CN101011742A - Controlled method of preparing metal nano particle - Google Patents
Controlled method of preparing metal nano particle Download PDFInfo
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- CN101011742A CN101011742A CN 200710026834 CN200710026834A CN101011742A CN 101011742 A CN101011742 A CN 101011742A CN 200710026834 CN200710026834 CN 200710026834 CN 200710026834 A CN200710026834 A CN 200710026834A CN 101011742 A CN101011742 A CN 101011742A
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Abstract
The controllable way of making metal nanometer grains features in using film coating technique to deposit a even thickness layer of metal coating on the liner surface, heat treating the liner in inert atmosphere to rise the temperature, turning off the inert gas to introduce hydrogen for further heating, smelting the metal thin film into scatter small drops, turning off hydrogen and stopping heating, with inert gas in to cool to normal temperature. It is simple in process, low in cost, feasible of making big area of metal nanometer grain.
Description
Technical field
The present invention relates to nano material design and fabrication technology field, relate in particular to a kind of controlled method for preparing nano particle.
Background technology
Metal nanoparticle is because its special photoelectric properties and catalysis characteristics are widely used in every field, and for example when the preparation monodimension nanometer material, metal nanoparticle is with regard to Chang Zuowei catalyst or etching mask.Utilizing metal nanoparticle to prepare in the process of monodimension nanometer material, the diameter of formed monodimension nanometer material depends on the diameter of nano particle, if therefore can control the monodimension nanometer material array that the diameter of nano particle just can obtain controllable diameter.The method for preparing at present the metal nanoparticle array mainly contains electron beam exposure method, template, colloidal crystal etching method etc.Wherein the electron beam exposure method can accurately be controlled the diameter and the distribution of formed nano particle, but it costs an arm and a leg, and therefore length consuming time be not suitable for large-scale production; Template and colloidal crystal etching method are also because exist complex manufacturing technology and can not adapt to shortcoming such as large-area preparation and can not get using widely.
Summary of the invention
At the deficiencies in the prior art, the present invention aims to provide a kind of controlled preparation method of metal nanoparticles, heat-treat and obtain metal nanoparticle at substrate surface being plated on metallic film on the smooth substrate under certain condition, the thickness of control film can be regulated the diameter of nano particle.
For achieving the above object, the present invention adopts following technical scheme: a kind of controlled preparation method of metal nanoparticles, it is characterized in that, and comprise following processing step:
A. utilize coating technique to deposit a layer thickness even metal film at the substrate surface of surfacing;
B. the substrate of the good metallic film of surface deposition is heat-treated, under inert gas atmosphere, heat up;
C. close inert gas, feed hydrogen and continue heating, make metallic film be fused into the droplet of dispersion;
D. close hydrogen, stop heating, feed inert gas and be cooled to room temperature.
The described coating technique of above-mentioned steps a adopts the method for sputter, or the method for electron beam evaporation.
The throughput of above-mentioned steps b, the described inert gas of steps d is 200sccm.
Above-mentioned inert gas is an Ar gas.
Half that the described intensification temperature of above-mentioned steps b is the metal block material fusing point is to the arbitrary temperature value that is lower than between 100 ℃ of the metal block material fusing points.
The described continuation heating of above-mentioned steps c, its time is 30 minutes.
The present invention compared with prior art, the diameter of nano particle increases along with the increase of film thickness, be plated in the diameter that film thickness on the substrate just can be regulated last resulting nano particle by control, production technology is simple, cost is low, and can be adapted to the large-area preparation metal nanoparticle, preparation large tracts of land monodimension nanometer material is had great importance.
Description of drawings
Fig. 1 is a tubular heater device schematic diagram, and 1 is substrate among the figure, and 2 is heater strip, and 3 is quartz ampoule.
Fig. 2 is SEM (SEM) figure and the average diameter distribution map thereof of the gold silver nanometer particle of resultant different-diameter after the heat treatment.Wherein:
Fig. 2 (a)-(f) be thickness by the electrum film of 2nm, 4nm, 6nm, 8nm, 10nm and 14nm after Overheating Treatment the SEM figure of formation nano particle.
Fig. 3 is the average diameter distribution map of electrum film formed nano particle after Overheating Treatment of different-thickness.
Fig. 4 is transmission electron microscope (TEM) figure and the energy spectrogram of electrum nano particle.Wherein:
Fig. 4 (a) is the TEM figure of electrum nano particle;
Fig. 4 (b) is the high-resolution TEM figure of electrum nano particle;
Fig. 4 (c) is the enlarged drawing of area I among Fig. 4 (b), and wherein illustration is an electron diffraction pattern.
Fig. 5 is the constituency X ray energy dispersion spectrum of electrum nano particle.
Fig. 6 is the distribution diagram of element of area I I among Fig. 4 (b).Wherein:
Fig. 6 (a) is the distribution map of gold element in nano particle;
Fig. 6 (b) is the distribution map of silver element in nano particle.
The specific embodiment
In general, the fusing point of metal block material structure is than higher, and along with the dwindling its fusing point and can descend significantly of size, for example Jin bulk fusing point is 1064 ℃, but when its yardstick narrowed down to 2nm, fusing point also dropped to 227 ℃.As seen, the metal of nanoscale, its fusing point is more much lower than bulk structure.The present invention is according to this principle; employing is heat-treated metallic film well below the temperature of melting point metal and is made its method that melts fast obtain metal nanoparticle; at first on the substrate of surfacing, obtain the even metal film by coating technique; under the protection of inert gas, metallic film is heat-treated then; continuing heating under hydrogen atmosphere makes metallic particles be fused into the drop of dispersion; at last under the protection of inert gas, be cooled to room temperature again, just can form metal nanoparticle.
The invention will be further described below in conjunction with accompanying drawing, and processing step of the present invention is as follows:
1. two cun (100) monocrystalline silicon pieces selecting surfacing for use are as substrate.
2. substrate is positioned over and carries out plated film, sputter electrum in the ion sputtering instrument.The electric current of sputter is 2mA, and sputtering voltage is 1000V, and sputter gas is air, and the sputter time is 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes and 7 minutes, and pairing film thickness is about 2nm, 4nm, 6nm, 8nm, 10nm and 14nm.
3. the sample of the good electrum film of surface deposition is put into tubular heater as shown in Figure 1, be warmed up to 500 ℃ under the protection of Ar gas, the flow of Ar gas is 200sccm.
4. when temperature reaches 500 ℃, close Ar gas, feed hydrogen the electrum film is continued heating, hydrogen flowing quantity is 200sccm, and the processing time is 30 minutes.
5. after treating that the electrum film melts becomes the droplet of dispersion, close hydrogen, the Ar gas that feeds 200sccm again cools to room temperature as protection, can obtain equally distributed electrum nano particle at silicon chip surface.
Because the bulk fusing point of electrum is between between the bulk fusing point of gold and the silver-colored bulk fusing point, about 1000 ℃, so the heat treated temperature of above-mentioned processing step is 500 ℃.The electrum nano particle for preparing is carried out SEM (SEM) analysis.As shown in Figure 2, wherein figure (a)-(f) be respectively the about 2nm of film thickness, 4nm, 6nm, 8nm, 10nm and 14nm the electrum film after treatment the SEM of formed nano-grain array scheme.As we can see from the figure, obtained equally distributed gold silver nanometer particle array at silicon chip surface, and the diameter of formed nano particle is distributed within the very little scope, as: thickness is that the particle diameter that the electrum film of 2nm forms after treatment is 5nm～20nm, and thickness is that the particle diameter that the electrum film of 8nm forms after treatment is 20nm～50nm.
As can be seen from Figure 3, the average diameter of metal nanoparticle increases along with the increase of thickness of metal film, therefore can regulate the diameter of metal nanoparticle by the thickness of control metallic film.In the present embodiment, the thickness of metallic film thickens with the growth of sputtering time, therefore can prepare the metal nanoparticle of different-diameter by adopting different sputtering times.
Sample is carried out further transmission electron microscope (TEM) analysis.As shown in Figure 4, wherein Fig. 4 (a) is the TEM figure of gold and silver particle, Fig. 4 (b) is the high-resolution TEM figure of gold and silver particle, Fig. 4 (c) is the enlarged drawing of area I among Fig. 4 (b), as can be seen, formed electrum nano particle is a crystal structure from Fig. 4 (c), and its interplanar distance is 0.204nm, (200) face of correspondence and electrum, electron diffraction pattern (illustration among Fig. 4 (c)) has proved that also it is crystal structure simultaneously.Survey the composition of electrum nano particle with constituency X ray energy dispersion spectrometer (SAEDX), its result as shown in Figure 5, in sample, detect Au, Ag, four kinds of elements of Cu, C, wherein Cu and C come from the carbon film on TEM copper mesh and the copper mesh respectively, Au, Ag element only contain two kinds of elements of Au, Ag then from nano particle from the prepared as can be seen electrum nano particle of the result of power spectrum, do not contain other impurity, wherein the content of Au element is 28at%, and the content of Ag element is 72at%.Area I I among Fig. 4 (b) is carried out the element distribution to be surveyed, Fig. 6 (a) is the distribution diagram of element of Au, Fig. 6 (b) is the distribution diagram of element of Ag, and two kinds of elements of Au, Ag are evenly distributed in the particle as we can see from the figure, and the content of Au element is lower than the content of Ag element.
Claims (5)
1. a controlled preparation method of metal nanoparticles is characterized in that, comprises following processing step:
A. utilize the surface deposition one layer thickness even metal film of coating technique at the substrate of surfacing;
B. the substrate of the good metallic film of surface deposition is heat-treated, under inert gas atmosphere, heat up;
C. close inert gas, feed hydrogen and continue heating, make the metallic film fusing form the drop that disperses;
D. close hydrogen, stop heating, feed inert gas and be cooled to room temperature.
2. a kind of controlled preparation method of metal nanoparticles according to claim 1, it is characterized in that: the throughput of step b, the described inert gas of steps d is 200sccm.
3. a kind of controlled preparation method of metal nanoparticles according to claim 1, it is characterized in that: described inert gas is an Ar gas.
4. a kind of controlled preparation method of metal nanoparticles according to claim 1 is characterized in that: the temperature of the described intensification of step b is that half of metal block material fusing point is to the arbitrary temperature value that is lower than between 100 ℃ of the metal block material fusing points.
5. a kind of controlled preparation method of metal nanoparticles according to claim 1 is characterized in that: the described continuation heating of step c, its time is 30 minutes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102310038A (en) * | 2011-09-29 | 2012-01-11 | 华东交通大学 | Method for improving surface hydrophobicity of metal film |
| CN102381676A (en) * | 2011-10-27 | 2012-03-21 | 无锡英普林纳米科技有限公司 | Quartz micro needle surface nano metal chain and preparation method thereof |
| CN102806354A (en) * | 2012-07-31 | 2012-12-05 | 东南大学 | Method for preparing gold nanoparticles by annealing of gold film |
| CN103691962A (en) * | 2013-12-20 | 2014-04-02 | 中山大学 | Preparation method of size-controllable metal nano particles |
| CN107132210A (en) * | 2017-05-03 | 2017-09-05 | 北京理工大学 | A kind of substrate manufacture method of the surface-enhanced Raman based on dynamic control |
| CN108807631A (en) * | 2018-05-03 | 2018-11-13 | 五邑大学 | A kind of LED epitaxial wafer and preparation method thereof of double mirror surface structures |
| CN115464149A (en) * | 2022-10-18 | 2022-12-13 | 厦门大学 | Preparation method of metal nanoparticles |
-
2007
- 2007-02-08 CN CN200710026834A patent/CN100586614C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102310038A (en) * | 2011-09-29 | 2012-01-11 | 华东交通大学 | Method for improving surface hydrophobicity of metal film |
| CN102381676A (en) * | 2011-10-27 | 2012-03-21 | 无锡英普林纳米科技有限公司 | Quartz micro needle surface nano metal chain and preparation method thereof |
| CN102381676B (en) * | 2011-10-27 | 2014-10-08 | 无锡英普林纳米科技有限公司 | Quartz micro needle surface nano metal chain and preparation method thereof |
| CN102806354A (en) * | 2012-07-31 | 2012-12-05 | 东南大学 | Method for preparing gold nanoparticles by annealing of gold film |
| CN103691962A (en) * | 2013-12-20 | 2014-04-02 | 中山大学 | Preparation method of size-controllable metal nano particles |
| CN103691962B (en) * | 2013-12-20 | 2016-06-01 | 中山大学 | The preparation method of the metal nanoparticle that a kind of size is controlled |
| CN107132210A (en) * | 2017-05-03 | 2017-09-05 | 北京理工大学 | A kind of substrate manufacture method of the surface-enhanced Raman based on dynamic control |
| CN107132210B (en) * | 2017-05-03 | 2019-09-17 | 北京理工大学 | A kind of substrate manufacturing method of the surface-enhanced Raman based on dynamic control |
| CN108807631A (en) * | 2018-05-03 | 2018-11-13 | 五邑大学 | A kind of LED epitaxial wafer and preparation method thereof of double mirror surface structures |
| CN115464149A (en) * | 2022-10-18 | 2022-12-13 | 厦门大学 | Preparation method of metal nanoparticles |
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Inventor after: Xu Ningsheng Inventor after: Yao Rihui Inventor after: She Juncong Inventor after: Deng Shaozhi Inventor after: Chen Jun Inventor before: Xu Ningsheng Inventor before: Yao Rihui Inventor before: She Juncong Inventor before: Deng Shaozhi Inventor before: Chen Jun |
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