CN107309422A - A kind of porous electrum nano material and preparation method and application - Google Patents
A kind of porous electrum nano material and preparation method and application Download PDFInfo
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- CN107309422A CN107309422A CN201710352124.XA CN201710352124A CN107309422A CN 107309422 A CN107309422 A CN 107309422A CN 201710352124 A CN201710352124 A CN 201710352124A CN 107309422 A CN107309422 A CN 107309422A
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/12—Making metallic powder or suspensions thereof using physical processes starting from gaseous material
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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
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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
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- 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
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- 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
- C23C14/223—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating specially adapted for coating particles
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- G—PHYSICS
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- 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
Abstract
The invention discloses a kind of porous electrum nano material and preparation method and application, the material is the porous electrum nanosphere oldered array of the non-solid matter of six sides, and its cycle is 350~750nm.The preparation method of the material includes：Using colloid monolayer micro-sphere array as template, and one layer of golden film is deposited on the surface of template using physical deposition method, then be heat-treated, gold nanosphere oldered array is made；One layer of silverskin is deposited on the surface of gold nanosphere oldered array using physical deposition method, heating anneal processing is then carried out, electrum nanosphere oldered array is made；Battle array orderly to the electrum nanosphere carries out chemical attack processing, so that the porous electrum nano material is made.The present invention can not only prepare cycle and the size controllable non-close multihode electrum nanosphere oldered array of six sides of large area, and need not bind agent and stabilizer, be easy to target molecule absorption, convenient reuse.
Description
Technical field
The present invention relates to gold-silver alloy field of nanometer material technology, more particularly to a kind of porous gold-silver alloy nano material and its
Preparation method and application.
Background technology
Gold-silver alloy nano material has local surface plasma resonance characteristic, can produce strong Electromagnetic enhancement
Effect, can be widely used in terms of the analysis detection based on SERS.Due to SERS
Sensitivity depends on electromagnetic field greatly enhanced " focus " position in nano material, therefore people have been prepared with thick
Rough surface, tip, the isostructural gold-silver alloy nano material of corner angle, but these have the gold-silver alloy of high density " focus "
The sensitivity of nano material SERS in actual applications is also less desirable.Closed with Jin-silver of other structures
Gold nano-material is compared, and the gold-silver alloy nano material (i.e. porous gold-silver alloy nano material) of loose structure has high compare
The features such as surface area, easy adsorption reaction thing, high " focus " density, therefore application potential is huger.
At present, the preparation method of porous gold-silver alloy nano material usually first prepares golden@galactic nucleus core/shell nanoparticles,
Then carry out high annealing, part silver element finally removed using electrochemistry, the method such as chemistry, but this preparation method compared with
For it is complicated, prepare cost it is higher, it is difficult to realize it is large-scale it is quick prepare, and high annealing easily cause particle between reunite,
The problems such as sintering, it is often more important that need to add end-capping reagent or stabilizer in preparation process, which prevent target molecule
Absorption, has a strong impact on its application value.
The content of the invention
In order to which the preparation method for solving existing porous gold-silver alloy nano material is complicated, it is higher to prepare cost and is making
End-capping reagent or stabilizer are needed to use during standby, the technical problems such as target molecule absorption are hindered, the invention provides one kind
Porous gold-silver alloy nano material and preparation method and application.Porous gold-silver alloy nano material provided by the present invention
Preparation method can not only prepare large area (area>1cm2) cycle and the size controllable non-close multihode of six sides
Gold-silver alloy nanosphere oldered array, and preparation method is simple, prepare that cost is relatively low, need not bind agent and stabilizer, easily
In target molecule absorption, convenient reuse；And use porous gold-silver alloy nanosphere oldered array made from this method
Strengthen Raman scattering performance with excellent surface.
The purpose of the present invention is achieved through the following technical solutions：
A kind of porous gold-silver alloy nano material, the porous gold-silver alloy nano material is many of the non-close-packed configuration of six sides
Kong Jin-silver alloy nanosphere oldered array, and the porous gold-silver alloy nanosphere oldered array cycle for 350~
750nm；In the porous gold-silver alloy nanosphere oldered array, the particle scale of porous gold-silver alloy nanosphere is uniform, and
And the diameter of each porous gold-silver alloy nanosphere is 204~330nm, have on each porous gold-silver alloy nanosphere
There are multiple perforates.
Preferably, the porous gold-silver alloy nanosphere is alloy structure, and its alloy tie is bicontinuous structure, and it is closed
Golden tie width is 7~16nm.
Preferably, the aperture of the perforate on porous gold-silver alloy nanosphere is 4~11nm.
A kind of preparation method of porous gold-silver alloy nano material, comprises the following steps：
Step A, using a diameter of 350~750nm of colloid micro ball colloid monolayer micro-sphere array as template, and using physics sink
Product method deposits one layer of golden film on the surface of the template, then colloid monolayer micro-sphere array is removed by being heat-treated, so as to make
Obtain gold nanosphere oldered array；
Step B, use physical deposition method deposited on the surface of the gold nanosphere oldered array a layer thickness for 400~
700nm silverskin, then carries out heating anneal processing in protective atmosphere, and gold-silver alloy nanosphere oldered array is made；
Step C, using the method for chemical attack the orderly battle array of gold-silver alloy nanosphere is handled, with remove gold-
The part silver element of silver alloy nanosphere, so that the porous gold-silver alloy nanometer material described in above-mentioned technical proposal is made
Material.
Preferably, the heating anneal processing that carried out in protective atmosphere described in step B includes：The gold for having silverskin will be deposited
Nanosphere oldered array is put into tube furnace, and with the heating of 600 DEG C of progress 2 hours in the mixed atmosphere of hydrogen and nitrogen
Annealing, silverskin and gold nanosphere can melt, merge, solidification in situ, so as to form gold-silver alloy nanosphere oldered array.
Preferably, the method for the use chemical attack described in step C is carried out to the orderly battle array of the gold-silver alloy nanosphere
Processing includes：Had using at least one of nitric acid, ferric nitrate or ammoniacal liquor as corrosive agent to the gold-silver alloy nanosphere
Sequence battle array carries out chemical attack processing, to remove part silver element.
Preferably, the physical deposition method uses magnetron sputtering deposition, thermal evaporation deposition or electron-beam evaporation.
Porous gold-silver alloy nano material described in above-mentioned technical proposal is used as the substrate of SERS.
As seen from the above technical solution provided by the invention, porous gold-silver alloy nanometer material provided by the present invention
Material is that the colloid monolayer micro-sphere array using a diameter of 350~750nm of colloid micro ball is existed as template, and using physical deposition method
The surface of the template deposits one layer of golden film, and removes colloid monolayer micro-sphere array by being heat-treated, so that gold nanosphere is made
Oldered array；Then use physical deposition method deposited on the surface of the gold nanosphere oldered array a layer thickness for 400~
700nm silverskin, and heating anneal processing is carried out, so that gold-silver alloy nanosphere oldered array is made；It is rotten using chemistry again
The method of erosion is handled the orderly battle array of gold-silver alloy nanosphere, to remove part silver element, so as to can be prepared by face
Product>1cm2The non-solid matter of six sides porous gold-silver alloy nanosphere oldered array.The porous orderly battle array of gold-silver alloy nanosphere
Row not only there is excellent surface to strengthen Raman scattering performance, and cycle and size are controllable, and preparation method is simple, be prepared into
This relatively low, need not bind agent and stabilizer, it is easy to target molecule absorption, convenient reuses.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, being used required in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For one of ordinary skill in the art, on the premise of not paying creative work, it can also be obtained according to these accompanying drawings
His accompanying drawing.
Fig. 1 is when micro- using a diameter of 350nm of colloid micro ball polystyrene colloid in the step b of the embodiment of the present invention 1
During ball suspension, using the silicon substrate individual layer polyphenyl of the field emission scanning electron microscopes of Sirion 200 respectively to being obtained in step d
The silicon substrate gold obtained in the silicon substrate gold nanosphere oldered array that is obtained in ethene colloid micro ball oldered array, step f, step g-
The porous gold-silver alloy nanosphere oldered array obtained in silver alloy nanosphere oldered array, step h is observed, so that
The electron scanning micrograph arrived.
Fig. 2 is the porous Jin-silver prepared using the field emission scanning electron microscopes of Sirion 200 to the embodiment of the present invention 1
Alloy nano-material is observed, low power scanning transmission electron microscope photo (the STEM photos) obtained from.
Fig. 3 is the porous Jin-silver prepared using JEOL-2100F high resolution transmission electron microscopies to the embodiment of the present invention 1
Single porous gold-silver alloy nanosphere is observed in alloy nano-material, and scanning transmission electron microscope is shone obtained from
Piece.
Fig. 4 is that the porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 is carried out using X-ray energy disperse spectroscopy
Observation, thus X-ray energy spectrum diagram.
Fig. 5 be using Sirion 200 field emission scanning electron microscopes the embodiment of the present invention 1 is carried out respectively 30min,
Porous gold-silver alloy nanosphere oldered array obtained by 60min, 90min chemical attack is observed, and is swept obtained from
Retouch electron micrograph and porous gold-silver alloy nanosphere pattern change comparison diagram.
Porous gold-silver alloy nano materials of the Fig. 6 prepared by the embodiment of the present invention 1 is to the sulfydryl benzenethiol of various concentrations 4
Ethanol solution detected, the surface-enhanced Raman signals comparison diagram obtained from.
Fig. 7 is that the porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 is detected to 4 sulfydryl benzenethiols,
And detect the stability and repeatability of SERS signal, the Raman signal intensity distribution map obtained from.
Fig. 8 for use the field emission scanning electron microscopes of Sirion 200 respectively to a diameter of 500nm of colloid micro ball with
750nm polystyrene colloid microsphere suspension liquid is that the final obtained porous gold-silver alloy nanosphere oldered array of raw material is carried out
Observation, the electron scanning micrograph obtained from.
It is that 350nm, 500nm, 750nm porous gold-silver alloy nanosphere oldered array enters to cycle spacing respectively that Fig. 9, which is,
Row SERS signal detection, the surface-enhanced Raman signals comparison diagram obtained from.
The flow signal of the preparation method for the porous gold-silver alloy nano material that Figure 10 is provided by the embodiment of the present invention 1
Figure.
Embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
The embodiment of invention, the every other reality that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example is applied, protection scope of the present invention is belonged to.
Porous gold-silver alloy nano material provided by the present invention and preparation method and application is retouched in detail below
State.
A kind of porous gold-silver alloy nano material, it is the area of the non-close-packed configuration of six sides>1cm2Porous Jin-silver close
Gold nanosphere oldered array, and its cycle regulate and control in the range of 350~750nm；Have in the porous gold-silver alloy nanosphere
In sequence array, the particle scale of porous gold-silver alloy nanosphere is uniform, and the diameter of each porous gold-silver alloy nanosphere
It is 204~330nm, multiple perforates is respectively provided with each porous gold-silver alloy nanosphere.
Wherein, the porous gold-silver alloy nanosphere is alloy structure, and its alloy tie is bicontinuous structure, its alloy
Tie width regulates and controls in the range of 7~16nm.The aperture of perforate on porous gold-silver alloy nanosphere is in the range of 4~11nm
Regulation and control.The porous gold-silver alloy nanosphere oldered array has good stability in room temperature environment.
Specifically, the preparation method of the porous gold-silver alloy nano material may comprise steps of：
Step A, using a diameter of 350~750nm of colloid micro ball colloid monolayer micro-sphere array as template, and using physics sink
Product method deposits one layer of golden film on the surface of the template, then colloid monolayer micro-sphere array is removed by being heat-treated, so as to make
Obtain gold nanosphere oldered array.
Further：Step A specific implementation process may comprise steps of：
(1) step A1, substrate be sequentially placed into ethanol, deionized water be cleaned by ultrasonic, it is all ultrasonic in every kind of liquid
20~60min is cleaned, then drying and processing is carried out (for example to the substrate after cleaning：It can be put into baking oven with 60 DEG C of drying
20min), it is then placed into UV ozone cleaning machine irradiating 20~60min, so as to obtain the substrate of surface hydrophilic.In reality
In, described substrate can use slide or silicon chip.
(2) step A2, in the substrate surface of the surface hydrophilic 1~2ml deionized waters are added dropwise, then by colloid micro ball diameter
The surface of the substrate is slowly dropped to along one jiao for 350~750nm colloid micro ball ethanol dilution, and passes through solution-air circle
A diameter of 350~the 750nm of colloid micro ball colloid monolayer micro-sphere array is made in face self-assembling method on the substrate.It is described
Colloid monolayer micro-sphere array is preferably transferred in silicon chip substrate.In actual applications, a diameter of 350~750nm of colloid micro ball is taken
Colloid micro ball suspension (the colloid micro ball suspension can using commercial means buy polystyrene colloid microsphere suspension liquid
Or polymethyl methacrylate colloid micro ball suspension), and mixed in equal volume with ethanol, then carry out 10~30min ultrasound point
Dissipate, so as to can be prepared by a diameter of 350~750nm of finely dispersed colloid micro ball colloid micro ball ethanol dilution.
(3) step A3, using a diameter of 350~750nm of colloid micro ball colloid monolayer micro-sphere array as template, and
Use physical deposition method to deposit golden film of a layer thickness for 16~200nm on the surface of the template, be then placed in annealing furnace
In heated 2 hours with 1000 DEG C, to remove colloid monolayer micro-sphere array, so that the gold nanosphere of six sides non-solid matter, which is made, to be had
Sequence array.In actual applications, described physical deposition method can use magnetron sputtering deposition, thermal evaporation deposition or electronics
Beam evaporation is deposited.
Step B, use physical deposition method deposited on the surface of the gold nanosphere oldered array a layer thickness for 400~
700nm silverskin, then carries out heating anneal processing in protective atmosphere, and gold-silver alloy nanosphere oldered array is made.
Further：Step B specific implementation process may comprise steps of：
(1) step B1, use physical deposition method deposited on the surface of the gold nanosphere oldered array a layer thickness for
400~700nm silverskin, so that deposition, which is made, the gold nanosphere oldered array of silverskin.In actual applications, described thing
Reason deposition process can use magnetron sputtering deposition, thermal evaporation deposition or electron-beam evaporation.
(2) step B2, the gold nanosphere oldered array that has silverskin will be deposited be put into tube furnace, and in hydrogen and nitrogen
Handled in mixed atmosphere with 600 DEG C of heating anneals carried out 2 hours, silverskin and gold nanosphere can melt, merge, solidification in situ,
So as to form gold-silver alloy nanosphere oldered array.In actual applications, the tube furnace can use Muffle furnace；Hydrogen with
In the mixed atmosphere of nitrogen, the percent by volume shared by hydrogen is 10%.
Step C, using the method for chemical attack the gold-silver alloy nanosphere oldered array is handled, to remove
The part silver element of gold-silver alloy nanosphere, so that area is made>1cm2Porous gold-silver alloy nanosphere oldered array,
Porous gold-silver alloy nano material i.e. described in above-mentioned technical proposal.Wherein, the method pair of described use chemical attack
The orderly battle array progress processing of gold-silver alloy nanosphere includes：Using the conduct of at least one of nitric acid, ferric nitrate or ammoniacal liquor
Corrosive agent carries out chemical attack processing to the orderly battle array of the gold-silver alloy nanosphere, to remove part silver element.
Compared with prior art, porous gold-silver alloy nano material provided by the present invention at least has following beneficial effect
Really：
(1) porous gold-silver alloy nano material provided by the present invention is a kind of porous orderly battle array of gold-silver alloy nanosphere
Row, the ordered structure with the non-solid matter of six sides, and porous gold-silver alloy nanosphere have good monodispersity and stably
Property, can for a long time it be preserved in room temperature and air.
(2) porous gold-silver alloy nano material provided by the present invention, the porous gold-silver alloy nanosphere of its non-solid matter
It is respectively provided with that many open perforates and surface are clean, the features such as having big specific surface area and easy adsorption reaction thing concurrently.
(3) there is porous gold-silver alloy nano material provided by the present invention excellent surface to strengthen Raman scattering performance, can
Substrate as SERS, not only detectable molecular species is more, test limit is low, sensitivity is high, stability
It is good, and it is excellent to detect that obtained SERS signal is respectively provided with 100um x 100um larger area
Stability and repeatability；For example：Porous gold-silver alloy nano material provided by the present invention can be used for 4 sulfydryl benzenethiols
Detection, and there is very strong humidification to the SERS signals of 4 sulfydryl benzenethiols, not only stability it is good,
Signal repeatability is strong, and test limit is low, detection limit can reach 10-10mol/L.It can be seen that, it is provided by the present invention porous
Gold-silver alloy nano material can be in Surface Enhanced Raman Scattering Spectrum, surface plasma bulk optics, catalytic reaction, information storage
Large-scale commercial application is realized in terms of depositing.
(4) preparation method of porous gold-silver alloy nano material provided by the present invention can prepare area>1cm2's
Porous gold-silver alloy nanosphere oldered array, and yield is high, can quickly prepare, and is appropriate for large area large-scale production.
(5) preparation method of porous gold-silver alloy nano material provided by the present invention passes through to gold and silver sedimentation time, heavy
The parameters such as product power, removal alloying time (i.e. chemical attack time) are adjusted, and can effectively control obtained porous gold
Open pore size in two kinds of element proportionings of diameter, gold and silver of-silver alloy nanosphere and porous gold-silver alloy nanosphere, so that
Different-diameter, different open pore sizes, the porous gold-silver alloy nanosphere of different gold and silver element ratios can be obtained.
(6) preparation method of porous gold-silver alloy nano material provided by the present invention only need using baking oven, annealing furnace,
Some conventional equipments such as glassware, without using the special equipment that price is high, without using agent and the stabilizer of binding,
Preparation technology is simple, with low cost, easily operated, convenient reuse.
As fully visible, the embodiment of the present invention can not only prepare large area (area>1cm2) cycle and size
The non-close multihode gold-silver alloy nanosphere oldered array of six sides of control, and preparation method is simple, it is relatively low to prepare cost, need not
Bind agent and stabilizer, be easy to target molecule absorption, it is convenient reuse, while prepared porous gold-silver alloy nanometer
Ball oldered array also there is excellent surface to strengthen Raman scattering performance.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below with tool
Porous gold-silver alloy nano material provided by the present invention and preparation method and application is described in detail body embodiment.
Embodiment 1
As shown in Figure 10, a kind of porous gold-silver alloy nano material, its preparation method comprises the following steps：
Step a, slide, silicon chip both substrates are sequentially placed into acetone, ethanol, deionized water to carry out ultrasound clear
Wash, 20~60min is all cleaned by ultrasonic in every kind of liquid, then the slide and silicon chip after cleaning are put into baking oven with 60 DEG C of bakings
Dry 20min, is then positioned over 20~60min of irradiation in UV ozone cleaning machine, so as to obtain by dry slide, silicon chip
The slide substrate and silicon chip substrate of surface hydrophilic.
Step b, the polystyrene colloid microsphere suspension liquid for taking a diameter of 350~750nm of 40mL colloid micro balls
(2.5wt.%), and be well mixed with isometric ethanol, then 10~30min ultrasonic disperse is carried out, it is uniformly dispersed so as to be made
The a diameter of 350~750nm of colloid micro ball polystyrene colloid microballoon ethanol dilution.
Step c, on the surface of the slide substrate of the surface hydrophilic 1~2ml deionized waters are added dropwise, then by the polyphenyl
The surface that ethene colloid micro ball ethanol dilution is slowly dropped to slide substrate along one jiao of slide substrate, and using gas-
Liquid interface self-assembling method is in slide substrate over-assemble into individual layer polystyrene colloid microballoon oldered array.
Step d, the individual layer polystyrene colloid microballoon oldered array in slide substrate is transferred in silicon chip substrate, from
And obtain silicon substrate individual layer polystyrene colloid microballoon oldered array.
Step e, using the silicon substrate individual layer polystyrene colloid microballoon oldered array as template, and use magnetron sputtering deposition
Method (electric current is 20mA, and the magnetron sputtering time is 3min) deposits a layer thickness on the surface of the template for 16~200nm
Golden film so that be made golden film covering silicon substrate individual layer polystyrene colloid microballoon oldered array.
Step f, the silicon substrate individual layer polystyrene colloid microballoon oldered array that the golden film is covered is positioned in Muffle furnace,
And heating anneal processing is carried out in air atmosphere, heating-up temperature is 1000 DEG C, and the heat time is 2 hours, to remove individual layer glue
Body micro-sphere array, so that the silicon substrate gold nanosphere oldered array of the non-solid matter of six sides is made.
Step g, magnetron sputtering deposition method (electric current for 20mA, the magnetron sputtering time is 6~12min) is used described
The surface of silicon substrate gold nanosphere oldered array deposits the silverskin that a layer thickness is 400~700nm, then puts it into tube furnace
It is interior, and handled in the mixed atmosphere of hydrogen and nitrogen with 600 DEG C of heating anneals carried out 2 hours, silverskin and gold nanosphere meeting
Fusing, fusion, solidification in situ, silicon substrate gold-silver alloy nanosphere oldered array is obtained after cooling.
Step h, the nitre that the orderly battle array of silicon substrate gold-silver alloy nanosphere is put into using the method for chemical attack 3mol/L
In acid, to remove part silver element, so that area is made>1cm2Porous gold-silver alloy nanosphere oldered array, i.e., it is described
Porous gold-silver alloy nano material.
Specifically, porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 is detected as follows：
(1) during stating the embodiment of the present invention 1 on the implementation, the polystyrene colloid microballoon used in step b suspends
Liquid uses a diameter of 350nm of colloid micro ball polystyrene colloid microsphere suspension liquid, while being swept using the Flied emissions of Sirion 200
Retouch electron microscope respectively to obtained in step d silicon substrate individual layer polystyrene colloid microballoon oldered array, obtain in step f
Silicon substrate gold nanosphere oldered array, the silicon substrate gold-silver alloy nanosphere oldered array obtained in step g, obtain in step h
Porous gold-silver alloy nanosphere oldered array be observed, so as to obtain electron scanning micrograph as shown in Figure 1；
Wherein, Fig. 1 a are the electron scanning micrograph for the silicon substrate individual layer polystyrene colloid microballoon oldered array that step d is obtained,
Fig. 1 b are the electron scanning micrograph of silicon substrate gold nanosphere oldered array obtained in step f, and Fig. 1 c are in step g
The electron scanning micrograph of the silicon substrate gold-silver alloy nanosphere oldered array arrived, Fig. 1 d are porous for what is obtained in step h
The electron scanning micrograph of gold-silver alloy nanosphere oldered array.As seen from Figure 1：The step h of the embodiment of the present invention 1
In the obtained array structure of porous gold-silver alloy nanosphere oldered array be the non-close-packed configuration of six sides.
(2) the porous Jin prepared using the field emission scanning electron microscopes of Sirion 200 to the embodiment of the present invention 1-silver is closed
Gold nano-material is observed, so as to obtain low power scanning transmission electron microscope photo (STEM photos) as shown in Figure 2.
As seen from Figure 2：Porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 is with fine periodic structure
Porous gold-silver alloy nanosphere oldered array.
(3) the porous Jin prepared using JEOL-2100F high resolution transmission electron microscopies to the embodiment of the present invention 1-silver is closed
Single porous gold-silver alloy nanosphere in gold nano-material is observed, so as to obtain scanning transmission electricity as shown in Figure 3
Sub- microphotograph；Wherein, Fig. 3 b are two kinds of gold and silver in single porous gold-silver alloy nanosphere prepared by the embodiment of the present invention 1
Element area profile (EDX mapping), Fig. 3 b1 are single porous gold-silver alloy nanosphere prepared by the embodiment of the present invention 1
Middle gold element mapping (EDX mapping), Fig. 3 b2 are that single porous gold-silver alloy prepared by the embodiment of the present invention 1 is received
Silver element mapping (EDX mapping) in rice ball.As seen from Figure 3：Prepared by the embodiment of the present invention 1 single porous
Two kinds of elements of gold, silver are uniformly distributed in gold-silver alloy nanosphere, and single porous gold prepared by this explanation embodiment of the present invention 1-
Silver alloy nanosphere is alloy structure.
(4) the porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 is visited using X-ray energy disperse spectroscopy
Survey, so as to obtain X-ray energy spectrum diagram as shown in Figure 4.As seen from Figure 4：Porous gold prepared by the embodiment of the present invention 1
- silver alloy nano material is only made up of two kinds of elements of gold, silver, and carbon (C) and copper (Cu) come from copper mesh in Fig. 4.
(5) during stating the embodiment of the present invention 1 on the implementation, when carrying out step h chemical attack, using Sirion
200 field emission scanning electron microscopes are respectively to the porous gold-silver alloy obtained by chemical attack 30min, 60min, 90min
Nanosphere oldered array is observed, so as to obtain electron scanning micrograph and porous gold-silver alloy as shown in Figure 5
Nanosphere pattern changes comparison diagram；Wherein, Fig. 5 a are porous obtained by the progress 30min chemical attacks of the embodiment of the present invention 1
The electron scanning micrograph of gold-silver alloy nanosphere oldered array, Fig. 5 b are that the embodiment of the present invention 1 carries out 60min chemistry
The electron scanning micrograph of the obtained porous gold-silver alloy nanosphere oldered array of corrosion, Fig. 5 c are implemented for the present invention
Example 1 carries out the electron scanning micrograph of the porous gold-silver alloy nanosphere oldered array obtained by 90min chemical attacks,
Fig. 5 d are the porous gold-silver alloy nanosphere obtained by progress 30min, 60min, 90min chemical attack of the embodiment of the present invention 1
The nanosphere diameter change comparison diagram of oldered array, Fig. 5 e are that the embodiment of the present invention 1 carries out 30min, 60min, 90min chemistry
The nanosphere open pore size and tie change width comparison diagram of the obtained porous gold-silver alloy nanosphere oldered array of corrosion,
Fig. 5 f are the porous gold-silver alloy nanosphere obtained by progress 30min, 60min, 90min chemical attack of the embodiment of the present invention 1
The nanosphere gold and silver element ratio change comparison diagram of oldered array；Fig. 5 d abscissa is that Dealloying time (go to close
Aurification time, unit is min), ordinate is Average partide size (i.e. average grain diameter, unit is nm)；Fig. 5 e's
Abscissa is Dealloying time (i.e. the removal alloying time, unit is min), and left side ordinate is Average width
Of ligaments (i.e. tie mean breadth, unit is nm), right side ordinate is that Average size of pores (are put down
Equal pore size, unit is nm)；Fig. 5 f abscissa is that (i.e. removal alloying time, unit is Dealloying time
Min), ordinate is Atomic percentage (i.e. atomic percentage).As seen from Figure 5：With the removal alloying time
Increase, the particle size and silver atoms percentage of porous gold-silver alloy nanosphere be gradually reduced, and nanosphere perforate is flat
Equal aperture, tie width and gold atom percentage gradually increase.
(6) during stating the embodiment of the present invention 1 on the implementation, the polystyrene colloid microballoon used in step b suspends
Liquid uses the chemistry for carrying out 60min in a diameter of 350nm of colloid micro ball polystyrene colloid microsphere suspension liquid, step h rotten
Erosion, so that the cycle of being made spacing is 350nm porous gold-silver alloy nanosphere oldered array.The embodiment of the present invention 1 is made
Cycle spacing be 350nm porous gold-silver alloy nanosphere oldered array to be respectively put into concentration be 10-6mol/L、10- 7mol/L、 10-8mol/L、10-9Mol/L and 10-10Soak 30 minutes, and use in mol/L 4 sulfydryl benzenethiol ethanol solutions
Intelligent fourier infrared-Raman spectrometer NEXUS respectively in the sulfydryl benzenethiol ethanol solution of various concentrations 4 it is porous gold-
The SERS signal of silver alloy nanosphere oldered array is detected (a length of 785cm of excitation light wave-1, exciting light
Power be 1mW, the time of integration be 15s), so as to obtain surface-enhanced Raman signals comparison diagram as shown in Figure 6；Wherein, Fig. 6
Abscissa for Raman shift (i.e. Raman signal displacement, its unit be cm-1), ordinate is that Intensity (i.e. believe by Raman
Number intensity).As seen from Figure 6：Porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 is to 4 sulfydryl benzene sulphur
The detection limit of phenol can reach 10-10mol/L。
(7) during stating the embodiment of the present invention 1 on the implementation, the polystyrene colloid microballoon used in step b suspends
Liquid uses the chemistry for carrying out 60min in a diameter of 350nm of colloid micro ball polystyrene colloid microsphere suspension liquid, step h rotten
Erosion, so that the cycle of being made spacing is 350nm porous gold-silver alloy nanosphere oldered array.It is made with the embodiment of the present invention 1
Cycle spacing be 350nm porous gold-silver alloy nanosphere oldered array be that substrate detecting concentration is 10-6Mol/L 4 mercaptos
Base benzenethiol (a length of 785cm of excitation light wave-1, excitation light power be 1mW, the time of integration be 1s), and surface-enhanced Raman is dissipated
Penetrate signal stability and repeatability detected (i.e. Raman mapping sign, surface sweeping area be 100um x 100um,
Scanning stride is 5um), so as to obtain Raman signal intensity distribution map (i.e. Raman mapping figures) as shown in Figure 7；Its
In, Fig. 7 ordinate is SERS signal intensity.By Fig. 7 to find out：It is many prepared by the embodiment of the present invention 1
SERS signal detected by the gold-silver alloy nano material of hole has good stability and repeatability.
(8) during stating the embodiment of the present invention 1 on the implementation, the polystyrene colloid microballoon used in step b suspends
Colloid micro ball a diameter of 500nm and 750nm polystyrene colloid microsphere suspension liquid is respectively adopted in liquid, then using Sirion
200 field emission scanning electron microscopes are respectively to using the polystyrene colloid microsphere suspension liquid of both colloid micro ball diameters as original
The final obtained porous gold-silver alloy nanosphere oldered array of material is observed, and is shown so as to obtain scanning electron as shown in Figure 8
Micro mirror photo；Wherein, Fig. 8 a are outstanding with a diameter of 500nm of colloid micro ball polystyrene colloid microballoon in the embodiment of the present invention 1
Supernatant liquid is the electron scanning micrograph of the final obtained porous gold-silver alloy nanosphere oldered array of raw material, and Fig. 8 b are this
It is final obtained many by raw material of a diameter of 750nm of colloid micro ball polystyrene colloid microsphere suspension liquid in inventive embodiments 1
The electron scanning micrograph of hole gold-silver alloy nanosphere oldered array.As seen from Figure 8：The embodiment of the present invention 1 is made
The non-close-packed configuration of six sides that the standby cycle still keeps for 500nm and 750nm porous gold-silver alloy nanosphere oldered array,
And each particle has many perforates.
(9) cycle spacing made from the embodiment of the present invention 1 is closed for 350nm, 500nm, 750nm porous Jin-silver respectively
It is 10 that gold nanosphere oldered array, which is put into concentration,-6Soaked 30 minutes in mol/L 4 sulfydryl benzenethiol ethanol solutions, and it is right respectively
The SERS signal of the porous gold-silver alloy nanosphere oldered array of different cycles spacing, which is detected, (to be excited
The a length of 785cm of light wave-1, excitation light power be 1mW, the time of integration be 1s), so as to obtain surface-enhanced Raman as shown in Figure 9
Signal contrast figure；Wherein, Fig. 9 abscissa is that (i.e. Raman signal displacement, its unit is cm to Raman shift-1), ordinate
For Intensity (i.e. Raman signal intensity).As seen from Figure 9：Porous gold-silver alloy prepared by the embodiment of the present invention 1
Nano material, its SERS signal intensity is reduced with the increase in cycle.
As fully visible, the embodiment of the present invention can not only prepare large area (area>1cm2) cycle and size
The non-close multihode gold-silver alloy nanosphere oldered array of six sides of control, and preparation method is simple, it is relatively low to prepare cost, need not
Bind agent and stabilizer, be easy to target molecule absorption, it is convenient reuse, while prepared porous gold-silver alloy nanometer
Ball oldered array also there is excellent surface to strengthen Raman scattering performance.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (8)
1. a kind of porous gold-silver alloy nano material, it is characterised in that the porous gold-silver alloy nano material is that six sides are non-close
The porous gold-silver alloy nanosphere oldered array of structure is arranged, and the cycle of the porous gold-silver alloy nanosphere oldered array is
350~750nm；In the porous gold-silver alloy nanosphere oldered array, the particle scale of porous gold-silver alloy nanosphere is equal
It is even, and the diameter of each porous gold-silver alloy nanosphere is 204~330nm, on each porous gold-silver alloy nanosphere
It is respectively provided with multiple perforates.
2. porous gold-silver alloy nano material according to claim 1, it is characterised in that the porous gold-silver alloy is received
Rice ball is alloy structure, and its alloy tie is bicontinuous structure, and its alloy tie width is 7~16nm.
3. porous gold-silver alloy nano material according to claim 1 or 2, it is characterised in that porous gold-silver alloy is received
The aperture of perforate on rice ball is 4~11nm.
4. a kind of preparation method of porous gold-silver alloy nano material, it is characterised in that comprise the following steps：
Step A, using a diameter of 350~750nm of colloid micro ball colloid monolayer micro-sphere array as template, and use physical deposition side
Method deposits one layer of golden film on the surface of the template, then removes colloid monolayer micro-sphere array by being heat-treated, so that gold is made
Nanosphere oldered array；
Step B, use physical deposition method deposited on the surface of the gold nanosphere oldered array a layer thickness for 400~
700nm silverskin, then carries out heating anneal processing in protective atmosphere, and gold-silver alloy nanosphere oldered array is made；
Step C, using the method for chemical attack the orderly battle array of gold-silver alloy nanosphere is handled, closed with removing Jin-silver
The part silver element of gold nanosphere, so that the porous gold-silver alloy being made any one of the claims 1 to 3 is received
Rice material.
5. the preparation method of porous gold-silver alloy nano material according to claim 4, it is characterised in that institute in step B
The heating anneal processing that carried out in protective atmosphere stated includes：The gold nanosphere oldered array that deposition has silverskin is put into tube furnace
It is interior, and handled in the mixed atmosphere of hydrogen and nitrogen with 600 DEG C of heating anneals carried out 2 hours, silverskin and gold nanosphere meeting
Fusing, fusion, solidification in situ, so as to form gold-silver alloy nanosphere oldered array.
6. the preparation method of the porous gold-silver alloy nano material according to claim 4 or 5, it is characterised in that step C
Described in use chemical attack method to the gold-silver alloy nanosphere orderly battle array progress processing include：Using nitric acid, nitre
At least one of sour iron or ammoniacal liquor carry out chemical attack processing as corrosive agent to the orderly battle array of the gold-silver alloy nanosphere,
To remove part silver element.
7. the preparation method of the porous gold-silver alloy nano material according to claim 4 or 5, it is characterised in that the thing
Manage deposition process and use magnetron sputtering deposition, thermal evaporation deposition or electron-beam evaporation.
8. the porous gold-silver alloy nano material any one of the claims 1 to 3 is used as SERS
Substrate.
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