CN107309422B - A kind of porous gold-silver alloy nano material and the preparation method and application thereof - Google Patents
A kind of porous gold-silver alloy nano material and the preparation method and application thereof Download PDFInfo
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- CN107309422B CN107309422B CN201710352124.XA CN201710352124A CN107309422B CN 107309422 B CN107309422 B CN 107309422B CN 201710352124 A CN201710352124 A CN 201710352124A CN 107309422 B CN107309422 B CN 107309422B
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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
- 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
- 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
- B82Y40/00—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
- 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
- C23C14/223—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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- 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
Abstract
The invention discloses a kind of porous gold-silver alloy nano material and the preparation method and application thereof, which is the porous gold-silver alloy nanosphere oldered array of the non-solid matter of six sides, and the period is 350~750nm.The preparation method of the material includes: and to deposit one layer of golden film on the surface of template using physical deposition method using colloid monolayer micro-sphere array as template, then is 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, gold-silver alloy nanosphere oldered array is made；Chemical attack processing is carried out to the orderly battle array of the gold-silver alloy nanosphere, to obtain the porous gold-silver alloy nano material.The present invention can not only prepare the period of large area and the non-close multihode gold-silver alloy nanosphere oldered array of six sides that size is controllable, and without bind agent and stabilizer, be easy to target molecule absorption, facilitate 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 technique
Gold-silver alloy nano material has local surface plasma resonance characteristic, can generate strong Electromagnetic enhancement
Effect can be widely used in the analysis detection etc. based on Surface enhanced Raman scattering.Due to Surface enhanced Raman scattering
Sensitivity depends on " hot spot " position that electromagnetic field in nano material greatly enhances, therefore people have prepared with thick
Rough surface, tip, the isostructural gold-silver alloy nano material of corner angle, but these gold-silver alloys with high density " hot spot "
The sensitivity of nano material Surface enhanced Raman scattering in practical applications is also less desirable.It is 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 porous structure has high ratio
The features such as surface area, easy adsorption reaction object, high " hot spot " density, therefore application potential is huger.
Currently, the preparation method of porous gold-silver alloy nano material usually first prepares golden@galactic nucleus core/shell nanoparticles,
Then carry out high annealing, finally using the methods of electrochemistry, chemistry remove part silver element, but this preparation method compared with
For complicated, preparation cost is higher, large-scale quickly preparation difficult to realize, and high annealing easily cause particle between reunite,
The problems such as sintering, it is often more important that need that end-capping reagent or stabilizer is added during the preparation process, which prevent target molecules
Absorption, seriously affects its application value.
Summary of the invention
In order to solve, the preparation method complexity of existing porous gold-silver alloy nano material, preparation cost is higher and is making
It needs to hinder the technical problems such as target molecule absorption, the present invention provides one kind using end-capping reagent or stabilizer during standby
Porous gold-silver alloy nano material and the preparation method and application thereof.Porous gold-silver alloy nano material provided by the present invention
Preparation method can not only prepare large area (area > 1cm2) period and the size controllable non-close multihode of six sides
Gold-silver alloy nanosphere oldered array, and preparation method is simple, preparation cost is lower, without bind agent and stabilizer, easily
In target molecule absorption, facilitate reuse；And use porous gold-silver alloy nanosphere oldered array made from this method
Enhance Raman scattering performance with excellent surface.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of porous gold-silver alloy nano material, the porous gold-silver alloy nano material are the more of the non-close-packed configuration of six sides
Kong Jin-silver alloy nanosphere oldered array, and the period of the porous gold-silver alloy nanosphere oldered array be 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, is had on each porous gold-silver alloy nanosphere
There are multiple apertures.
Preferably, the porous gold-silver alloy nanosphere is alloy structure, and alloy tie is bicontinuous structure, is closed
Golden tie width is 7~16nm.
Preferably, the aperture of the aperture on porous gold-silver alloy nanosphere is 4~11nm.
A kind of preparation method of porous gold-silver alloy nano material, comprising the following steps:
Step A, the colloid monolayer micro-sphere array for being 350~750nm using colloid micro ball diameter is sunk as template, and using physics
Product method deposits one layer of golden film on the surface of the template, then by heat treatment removal colloid monolayer micro-sphere array, to make
Obtain gold nanosphere oldered array；
Step B, use physical deposition method the surface of the gold nanosphere oldered array deposit a layer thickness for 400~
Then the silverskin of 700nm carries out heating anneal processing in protective atmosphere, gold-silver alloy nanosphere oldered array is made；
Step C, the orderly battle array of gold-silver alloy nanosphere is handled using the method for chemical attack, with removal gold-
The part silver element of silver alloy nanosphere, to obtain porous gold-silver alloy nanometer material as described in the above technical scheme
Material.
Preferably, carrying out heating anneal processing described in step B in protective atmosphere includes: that will be deposited with the gold of silverskin
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 be melted, be merged, original position solidifies, to form gold-silver alloy nanosphere oldered array.
Preferably, the orderly battle array of the gold-silver alloy nanosphere is carried out using the method for chemical attack described in step C
Processing includes: to be had as corrosive agent to the gold-silver alloy nanosphere using at least one of nitric acid, ferric nitrate or ammonium hydroxide
Sequence battle array carries out chemical attack processing, to remove part silver element.
Preferably, the physical deposition method is using magnetron sputtering deposition, thermal evaporation deposition or electron beam evaporation deposition.
Porous gold-silver alloy nano material as described in the above technical scheme is used as the substrate of Surface enhanced Raman scattering.
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 for being 350~750nm using colloid micro ball diameter is existed as template, and using physical deposition method
The surface of the template deposits one layer of golden film, and by heat treatment removal colloid monolayer micro-sphere array, so that gold nanosphere be made
Oldered array；Then use physical deposition method the surface of the gold nanosphere oldered array deposit a layer thickness for 400~
The silverskin of 700nm, and heating anneal processing is carried out, so that gold-silver alloy nanosphere oldered array be made；It is rotten using chemistry again
The method of erosion handles the orderly battle array of gold-silver alloy nanosphere, to remove part silver element, 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
Column not only there is excellent surface to enhance Raman scattering performance, and period and size are controllable, and preparation method is simple, is prepared into
This is lower, without bind agent and stabilizer, be easy to target molecule absorption, facilitate reuse.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those skilled in the art, without creative efforts, it can also be obtained according to these attached drawings
His attached drawing.
Fig. 1 is when the polystyrene colloid for the use of colloid micro ball diameter being 350nm in the step b of the embodiment of the present invention 1 is micro-
When ball suspension, using 200 field emission scanning electron microscope of Sirion respectively to silicon substrate single layer polyphenyl obtained in step d
The gold of silicon substrate obtained in silicon substrate gold nanosphere oldered array, step g obtained in ethylene colloid micro ball oldered array, step f-
Porous gold-silver alloy nanosphere oldered array obtained in silver alloy nanosphere oldered array, step h is observed, thus
The electron scanning micrograph arrived.
Fig. 2 is the porous Jin-silver prepared using 200 field emission scanning electron microscope of Sirion to the embodiment of the present invention 1
Alloy nano-material is observed, low power scanning transmission electron microscope photo (the STEM photo) obtained from.
Fig. 3 is the porous Jin-silver prepared using JEOL-2100F high resolution transmission electron microscopy to the embodiment of the present invention 1
Single porous gold-silver alloy nanosphere is observed in alloy nano-material, and the scanning transmission electron microscope obtained from is shone
Piece.
Fig. 4 is to be carried out using X-ray energy disperse spectroscopy to porous gold-silver alloy nano material prepared by the embodiment of the present invention 1
Observation, thus X-ray energy spectrum diagram.
Fig. 5 be using 200 field emission scanning electron microscope of Sirion respectively to the embodiment of the present invention 1 carry out 30min,
The obtained porous gold-silver alloy nanosphere oldered array of 60min, 90min chemical attack is observed, and is swept obtained from
Retouch electron micrograph and porous gold-silver alloy nanosphere pattern variation comparison diagram.
Fig. 6 is porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 to 4 sulfydryl benzenethiol of various concentration
Ethanol solution is detected, the surface-enhanced Raman signals comparison diagram obtained from.
Fig. 7 is that porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 detects 4 sulfydryl benzenethiols,
And detect the stability and repeatability of Surface enhanced Raman scattering signal, the Raman signal intensity distribution map obtained from.
Fig. 8 be use 200 field emission scanning electron microscope of Sirion respectively to colloid micro ball diameter be 500nm and
The polystyrene colloid microsphere suspension liquid of 750nm is that the final porous gold-silver alloy nanosphere oldered array obtained of raw material carries out
Observation, the electron scanning micrograph obtained from.
Fig. 9 be respectively to the porous gold-silver alloy nanosphere oldered array that period spacing is 350nm, 500nm, 750nm into
Row Surface enhanced Raman scattering signal detection, the surface-enhanced Raman signals comparison diagram obtained from.
Figure 10 is the process signal of the preparation method of porous gold-silver alloy nano material provided by the embodiment of the present invention 1
Figure.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, every other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, protection scope of the present invention is belonged to.
Porous gold-silver alloy nano material provided by the present invention and the preparation method and application thereof is retouched in detail below
It states.
A kind of porous gold-silver alloy nano material, it is area > 1cm of the non-close-packed configuration of six sides2Porous Jin-silver close
Gold nanosphere oldered array, and its period regulates and controls within the scope 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, all has multiple apertures on each porous gold-silver alloy nanosphere.
Wherein, the porous gold-silver alloy nanosphere is alloy structure, and alloy tie is bicontinuous structure, alloy
Tie width regulates and controls within the scope of 7~16nm.The aperture of aperture on porous gold-silver alloy nanosphere is within the scope of 4~11nm
Regulation.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, the colloid monolayer micro-sphere array for being 350~750nm using colloid micro ball diameter is sunk as template, and using physics
Product method deposits one layer of golden film on the surface of the template, then by heat treatment removal colloid monolayer micro-sphere array, to make
Obtain gold nanosphere oldered array.
Further: the specific implementation process of step A may comprise steps of:
(1) step A1, substrate is sequentially placed into ethyl alcohol, is cleaned by ultrasonic in deionized water, it is all ultrasonic in every kind of liquid
Clean 20~60min, then to after cleaning substrate carry out drying and processing (such as: can be put into baking oven with 60 DEG C dry
20min), it is then placed into 20~60min of irradiation in UV ozone cleaning machine, to obtain the substrate of surface hydrophilic.In reality
In, the substrate can use glass slide or silicon wafer.
(2) step A2, in the substrate surface of the surface hydrophilic 1~2ml deionized water is added dropwise, then by colloid micro ball diameter
It is slowly dropped to along one jiao the surface of the substrate for the colloid micro ball ethyl alcohol dilution of 350~750nm, and passes through solution-air circle
The colloid monolayer micro-sphere array that colloid micro ball diameter is 350~750nm is made in face self-assembling method on the substrate.It is described
Colloid monolayer micro-sphere array is preferably transferred in silicon wafer substrate.In practical applications, taking colloid micro ball diameter is 350~750nm
Colloid micro ball suspension (the colloid micro ball suspension can using commercial means purchase polystyrene colloid microsphere suspension liquid
Or polymethyl methacrylate colloid micro ball suspension), and mixed in equal volume with ethyl alcohol, then carry out the ultrasound point of 10~30min
It dissipates, to can be prepared by the colloid micro ball ethyl alcohol dilution that finely dispersed colloid micro ball diameter is 350~750nm.
(3) step A3, be 350~750nm using the colloid micro ball diameter colloid monolayer micro-sphere array as template, and
The golden film for using physical deposition method to deposit a layer thickness on the surface of the template as 16~200nm, is then placed in annealing furnace
In with 1000 DEG C heat 2 hours, to remove colloid monolayer micro-sphere array, so that obtaining the gold nanosphere of the non-solid matter of six sides has
Sequence array.In practical applications, magnetron sputtering deposition, thermal evaporation deposition or electronics can be used in the physical deposition method
Beam evaporation deposition.
Step B, use physical deposition method the surface of the gold nanosphere oldered array deposit a layer thickness for 400~
Then the silverskin of 700nm carries out heating anneal processing in protective atmosphere, gold-silver alloy nanosphere oldered array is made.
Further: the specific implementation process of step B may comprise steps of:
(1) step B1, use physical deposition method the surface of the gold nanosphere oldered array deposit a layer thickness for
The silverskin of 400~700nm, so that the gold nanosphere oldered array for being deposited with silverskin be made.In practical applications, the object
Magnetron sputtering deposition, thermal evaporation deposition or electron beam evaporation deposition can be used in reason deposition method.
(2) step B2, the gold nanosphere oldered array for being deposited with silverskin is put into tube furnace, and in hydrogen and nitrogen
The heating anneal carried out 2 hours in mixed atmosphere with 600 DEG C is handled, and silverskin and gold nanosphere can be melted, be merged, solidifying in situ,
To form gold-silver alloy nanosphere oldered array.In practical applications, Muffle furnace can be used in the tube furnace；Hydrogen with
In the mixed atmosphere of nitrogen, percent by volume shared by hydrogen is 10%.
Step C, the gold-silver alloy nanosphere oldered array is handled using the method for chemical attack, with removal
Gold-silver alloy nanosphere part silver element, so that area > 1cm be made2Porous gold-silver alloy nanosphere oldered array,
Porous gold-silver alloy nano material i.e. as described in the above technical scheme.Wherein, the method pair using chemical attack
It includes: using the conduct of at least one of nitric acid, ferric nitrate or ammonium hydroxide that the orderly battle array of gold-silver alloy nanosphere, which carries out processing,
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 below beneficial to effect
Fruit:
(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
Column, the ordered structure with the non-solid matter of six sides, and porous gold-silver alloy nanosphere has good monodispersity and stabilization
Property, it can be saved for a long time in room temperature and air.
(2) porous gold-silver alloy nano material provided by the present invention, the porous gold-silver alloy nanosphere of non-solid matter
The features such as all having the aperture of many openings and surface be clean, having both big specific surface area and easy adsorption reaction object.
(3) there is porous gold-silver alloy nano material provided by the present invention excellent surface to enhance Raman scattering performance, can
Substrate as Surface enhanced Raman scattering, not only detectable molecular species is more, detection limits low, high sensitivity, stability
It is good, and the obtained Surface enhanced Raman scattering signal of detection all had in the larger area of 100um x 100um it is excellent
Stability and repeatability；Such as: porous gold-silver alloy nano material provided by the present invention can be used for 4 sulfydryl benzenethiols
Detection, and to the Surface enhanced Raman scattering signal of 4 sulfydryl benzenethiols have very strong humidification, not only stability it is good,
Signal repeatability is strong, and detection limit is low, detection limit can achieve 10-10mol/L.As it can be seen that provided by the present invention porous
Gold-silver alloy nano material can be in Surface Enhanced Raman Scattering Spectrum, surface plasma bulk optics, catalysis reaction, information storage
Deposit etc. realizes large-scale commercial application.
(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 proportions of diameter, gold and silver of silver alloy nanosphere and porous gold-silver alloy nanosphere, thus
The porous gold-silver alloy nanosphere of different-diameter, different open pore sizes, 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 expensive special equipment, without using bind agent and stabilizer,
Preparation process is simple, it is low in cost, easily operated, facilitate reuse.
To sum up, the embodiment of the present invention can not only prepare large area (area > 1cm2) period and size
The non-close multihode gold-silver alloy nanosphere oldered array of six sides of control, and preparation method is simple, preparation cost is lower, is not necessarily to
Bind agent and stabilizer, be easy to target molecule absorption, facilitate reuse, while prepared porous gold-silver alloy nanometer
Also there is ball oldered array excellent surface to enhance Raman scattering performance.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
Porous gold-silver alloy nano material provided by the present invention and the preparation method and application thereof is described in detail in body embodiment.
Embodiment 1
As shown in Figure 10, a kind of porous gold-silver alloy nano material, preparation method includes the following steps:
Step a, glass slide, silicon wafer both substrates are sequentially placed into acetone, ethyl alcohol, to carry out ultrasound in deionized water clear
Wash, be all cleaned by ultrasonic 20~60min in every kind of liquid, then by after cleaning glass slide and silicon wafer be put into baking oven and dried with 60 DEG C
Then dry glass slide, silicon wafer are placed in 20~60min of irradiation in UV ozone cleaning machine, to obtain by dry 20min
The glass slide substrate and silicon wafer substrate of surface hydrophilic.
Step b, taking 40mL colloid micro ball diameter is the polystyrene colloid microsphere suspension liquid of 350~750nm
(2.5wt.%), and be uniformly mixed with isometric ethyl alcohol, then carry out the ultrasonic disperse of 10~30min, it is uniformly dispersed to be made
Colloid micro ball diameter be 350~750nm polystyrene colloid microballoon ethyl alcohol dilution.
Step c, 1~2ml deionized water is added dropwise on the surface of the glass slide substrate of the surface hydrophilic, then by the polyphenyl
Ethylene colloid micro ball ethyl alcohol dilution is slowly dropped to the surface of glass slide substrate along one jiao of glass slide substrate, and uses gas-
Liquid interface self-assembling method is in glass slide substrate over-assemble at single layer polystyrene colloid microballoon oldered array.
Step d, the single layer polystyrene colloid microballoon oldered array in glass slide substrate is transferred in silicon wafer substrate, from
And obtain silicon substrate single layer polystyrene colloid microballoon oldered array.
Step e, it using the silicon substrate single layer polystyrene colloid microballoon oldered array as template, and is deposited using magnetron sputtering
It is 16~200nm that method (electric current 20mA, magnetron sputtering time are 3min), which deposits a layer thickness on the surface of the template,
Golden film, thus be made golden film covering silicon substrate single layer polystyrene colloid microballoon oldered array.
Step f, the silicon substrate single layer polystyrene colloid microballoon oldered array that the golden film covers is placed in Muffle furnace,
And heating anneal processing is carried out in air atmosphere, heating temperature is 1000 DEG C, and heating time is 2 hours, to remove single layer glue
Body micro-sphere array, so that the silicon substrate gold nanosphere oldered array of the non-solid matter of six sides be made.
Step g, use magnetron sputtering deposition method (electric current 20mA, magnetron sputtering time are 6~12min) 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 the heating anneal carried out 2 hours in the mixed atmosphere of hydrogen and nitrogen with 600 DEG C is handled, silverskin and gold nanosphere meeting
Fusing, fusion, solidification in situ, obtain silicon substrate gold-silver alloy nanosphere oldered array after cooling.
Step h, the orderly battle array of silicon substrate gold-silver alloy nanosphere is put into the nitre of 3mol/L using the method for chemical attack
In acid, to remove part silver element, so that area > 1cm be made2Porous gold-silver alloy nanosphere oldered array, i.e., it is described
Porous gold-silver alloy nano material.
Specifically, the porous gold-silver alloy nano material prepared to the embodiment of the present invention 1 is detected as follows:
(1) during stating the embodiment of the present invention 1 on the implementation, polystyrene colloid microballoon used in step b suspends
Liquid uses colloid micro ball diameter for the polystyrene colloid microsphere suspension liquid of 350nm, while being swept using 200 Flied emission of Sirion
Electron microscope is retouched respectively to obtaining in silicon substrate single layer polystyrene colloid microballoon oldered array, step f obtained in step d
Silicon substrate gold nanosphere oldered array, obtain in silicon substrate gold-silver alloy nanosphere oldered array, step h obtained in step g
Porous gold-silver alloy nanosphere oldered array be observed, to obtain electron scanning micrograph as shown in Figure 1；
Wherein, Fig. 1 a is the electron scanning micrograph for the silicon substrate single layer polystyrene colloid microballoon oldered array that step d is obtained,
Fig. 1 b is the electron scanning micrograph of silicon substrate gold nanosphere oldered array obtained in step f, and Fig. 1 c is to obtain in step g
The electron scanning micrograph of the silicon substrate gold-silver alloy nanosphere oldered array arrived, Fig. 1 d are porous obtained in step h
The electron scanning micrograph of gold-silver alloy nanosphere oldered array.As seen from Figure 1: 1 step h of the embodiment of the present invention
Obtained in porous gold-silver alloy nanosphere oldered array array structure be the non-close-packed configuration of six sides.
(2) it is closed using porous Jin-silver that 200 field emission scanning electron microscope of Sirion prepares the embodiment of the present invention 1
Gold nano-material is observed, to obtain low power scanning transmission electron microscope photo (STEM photo) 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 has fine periodic structure
Porous gold-silver alloy nanosphere oldered array.
(3) it is closed using porous Jin-silver that JEOL-2100F high resolution transmission electron microscopy prepares the embodiment of the present invention 1
Single porous gold-silver alloy nanosphere in gold nano-material is observed, to obtain scanning transmission electricity as shown in Figure 3
Sub- microscope photo；Wherein, Fig. 3 b is two kinds of gold and silver in the single porous gold-silver alloy nanosphere of the preparation of 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: the embodiment of the present invention 1 is prepared single porous
Two kinds of elements of gold, silver are uniformly distributed in gold-silver alloy nanosphere, this illustrates single porous gold-prepared by the embodiment of the present invention 1
Silver alloy nanosphere is alloy structure.
(4) porous gold-silver alloy nano material prepared by the embodiment of the present invention 1 is visited using X-ray energy disperse spectroscopy
It surveys, 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 of two kinds of elements of gold, silver, and carbon (C) and copper (Cu) are from copper mesh in Fig. 4.
(5) during stating the embodiment of the present invention 1 on the implementation, when carrying out the chemical attack of step h, using Sirion
200 field emission scanning electron microscopes porous gold-silver alloy obtained to chemical attack 30min, 60min, 90min respectively
Nanosphere oldered array is observed, to obtain electron scanning micrograph and porous gold-silver alloy as shown in Figure 5
Nanosphere pattern changes comparison diagram；Wherein, Fig. 5 a is porous obtained by the progress 30min chemical attack 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 that the present invention is implemented
Example 1 carries out the electron scanning micrograph of porous gold-silver alloy nanosphere oldered array obtained by 90min chemical attack,
Fig. 5 d is that the embodiment of the present invention 1 carries out porous gold-silver alloy nanosphere obtained by 30min, 60min, 90min chemical attack
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 is that the embodiment of the present invention 1 carries out porous gold-silver alloy nanosphere obtained by 30min, 60min, 90min chemical attack
The nanosphere gold and silver element ratio of oldered array changes comparison diagram；The abscissa of Fig. 5 d is that Dealloying time (goes to close
Aurification time, unit min), ordinate is Average partide size (i.e. average grain diameter, unit nm)；Fig. 5 e's
Abscissa is Dealloying time (i.e. removal alloying time, unit min), and left side ordinate is Average width
Of ligaments (i.e. tie mean breadth, unit nm), right side ordinate are Average size of pores (i.e. flat
Equal pore size, unit nm)；The abscissa of Fig. 5 f is that (i.e. removal alloying time, unit are 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 aperture 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, polystyrene colloid microballoon used in step b suspends
Liquid uses colloid micro ball diameter for the polystyrene colloid microsphere suspension liquid of 350nm, and the chemistry that 60min is carried out in step h is rotten
Erosion, so that the porous gold-silver alloy nanosphere oldered array that period spacing is 350nm be made.The embodiment of the present invention 1 is made
Period 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 10-10It impregnates 30 minutes, and uses in the 4 sulfydryl benzenethiol ethanol solutions of mol/L
Intelligent fourier infrared-Raman spectrometer NEXUS is respectively to the porous gold-in 4 sulfydryl benzenethiol ethanol solution of various concentration
The Surface enhanced Raman scattering signal of silver alloy nanosphere oldered array is detected (a length of 785cm of excitation light wave-1, exciting light
Power is 1mW, time of integration 15s), to obtain surface-enhanced Raman signals comparison diagram as shown in FIG. 6；Wherein, Fig. 6
Abscissa be Raman shift (i.e. Raman signal be displaced, unit 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 achieve 10-10mol/L。
(7) during stating the embodiment of the present invention 1 on the implementation, polystyrene colloid microballoon used in step b suspends
Liquid uses colloid micro ball diameter for the polystyrene colloid microsphere suspension liquid of 350nm, and the chemistry that 60min is carried out in step h is rotten
Erosion, so that the porous gold-silver alloy nanosphere oldered array that period spacing is 350nm be made.It is made with the embodiment of the present invention 1
Period spacing be 350nm porous gold-silver alloy nanosphere oldered array be substrate detecting concentration be 10-64 mercaptos of mol/L
Base benzenethiol (a length of 785cm of excitation light wave-1, excitation light power 1mW, time of integration 1s), and to surface-enhanced Raman dissipate
The stability and repeatability for penetrating signal detected (i.e. Raman mapping characterization, surface sweeping area be 100um x 100um,
Scanning stride is 5um), to obtain Raman signal intensity distribution map as shown in Figure 7 (i.e. Raman mapping figure)；Its
In, the ordinate of Fig. 7 is Surface enhanced Raman scattering signal strength.As Fig. 7 to find out: more prepared by the embodiment of the present invention 1
Surface enhanced Raman scattering 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, polystyrene colloid microballoon used in step b suspends
The polystyrene colloid microsphere suspension liquid that colloid micro ball diameter is 500nm and 750nm is respectively adopted in liquid, then uses Sirion
200 field emission scanning electron microscopes respectively to the polystyrene colloid microsphere suspension liquid of both colloid micro ball diameters be original
The final porous gold-silver alloy nanosphere oldered array obtained of material is observed, so that it is aobvious to obtain scanning electron as shown in Figure 8
Micro mirror photo；Wherein, Fig. 8 a is outstanding for the polystyrene colloid microballoon of 500nm with colloid micro ball diameter in the embodiment of the present invention 1
Supernatant liquid is the electron scanning micrograph of the final porous gold-silver alloy nanosphere oldered array obtained of raw material, and Fig. 8 b is this
It is final obtained more as raw material for the polystyrene colloid microsphere suspension liquid of 750nm using colloid micro ball diameter 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 standby period is the non-close-packed configuration of six sides that the porous gold-silver alloy nanosphere oldered array of 500nm and 750nm is still kept,
And there are many apertures for each particle.
(9) porous Jin-silver that period spacing made from the embodiment of the present invention 1 is 350nm, 500nm, 750nm is closed respectively
It is 10 that gold nanosphere oldered array, which is put into concentration,-6It is impregnated 30 minutes in the 4 sulfydryl benzenethiol ethanol solutions of mol/L, and right respectively
The Surface enhanced Raman scattering signal of the porous gold-silver alloy nanosphere oldered array of different cycles spacing is detected (excitation
The a length of 785cm of light wave-1, excitation light power 1mW, time of integration 1s), to obtain surface-enhanced Raman as shown in Figure 9
Signal contrast figure；Wherein, the abscissa of Fig. 9 is that (i.e. Raman signal is displaced Raman shift, unit cm-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, Surface enhanced Raman scattering signal strength are reduced with the increase in period.
To sum up, the embodiment of the present invention can not only prepare large area (area > 1cm2) period and size
The non-close multihode gold-silver alloy nanosphere oldered array of six sides of control, and preparation method is simple, preparation cost is lower, is not necessarily to
Bind agent and stabilizer, be easy to target molecule absorption, facilitate reuse, while prepared porous gold-silver alloy nanometer
Also there is ball oldered array excellent surface to enhance Raman scattering performance.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (7)
1. a kind of porous gold-silver alloy nano material, which is characterized in that the porous gold-silver alloy nano material is six Fang Feimi
The porous gold-silver alloy nanosphere oldered array of structure is arranged, and the period 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
All have multiple apertures；
The porous gold-silver alloy nanosphere is alloy structure, and alloy tie is bicontinuous structure, and alloy tie width is
7~16nm.
2. porous gold-silver alloy nano material according to claim 1, which is characterized in that porous gold-silver alloy nanosphere
On aperture aperture be 4~11nm.
3. a kind of preparation method of porous gold-silver alloy nano material, which comprises the following steps:
Step A, the colloid monolayer micro-sphere array for being 350~750nm using colloid micro ball diameter is template, and uses physical deposition side
Method deposits one layer of golden film on the surface of the template, then by heat treatment removal colloid monolayer micro-sphere array, so that gold be made
Nanosphere oldered array；
Step B, use physical deposition method the surface of the gold nanosphere oldered array deposit a layer thickness for 400~
Then the silverskin of 700nm carries out heating anneal processing in protective atmosphere, gold-silver alloy nanosphere oldered array is made；
Step C, the orderly battle array of gold-silver alloy nanosphere is handled using the method for chemical attack, is closed with removing Jin-silver
The part silver element of gold nanosphere is received to obtain porous gold-silver alloy described in any one of the claims 1 to 2
Rice material.
4. the preparation method of porous gold-silver alloy nano material according to claim 3, which is characterized in that institute in step B
The heating anneal processing that carries out in protective atmosphere stated includes: that the gold nanosphere oldered array for being deposited with silverskin is put into tube furnace
It is interior, and the heating anneal carried out 2 hours in the mixed atmosphere of hydrogen and nitrogen with 600 DEG C is handled, silverskin and gold nanosphere meeting
Fusing, fusion, solidification in situ, to form gold-silver alloy nanosphere oldered array.
5. the preparation method of porous gold-silver alloy nano material according to claim 3 or 4, which is characterized in that step C
Described in the method using chemical attack to the orderly battle array of gold-silver alloy nanosphere carry out processing include: using nitric acid, nitre
At least one of sour iron or ammonium hydroxide carry out chemical attack processing to the orderly battle array of the gold-silver alloy nanosphere as corrosive agent,
To remove part silver element.
6. the preparation method of porous gold-silver alloy nano material according to claim 3 or 4, which is characterized in that the object
Deposition method is managed using magnetron sputtering deposition, thermal evaporation deposition or electron beam evaporation deposition.
7. porous gold-silver alloy applications to nanostructures described in any one of the claims 1 to 2, which is characterized in that use
Make the substrate of Surface enhanced Raman scattering.
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| CN108044127B (en) * | 2017-12-14 | 2020-11-06 | 中国科学院合肥物质科学研究院 | Three-dimensional porous gold-silver-platinum ternary alloy nano material and preparation method and application thereof |
| CN109738417B (en) * | 2019-01-25 | 2020-02-18 | 中南大学 | Method for detecting tumor cells by using porous gold nanospheres |
| CN110044872B (en) * | 2019-05-10 | 2021-02-12 | 山东大学 | Surface-enhanced Raman substrate and preparation method and application thereof |
| CN111364092B (en) * | 2020-03-26 | 2021-06-08 | 新疆艾旗斯德检测科技有限公司 | Preparation method of silver-porous silicon-based surface enhanced Raman scattering biological detection chip |
| CN111398248A (en) * | 2020-04-22 | 2020-07-10 | 南通大学 | Preparation method of nanogold film SERS substrate based on multi-morphology silver modification |
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