CN111455319A - Gold-silver nanocone array with body-enhanced Raman scattering effect and preparation method and application thereof - Google Patents
Gold-silver nanocone array with body-enhanced Raman scattering effect and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a gold-silver nanocone array with a body-enhanced Raman scattering effect, and a preparation method and application thereof. The array is a nano cone ordered array which is formed by coating a gold nano cone film and a silver nano film outside the gold nano cone film and has the cone bottom diameter of 500-520nm, the cone top diameter of 115-125nm, the cone height of 465-475nm and the distance between two adjacent cone bottoms of less than or equal to 10nm, and is arranged on a flat polymethyl methacrylate substrate; the method comprises the steps of firstly attaching a nickel stamping die with a hexagonal array nano-column array to an aluminum sheet, then conducting anodic oxidation and wet etching on the aluminum sheet with a concave mark for multiple times, then evaporating a gold film on the obtained inverted cone-shaped porous alumina template, then coating a methyl methacrylate solution on the inverted cone-shaped porous alumina template, then etching the alumina template in the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated, and then sputtering a silver film on the gold nano-cone ordered array on the methyl methacrylate substrate to obtain the target product. The method can be used as a body-enhanced Raman scattering active substrate for detecting rhodamine or crystal violet or malachite green in trace.
Description
Technical Field
The invention relates to a nano-cone array and a preparation method and application thereof, in particular to a gold-silver nano-cone array with a volume-enhanced Raman scattering effect and a preparation method and application thereof.
Background
The Surface Enhanced Raman Scattering (SERS) spectrum has the advantages of high sensitivity, short detection time, fingerprint information characteristics, no need of complex sample pretreatment and the like, and has wide application prospects in the fields of environmental pollutant detection, reaction monitoring, food safety detection, biosensing and the like. At present, based on the single "hot spot" mode of the SERS substrate, some beneficial attempts and efforts are made to further improve the Detection performance of the SERS substrate, such as an article entitled "Volume-Enhanced raman scattering Detection of Viruses", Small, 2019, 15(11):1805516. ("Volume-Enhanced raman scattering for virus Detection", Small, 2019, Volume 15: 1805516). The bulk enhanced Raman scattering substrate mentioned in the article is a substrate formed by a gold micrometer bowl, and a gold nanometer taper hole is arranged on the substrate; the preparation method comprises the steps of firstly etching the double-layer polystyrene sphere template with different diameters by using an oxygen plasma etching machine, then depositing a gold film with the thickness of 100nm on the etched polystyrene sphere template, and turning over and removing the polystyrene sphere template to obtain the product. Although the product has a certain body-enhanced Raman scattering effect, the product and the preparation method thereof have unsatisfactory points, firstly, the enhancement mode of the product is single, and high-intensity electromagnetic fields are distributed only in the hollow area of the nanocone, so that the promotion of the VERS activity is limited; secondly, because the high-intensity electromagnetic field is mainly concentrated at the upper end of the hollow nano-cone with the aperture of about 100nm, the size of the analyte to be detected is greatly limited due to a small range; thirdly, due to the restriction of the bowl-shaped substrate, the uniformity of an array formed by the nano-cone holes is poor, and the repeatability of a detection signal is influenced; secondly, the evaporated gold film is very thin and has no stable support, so that the stability of the product is poor; finally, the preparation process is complex, large-scale manufacturing is difficult to realize, and a detection substrate with a better body-enhanced Raman scattering effect cannot be obtained.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a gold-silver nanocone array with a bulk-enhanced Raman scattering effect, which has high sensitivity, good signal repeatability and a stable structure.
The invention also provides a preparation method of the gold-silver nanocone array with the body-enhanced Raman scattering effect.
The invention also provides application of the gold-silver nanocone array with the body-enhanced Raman scattering effect.
In order to solve the technical problem of the invention, the adopted technical scheme is that the gold-silver nanocone array with the bulk enhanced Raman scattering effect comprises a substrate and a cone arranged on the substrate, and particularly comprises the following components in percentage by weight:
the substrate is a flat polymethyl methacrylate substrate;
the cone is a nano cone ordered array;
the nanocones forming the nanocone ordered array are cones and are formed by covering a gold nanocone film with a silver nanofilm;
the diameter of the cone bottom of the cone with the gold nanometer cone film coated with the silver nanometer film is 500-520nm, the diameter of the cone top is 115-125nm, the cone height is 465-475nm, and the distance between the two adjacent cone bottoms is less than or equal to 10 nm.
As a further improvement of gold-silver nanocone arrays with volume enhanced raman scattering effect:
preferably, the thickness of the gold nanocone film is 70-90 nm.
Preferably, the film thickness of the silver nano-film is 25-35 nm.
In order to solve another technical problem of the present invention, another technical solution is adopted in that the method for preparing the gold-silver nanocone array having the bulk-enhanced raman scattering effect includes a template method, and particularly, the method mainly includes the following steps:
step 1, adhering a nickel imprint mold of a hexagonal array nano-pillar array with the period of 495-2Obtaining an aluminum sheet with the concave marks after at least 3min under the pressure of the pressure, and sequentially carrying out anodic oxidation, wet etching, anodic oxidation for 3-5min, wet etching and anodic oxidation for 3-5min on the aluminum sheet with the concave marks to obtain an inverted cone-shaped porous alumina template;
step 2, evaporating a gold film with the thickness of 70-90nm on the inverted cone-shaped porous alumina template to obtain an inverted cone-shaped porous alumina template with the surface covered with the gold film, coating a methyl methacrylate solution on the inverted cone-shaped porous alumina template with the surface covered with the gold film, and curing to obtain the inverted cone-shaped porous alumina template with the gold film and the methyl methacrylate sequentially covered on the inverted cone-shaped porous alumina template;
and 3, placing the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated in an alkaline solution to etch away the inverted cone-shaped porous alumina template to obtain a methyl methacrylate substrate on which the gold nano-cone ordered array is placed, placing the methyl methacrylate substrate on which the gold nano-cone ordered array is placed in an ion sputtering machine, and sputtering a silver film under the current of 10mA for 2-9min to obtain the gold-silver nano-cone array with the bulk enhanced Raman scattering effect.
The preparation method of the gold-silver nanocone array with the body-enhanced Raman scattering effect is further improved as follows:
preferably, the voltage of the anodic oxidation is 200V, and the volume ratio of the electrolyte at the temperature of 10 ℃ is 100: 100: 0.5-2 wt% of ethylene glycol, 5 wt% of citric acid and 85 wt% of phosphoric acid.
Preferably, the etching solution for wet etching is 5 wt% phosphoric acid solution with the temperature of 45-55 ℃, and the soaking time is 60-80 min.
Preferably, the methyl methacrylate solution is prepolymerized at 70 ℃ for 5 to 7h in a weight ratio of 0.1: 30 of dibenzoyl peroxide (BPO) and Methyl Methacrylate (MMA).
Preferably, the alkali solution is a sodium hydroxide solution, or a potassium hydroxide solution, or a lithium hydroxide solution, both of which have a concentration of 3 mol/L.
In order to solve another technical problem of the present invention, another technical solution is that the gold-silver nanocone array having a bulk-enhanced raman scattering effect is used in the following applications:
the gold-silver nanocone array with the body-enhanced Raman scattering effect is used as a body-enhanced Raman scattering active substrate, and rhodamine 6G (R6G), or Crystal Violet (CV), or Malachite Green (MG) attached to the gold-silver nanocone array is measured by using a laser Raman spectrometer.
Further improvements as to the use of gold-silver nanocone arrays with volume enhanced raman scattering effects:
preferably, the excitation light of the laser Raman spectrometer has the wavelength of 532nm, the power of 0.2-0.4mW and the integration time of 6-10 s.
Compared with the prior art, the beneficial effects are that:
firstly, respectively representing the prepared target product by using a scanning electron microscope and an attached energy spectrum tester, FDTD simulation software and an ultraviolet-visible spectrometer, and obtaining the target product by combining the result with a preparation method, wherein the target product is a flat substrate on which a nano cone ordered array is arranged; wherein the nano-cone forming the nano-cone ordered array is a cone, the diameter of the cone bottom of the cone is 500-520nm, the diameter of the cone top is 115-125nm, the cone height is 465-475nm, and the distance between the two adjacent cones is less than or equal to 10 nm. The flat substrate is a polymethyl methacrylate substrate, the cone is formed by coating a gold nanometer cone film with a silver nanometer film, the thickness of the gold nanometer cone film is 70-90nm, and the thickness of the silver nanometer film is 25-35 nm. The target product assembled by the ordered nano-cone array consisting of the cones formed by the gold nano-cone film and the silver nano-film coated outside the gold nano-cone film is arranged on the polymethyl methacrylate substrate, not only is the target product provided with three enhanced modes of high electromagnetic field due to the ordered nano-cone array consisting of the orderly-scribed and highly ordered cones, namely the top of each nano-cone is provided with a tip with a lightning rod effect, a large-range hollow 'hot body' area between the adjacent nano-cones and a sub-10 nm gap between the adjacent nano-cones at the bottom, and the high repeatability of signals, so that the Raman-enhanced Raman scattering (VERS) substrate becomes an active substrate with a real body-enhanced Raman scattering effect, a target molecule to be detected can be easily captured by any high-enhancement region, the steric hindrance effect in actual Raman detection is effectively overcome, and the sensitivity of the Raman detection is greatly improved; the range of the hollow 'hot body' area is larger-40-250 nm, and high-strength electromagnetic fields are uniformly distributed, so that the size limit of the analyte to be detected is very small; the cone is a bimetal structure formed by integrating gold and silver elements, so that the cone has high stability of a gold material and high reinforcement of a silver material, and the VERS activity of the substrate is enhanced more remarkably under the synergistic effect; and the polymethyl methacrylate substrate can be bent for multiple times without deformation due to the flexibility of the polymethyl methacrylate substrate, has the characteristics of deformation resistance and impact resistance, greatly improves the structural stability, and is easy to handle, carry and transport.
Secondly, the prepared target product is used as a VERS active substrate, and multiple times of multiple batches of tests are respectively carried out on rhodamine, crystal violet and malachite green under different concentrations, and when the concentration of the rhodamine to be tested is as low as 10-12mol/L, concentration of crystal violet as low as 10-10mol/L, concentration of malachite green as low as 10-11At mol/L, it can still be detected effectively, and the consistency and repeatability of detection are very good at multiple points and any point on the target product.
Thirdly, the preparation method is simple, scientific and effective. Not only the target product with high sensitivity, good signal repeatability and stable structure, namely the gold-silver nanocone array with the body-enhanced Raman scattering effect is prepared; the manufacturing is convenient and the cost is low; further, the target product is easy to be widely commercialized as a body-enhanced Raman scattering active substrate for trace detection of rhodamine 6G or crystal violet or malachite green.
Drawings
FIG. 1 is one of the results of characterization of the objective product obtained by the preparation method using a Scanning Electron Microscope (SEM) and an energy spectrum (EDS) tester attached thereto, respectively. Wherein, fig. 1a and fig. 1b are SEM images of a top view and a cross section of the inverted conical porous alumina template, respectively; FIG. 1c is an oblique SEM image of a gold nanocone array, the inset in the upper right corner of the figure is an EDS spectrogram of the gold nanocone array; fig. 1d is an SEM image of gold-silver nanocone array in oblique view, and the inset in the upper right corner of the figure is the EDS spectrum of the gold-silver nanocone array.
Fig. 2 is one of the results of characterization of the prepared objective product using FDTD simulation software and uv-vis spectrometer. Wherein fig. 2a and 2b are top view and cross-sectional images, respectively, of the simulated electromagnetic field strength distribution under 532nm excitation light, with the K and E vectors in the figures corresponding to the incident direction and polarization direction of the laser light, respectively; FIG. 2c is a diagram showing the UV-VIS absorption spectrum of the objective product.
FIG. 3 is one of the results of the characterization of target products containing rhodamine 6G using a laser Raman spectrometer. Wherein FIG. 3a is a graph containing 10-7-10-12A Raman spectrum of a target product of rhodamine 6G with mol/L, and FIG. 3b shows 10 points collected by randomly selecting 10 points on the target product-7Raman spectrum of R6G at mol/L.
Fig. 4 is one of the results of the characterization of the objective products containing crystal violet and malachite green, respectively, using a laser raman spectrometer. Wherein FIG. 4a is a graph containing 10-6-10-10Raman spectrum of desired product of crystal violet of mol/L, FIG. 4b shows a spectrum containing 10-7-10-11Raman spectrum of target product of malachite green of mol/L.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
First commercially available or manufactured on its own:
the period is 495-;
soaking an aluminum sheet with the purity of 99.999% in acetone, ethanol and deionized water in sequence, ultrasonically cleaning for 3-5min, placing in a mixed solution of perchloric acid and ethanol with the volume ratio of 1:9, taking a graphite sheet as a cathode, and performing electrochemical polishing for 2-3min at the temperature of 0 ℃;
ethylene glycol;
citric acid;
phosphoric acid;
dibenzoyl peroxide;
methyl methacrylate;
sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution as alkali solutions.
Then:
example 1
The preparation method comprises the following specific steps:
step 1, firstly, attaching a nickel stamping die with a hexagonal array nano-pillar array having a period of 495nm, a diameter of 105nm and a height of 150nm to an aluminum sheet, and then placing the nickel stamping die in a position of 8kN/cm2And (3) performing pressure reduction for 5min to obtain the aluminum sheet with the concave marks. Sequentially carrying out anodic oxidation, wet etching, anodic oxidation for 5min, wet etching and anodic oxidation for 3min on the aluminum sheet with the concave marks; wherein the voltage of anodic oxidation is 200V, the volume ratio of the electrolyte at the temperature of 10 ℃ is 100: 100: 2, 5 wt% of citric acid and 85 wt% of phosphoric acid, and soaking the etching solution subjected to wet etching in a 5 wt% phosphoric acid solution at the temperature of 45 ℃ for 80min to obtain the inverted cone-shaped porous alumina template.
And 2, evaporating a gold film with the thickness of 70nm on the reverse taper porous alumina template to obtain the reverse taper porous alumina template with the surface coated with the gold film. Then coating the methyl methacrylate solution on the inverted cone-shaped porous alumina template with the surface covered with the gold film; wherein the methyl methacrylate solution is prepolymerized for 5 hours at 70 ℃ in a weight ratio of 0.1: 30, curing the mixture to obtain the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated.
And 3, placing the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated in an alkaline solution to etch away the inverted cone-shaped porous alumina template, wherein the alkaline solution is a sodium hydroxide solution with the concentration of 3 mol/L to obtain a methyl methacrylate substrate on which the gold nano-cone ordered array is placed, then placing the methyl methacrylate substrate on which the gold nano-cone ordered array is placed in an ion sputtering machine, and sputtering a silver film at the current of 10mA for 2min to obtain the gold-silver nano-cone array which is similar to the gold-silver nano-cone array with the bulk-enhanced Raman scattering effect shown in the graph 2c and is similar to the graph in the graph 1d and the graph in the.
Example 2
The preparation method comprises the following specific steps:
step 1, adhering a nickel stamping die with a hexagonal array nano-pillar array with the period of 498nm, the diameter of 103nm and the height of 163nm to an aluminum sheet, and placing the nickel stamping die in a 9kN/cm2Under the pressure of (3) for 4.5min, and obtaining the aluminum sheet with the concave marks. Sequentially carrying out anodic oxidation, wet etching, anodic oxidation for 4.5min, wet etching and anodic oxidation for 3.5min on the aluminum sheet with the concave marks; wherein the voltage of anodic oxidation is 200V, the volume ratio of the electrolyte at the temperature of 10 ℃ is 100: 100: 1.7 of mixed solution of ethylene glycol, 5 wt% of citric acid and 85 wt% of phosphoric acid, and soaking the etching solution subjected to wet etching in 5 wt% of phosphoric acid solution at the temperature of 48 ℃ for 75min to obtain the inverted cone-shaped porous alumina template.
And 2, evaporating a gold film with the thickness of 75nm on the reverse taper porous alumina template to obtain the reverse taper porous alumina template with the surface coated with the gold film. Then coating the methyl methacrylate solution on the inverted cone-shaped porous alumina template with the surface covered with the gold film; wherein, the methyl methacrylate solution is prepolymerized for 5.5h at 70 ℃ in a weight ratio of 0.1: 30, curing the mixture to obtain the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated.
And 3, placing the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated in an alkaline solution to etch away the inverted cone-shaped porous alumina template, wherein the alkaline solution is a sodium hydroxide solution with the concentration of 3 mol/L to obtain a methyl methacrylate substrate on which the gold nano-cone ordered array is placed, then placing the methyl methacrylate substrate on which the gold nano-cone ordered array is placed in an ion sputtering machine, and sputtering a silver film at the current of 10mA for 4min to obtain the gold-silver nano-cone array which is similar to the gold-silver nano-cone array with the bulk-enhanced Raman scattering effect shown in the graph 2c and is similar to the graph in the graph 1d and the graph in the.
Example 3
The preparation method comprises the following specific steps:
step 1, adhering a nickel stamping die with a hexagonal array nano-pillar array with a period of 500nm, a diameter of 100nm and a height of 175nm to an aluminum sheet, and placing the nickel stamping die in a position of 10kN/cm2Under the pressure of (3) for 4min, obtaining the aluminum sheet with the concave marks. Sequentially carrying out anodic oxidation, wet etching, anodic oxidation for 4min, wet etching and anodic oxidation for 4min on the aluminum sheet with the concave marks; wherein the voltage of anodic oxidation is 200V, the volume ratio of the electrolyte at the temperature of 10 ℃ is 100: 100: 1.3 of mixed solution of ethylene glycol, 5 wt% of citric acid and 85 wt% of phosphoric acid, and soaking the etching solution subjected to wet etching in 5 wt% of phosphoric acid solution at the temperature of 50 ℃ for 70min to obtain the inverted cone-shaped porous alumina template.
And 2, evaporating a gold film with the thickness of 80nm on the inverted cone-shaped porous alumina template to obtain the inverted cone-shaped porous alumina template with the surface coated with the gold film. Then coating the methyl methacrylate solution on the inverted cone-shaped porous alumina template with the surface covered with the gold film; wherein the methyl methacrylate solution is prepolymerized for 6 hours at 70 ℃ in a weight ratio of 0.1: 30, curing the mixture to obtain the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated.
And 3, placing the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated in an alkaline solution to etch away the inverted cone-shaped porous alumina template, wherein the alkaline solution is a sodium hydroxide solution with the concentration of 3 mol/L to obtain a methyl methacrylate substrate on which the gold nano-cone ordered array is placed, then placing the methyl methacrylate substrate on which the gold nano-cone ordered array is placed in an ion sputtering machine, and sputtering a silver film at the current of 10mA for 6min to obtain the gold-silver nano-cone array with the bulk-enhanced Raman scattering effect as shown in the graph of fig. 1d, fig. 2a and fig. 2b and the curve of fig. 2 c.
Example 4
The preparation method comprises the following specific steps:
step 1, adhering a nickel stamping die with a hexagonal array nano-pillar array with the period of 503nm, the diameter of 98nm and the height of 188nm to an aluminum sheet, and placing the nickel stamping die in a position of 11kN/cm2Under the pressure of the aluminum sheet for 3.5min, the aluminum sheet with the concave marks is obtained. Sequentially carrying out anodic oxidation, wet etching, anodic oxidation for 3.5min, wet etching and anodic oxidation for 4.5min on the aluminum sheet with the concave marks; wherein the voltage of anodic oxidation is 200V, the volume ratio of the electrolyte at the temperature of 10 ℃ is 100: 100: 0.9 of mixed solution of ethylene glycol, 5 wt% of citric acid and 85 wt% of phosphoric acid, and the etching solution for wet etching is 5 wt% of phosphoric acid solution with the temperature of 53 ℃, and the soaking time is 65min, so that the inverted cone-shaped porous alumina template is obtained.
And 2, evaporating a gold film with the thickness of 85nm on the inverted cone-shaped porous alumina template to obtain the inverted cone-shaped porous alumina template with the surface coated with the gold film. Then coating the methyl methacrylate solution on the inverted cone-shaped porous alumina template with the surface covered with the gold film; wherein, the methyl methacrylate solution is prepolymerized for 6.5h at 70 ℃ in a weight ratio of 0.1: 30, curing the mixture to obtain the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated.
And 3, placing the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated in an alkaline solution to etch away the inverted cone-shaped porous alumina template, wherein the alkaline solution is a sodium hydroxide solution with the concentration of 3 mol/L to obtain a methyl methacrylate substrate on which the gold nano-cone ordered array is placed, then placing the methyl methacrylate substrate on which the gold nano-cone ordered array is placed in an ion sputtering machine, and sputtering a silver film at the current of 10mA for 8min to obtain the gold-silver nano-cone array which is similar to the gold-silver nano-cone array with the bulk-enhanced Raman scattering effect shown in the graph 2c and is similar to the graph in the graph 1d and the graph in the.
Example 5
The preparation method comprises the following specific steps:
step 1, adhering a nickel stamping die with a period of 505nm, a diameter of 95nm and a height of 200nm and a hexagonal nano-pillar array with an aluminum sheet, and placing the nickel stamping die in a position of 12kN/cm2Under the pressure of (3) for 3min, obtaining the aluminum sheet with the concave marks. Sequentially carrying out 5min of anodic oxidation, wet etching, 3min of anodic oxidation, wet etching and 5min of anodic oxidation on the aluminum sheet with the concave marks; wherein the voltage of anodic oxidation is 200V, the volume ratio of the electrolyte at the temperature of 10 ℃ is 100: 100: 0.5 of mixed solution of ethylene glycol, 5 wt% of citric acid and 85 wt% of phosphoric acid, and the etching solution for wet etching is 5 wt% of phosphoric acid solution with the temperature of 55 ℃, and the soaking time is 60min, so that the inverted cone-shaped porous alumina template is obtained.
And 2, evaporating a gold film with the thickness of 90nm on the inverted cone-shaped porous alumina template to obtain the inverted cone-shaped porous alumina template with the surface coated with the gold film. Then coating the methyl methacrylate solution on the inverted cone-shaped porous alumina template with the surface covered with the gold film; wherein, the methyl methacrylate solution is prepolymerized for 7 hours at 70 ℃ in a weight ratio of 0.1: 30, curing the mixture to obtain the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated.
And 3, placing the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated in an alkaline solution to etch away the inverted cone-shaped porous alumina template, wherein the alkaline solution is a sodium hydroxide solution with the concentration of 3 mol/L to obtain a methyl methacrylate substrate on which the gold nano-cone ordered array is placed, then placing the methyl methacrylate substrate on which the gold nano-cone ordered array is placed in an ion sputtering machine, and sputtering a silver film at the current of 10mA for 9min to obtain the gold-silver nano-cone array which is similar to the gold-silver nano-cone array with the bulk-enhanced Raman scattering effect shown in the graph 2c and is similar to the graph in.
And repeating the above examples 1-5 by using potassium hydroxide solution or lithium hydroxide solution of alkali solution, respectively, to obtain gold-silver nanocone arrays having bulk enhanced raman scattering effect as shown or similar to the graphs in fig. 1d, fig. 2a and fig. 2b, and the graph in fig. 2 c.
The application of the gold-silver nanocone array with the body-enhanced Raman scattering effect is as follows:
taking a gold-silver nanocone array with a body-enhanced Raman scattering effect as a body-enhanced Raman scattering active substrate, and measuring rhodamine 6G, or crystal violet, or malachite green attached to the gold-silver nanocone array by using a laser Raman spectrometer to obtain a result as or similar to that shown in figure 3 or figure 4; wherein the wavelength of exciting light of the laser Raman spectrometer is 532nm, the power is 0.2-0.4mW, and the integration time is 6-10 s.
It is apparent that those skilled in the art can make various changes and modifications to the gold-silver nanocone array having a body-enhanced raman scattering effect of the present invention, and the preparation method and use thereof, without departing from the spirit and scope of the present invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (10)
1. A gold-silver nanocone array with a volume-enhanced Raman scattering effect, comprising a substrate and a cone disposed thereon, characterized in that:
the substrate is a flat polymethyl methacrylate substrate;
the cone is a nano cone ordered array;
the nanocones forming the nanocone ordered array are cones and are formed by covering a gold nanocone film with a silver nanofilm;
the diameter of the cone bottom of the cone with the gold nanometer cone film coated with the silver nanometer film is 500-520nm, the diameter of the cone top is 115-125nm, the cone height is 465-475nm, and the distance between the two adjacent cone bottoms is less than or equal to 10 nm.
2. The gold-silver nanocone array having a bulk-enhanced raman scattering effect of claim 1, wherein the gold nanocone film has a film thickness of 70 to 90 nm.
3. The gold-silver nanocone array having a bulk-enhanced raman scattering effect of claim 1, wherein the silver nanofilm has a film thickness of 25-35 nm.
4. A preparation method of the gold-silver nanocone array with the body-enhanced Raman scattering effect according to claim 1, which comprises a template method and is characterized by mainly comprising the following steps:
step 1, adhering a nickel imprint mold of a hexagonal array nano-pillar array with the period of 495-2Obtaining an aluminum sheet with the concave marks after at least 3min under the pressure of the pressure, and sequentially carrying out anodic oxidation, wet etching, anodic oxidation for 3-5min, wet etching and anodic oxidation for 3-5min on the aluminum sheet with the concave marks to obtain an inverted cone-shaped porous alumina template;
step 2, evaporating a gold film with the thickness of 70-90nm on the inverted cone-shaped porous alumina template to obtain an inverted cone-shaped porous alumina template with the surface covered with the gold film, coating a methyl methacrylate solution on the inverted cone-shaped porous alumina template with the surface covered with the gold film, and curing to obtain the inverted cone-shaped porous alumina template with the gold film and the methyl methacrylate sequentially covered on the inverted cone-shaped porous alumina template;
and 3, placing the inverted cone-shaped porous alumina template on which the gold film and the methyl methacrylate are sequentially coated in an alkaline solution to etch away the inverted cone-shaped porous alumina template to obtain a methyl methacrylate substrate on which the gold nano-cone ordered array is placed, placing the methyl methacrylate substrate on which the gold nano-cone ordered array is placed in an ion sputtering machine, and sputtering a silver film under the current of 10mA for 2-9min to obtain the gold-silver nano-cone array with the bulk enhanced Raman scattering effect.
5. The method for preparing gold-silver nanocone array having a bulk-enhanced raman scattering effect according to claim 4, wherein the voltage of anodic oxidation is 200V, and the volume ratio of the electrolyte at a temperature of 10 ℃ is 100: 100: 0.5-2 wt% of ethylene glycol, 5 wt% of citric acid and 85 wt% of phosphoric acid.
6. The method for preparing gold-silver nanocone array with bulk enhanced Raman scattering effect according to claim 4, wherein the etching solution for wet etching is 5 wt% phosphoric acid solution at 45-55 ℃ and the soaking time is 60-80 min.
7. The method for preparing gold-silver nanocone array having a bulk-enhanced raman scattering effect according to claim 4, wherein the methyl methacrylate solution is pre-polymerized at 70 ℃ for 5 to 7 hours in a weight ratio of 0.1: 30 of a mixture of dibenzoyl peroxide and methyl methacrylate.
8. The method of claim 4, wherein the alkali solution is sodium hydroxide solution, potassium hydroxide solution, or lithium hydroxide solution with a concentration of 3 mol/L.
9. Use of an array of gold-silver nanocones with volume-enhanced raman scattering effect according to claim 1, characterized in that:
the gold-silver nanocone array with the body-enhanced Raman scattering effect is used as a body-enhanced Raman scattering active substrate, and a laser Raman spectrometer is used for measuring rhodamine 6G, or crystal violet, or malachite green attached to the gold-silver nanocone array.
10. Use of an array of gold-silver nanocones with volume-enhanced raman scattering effect according to claim 9, characterized in that the laser raman spectrometer has excitation light with a wavelength of 532nm, a power of 0.2-0.4mW and an integration time of 6-10 s.
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