CN104977289A - Ordered nanostructured precious metal array, and preparation method and use thereof - Google Patents
Ordered nanostructured precious metal array, and preparation method and use thereof Download PDFInfo
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Abstract
The invention discloses an ordered nanostructured precious metal array, and a preparation method and a use thereof. The array is characterized in that projections with the height positioned in hexagons being not greater than 20nm are arranged at the column ends of a nanometer hexagonal prism for composing a gold-silver alloy nanometer hexagonal prism array or a porous gold nanometer hexagonal prism array, the column structure cycle of the nanometer hexagonal prism is 470-500nm, the column height of the nanometer hexagonal prism is 50-200nm, the column wall of the nanometer hexagonal prism has a concave arc shape, and the column gap of adjacent nanometer hexagonal prisms is 5-50nm. The method comprises the following steps: producing a through-hole alumina template with the hole diameter of 160-380nm, the hole cycle of 470-500nm and the hole gap of a hexagonal concave-convex structure array by using a two-stage anode oxidation technology, coating the through-hole alumina template as a die on a gold-silver alloy film or a porous gold film, and applying a pressure being not greater than 5.7*10<6>N/m<2> to the through-hole alumina template to prepare a target product. The ordered nanostructured precious metal array can be used as a surface enhanced Raman scattering active substrate, and the content of rhodamine or methyl parathion or polychlorinated biphenyl-3 adhered on the active substrate can be measured by using a laser Raman spectrometer.
Description
Technical field
The present invention relates to a kind of ordered nano-structure array and preparation method and purposes, especially a kind of noble metal ordered nano-structure array and its production and use.
Background technology
In recent years, Surface enhanced raman spectroscopy (SERS) technology based on the noble metal nano such as gold, silver, copper structure Electromagnetic enhancement mechanism has simply, quick, sensitivity advantages of higher, accurately can reflect the finger print information of chemistry and biomolecular structure, develop into one of noticeable trace detection technology.Theoretical and experimental study shows, SERS effect is mainly derived from the Electromagnetic enhancement produced between nano unit.When gap between nano unit is less than 10nm, its gap location can produce very strong local coupling electric field, is usually referred to as SERS " focus ".Therefore, people are in order to obtain noble metal ordered nano-structure, some good tries and effort are done, gold nano stick array of a kind of top coated with silver of the applicant announced on April 25th, 2012 as Chinese invention patent CN 102041507B and its preparation method and application.The array mentioned in this invention is be equipped with on golden film that its top is coated with gold nano stick array that diameter is the silver nano-grain of 60 ~ 90nm, bottom surface is equipped with the organic substrate that thickness is 50 ~ 100 μm, preparation method first uses anodizing to obtain nanometer nanohole alumine template, gold nano stick array is grown again in a gold evaporation film of nanometer nanohole alumine template and the hole in this template, afterwards, liquid state organics is applied prior to not growing to have on gold nano stick array golden film simultaneously, after its solidification, again its evaporation there is golden film, deposit in hole and gold nano stick array and golden film are coated with organic alumina formwork are placed in acid or aqueous slkali, erode alumina formwork, then, use film vapor deposition technology in the top evaporation silver of gold nano stick array, obtained product.Though product can be used as the active substrate of Surface enhanced raman spectroscopy, laser Raman spectrometer is used to measure the trace rhodamine or 2 of attachment on it, 3,3 '-trichloro biphenyl, there is unsatisfactory part also, first, the interrod spacing forming the gold nanorods of gold nano stick array in product is same as excellent diameter 40 ~ 80nm, spacing between the silver nano-grain that gold nanorods top is coated with is also identical with its particle diameter, and gap larger between this nano unit is difficult to produce stronger electromagnetic field; Secondly, preparation method can not obtain between nano unit has more closely spaced product, have again that Making programme is complicated, time-consuming consumptive material---Template preparation, electrode evaporation, product production, reinforcing substrate and go the defects such as template, alumina formwork can't be made to be reused, cause cost higher, be unfavorable for the commercial applications of product.
Summary of the invention
The technical problem to be solved in the present invention, for overcoming shortcoming part of the prior art, provides the noble metal ordered nano-structure array that a kind of nano unit gap on it is less.
Another technical matters that the present invention will solve is for providing a kind of preparation method that can reuse the above-mentioned noble metal ordered nano-structure array of alumina formwork.
Another technical matters that the present invention will solve is for providing a kind of purposes of above-mentioned noble metal ordered nano-structure array.
For solving technical matters of the present invention, the technical scheme adopted is: noble metal ordered nano-structure array comprises noble metal film, particularly,
Described noble metal film is gold-silver alloy film or porous gold thin film;
Described gold-silver alloy film is equipped with gold-silver alloy nanometer six array of prisms;
Described porous gold thin film is equipped with porous gold nano six array of prisms;
The styletable of nanometer six prism of described composition gold-silver alloy nanometer six array of prisms or porous gold nano six array of prisms is equipped with the projection of the height≤20nm being positioned at hexagonal place, the rod structure cycle of nanometer six prism is 470 ~ 500nm, the post of nanometer six prism is high is 50 ~ 200nm, the post jamb of nanometer six prism is arcs of recesses, the intercolumniation gap of adjacent nano six prism is 5 ~ 50nm, wherein, the intercolumniation gap at nanometer six prism hexagonal place is 5 ~ 15nm, the intercolumniation gap at nanometer six prism arcs of recesses post jamb place is 20 ~ 50nm.
Further improvement as noble metal ordered nano-structure array:
Preferably, nanometer six prism being equipped with that excellent diameter is 160 ~ 380nm, rod is high is the nanometer rods of 10 ~ 200nm.
Preferably, a pair of nanometer six prism adjacent two prism limits are equipped with the quadrangular that width is 20 ~ 65nm.
For solving another technical matters of the present invention, another technical scheme adopted is: the preparation method of above-mentioned noble metal ordered nano-structure array comprises anodizing, and particularly key step is as follows:
Step 1, first aluminium flake is placed in-1 ~ 3 DEG C, in the phosphoric acid solution of 0.5 ~ 1.5wt%, in the DC constant voltage anodic oxygenization 3.5 ~ 4.5h of 190 ~ 200V, be placed on again in the phosphorus chromic acid mixture of 55 ~ 65 DEG C and soak 9 ~ 11h, then, after carrying out second time anodic oxidation 13 ~ 15h under it being placed in again same process conditions, first remove the unoxidized aluminium in the back side with saturated tin chloride solution, be placed on again in the phosphoric acid solution of the 8 ~ 12wt% of 48 ~ 52 DEG C and remove reaming 5 ~ 25min after barrier layer, obtaining bore dia is 160 ~ 380nm, the hole cycle is 470 ~ 500nm, it is the nanohole alumine template of hexagon concaveconvex structure array between hole, wherein, the outer wall that hexagon concaveconvex structure is formed by hole and periphery pit, the inwall formed between adjacent pit between hole is formed, pit wherein is all positioned at the hexagonal place of hexagon concaveconvex structure, the thickness of inwall is 5 ~ 50nm, the relative height difference of outer wall and inwall is 50 ~ 200nm,
Step 2, is first overlying on nanohole alumine template in gold-silver alloy film or porous gold thin film as mould, then applies≤5.7 × 10 to nanohole alumine template
6n/m
2pressure, obtained noble metal ordered nano-structure array.
Further improvement as the preparation method of noble metal ordered nano-structure array:
Preferably, before carrying out anodic oxidation to aluminium flake, after the 5h that anneals at being placed on 500 DEG C, the volume ratio being placed in perchloric acid and ethanol is the perchloric acid ethanolic solution of 1:3, electrochemical polish 2min under direct current 18V.
Preferably, phosphorus chromic acid mixture is the mixed solution of the phosphoric acid solution of 6wt% and the chromic acid solution of 1.8wt%.
Preferably, before exerting pressure to nanohole alumine template, α – cyanacrylate is used to be fixed on silicon chip.
Preferably, before carrying out mold pressing to gold-silver alloy film, after the 10h that anneals at being placed on 850 DEG C, α – cyanacrylate is used to be fixed on silicon chip.
Preferably, the manufacturing process of porous gold thin film is, after the 10h that anneals, is placed in 0 DEG C, the salpeter solution of 65wt%, galvanic corrosion 6min under the DC constant voltage of 0.4V at first gold-silver alloy film being placed in 850 DEG C, then uses washed with de-ionized water to it and dry.
Preferably, before carrying out mold pressing to porous gold thin film, α – cyanacrylate is used to be fixed on silicon chip.
Preferably, >5.7 × 10 are applied to nanohole alumine template
6n/m
2pressure, obtain noble metal ordered nano-structure array nanometer six prism being equipped with nanometer rods.
Preferably, after nanohole alumine template is moved in parallel 20 ~ 65nm along an opposite side of nanometer six prism ,≤5.7 × 10 are applied to nanohole alumine template
6n/m
2pressure, a pair adjacent two prism limit obtaining nanometer six prism are equipped with the noble metal ordered nano-structure array of quadrangular.
For solving another technical matters of the present invention, another technical scheme adopted is: the purposes of above-mentioned noble metal ordered nano-structure array is,
Using the active substrate of noble metal ordered nano-structure array as Surface enhanced raman spectroscopy, laser Raman spectrometer is used to measure the rhodamine (R6G) of attachment or the content of parathion-methyl or polychlorinated biphenyl-3 (PCB-3) on it.
Further improvement as the purposes of noble metal ordered nano-structure array:
Preferably, the excitation wavelength of laser Raman spectrometer is 633nm, output power is 0.4 ~ 0.6mW, integral time is 25 ~ 35s.
Relative to the beneficial effect of prior art be:
One, use scanning electron microscope to characterize to obtained object product, from its result, object product is gold-silver alloy film is equipped with in gold-silver alloy nanometer six array of prisms or porous gold thin film to be equipped with porous gold nano six array of prisms; Wherein, the styletable of nanometer six prism of composition gold-silver alloy nanometer six array of prisms or porous gold nano six array of prisms is equipped with the projection of the height≤20nm being positioned at hexagonal place, the rod structure cycle of nanometer six prism is 470 ~ 500nm, the post of nanometer six prism is high is 50 ~ 200nm, the post jamb of nanometer six prism is arcs of recesses, the intercolumniation gap of adjacent nano six prism is 5 ~ 50nm, wherein, the intercolumniation gap at nanometer six prism hexagonal place is 5 ~ 15nm, the intercolumniation gap at nanometer six prism arcs of recesses post jamb place is 20 ~ 50nm.Nanometer six prism being equipped with excellent diameter is 160 ~ 380nm, rod is high is the nanometer rods of 10 ~ 200nm.A pair adjacent two prism limit of nanometer six prism are equipped with the quadrangular that width is 20 ~ 65nm.Thisly be equipped with porous gold nano six array of prisms by gold-silver alloy film being equipped with in gold-silver alloy nanometer six array of prisms or porous gold thin film, or the nanometer rods that affix nanometer six prism is equipped with, the object product that the quadrangular that a pair adjacent two prism limit of nanometer six prism are equipped with is assembled into, both due to the more closely spaced existence between nanometer six prism, and the local coupling electric field of gap location is drastically increased; Again because forming a large amount of nanometer six prism of array, and further increasing the electromagnetic intensity of object product entirety; Also the surfaceness of object product and specific surface area is made to obtain larger lifting due to the intercolumniation gap of adjacent nano six prism of magnanimity, also make it have significant raising to the adsorptive power of testing molecule, thus make the active and cost performance of its SERS all obtain raising in various degree.
Its two, using obtained object product as SERS active-substrate, through carrying out the tests of the repeatedly many batches under variable concentrations respectively to rhodamine, parathion-methyl and polychlorinated biphenyl-3, when the concentration of measured object rhodamine is low to moderate 10
-11the concentration of mol/L, parathion-methyl is low to moderate 10
-7the concentration of mol/L, polychlorinated biphenyl-3 is low to moderate 10
-5during mol/L, still it can be detected effectively, and its consistance detected and the multiple spot of repeatability on object product and any point all very good.
Its three, preparation method is simple, science, efficient.Not only obtain object product---the noble metal ordered nano-structure array that nano unit gap on it is less; After also making object product coordinate with laser Raman spectrometer, possesses the function of rhodamine, parathion-methyl and environmental toxic pollutant polychlorinated biphenyl-3 being carried out to quick trace detection; More have technique simple, save time convenient, cost is low, and environmental protection---alumina formwork is reusable, the feature that the consistance of object product morphology is good; Thus make object product very easily in the quick detection being widely used for the fields such as environment, chemistry, biology, and large-scale commercial applications.
Accompanying drawing explanation
Fig. 1 is the mould to making---one of result that nanohole alumine template uses scanning electron microscope (SEM) to characterize.Wherein, Fig. 1 a be mould overlook SEM image, Fig. 1 b is stravismus (about 45 degree, inclination angle) the SEM image of mould.
Fig. 2 is to one of result that the object product adopting gold-silver alloy film to obtain uses scanning electron microscope to characterize.Wherein, the SEM image of product for the purpose of Fig. 2 a, Fig. 2 b is the partial enlargement SEM image of Fig. 2 a, and Fig. 2 c is the SEM image of object product nanometer six prism being equipped with nanometer rods, and Fig. 2 d is the partial enlargement SEM image of Fig. 2 c.
Fig. 3 is to one of result that the object product adopting porous gold thin film to obtain uses scanning electron microscope to characterize.Wherein, the SEM image of product for the purpose of Fig. 3 a, Fig. 3 b is the partial enlargement SEM image of Fig. 3 a, and Fig. 3 c is the SEM image of object product nanometer six prism being equipped with nanometer rods, and Fig. 3 d is the partial enlargement SEM image of Fig. 3 c.
Fig. 4 is to one of result that the object product adopting gold-silver alloy film to obtain uses scanning electron microscope to characterize.As seen from Figure 4, the width of quadrangular that a pair of nanometer six prism adjacent two prism limit are equipped be respectively 20nm (Fig. 4 a), 40nm (Fig. 4 b) and 65nm (Fig. 4 c).
Fig. 5 is to one of result that the object product containing variable concentrations rhodamine uses laser Raman spectrometer to characterize.
Fig. 6 is respectively to one of result that the object product containing parathion-methyl and polychlorinated biphenyl-3 uses laser Raman spectrometer to characterize.Wherein, for the purpose of Fig. 6 a product to containing the susceptibility of variable concentrations parathion-methyl; For the purpose of Fig. 6 b, product is to the susceptibility containing variable concentrations polychlorinated biphenyl-3.
Embodiment
Below in conjunction with accompanying drawing, optimal way of the present invention is described in further detail.
First buy from market or obtain voluntarily:
The aluminium flake of purity >=99%; Phosphoric acid solution; Phosphorus chromic acid mixture; Tin chloride solution; As gold-silver alloy film and the porous gold thin film of noble metal film; α – cyanacrylate.Wherein,
Before carrying out anodic oxidation to aluminium flake, after the 5h that anneals at being placed on 500 DEG C, the volume ratio being placed in perchloric acid and ethanol is the perchloric acid ethanolic solution of 1:3, electrochemical polish 2min under direct current 18V.
Phosphorus chromic acid mixture is the mixed solution of the phosphoric acid solution of 6wt% and the chromic acid solution of 1.8wt%.
Gold-silver alloy film, after the 10h that anneals at 850 DEG C, uses α – cyanacrylate to be fixed on silicon chip.
The manufacturing process of porous gold thin film is, after the 10h that anneals, is placed in 0 DEG C, the salpeter solution of 65wt%, galvanic corrosion 6min under the DC constant voltage of 0.4V at first gold-silver alloy film being placed in 850 DEG C, then uses washed with de-ionized water to it and dry.
Porous gold thin film Jing α – cyanacrylate is fixed on silicon chip.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, is first placed in-1 DEG C, the phosphoric acid solution of 1.5wt% by aluminium flake, in the DC constant voltage anodic oxygen 4.5h of 190V, then soak 11h in the phosphorus chromic acid mixture being placed on 55 DEG C.Then, after carrying out second time anodic oxidation 13h under it being placed in again same process conditions, first remove the unoxidized aluminium in the back side with saturated tin chloride solution, be placed on again in the phosphoric acid solution of the 12wt% of 48 DEG C and remove reaming 5min after barrier layer, obtain that bore dia is 160nm, the hole cycle is nanohole alumine template for hexagon concaveconvex structure array between 470nm, hole; Wherein, the inwall formed between adjacent pit between the outer wall that hexagon concaveconvex structure is formed by hole and periphery pit, hole is formed, and the relative height difference that pit wherein is all positioned at the hexagonal place of hexagon concaveconvex structure, the thickness of inwall is 50nm, outer wall and inwall is 50nm.
Step 2, first uses α – cyanacrylate nanohole alumine template to be fixed on after on silicon chip, it can be used as mould to be overlying on to be fixed on the gold-silver alloy film on silicon chip.Again 1 × 10 is applied to the silicon chip on nanohole alumine template back surface
5n/m
2pressure, obtained be similar to the noble metal ordered nano-structure array shown in Fig. 2 a and Fig. 2 b.
Embodiment 2
The concrete steps of preparation are:
Step 1, is first placed in 0 DEG C, the phosphoric acid solution of 1.3wt% by aluminium flake, in the DC constant voltage anodic oxygen 4.3h of 193V, then soak 10.5h in the phosphorus chromic acid mixture being placed on 58 DEG C.Then, after carrying out second time anodic oxidation 13.5h under it being placed in again same process conditions, first remove the unoxidized aluminium in the back side with saturated tin chloride solution, be placed on again in the phosphoric acid solution of the 11wt% of 49 DEG C and remove reaming 10min after barrier layer, obtain that bore dia is 215nm, the hole cycle is nanohole alumine template for hexagon concaveconvex structure array between 478nm, hole; Wherein, the inwall formed between adjacent pit between the outer wall that hexagon concaveconvex structure is formed by hole and periphery pit, hole is formed, and the relative height difference that pit wherein is all positioned at the hexagonal place of hexagon concaveconvex structure, the thickness of inwall is 39nm, outer wall and inwall is 90nm.
Step 2, first uses α – cyanacrylate nanohole alumine template to be fixed on after on silicon chip, it can be used as mould to be overlying on to be fixed on the gold-silver alloy film on silicon chip.Again 5 × 10 are applied to the silicon chip on nanohole alumine template back surface
5n/m
2pressure, obtained be similar to the noble metal ordered nano-structure array shown in Fig. 2 a and Fig. 2 b.
Embodiment 3
The concrete steps of preparation are:
Step 1, is first placed in 1 DEG C, the phosphoric acid solution of 1wt% by aluminium flake, in the DC constant voltage anodic oxygen 4h of 195V, then soak 10h in the phosphorus chromic acid mixture being placed on 60 DEG C.Then, after carrying out second time anodic oxidation 14h under it being placed in again same process conditions, first remove the unoxidized aluminium in the back side with saturated tin chloride solution, be placed on again in the phosphoric acid solution of the 10wt% of 50 DEG C and remove reaming 15min after barrier layer, obtain that bore dia is 270nm, the hole cycle is nanohole alumine template for hexagon concaveconvex structure array between 486nm, hole; Wherein, the inwall formed between adjacent pit between the outer wall that hexagon concaveconvex structure is formed by hole and periphery pit, hole is formed, and the relative height difference that pit wherein is all positioned at the hexagonal place of hexagon concaveconvex structure, the thickness of inwall is 27nm, outer wall and inwall is 130nm.
Step 2, first uses α – cyanacrylate nanohole alumine template to be fixed on after on silicon chip, it can be used as mould to be overlying on to be fixed on the gold-silver alloy film on silicon chip.Again 1 × 10 is applied to the silicon chip on nanohole alumine template back surface
6n/m
2pressure, obtained noble metal ordered nano-structure array as shown in Figure 2 a and 2 b.
Embodiment 4
The concrete steps of preparation are:
Step 1, is first placed in 2 DEG C, the phosphoric acid solution of 0.8wt% by aluminium flake, in the DC constant voltage anodic oxygen 3.8h of 198V, then soak 9.5h in the phosphorus chromic acid mixture being placed on 63 DEG C.Then, after carrying out second time anodic oxidation 14.5h under it being placed in again same process conditions, first remove the unoxidized aluminium in the back side with saturated tin chloride solution, be placed on again in the phosphoric acid solution of the 9wt% of 51 DEG C and remove reaming 20min after barrier layer, obtain that bore dia is 325nm, the hole cycle is nanohole alumine template for hexagon concaveconvex structure array between 492nm, hole; Wherein, the inwall formed between adjacent pit between the outer wall that hexagon concaveconvex structure is formed by hole and periphery pit, hole is formed, and the relative height difference that pit wherein is all positioned at the hexagonal place of hexagon concaveconvex structure, the thickness of inwall is 16nm, outer wall and inwall is 165nm.
Step 2, first uses α – cyanacrylate nanohole alumine template to be fixed on after on silicon chip, it can be used as mould to be overlying on to be fixed on the gold-silver alloy film on silicon chip.Again 3 × 10 are applied to the silicon chip on nanohole alumine template back surface
6n/m
2pressure, obtained be similar to the noble metal ordered nano-structure array shown in Fig. 2 a and Fig. 2 b.
Embodiment 5
The concrete steps of preparation are:
Step 1, is first placed in 3 DEG C, the phosphoric acid solution of 0.5wt% by aluminium flake, in the DC constant voltage anodic oxygen 3.5h of 200V, then soak 9h in the phosphorus chromic acid mixture being placed on 65 DEG C.Then, after carrying out second time anodic oxidation 15h under it being placed in again same process conditions, first remove the unoxidized aluminium in the back side with saturated tin chloride solution, be placed on again in the phosphoric acid solution of the 8wt% of 52 DEG C and remove reaming 25min after barrier layer, obtain that bore dia is 380nm, the hole cycle is nanohole alumine template for hexagon concaveconvex structure array between 500nm, hole; Wherein, the inwall formed between adjacent pit between the outer wall that hexagon concaveconvex structure is formed by hole and periphery pit, hole is formed, and the relative height difference that pit wherein is all positioned at the hexagonal place of hexagon concaveconvex structure, the thickness of inwall is 5nm, outer wall and inwall is 200nm.
Step 2, first uses α – cyanacrylate nanohole alumine template to be fixed on after on silicon chip, it can be used as mould to be overlying on to be fixed on the gold-silver alloy film on silicon chip.Again 5.7 × 10 are applied to the silicon chip on nanohole alumine template back surface
6n/m
2pressure, obtained be similar to the noble metal ordered nano-structure array shown in Fig. 2 a and Fig. 2 b.
Select the porous gold thin film as noble metal film again, repeat above-described embodiment 1 ~ 5, obtained as or be similar to the noble metal ordered nano-structure array shown in Fig. 3 a and Fig. 3 b equally.
If improve surfaceness and the specific surface area of object product further, >5.7 × 10 can be applied to the silicon chip on nanohole alumine template back surface
6n/m
2pressure, obtained as or be similar to noble metal ordered nano-structure array nanometer six prism shown in Fig. 2 c, Fig. 2 d, Fig. 3 c and Fig. 3 d being equipped with nanometer rods.
Or, more obtained object product to be proceeded as follows, after nanohole alumine template is moved in parallel 20 ~ 65nm along an opposite side of nanometer six prism ,≤5.7 × 10 is applied to the silicon chip on nanohole alumine template back surface
6n/m
2pressure, obtained as or be similar to the noble metal ordered nano-structure array shown in Fig. 4.
The purposes of noble metal ordered nano-structure array is,
Using the active substrate of noble metal ordered nano-structure array as Surface enhanced raman spectroscopy, use laser Raman spectrometer to measure the rhodamine of attachment or the content of parathion-methyl or polychlorinated biphenyl-3 on it, obtain result as shown in Figure 5 or Figure 6; Wherein, the excitation wavelength of laser Raman spectrometer is 633nm, output power is 0.4 ~ 0.6mW, integral time is 25 ~ 35s.
Obviously, those skilled in the art can carry out various change and modification to noble metal ordered nano-structure array of the present invention and its production and use and not depart from the spirit and scope of the present invention.Like this, if belong within the scope of the claims in the present invention and equivalent technologies thereof to these amendments of the present invention and modification, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. a noble metal ordered nano-structure array, comprises noble metal film, it is characterized in that:
Described noble metal film is gold-silver alloy film or porous gold thin film;
Described gold-silver alloy film is equipped with gold-silver alloy nanometer six array of prisms;
Described porous gold thin film is equipped with porous gold nano six array of prisms;
The styletable of nanometer six prism of described composition gold-silver alloy nanometer six array of prisms or porous gold nano six array of prisms is equipped with the projection of the height≤20nm being positioned at hexagonal place, the rod structure cycle of nanometer six prism is 470 ~ 500nm, the post of nanometer six prism is high is 50 ~ 200nm, the post jamb of nanometer six prism is arcs of recesses, the intercolumniation gap of adjacent nano six prism is 5 ~ 50nm, wherein, the intercolumniation gap at nanometer six prism hexagonal place is 5 ~ 15nm, the intercolumniation gap at nanometer six prism arcs of recesses post jamb place is 20 ~ 50nm.
2. noble metal ordered nano-structure array according to claim 1, is characterized in that nanometer six prism is equipped with that excellent diameter is 160 ~ 380nm, rod is high is the nanometer rods of 10 ~ 200nm.
3. noble metal ordered nano-structure array according to claim 1, is characterized in that a pair of nanometer six prism adjacent two prism limits are equipped with the quadrangular that width is 20 ~ 65nm.
4. a preparation method for noble metal ordered nano-structure array described in claim 1, comprises anodizing, it is characterized in that key step is as follows:
Step 1, first aluminium flake is placed in-1 ~ 3 DEG C, in the phosphoric acid solution of 0.5 ~ 1.5wt%, in the DC constant voltage anodic oxygenization 3.5 ~ 4.5h of 190 ~ 200V, be placed on again in the phosphorus chromic acid mixture of 55 ~ 65 DEG C and soak 9 ~ 11h, then, after carrying out second time anodic oxidation 13 ~ 15h under it being placed in again same process conditions, first remove the unoxidized aluminium in the back side with saturated tin chloride solution, be placed on again in the phosphoric acid solution of the 8 ~ 12wt% of 48 ~ 52 DEG C and remove reaming 5 ~ 25min after barrier layer, obtaining bore dia is 160 ~ 380nm, the hole cycle is 470 ~ 500nm, it is the nanohole alumine template of hexagon concaveconvex structure array between hole, wherein, the outer wall that hexagon concaveconvex structure is formed by hole and periphery pit, the inwall formed between adjacent pit between hole is formed, pit wherein is all positioned at the hexagonal place of hexagon concaveconvex structure, the thickness of inwall is 5 ~ 50nm, the relative height difference of outer wall and inwall is 50 ~ 200nm,
Step 2, is first overlying on nanohole alumine template in gold-silver alloy film or porous gold thin film as mould, then applies≤5.7 × 10 to nanohole alumine template
6n/m
2pressure, obtained noble metal ordered nano-structure array.
5. the preparation method of noble metal ordered nano-structure array according to claim 4, it is characterized in that before anodic oxidation is carried out to aluminium flake, anneal after 5h at being placed on 500 DEG C, the volume ratio being placed in perchloric acid and ethanol is the perchloric acid ethanolic solution of 1:3, electrochemical polish 2min under direct current 18V.
6. the preparation method of noble metal ordered nano-structure array according to claim 5, is characterized in that before carrying out mold pressing to gold-silver alloy film, after the 10h that anneals, uses α – cyanacrylate to be fixed on silicon chip at being placed on 850 DEG C.
7. the preparation method of noble metal ordered nano-structure array according to claim 6, is characterized in that applying >5.7 × 10 to nanohole alumine template
6n/m
2pressure, obtain noble metal ordered nano-structure array nanometer six prism being equipped with nanometer rods.
8. the preparation method of noble metal ordered nano-structure array according to claim 6, after it is characterized in that nanohole alumine template is moved in parallel 20 ~ 65nm along an opposite side of nanometer six prism, applies≤5.7 × 10 to nanohole alumine template
6n/m
2pressure, a pair adjacent two prism limit obtaining nanometer six prism are equipped with the noble metal ordered nano-structure array of quadrangular.
9. a purposes for noble metal ordered nano-structure array described in claim 1, is characterized in that:
Using the active substrate of noble metal ordered nano-structure array as Surface enhanced raman spectroscopy, laser Raman spectrometer is used to measure the rhodamine of attachment or the content of parathion-methyl or polychlorinated biphenyl on it.
10. the purposes of noble metal ordered nano-structure array according to claim 9, is characterized in that the excitation wavelength of laser Raman spectrometer is 633nm, output power is 0.4 ~ 0.6mW, integral time is 25 ~ 35s.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017080088A1 (en) * | 2015-11-11 | 2017-05-18 | 北京工业大学 | High-stability, non-polarisation-dependent, surface-enhanced raman scattering substrate, and preparation and use thereof |
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| WO2017080088A1 (en) * | 2015-11-11 | 2017-05-18 | 北京工业大学 | High-stability, non-polarisation-dependent, surface-enhanced raman scattering substrate, and preparation and use thereof |
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| CN111041427A (en) * | 2019-11-27 | 2020-04-21 | 南通大学 | Simple preparation method of Ag-Au composite nano periodic structure with high SERS activity |
| CN111337474A (en) * | 2020-03-19 | 2020-06-26 | 山东大学 | Raman detection chip based on micro-nano composite structure and nano particles and preparation method and application thereof |
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