystal Cu nano wire of the present invention is as follows:
1) determines to mix the concentration of the various materials in back, and select to mix the cumulative volume V of back solution
0, take by weighing divalent metal mantoquita and highly basic, and be dissolved in the deionized water respectively;
2) measure quadrol, it is splashed in the ready copper salt solution of step 1) and fully stir and obtain mixing solutions 1, make it to form single, stable cupric ion inner complex [Cu (EDA)
2]
2+Measure hydrazine hydrate, splash into it in ready strong base solution of step 1) and fully stir and obtain mixing solutions 2, after building mixing solutions 1 and mixing solutions 2 are placed the water-bath thermostatically heating simultaneously, the volume sum of mixing solutions 1 and mixing solutions 2 should be less than the cumulative volume V that mixes back solution
0
3) with step 2) mixing solutions 1 and the mixing solutions 2 that obtain change in the reaction vessel fully, and dripping deionized water, to make the cumulative volume of solution be V
0, build after fully shaking up and obtain mixing solutions 3, place and step 2 then) and the water-bath reacting by heating of uniform temp, the preparation copper nano-wire;
4) the sheet of copper nano wire that will swim in the solution upper strata is salvaged out, uses deionized water and absolute ethanol washing more than three times successively, promptly gets the product copper nano-wire; Can be in preparation process by the controlled preparation copper nano-wire of control reaction conditions;
5) copper nano-wire that step 4) is obtained was placed under the condition of room temperature and protection of inert gas 2 ~ 4 hours, promptly got the exsiccant copper nano-wire, with the quality of digital calculation balance weighing product, get final product the productive rate of copper nano-wire.
In step 1), described concentration is the cumulative volume V of the amount of substance of various materials than mixing back solution
0The amount of substance concentration that obtains; The described cumulative volume V that mixes back solution
0〉=5ml; Described divalent metal mantoquita is meant that mixing back concentration is the Cu (NO of 3 ~ 8mM
3)
2, CuCl
2Or CuSO
4Solid (analytical pure); Described highly basic is meant that mixing back concentration is NaOH or the KOH solid (analytical pure) of 5 ~ 15M.
In step 2) in, the massfraction of described quadrol is 99%, mixing back concentration is 0.02 ~ 0.25M; The massfraction of described hydrazine hydrate is 80%, and mixing back concentration is 5 ~ 80mM; The temperature of described constant temperature water bath heating is 40 ~ 80 ℃, and be 10 ~ 15min heat-up time.
In step 3), the time of described heating in water bath for reaction is 0.5 ~ 2 hour.
In step 4), described reaction conditions is meant the concentration and the bath temperature of divalent metal mantoquita, quadrol, highly basic, hydrazine hydrate; Described controlled length and the controllable diameter that is meant copper nano-wire, their scope is respectively 2～30 μ m and 50～160 nm.
In step 1), 3) and 4) in, described deionization resistivity of water is 18.2M Ω cm.
In step 5), described rare gas element is meant purity at the Ar gas more than 99%, and the precision of described digital calculation balance is not less than 0.1mg, and the productive rate of described copper nano-wire can reach more than 95%.
Utilize the length of copper nano-wire of method for preparing and the diameter can be by the control reaction conditions: the concentration (comprising divalent metal mantoquita, quadrol, highly basic, hydrazine hydrate), the bath temperature that mix the various materials in back be regulated and control; The prepared single crystal Cu nanowire surface of the present invention is smooth relatively, even thickness radially, length and controllable diameter and more even, be expected to be made into the copper nano-wire film and be expected to be applied to fields such as touch-screen, solar cell as the material that is connected between the construction unit of microelectronics and nano-device or the unit.
The present invention has done further improvement to the method for Chang etc., the concentration and the volume that replace mixing preceding various materials with the actual concentration of mixing the various materials in back, reduced the number of processing parameter (4 kinds of materials have reduced by 4 parameters), make preparation process simple, workable, in preparation process, the present invention mixes divalent metal copper salt solution and quadrol earlier, and in water-bath, preheat, make it to form single, stable cupric ion inner complex [Cu (EDA)
2]
2+Thereby guarantee to obtain the better copper nano-wire of homogeneity, in the present invention, the length of copper nano-wire and diameter can be by the control reaction conditionss: the concentration and the bath temperature that mix the various materials in back are regulated and control, the prepared copper nano-wire of the present invention is a single crystal structure, and its surface is smooth relatively, radially even thickness, length and diameter are more even, and purity height and productive rate can reach more than 95%.
Compare other preparation method, the invention has the advantages that: 1) device is simple, and the raw material cheapness is fit to large-scale production; 2) processing parameter is less, and technology is simple, effective; 3) with short production cycle; 4) productive rate height can reach more than 95%; 5) the copper nano-wire homogeneity is better; 6) copper nano-wire length and controllable diameter; 7) the copper nano-wire surface is smooth relatively, radially even thickness; 8) copper nano-wire is that single crystal structure and purity are higher.
Description of drawings
Fig. 1 is the metallography microscope photo of embodiment 1 prepared copper nano-wire;
Fig. 2 is the metallography microscope photo of embodiment 2 prepared copper nano-wires;
Fig. 3 is the metallography microscope photo of embodiment 3 prepared copper nano-wires;
Fig. 4 is the metallography microscope photo of embodiment 4 prepared copper nano-wires;
Fig. 5 is the transmission electron microscope photo (illustration is corresponding selected area electron diffraction photo) of embodiment 4 prepared copper nano-wires.
Embodiment
The invention will be further described in conjunction with the accompanying drawings below by embodiment.
Embodiment 1:
Determine to mix back Cu (NO
3)
2, EDA, NaOH, H
2NNH
2Concentration be respectively 5.3mM, 0.16M, 8.3M, 68.8mM, the cumulative volume that select to mix back solution is 30ml, takes by weighing Cu (NO
3)
2Solid and NaOH solid are dissolved in respectively in a certain amount of deionized water, measure quadrol and hydrazine hydrate, splash into Cu (NO respectively
3)
2Stir in solution and the NaOH solution and fully; place 60 ℃ of water-bath heating 10 minutes after building simultaneously; then they are changed in the glass reactor; and dripping deionized water, to make the cumulative volume of solution be 30ml; build after fully shaking up; placed 60 ℃ of water-bath reacting by heating 2 hours; the sheet of copper nano wire that swims in the solution upper strata is salvaged out; use deionized water and absolute ethanol washing more than three times successively; drying is 4 hours under room temperature and Ar gas shiled condition, and promptly getting mean diameter is that 80nm, mean length are the single crystal Cu nano wire of 6 μ m.With the quality of digital calculation balance weighing product, the productive rate that gets copper nano-wire is 95%.
Embodiment 2:
Determine to mix back Cu (NO
3)
2, EDA, NaOH, H
2NNH
2Concentration be respectively 5.3mM, 0.14M, 8.3M, 8.6mM, the cumulative volume that select to mix back solution is 30ml.Take by weighing Cu (NO
3)
2Solid and NaOH solid are dissolved in respectively in a certain amount of deionized water, measure quadrol and hydrazine hydrate, splash into Cu (NO respectively
3)
2Stir in solution and the NaOH solution and fully; place 60 ℃ of water-bath heating 15 minutes after building simultaneously; then they are changed in the glass reactor; and dripping deionized water, to make the cumulative volume of solution be 30ml; build after fully shaking up; placed 60 ℃ of water-bath reacting by heating 2 hours; the sheet of copper nano wire that swims in the solution upper strata is salvaged out; use deionized water and absolute ethanol washing more than three times successively; drying is 3 hours under room temperature and Ar gas shiled condition; promptly getting mean diameter is 120nm; mean length is the single crystal Cu nano wire of 13 μ m, and with the quality of digital calculation balance weighing product, the productive rate that gets copper nano-wire is 96%.
Embodiment 3:
Determine to mix back Cu (NO
3)
2, EDA, NaOH, H
2NNH
2Concentration be respectively 5.3mM, 0.03M, 13.3M, 8.6mM, the cumulative volume that select to mix back solution is 30ml, takes by weighing Cu (NO
3)
2Solid and NaOH solid are dissolved in respectively in a certain amount of deionized water.Measure quadrol and hydrazine hydrate, splash into Cu (NO respectively
3)
2Stir in solution and the NaOH solution and fully; place 50 ℃ of water-bath heating 12 minutes after building simultaneously; then they are changed in the glass reactor; and dripping deionized water, to make the cumulative volume of solution be 30ml; build after fully shaking up; placed 50 ℃ of water-bath reacting by heating 2 hours; the sheet of copper nano wire that swims in the solution upper strata is salvaged out; use deionized water and absolute ethanol washing more than three times successively; drying is 2 hours under room temperature and Ar gas shiled condition; promptly getting mean diameter is 160nm; mean length is the single crystal Cu nano wire of 23 μ m, and with the quality of digital calculation balance weighing product, the productive rate that gets copper nano-wire is 98%.
Embodiment 4:
Determine to mix back Cu (NO
3)
2, EDA, NaOH, H
2NNH
2Concentration be respectively 4.0mM, 0.04M, 8.1M, 6.5mM, the cumulative volume that select to mix back solution is 40ml.Take by weighing Cu (NO
3)
2Solid and NaOH solid are dissolved in respectively in a certain amount of deionized water.Measure quadrol and hydrazine hydrate, splash into Cu (NO respectively
3)
2Stir in solution and the NaOH solution and fully; place 60 ℃ of water-bath heating 10 minutes after building simultaneously; then they are changed in the glass reactor; and dripping deionized water, to make the cumulative volume of solution be 40ml; build after fully shaking up; placed 60 ℃ of water-bath reacting by heating 1.5 hours; the sheet of copper nano wire that swims in the solution upper strata is salvaged out; use deionized water and absolute ethanol washing more than three times successively; drying is 2 hours under room temperature and Ar gas shiled condition; promptly getting mean diameter is 60nm; mean length is the single crystal Cu nano wire of 15 μ m, and with the quality of digital calculation balance weighing product, the productive rate that gets copper nano-wire is 96%.
Claims (7)
1. the controllable method for preparing of a single crystal Cu nano wire, form by following steps:
1) determines to mix the concentration of the various materials in back, and select to mix the cumulative volume V of back solution
0, take by weighing divalent metal mantoquita and highly basic, and be dissolved in the deionized water respectively;
2) measure quadrol, it is splashed in the ready copper salt solution of step 1) and fully stir and obtain mixing solutions 1, make it to form single, stable cupric ion inner complex [Cu (EDA)
2]
2+Measure hydrazine hydrate, splash into it in ready strong base solution of step 1) and fully stir and obtain mixing solutions 2, after building mixing solutions 1 and mixing solutions 2 are placed the water-bath thermostatically heating simultaneously, the volume sum of mixing solutions 1 and mixing solutions 2 should be less than the cumulative volume V that mixes back solution
0
3) with step 2) mixing solutions 1 and the mixing solutions 2 that obtain change in the reaction vessel fully, and dripping deionized water, to make the cumulative volume of solution be V
0, build after fully shaking up and obtain mixing solutions 3, place and step 2 then) and the water-bath reacting by heating of uniform temp, the preparation copper nano-wire;
4) the sheet of copper nano wire that will swim in the solution upper strata is salvaged out, uses deionized water and absolute ethanol washing more than three times successively, promptly gets the product copper nano-wire;
5) copper nano-wire that step 4) is obtained was placed under the condition of room temperature and protection of inert gas 2 ~ 4 hours, promptly got the exsiccant copper nano-wire, with the quality of digital calculation balance weighing product, promptly got the productive rate of copper nano-wire.
2. the controllable method for preparing of a kind of single crystal Cu nano wire according to claim 1 is characterized in that: in step 1), the amount of substance that described concentration of mixing the various materials in back is various materials is than the cumulative volume V that mixes back solution
0The amount of substance concentration that obtains; The described cumulative volume V that mixes back solution
0〉=5ml; Described divalent metal mantoquita is meant that mixing back concentration is the Cu (NO of 3 ~ 8mM
3)
2, CuCl
2Or CuSO
4Solid (analytical pure); Described highly basic is meant that mixing back concentration is NaOH or the KOH solid (analytical pure) of 5 ~ 15M.
3. the controllable method for preparing of a kind of single crystal Cu nano wire according to claim 1 is characterized in that: step 2) in, the massfraction of described quadrol is 99%, mixing back concentration is 0.02 ~ 0.25M; The massfraction of described hydrazine hydrate is 80%, and mixing back concentration is 5 ~ 80mM; The temperature of described constant temperature water bath heating is 40 ~ 80 ℃, and be 10～15min heat-up time.
4. the controllable method for preparing of a kind of single crystal Cu nano wire according to claim 1 is characterized in that: in the step 3), the time of described heating in water bath for reaction is 0.5 ~ 2 hour.
5. the controllable method for preparing of a kind of single crystal Cu nano wire according to claim 1 is characterized in that: in step 4), the length of described copper nano-wire and controllable diameter, their scope are respectively 2～30 μ m and 50～160 nm.
6. the controllable method for preparing of a kind of single crystal Cu nano wire according to claim 1 is characterized in that: step 1), 3) and 4) in, described deionization resistivity of water is 18.2M Ω cm.
7. the controllable method for preparing of a kind of single crystal Cu nano wire according to claim 1, it is characterized in that: in step 5), described rare gas element is meant purity at the Ar gas more than 99%, and the precision of described digital calculation balance is not less than 0.1mg, and the productive rate of described copper nano-wire can reach more than 95%.
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| CN110355379A (en) * | 2019-07-31 | 2019-10-22 | 江苏大学 | A kind of difference draw ratio NANO CRYSTAL COPPER WIRE and its synthetic method |
| CN110385444A (en) * | 2019-07-31 | 2019-10-29 | 江苏大学 | A kind of method of NANO CRYSTAL COPPER WIRE and wet chemistry method preparation NANO CRYSTAL COPPER WIRE |
| CN110385444B (en) * | 2019-07-31 | 2022-06-21 | 江苏大学 | Nano copper wire and method for preparing nano copper wire by wet chemical method |
| CN110560702A (en) * | 2019-09-16 | 2019-12-13 | 上海交通大学 | method for preparing micron-sized single crystal copper powder at room temperature |
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