CN110468376A - A kind of carbon-coated Silver nanorod array and its preparation method and application - Google Patents

A kind of carbon-coated Silver nanorod array and its preparation method and application Download PDF

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CN110468376A
CN110468376A CN201910794516.0A CN201910794516A CN110468376A CN 110468376 A CN110468376 A CN 110468376A CN 201910794516 A CN201910794516 A CN 201910794516A CN 110468376 A CN110468376 A CN 110468376A
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carbon
substrate
preparation
coated silver
silver nanorod
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CN110468376B (en
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文懋
王美佳
任萍
张侃
郑伟涛
郑先亮
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Jilin University
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Jilin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons

Abstract

The present invention relates to technical field of function materials more particularly to a kind of carbon-coated Silver nanorod array and its preparation method and application.The preparation method of carbon-coated Silver nanorod array provided by the invention includes the following steps: to provide the substrate that surface has metallic film；It heats substrate and carries out wetting removal, then maintain substrate temperature constant, using methane as reaction gas, using silver-colored target as sputtering target, sputtered, obtain carbon-coated Silver nanorod array on substrate.The preparation method step is succinct, technique is controllable, at low cost, products pure, carbon-coated nanometer rods are strong in conjunction with substrate, can be mass, the disadvantages of product for overcoming liquid phase method and template is impure, the difficult control of cumbersome, structure, and, this method can both prepare carbon-coated Silver nanorod array in rigid substrate, carbon-coated Silver nanorod array can also be prepared on flexible substrates, with the advantages such as light weight, portable, foldable, high degree extends application range.

Description

A kind of carbon-coated Silver nanorod array and its preparation method and application
Technical field
The present invention relates to technical field of function materials more particularly to a kind of carbon-coated Silver nanorod array and its preparation sides Method and application.
Background technique
Ag nanometer rods are because having big specific surface area, higher surface-active, high stability, stronger catalytic activity, excellent Different antibiotic property, good electric conductivity and unique optical property etc., are widely used in catalysis, photoelectric material, the energy, life The fields such as object medical treatment.Wherein, it since the surface plasmon resonance of Ag enhance region electromagnetic field can efficiently quickly, and receives Rice stick large specific surface area, draw ratio is controllable, and absorption detection molecules are more, therefore are commonly used for Surface enhanced Raman spectroscopy (SERS) it detects.However, simple Silver nanorod structure is easily detected molecule or detection environmental oxidation or dirt in SERS detection Dye, and certain organic molecules to be measured enhance in the poor Raman that is unfavorable for of adsorption.
Carbon solubility very little in liquid or solid-state Ag is precipitated and coats conducive to original position during the reaction, has simultaneously Good stability and excellent electric conductivity with effective protection Ag and can be improved to the knot of organic molecule as coating Conjunction ability.If Jiang Meng et al. uses solvent thermal reaction, being restored after noble metal by carbon quantum dot using crystal seed is core packet in situ It covers and is grown in its surface, avoid noble metal reunion, be prepared for a kind of noble metal nano particles application that carbon is shell isolated In Surface enhanced Raman spectroscopy (CN105798289B).Therefore, it by Silver nanorod carbon coating, is expected to improve the steady of Silver nanorod Qualitative and absorption property.
But in the prior art there is complex process, at high cost, not easy-regulating in the preparation method of Silver nanorod, It is limited by template as synthesized Ag stick draw ratio in template, and prepares and goes removing template cumbersome, higher cost；Liquid phase synthesizing method is deposited The problems such as complex for operation step, product is impure, nanowire alignment is unordered, poor with substrate caking power；Vapor phase method growth course shadow The factor of sound is more, regulation process is complicated, nanometer rods are difficult to ordered arrangement.These methods are used to prepare carbon-coated Silver nanorod There is very big difficulty in array.Therefore, need to develop that a kind of preparation process is simple, at low cost, no coupling product, can be mass-produced Carbon-coated Silver nanorod array preparation method.
Summary of the invention
The purpose of the present invention is to provide a kind of carbon-coated Silver nanorod array and its preparation method and application, the present invention The preparation method of the carbon-coated Silver nanorod array provided is simple, is easily manipulated, and no coupling product generates, and suitable industrialization is answered With.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of carbon-coated Silver nanorod array, include the following steps:
The substrate that surface has metallic film is provided；
It heats substrate and carries out wetting removal, then maintain substrate temperature constant, be to splash with silver-colored target using methane as reaction gas It shoots at the target, is sputtered, obtain carbon-coated Silver nanorod array on substrate.
Preferably, the material of the metallic film includes Ag or Au.
Preferably, the metallic film with a thickness of 10~100nm.
Preferably, the metallic film is prepared by magnetron sputtering method.
Preferably, the substrate is silicon wafer or carbon cloth.
Preferably, the temperature of the wetting removal is 400~800 DEG C, and the time is 50~70s.
Preferably, the sputtering is argon gas with sputter gas, and the operating pressure of the sputtering is 0.5~1.5Pa, described to splash Substrate temperature is 400~600 DEG C during penetrating, and the power of the sputtering is 10~100W, the time of the sputtering is 60~ 100min。
Preferably, during the sputtering, the flow-rate ratio of sputter gas and reaction gas is 1:0.6~2.7.
The present invention also provides a kind of carbon-coated Silver nanorod array, the preparation method system as described in above-mentioned technical proposal It is standby to obtain.
The present invention also provides carbon-coated Silver nanorod array the answering as SERS substrate described in above-mentioned technical proposal With.
The present invention provides a kind of preparation method of carbon-coated Silver nanorod array, include the following steps: to provide surface Substrate with metallic film；It heats substrate and carries out wetting removal, then maintain substrate temperature constant, using methane as reaction gas Body is sputtered using silver-colored target as sputtering target, obtains carbon-coated Silver nanorod array on substrate.In the present invention, it is based on poplar Family name's equation: rs=ri+rfcosθ(rsFor the substrate surface energy of unit area, riFor unit area substrate and metal interface can, rfFor the metal surface energy of unit area), metallic atom diffusion limited in the lower situation of energy is unfavorable for generation solid-state and goes to moisten It is wet, and heat can the amount of enabling the system to increase, the enhancing of the nuclear energy of metal is rapidly achieved thermodynamic equilibrium state, to effectively swash Wetting removal process is sent out, assembles metal easily on substrate in the form of nano island, metal nano island is formed, is then with methane Reaction gas is sputtered using silver-colored target as sputtering target, after the carbon atom and silver atoms mixture sputtered reaches substrate, in height Under the conditions of temperature silver atoms transfer ability enhance, preferentially captured by metal nano island and grown using it as seed, carbon atom because Lower solubility is precipitated is coated on external and confinement Ag atom cross growth in situ, to realize high stability Ag nanometer rods battle array The controllable preparation of column, and the carbon-coated Silver nanorod queueing discipline of gained, be evenly distributed.
The preparation method step is succinct, technique is controllable, at low cost, products pure, carbon-coated nanometer rods are in conjunction with substrate By force, it can be mass, overcome the disadvantages of product in liquid phase method and template is impure, the difficult control of cumbersome, structure, also, This method can both prepare carbon-coated Silver nanorod array in rigid substrate, can also prepare on flexible substrates carbon-coated Silver nanorod array, has the advantages such as light weight, portable, foldable, and high degree extends application range.In addition, passing through carbon Ag nanometer rods are inside cladding effective protection to increase its stability, accuracy, and prolong the service life.
Detailed description of the invention
The schematic diagram of Fig. 1 preparation method provided by the present invention；
The SEM figure of the 1 carbon-coated Silver nanorod of gained of Fig. 2 embodiment；
The TEM figure of the 1 carbon-coated Silver nanorod of gained of Fig. 3 embodiment；
The SEM figure of the 2 carbon-coated Silver nanorod of gained of Fig. 4 embodiment；
The SEM figure of the 4 carbon-coated Silver nanorod of gained of Fig. 5 embodiment；
The SEM of 1 products obtained therefrom of Fig. 6 comparative example schemes；
The SEM of 2 products obtained therefrom of Fig. 7 comparative example schemes；
The SEM of 3 products obtained therefrom of Fig. 8 comparative example schemes；
The carbon-coated Silver nanorod of 1,4 gained of Fig. 9 embodiment, 1~2 products obtained therefrom of comparative example and silicon are examined as SERS substrate Survey the Raman spectrogram of 4- mercaptobenzoic acid；
The Raman spectrogram of 3 products obtained therefrom of Figure 10 comparative example and silicon as the detection 4- mercaptobenzoic acid of SERS substrate.
Specific embodiment
The present invention provides a kind of preparation methods of carbon-coated Silver nanorod array, include the following steps:
The substrate that surface has metallic film is provided；
It heats substrate and carries out wetting removal, then maintain substrate temperature constant, be to splash with silver-colored target using methane as reaction gas It shoots at the target, is sputtered, obtain carbon-coated Silver nanorod array on substrate.
Present invention firstly provides the substrates that surface has metallic film.
In the present invention, the substrate is preferably silicon wafer or carbon cloth.
As shown in Figure 1, being the principle of the present invention figure, the silicon by surface with metallic film carries out wetting removal (i.e. Hot activation " dewetting "), metallic atom starts to reunite and formed nano island (i.e. metal nano island) by diffusion, sputters Carbon atom and silver atoms mixture reach substrate, and Ag atoms are gathered in metal nano island under the high temperature conditions, and carbon Atom is diffused into the outside of metal island, separates the two and promotes the oriented growth of nano island, to form the silver of clad structure Nanometer stick array.
Substrate is preferably carried out pretreatment and is used further to prepare metallic film by the present invention；It is described pretreatment preferably include cleaning and It is dry；The cleaning includes acetone washing, ethanol washing and the washing successively carried out；The acetone washing, ethanol washing and water It washes and is both preferably cleaned by ultrasonic, the acetone washing, ethanol washing and the time of washing are independently preferably 15~25min；Institute Stating dry is preferably forced air drying, and the temperature of the drying is preferably 40~60 DEG C, and the time is preferably 1~1.5h.
In the present invention, the material of the metallic film preferably includes Ag or Au.In the present invention, the metallic film exists During wetting removal, nano island can be formed on the substrate, in favor of subsequent capture silver atoms, and then form nanometer rods kind Son.
In the present invention, the thickness of the metallic film is preferably 10~100nm, more preferably 30~70nm.In this hair In bright, the film of above-mentioned thickness is conducive to form the suitable metal nano island of size during wetting removal.
In the present invention, the metallic film is preferably prepared by magnetron sputtering method；The preparation of the metallic film In the process: metal targets used are parallel with substrate, and target-substrate distance is preferably 6~10cm, and sputter gas used is preferably argon gas, argon gas Flow be preferably 60sccm, operating pressure is preferably 0.5~1.5Pa, and the substrate temperature is preferably room temperature, more preferably 10~40 DEG C, most preferably 25 DEG C；The power of the sputtering of metal targets used is preferably 10~50W, and the time of sputtering is preferably 1 ~5min；The specific preparation method of the metallic film preferably includes following steps: metal targets and substrate are mounted on magnetic control In the vacuum sputtering cavity of sputtering equipment, after adjusting target-substrate distance, cavity is evacuated to 4.0 × 10-4Pa is hereinafter, be passed through sputtering gas Body sets the sputtering power of metal targets, is sputtered on substrate to operating pressure.
After surface is obtained with the substrate of metallic film, then it is anti-with methane that the present invention, which heats substrate and carries out wetting removal, Gas is answered, using silver-colored target as sputtering target, is sputtered, obtains carbon-coated Silver nanorod array on substrate.
After obtaining the substrate with metallic film, the present invention will lining preferably in the vacuum sputtering cavity of magnetic control sputtering device Bottom heating carries out wetting removal.In the present invention, during wetting removal, preferably the maintenance intracorporal atmosphere of chamber is metallic film preparation When atmosphere, metal nano island is formed on the substrate in metallic film.In the present invention, temperature (the i.e. substrate of the wetting removal Temperature) it is preferably 400~800 DEG C, more preferably 500~700 DEG C, the time is preferably 50~70s.
After the completion of wetting removal, the present invention maintains substrate temperature constant, is sputtering with silver-colored target using methane as reaction gas Target is sputtered；Concrete operations are preferred are as follows: are passed through methane gas, open silver-colored target power supply, sputtered.In the present invention, methane As carbon source, in sputtering process, Ag atomic migration ability enhances after the carbon atom and silver atoms sputtered reaches substrate, preferentially It is captured and grown using it as seed by nano island, carbon atom is coated on external and confinement because lower solubility is precipitated in situ Ag atom cross growth, to realize the controllable preparation of high stability Ag nanometer stick array.
In the present invention, the sputtering is preferably argon gas with sputter gas, and the operating pressure of the sputtering is preferably 0.5~ 1.5Pa, more preferably 0.8~1.2Pa, substrate temperature is preferably 400~600 DEG C in the sputtering process, the sputtering Power is preferably 10~100W, more preferably 30~80W；The time of the sputtering is preferably 60~100min, and more preferably 70 ~80min.In the present invention, pass through the sputtering power of target silver-colored in regulation substrate temperature and deposition process, adjustable carbon cladding Silver nanorod draw ratio, and the power of above-mentioned sputtering and other parameters are combined with and are conducive to obtain the uniform nanometer of structure snd size Stick, and power is too high or too low can make nanometer rods size uneven and structure is more mixed and disorderly unordered.
In the present invention, during the sputtering, the flow-rate ratio of sputter gas and reaction gas be preferably 1:0.6~ 2.7, more preferably 1:1~2.5, most preferably 1:1.5~2.0.In embodiments of the present invention, the flow of the sputter gas is excellent It is selected as 30sccm, the flow of reaction gas is preferably 20~80sccm；The total deposition of film is preferably 10~18nm/min.At this In invention, by regulating and controlling the ratio of reaction gas, the thickness of controllable carbon coating layer, reaction gas ratio is higher, carbon coating layer It is thicker.
After the completion of sputtering, cavity is preferably cooled to room temperature by the present invention, is taken out product, is obtained carbon-coated silver on substrate Nanometer stick array.
The present invention also provides a kind of carbon-coated Silver nanorod array, the preparation method system as described in above-mentioned technical proposal It is standby to obtain；The diameter of the carbon-coated Silver nanorod is preferably 50~250nm, and length is preferably 500~1100nm, carbon coating The thickness of layer is preferably 8~12nm, and the carbon of carbon coating layer is amorphous carbon.
The present invention also provides application of the carbon-coated Silver nanorod array as SERS substrate described in above-mentioned technical proposal. Carbon-coated Silver nanorod array provided by the present invention has good Raman signal humidification, is a kind of excellent SERS Substrate.
It to a kind of carbon-coated Silver nanorod array provided by the invention and preparation method thereof and is answered below with reference to embodiment With being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
1) using silicon wafer as substrate, substrate is placed in acetone soln and is cleaned by ultrasonic 20min；Then it places the substrate into ethyl alcohol It is cleaned by ultrasonic 20min；Substrate is finally cleaned by ultrasonic 20min in deionized water, taking-up is placed in drying box dry in 60 DEG C Dry 1.5 hours, obtain clean substrate；
2) the clean substrate is put into the vacuum cavity of magnetic control sputtering device, adjusting angle of deposit is 0 °, with Au Target is metallic target, installs metallic target, makes its distance 10cm between substrate, be evacuated to 4 × 10 to cavity-4Pa or less；
3) it is passed through sputter gas Ar gas, setting Ar gas gas flow is 60sccm, operating pressure 0.8Pa, underlayer temperature It is 25 DEG C, sputtering power 50W, sputters 5min, closes target power supply, obtain Au film on substrate；Gained Au film with a thickness of 60nm；
4) in the argon atmosphere that pressure is 0.8Pa, substrate is heated to 400 DEG C, 60s is kept the temperature, then maintains underlayer temperature It is constant, it is passed through CH4, adjusting argon flow is 40sccm, CH4Flow is 20sccm, operating pressure 0.8Pa, opens Ag target power supply It being sputtered, substrate temperature is 400 DEG C, sputtering power 30W in sputtering process, after sputtering 55min, Ag target power supply is closed, It is cooled to room temperature in the cavity, takes out sample, obtain carbon-coated Silver nanorod array on substrate.
The pattern of carbon-coated Silver nanorod array obtained by the present embodiment is characterized, as a result as shown in Figures 2 and 3, Middle Fig. 2 is SEM figure, and Fig. 3 is TEM figure.The present embodiment has obtained equally distributed carbon-coated Silver nanorod battle array as shown in Figure 2 Column, carbon coating layer are amorphous carbon, and the diameter of the carbon-coated Silver nanorod array of gained is 100~200nm, length is 520~ 1100nm；The carbon coating layer of carbon-coated Silver nanorod is measured by Fig. 3 with a thickness of 10nm.
Embodiment 2
1) using carbon cloth as substrate, substrate is placed in acetone soln and is cleaned by ultrasonic 20min；Then second is placed the substrate into It is cleaned by ultrasonic 20min in alcohol；Substrate is finally cleaned by ultrasonic 20min in deionized water, taking-up is placed in drying box in 60 DEG C dry 1.5 hours, obtain clean substrate；
2) the clean substrate is put into the vacuum cavity of magnetic control sputtering device, adjusting angle of deposit is 0 °, with Au Target is metallic target, installs metallic target, makes its distance 10cm between substrate, be evacuated to 4 × 10 to cavity-4Pa or less；
3) it is passed through sputter gas Ar gas, setting Ar gas gas flow is 60sccm, operating pressure 0.8Pa, underlayer temperature It is 25 DEG C, sputtering power 40W, sputters 5min, closes target power supply, obtain Au film on substrate；Gained Au film with a thickness of 50nm；
4) in the argon atmosphere that pressure is 0.8Pa, substrate is heated to 600 DEG C, 60s is kept the temperature, then passes to CH4, adjust Argon flow is 40sccm, CH4Flow is 20sccm, operating pressure 0.8Pa, opens Ag target power supply and is sputtered, sputtering temperature Degree is 500 DEG C, sputtering power 40W, after sputtering 55min, closes Ag target power supply, is cooled to room temperature in the cavity, takes out sample, Carbon-coated Silver nanorod array is obtained on substrate.
The pattern of carbon-coated Silver nanorod array obtained by the present embodiment is characterized, as a result as shown in figure 4, wherein (a) scheme for low power SEM, (b) scheme for high power SEM.As shown in Figure 4, the present embodiment has obtained equally distributed carbon-coated silver and has received Rice stick array, carbon coating layer are amorphous carbon, and the diameter of the carbon-coated Silver nanorod array of gained is 100~250nm, and length is 500~1000nm.
Tested by TEM, measurement obtain carbon coating layer with a thickness of 9nm.
Embodiment 3
Carbon-coated Silver nanorod array is prepared according to the method for embodiment 2, the difference is that, by the Au in step 3) Target replaces with Ag target, in step 4) Ag target sputtering power be 40W, gained metallic film with a thickness of 40nm.
It is characterized by SEM, it is known that the present embodiment is evenly distributed, the carbon-coated Silver nanorod battle array of size uniformity Column, and carbon coating layer is amorphous carbon, the diameter of the carbon-coated Silver nanorod array of gained are 100~200nm, length is 500~ 1000nm。
The carbon coating layer of carbon-coated Silver nanorod is with a thickness of 10nm.
Embodiment 4
Carbon-coated Silver nanorod array is prepared according to the method for embodiment 3, the difference is that, function is sputtered in step 4) Rate is 20W.
The pattern of the present embodiment products obtained therefrom is characterized, as a result as shown in figure 5, the diameter of carbon-coated Silver nanorod For 50~100nm, length is 600~1100nm.Thus illustrate, sputtering power reduces, and draw ratio improves, can be by adjusting splashing The draw ratio of the carbon-coated Silver nanorod of the power adjustment penetrated.
The carbon coating layer of carbon-coated Silver nanorod is measured with a thickness of 11nm.
Comparative example 1
Carbon-coated Silver nanorod array is prepared according to the method for embodiment 1, the difference is that, it is right in step 4) to omit The operation of silicon, and when the sputtering of Ag target, also maintain substrate at 25 DEG C.
The pattern of this comparative example products obtained therefrom is characterized, the results showed that the surface of products obtained therefrom is the thin of smooth densification Film does not occur the feature of nanometer rods, as shown in Figure 6.Its reason transfer ability deficiency nothing after atom at room temperature reaches substrate Method is combined into cluster and forms nano island, and then in sputtering process, Ag, which can not preferentially be captured, forming core and to be assembled, so formed two-dimentional Noncrystal membrane.
Comparative example 2
Carbon-coated Silver nanorod array is prepared according to the method for embodiment 3, the difference is that, preparation gold in step 3) When belonging to film, time of sputtering is 20min, gained Ag film with a thickness of 300nm.
The pattern of this comparative example products obtained therefrom is characterized, as a result as shown in fig. 7, this comparative example obtained it is extremely coarse Nano-pillar, and structure is very uneven, and part club shaped structure collapses, and the diameter of carbon-coated Silver nanorod is 80~260nm, Length is 700~1600nm.Illustrate that thicker metallic film is unfavorable for forming the nano island being evenly distributed, is unfavorable for subsequent silver and receives The formation of rice stick.
Comparative example 3
Carbon-coated Silver nanorod array is prepared according to the method for embodiment 2, the difference is that, argon is maintained in step 4) Atmosphere is enclosed, and methane is not passed through.
The pattern of this comparative example products obtained therefrom is characterized, as a result explanation forms coarse column crystal film, does not go out The high nanometer rods feature of existing draw ratio, as shown in Figure 8.The reason is that carbon source (i.e. reaction gas) is not added, silver atoms cannot be along receiving The growth of rice island, but with the growth of layer island mixed mode, result in the column crystal film of minim gap.
Application examples
Using 4- mercaptobenzoic acid, as probe molecule, (Raman signal is located at 1078cm-1With 1588cm-1Etc.), with second Alcohol is solvent, and preparation concentration is 10-5The test solution of M；Embodiment 1,4 and 1~3 products obtained therefrom of comparative example are divided into respectively 5mm × 5mm fritter, and add probe molecule to test as a comparison pure silicon piece, progress Raman spectrum test is air-dried after solution is added dropwise； Excitation wavelength 532nm is detected, power 10.7mW, laser intensity 50%, time of integration 10s are detected.Testing result such as Fig. 9 and 10 institute Show.
By Fig. 9 and Figure 10 it is found that 1, the 4 carbon-coated Silver nanorod of gained of embodiment is used for Raman spectrum as SERS substrate When test, all have and effect be remarkably reinforced, pure silicon piece be added probe molecule after without any reinforcing effect, the increasing of comparative example 1 and 2 Strong poor effect illustrates that the carbon-coated Silver nanorod structure of the gained of comparative example 2 is uneven, for reinforcing effect is compared with both of the above It is not significant；The two-dimentional noncrystal membrane that comparative example 1 obtains can not enhance Raman signal, and by its sp2With sp3Bonding mode influences Carbon peak is divided into the peak D and the peak G (corresponds respectively to 1325cm-1With 1595cm-1)；Comparative example 3 is then without being remarkably reinforced effect.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of carbon-coated Silver nanorod array, which comprises the steps of:
The substrate that surface has metallic film is provided；
It heats substrate and carries out wetting removal, then maintain substrate temperature constant, be sputtering with silver-colored target using methane as reaction gas Target is sputtered, and obtains carbon-coated Silver nanorod array on substrate.
2. preparation method according to claim 1, which is characterized in that the material of the metallic film includes Ag or Au.
3. preparation method according to claim 1 or 2, which is characterized in that the metallic film with a thickness of 10~ 100nm。
4. preparation method according to claim 1 or 2, which is characterized in that the metallic film passes through magnetron sputtering legal system It is standby to obtain.
5. preparation method according to claim 1, which is characterized in that the substrate is silicon wafer or carbon cloth.
6. preparation method according to claim 1, which is characterized in that the temperature of the wetting removal is 400~800 DEG C, when Between be 50~70s.
7. preparation method according to claim 1, which is characterized in that the sputtering is argon gas with sputter gas, described to splash The operating pressure penetrated is 0.5~1.5Pa, and substrate temperature is 400~600 DEG C in the sputtering process, the power of the sputtering For 10~100W, the time of the sputtering is 60~100min.
8. preparation method according to claim 1 or claim 7, which is characterized in that during the sputtering, sputter gas and anti- The flow-rate ratio for answering gas is 1:0.6~2.7.
9. a kind of carbon-coated Silver nanorod array, is prepared by preparation method according to any one of claims 1 to 8.
10. application of the carbon-coated Silver nanorod array as claimed in claim 9 as SERS substrate.
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