CN102251278B - Controllable preparation method of monocrystal copper nanowires - Google Patents
Controllable preparation method of monocrystal copper nanowires Download PDFInfo
- Publication number
- CN102251278B CN102251278B CN201110144380.2A CN201110144380A CN102251278B CN 102251278 B CN102251278 B CN 102251278B CN 201110144380 A CN201110144380 A CN 201110144380A CN 102251278 B CN102251278 B CN 102251278B
- Authority
- CN
- China
- Prior art keywords
- copper
- wire
- solution
- mixing
- copper nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
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 of preparing high yield monocrystal copper nanowires of especially a kind of liquid-phase reduction.
Background technology
As a kind of typical quasi-one-dimensional nanometer material, nano wire, due to self small-size effect and structural anisotropy, shows many physics, chemical property that are different from conventional blocks material; In the middle of numerous nano wires; metal nanometer line because of its metal properties as micro-/receive the construction unit of device and the aspects such as connecting material between unit and there is potential application foreground; because copper has than the better electroconductibility of aluminium and deelectric transferred performance; be beneficial to the electric current that improves the running frequency of device and allow larger 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), the solid phase reduction method based on gas-solid reaction growth mechanism is (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, and condition is harsh, and cost is higher, is not suitable for large-scale production; Template complex process, conventionally need to remove template by thermal treatment or dissolution with solvents way, and easily established nanostructure be destroyed to some extent when removing template framework.
And liquid phase reduction generally flexibly, effectively and can 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 a kind of by regulating various materials (to comprise NaOH solution, Cu (NO
3)
2solution, quadrol (EDA), hydrazine (H
2nNH
2)) concentration and volume, and the parameter such as bath temperature, reaction times is reduced and is prepared the method for copper nano-wire (length approximately 40～50 μ m, diameter 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 the copper nano-wire (length approximately 10 ± 3 μ ms, diameter 90 ± 10nm) of one end with particle, their preparation method's cost is lower, can produce in a large number, but all come with some shortcomings, for the former, due to processing parameter more (approximately 10), wayward and complex operation, and, change the wherein volume of any one material, by cause mix after the variation of other material actual concentration, make above-mentioned processing parameter lose reference value, and cause the preparation process of copper nano-wire and formation mechanism study complicated, in other words, the concentration of their this front various materials of mixing and volume seem inadvisable even unreliable as the way of processing parameter, for the latter, due to copper nano-wire radially general inhomogeneous the and one end of thickness with copper particle, may make the popularization of its potential application be restricted, and, changing in the method for copper nano-wire length, Rathmell etc. adopt and reduce the reaction times, but this method is generally because reaction causes productive rate lower not yet completely, product is also not easy to separate from solution, in addition, in preparation process, Chang etc. and Rathmell etc. are just placed in water-bath and heat and prepare copper nano-wire after just simply will above-mentioned several materials mixing, this way may cause existing in 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 reduzate that copper particle or one end are with the copper nano-wire of the copper nano-wire of copper particle or length, diameter inequality.
Summary of the invention
The object of the invention is to solve current copper nano-wire preparation cost high, productive rate is low, complex process, homogeneity and poor controllability, and copper nano-wire pattern is non-linear and be the shortcomings such as polycrystalline structure, thereby provide that a kind of low cost, high yield, technique are simple, the preparation method of length and the more even and controlled monocrystal copper nanowires of diameter.
Technical scheme of the present invention is that to take single, the stable copper ion chelated that divalent metal copper salt solution and quadrol Hybrid Heating form be presoma, the mixed solution of highly basic and hydrazine hydrate of take is reductive agent, the parameter such as the concentration of various materials and bath temperature after mixing by suitable adjusting, thereby controlled preparation high yield monocrystal copper nanowires.
The preparation method of high yield monocrystal copper nanowires of the present invention is as follows:
1) concentration of various materials after definite mixing, and selection mixes the cumulative volume V of rear solution
0, take divalent metal mantoquita and highly basic, and be dissolved in respectively in deionized water;
2) measure quadrol, splashed in the ready copper salt solution of step 1) and fully and stir and obtain mixing solutions 1, make it to form single, stable copper ion chelated [Cu (EDA)
2]
2+; Measure hydrazine hydrate, splashed in the ready strong base solution of step 1) and fully and stir and obtain mixing solutions 2, after building, mixing solutions 1 and mixing solutions 2 are placed in to water-bath thermostatically heating simultaneously, the cumulative volume V of solution after the volume sum of mixing solutions 1 and mixing solutions 2 should be less than and mix
0;
3) by step 2) mixing solutions 1 and the mixing solutions 2 that obtain proceed in reaction vessel completely, and to drip the cumulative volume that deionized water makes solution be V
0, after fully shaking up, build and obtain mixing solutions 3, be then placed in and step 2) and the water-bath reacting by heating of uniform temp, prepare copper nano-wire;
4) the sheet of copper nano wire that swims in solution upper strata is salvaged out, use successively deionized water and absolute ethanol washing more than three times, obtain product copper nano-wire; Can be by controlling the controlled copper nano-wire of preparing of reaction conditions in preparation process;
5) copper nano-wire step 4) being obtained is placed 2 ~ 4 hours under the condition of room temperature and protection of inert gas, obtains dry copper nano-wire, weighs the quality of product with digital calculation balance, gets final product to obtain the productive rate of copper nano-wire.
In step 1), the amount of substance that described concentration is various materials is than the cumulative volume V that mixes rear solution
0the amount of substance concentration obtaining; The cumulative volume V of solution after described mixing
0>=5ml; Cu (the NO that after described divalent metal mantoquita refers to and mixes, concentration is 3 ~ 8mM
3)
2, CuCl
2or CuSO
4solid (analytical pure); NaOH or KOH solid (analytical pure) that after described highly basic refers to and mixes, concentration is 5 ~ 15M.
In step 2) in, the massfraction of described quadrol is 99%, after mixing, concentration is 0.02 ~ 0.25M; The massfraction of described hydrazine hydrate is 80%, and after mixing, 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 refers to concentration and the bath temperature of divalent metal mantoquita, quadrol, highly basic, hydrazine hydrate; Described controlled refer to the length of copper nano-wire and diameter controlled, 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 refers to that purity is at more than 99% Ar gas, 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 prepared by aforesaid method and the diameter can be by controlling reaction conditions: after mixing, concentration (comprising divalent metal mantoquita, quadrol, highly basic, hydrazine hydrate), the bath temperature of various materials are regulated and controled; The prepared monocrystal copper nanowires surface of the present invention is relatively smooth, even thickness radially, length and diameter are controlled and more even, be expected to, as the construction unit of microelectronics and nano-device or the connecting material between unit, be made into copper nano-wire film and be expected to be applied to the fields such as touch-screen, solar cell.
The present invention has done further improvement to the method for Chang etc., the concentration and the volume that to mix the actual concentration of rear various materials, replace mixing front various materials, 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 first mixes divalent metal copper salt solution and quadrol, and preheat in water-bath, make it to form single, stable copper ion chelated [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 controlling reaction conditions: after mixing, concentration and the bath temperature of various materials are regulated and controled, the prepared copper nano-wire of the present invention is single crystal structure, and its surface is relatively smooth, radially even thickness, length and diameter are more even, and the high and productive rate of purity can reach more than 95%.
Compare other preparation method, the invention has the advantages that: 1) device is simple, raw material is cheap, is applicable to large-scale production; 2) processing parameter is less, and technique is simple, effective; 3) with short production cycle; 4) productive rate is high, can reach more than 95%; 5) copper nano-wire homogeneity is better; 6) copper nano-wire length and diameter are controlled; 7) copper nano-wire surface is relatively smooth, radially even thickness; 8) copper nano-wire is that single crystal structure and purity are higher.
Accompanying drawing explanation
Fig. 1 is the Metallograph of embodiment 1 prepared copper nano-wire;
Fig. 2 is the Metallograph of embodiment 2 prepared copper nano-wires;
Fig. 3 is the Metallograph of embodiment 3 prepared copper nano-wires;
Fig. 4 is the Metallograph 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
Below by embodiment, the invention will be further described by reference to the accompanying drawings.
Embodiment 1:
Determine and mix rear Cu (NO
3)
2, EDA, NaOH, H
2nNH
2concentration be respectively 5.3mM, 0.16M, 8.3M, 68.8mM, after select mixing, the cumulative volume of solution is 30ml, takes Cu (NO
3)
2solid and NaOH solid, be dissolved in respectively in a certain amount of deionized water, measures quadrol and hydrazine hydrate, splashes into respectively Cu (NO
3)
2in solution and NaOH solution and fully, stir; build and be placed in 60 ℃ of water-baths simultaneously and heat 10 minutes afterwards; then they are proceeded in glass reactor; and to drip the cumulative volume that deionized water makes solution be 30ml; after fully shaking up, build; be placed in 60 ℃ of water-bath reacting by heating 2 hours; the sheet of copper nano wire that swims in solution upper strata is salvaged out; use successively deionized water and absolute ethanol washing more than three times; under room temperature and Ar gas protective condition, be dried 4 hours, obtaining mean diameter is that 80nm, mean length are the monocrystal copper nanowires of 6 μ m.The quality that weighs product with digital calculation balance, the productive rate that obtains copper nano-wire is 95%.
Embodiment 2:
Determine and mix rear Cu (NO
3)
2, EDA, NaOH, H
2nNH
2concentration be respectively 5.3mM, 0.14M, 8.3M, 8.6mM, after select mixing, the cumulative volume of solution is 30ml.Take Cu (NO
3)
2solid and NaOH solid, be dissolved in respectively in a certain amount of deionized water, measures quadrol and hydrazine hydrate, splashes into respectively Cu (NO
3)
2in solution and NaOH solution and fully, stir, build and be placed in 60 ℃ of water-baths simultaneously and heat 15 minutes afterwards, then they are proceeded in glass reactor, and to drip the cumulative volume that deionized water makes solution be 30ml, after fully shaking up, build, be placed in 60 ℃ of water-bath reacting by heating 2 hours, the sheet of copper nano wire that swims in solution upper strata is salvaged out, use successively deionized water and absolute ethanol washing more than three times, under room temperature and Ar gas protective condition, be dried 3 hours, obtaining mean diameter is 120nm, mean length is the monocrystal copper nanowires of 13 μ m, with digital calculation balance, weigh the quality of product, the productive rate that obtains copper nano-wire is 96%.
Embodiment 3:
Determine and mix rear Cu (NO
3)
2, EDA, NaOH, H
2nNH
2concentration be respectively 5.3mM, 0.03M, 13.3M, 8.6mM, after select mixing, the cumulative volume of solution is 30ml, takes Cu (NO
3)
2solid and NaOH solid, be dissolved in respectively in a certain amount of deionized water.Measure quadrol and hydrazine hydrate, splash into respectively Cu (NO
3)
2in solution and NaOH solution and fully, stir, build and be placed in 50 ℃ of water-baths simultaneously and heat 12 minutes afterwards, then they are proceeded in glass reactor, and to drip the cumulative volume that deionized water makes solution be 30ml, after fully shaking up, build, be placed in 50 ℃ of water-bath reacting by heating 2 hours, the sheet of copper nano wire that swims in solution upper strata is salvaged out, use successively deionized water and absolute ethanol washing more than three times, under room temperature and Ar gas protective condition, be dried 2 hours, obtaining mean diameter is 160nm, mean length is the monocrystal copper nanowires of 23 μ m, with digital calculation balance, weigh the quality of product, the productive rate that obtains copper nano-wire is 98%.
Embodiment 4:
Determine and mix rear Cu (NO
3)
2, EDA, NaOH, H
2nNH
2concentration be respectively 4.0mM, 0.04M, 8.1M, 6.5mM, after select mixing, the cumulative volume of solution is 40ml.Take Cu (NO
3)
2solid and NaOH solid, be dissolved in respectively in a certain amount of deionized water.Measure quadrol and hydrazine hydrate, splash into respectively Cu (NO
3)
2in solution and NaOH solution and fully, stir, build and be placed in 60 ℃ of water-baths simultaneously and heat 10 minutes afterwards, then they are proceeded in glass reactor, and to drip the cumulative volume that deionized water makes solution be 40ml, after fully shaking up, build, be placed in 60 ℃ of water-bath reacting by heating 1.5 hours, the sheet of copper nano wire that swims in solution upper strata is salvaged out, use successively deionized water and absolute ethanol washing more than three times, under room temperature and Ar gas protective condition, be dried 2 hours, obtaining mean diameter is 60nm, mean length is the monocrystal copper nanowires of 15 μ m, with digital calculation balance, weigh the quality of product, the productive rate that obtains copper nano-wire is 96%.
Claims (5)
1. a controllable method for preparing for monocrystal copper nanowires, is comprised of following steps:
1) concentration of various materials after definite mixing, and selection mixes the cumulative volume V of rear solution
0, take divalent metal mantoquita and highly basic, and be dissolved in respectively in deionized water; The amount of substance that after described mixing, the concentration of various materials is various materials is than the cumulative volume V that mixes rear solution
0the amount of substance concentration obtaining; The cumulative volume V of solution after described mixing
0>=5ml; After described divalent metal mantoquita refers to and mixes, concentration is the analytically pure Cu (NO of 3 ~ 8mM
3)
2, CuCl
2or CuSO
4solid; After described highly basic refers to and mixes, concentration is the analytically pure NaOH of 5 ~ 15M or KOH solid.
2) measure quadrol, splashed in the ready copper salt solution of step 1) and fully and stir and obtain mixing solutions 1, make it to form single, stable copper ion chelated [Cu (EDA)
2]
2+; Measure hydrazine hydrate, splashed in the ready strong base solution of step 1) and fully and stir and obtain mixing solutions 2, after building, mixing solutions 1 and mixing solutions 2 are placed in to water-bath thermostatically heating simultaneously, the cumulative volume V of solution after the volume sum of mixing solutions 1 and mixing solutions 2 should be less than and mix
0; The massfraction of described quadrol is 99%, and after mixing, concentration is 0.02 ~ 0.25M; The massfraction of described hydrazine hydrate is 80%, and after mixing, concentration is 5 ~ 80mM; The temperature of described constant temperature water bath heating is 40 ~ 80 ℃, and be 10～15min heat-up time;
3) by step 2) mixing solutions 1 and the mixing solutions 2 that obtain proceed in reaction vessel completely, and to drip the cumulative volume that deionized water makes solution be V
0, after fully shaking up, build and obtain mixing solutions 3, be then placed in and step 2) and the water-bath reacting by heating of uniform temp, prepare copper nano-wire;
4) the sheet of copper nano wire that swims in solution upper strata is salvaged out, use successively deionized water and absolute ethanol washing more than three times, obtain product copper nano-wire;
5) copper nano-wire step 4) being obtained is placed 2 ~ 4 hours under the condition of room temperature and protection of inert gas, obtains dry copper nano-wire, weighs the quality of product with digital calculation balance, obtains the productive rate of copper nano-wire.
2. the controllable method for preparing of a kind of monocrystal copper nanowires according to claim 1, is characterized in that: in step 3), the time of described heating in water bath for reaction is 0.5 ~ 2 hour.
3. the controllable method for preparing of a kind of monocrystal copper nanowires according to claim 1, is characterized in that: in step 4), length and the diameter of described copper nano-wire are controlled, and their scope is respectively 2～30 μ m and 50～160 nm.
4. the controllable method for preparing of a kind of monocrystal copper nanowires according to claim 1, is characterized in that: step 1), 3) and 4) in, described deionization resistivity of water is 18.2M Ω cm.
5. the controllable method for preparing of a kind of monocrystal copper nanowires according to claim 1, it is characterized in that: in step 5), described rare gas element refers to that purity is at more than 99% Ar gas, 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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110144380.2A CN102251278B (en) | 2011-05-31 | 2011-05-31 | Controllable preparation method of monocrystal copper nanowires |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110144380.2A CN102251278B (en) | 2011-05-31 | 2011-05-31 | Controllable preparation method of monocrystal copper nanowires |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102251278A CN102251278A (en) | 2011-11-23 |
| CN102251278B true CN102251278B (en) | 2014-04-30 |
Family
ID=44978835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110144380.2A Expired - Fee Related CN102251278B (en) | 2011-05-31 | 2011-05-31 | Controllable preparation method of monocrystal copper nanowires |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102251278B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787347B (en) * | 2012-09-04 | 2015-10-21 | 上海师范大学 | The preparation method of a kind of super long copper nano wire and copper nano-wire conductive film |
| JP6440352B2 (en) * | 2012-12-14 | 2018-12-19 | ユニチカ株式会社 | Method for producing aggregate of fibrous copper fine particles |
| CN103212721B (en) * | 2013-05-10 | 2014-12-10 | 厦门大学 | Method for synthesizing copper nanowire under catalysis of nickel ions |
| CN104162657A (en) * | 2014-07-21 | 2014-11-26 | 江苏大学 | Super-long copper nanowire and preparing method thereof |
| CN104162680B (en) * | 2014-07-28 | 2016-06-29 | 江苏大学 | A kind of method of continuous synthesis copper nano-wire |
| CN104493195B (en) * | 2014-12-05 | 2017-04-12 | 北京化工大学 | Amorphous-state copper-platinum alloy nanotube and preparation method thereof |
| CN105712741A (en) * | 2015-12-25 | 2016-06-29 | 李�浩 | Preparation method of copper oxide nanowires |
| CN105817616A (en) * | 2016-05-30 | 2016-08-03 | 李�浩 | Copper nano-film loaded on substrate and preparation method and application thereof |
| CN106238747A (en) * | 2016-07-12 | 2016-12-21 | 中国石油化工股份有限公司 | The preparation method of a kind of multistage copper/nano cuprous oxide wire material and glucose sensor electrode based on this material |
| CN109420772A (en) * | 2017-08-25 | 2019-03-05 | Tcl集团股份有限公司 | Hud typed Cu/SnO2Nano wire, preparation method and application |
| CN108393501B (en) * | 2018-04-13 | 2020-11-06 | 哈尔滨理工大学 | Preparation method of Cu nanowire with controllable diameter |
| CN109742366A (en) * | 2019-01-09 | 2019-05-10 | 江西理工大学 | Modified tertiary cathode material of the copper fiber of a kind of high conductivity and preparation method thereof |
| 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843932A (en) * | 2006-03-03 | 2006-10-11 | 中山大学 | Localized growth method of nanowire array of copper oxide |
| CN101514486A (en) * | 2009-02-27 | 2009-08-26 | 华东师范大学 | Cu dendritic single crystalline nano material and preparation method thereof |
| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN101665984A (en) * | 2008-09-01 | 2010-03-10 | 西北工业大学 | Copper zinc alloy nanowire and preparation method thereof |
| CN102051675A (en) * | 2010-10-28 | 2011-05-11 | 中山大学 | Method for manufacturing CuO nanowire |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100374704B1 (en) * | 2000-04-07 | 2003-03-04 | 한국기계연구원 | A Process for Manufacturing Nano Copper- Alumina Complex Powder |
-
2011
- 2011-05-31 CN CN201110144380.2A patent/CN102251278B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843932A (en) * | 2006-03-03 | 2006-10-11 | 中山大学 | Localized growth method of nanowire array of copper oxide |
| CN101665984A (en) * | 2008-09-01 | 2010-03-10 | 西北工业大学 | Copper zinc alloy nanowire and preparation method thereof |
| CN101514486A (en) * | 2009-02-27 | 2009-08-26 | 华东师范大学 | Cu dendritic single crystalline nano material and preparation method thereof |
| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN102051675A (en) * | 2010-10-28 | 2011-05-11 | 中山大学 | Method for manufacturing CuO nanowire |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102251278A (en) | 2011-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102251278B (en) | Controllable preparation method of monocrystal copper nanowires | |
| WO2011071885A2 (en) | Compositions and methods for growing copper nanowires | |
| CN104646683B (en) | Controllable ball shape silver powder of a kind of granularity and preparation method thereof | |
| US10214656B2 (en) | Copper nanoparticles and production method for same, copper nanoparticle fluid dispersion, copper nanoink, copper nanoparticle preservation method, and copper nanoparticle sintering method | |
| Ye et al. | The Role of Cuprous Oxide Seeds in the One‐Pot and Seeded Syntheses of Copper Nanowires | |
| CN104148665B (en) | Preparation method of crystalized sliver powder | |
| JP2013503260A (en) | Method for controlling the morphology of metal nanowires | |
| CN104959626A (en) | Method for preparing multifunctional core-shell nano-material by using alloy to wrap copper nanowires | |
| CN106903324A (en) | A kind of preparation method of Graphene-nano silver dispersion | |
| TW201402252A (en) | Silver microparticles, method for producing same, and electronic device, conductive film, and conductive paste containing said silver microparticles | |
| CN105817645A (en) | Ultra-pure silver powder preparation method capable of controlling particle size | |
| CN106986553A (en) | A kind of preparation method of high efficiency coating silica crucible | |
| CN102974839B (en) | Method for preparing nanometer flake silver powder through chemical deposition | |
| CN104141120B (en) | Cuprous chemical copper plating solution | |
| TWI695848B (en) | Silver nanowire synthesis with (meth) acrylate based capping agents | |
| CN204111926U (en) | Polysilicon efficient silicon ingot seeding particle | |
| Sun et al. | Single-crystalline Ag2S hollow nanohexagons and their assembly into ordered arrays | |
| CN104607656B (en) | A kind of ultra-long silver nanowire and preparation method thereof | |
| Jiang et al. | Morphology-controlled synthesis of silver nanoparticles on the silicon substrate by a facile silver mirror reaction | |
| CN103624249B (en) | A kind of preparation method of high tap density silver powder | |
| Xi et al. | Novel enhancing impurities purification from silicon powder through metal-catalyzed chemical corrosion | |
| Ru et al. | Effects of ionic liquid additive [bmim] BF4 on fabrication of Ni-decorated Al2O3 powders by electroless deposition | |
| CN107522191A (en) | A kind of large-size high-quality graphene preparation method based on from limitation forming core growth | |
| Zheng et al. | Special fractal growth of dendrite copper using a hydrothermal method | |
| Gotoh et al. | Ga segregation during Czochralski-Si crystal growth with Ge codoping |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 213016 Baiyun District, Changzhou, Jiangsu Patentee after: Changzhou University Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140430 Termination date: 20210531 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |