CN110863226A - SERS substrate with composite gold and silver nano array structure and preparation method thereof - Google Patents
SERS substrate with composite gold and silver nano array structure and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
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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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention relates to a SERS substrate with a composite gold and silver nano array structure, belonging to the field of nanotechnology. The SERS substrate provided by the invention comprises a columnar nano array structure with a gold-silver composite material on the surface and uniform distribution. The SERS substrate has better uniformity, chemical stability and higher SERS activity, has detection advantages compared with single metal, and has high controllability and good repeatability in the operation mode related to the patent. The invention also discloses a preparation method of the SERS substrate, which comprises the steps of taking the single-pass AAO as a template, and preparing the template of the double-pass porous alumina (AAO) through reactions such as coating, replacement and the like; then placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation silver plating to obtain a periodic silver circular table array structure; and finally, evaporating gold with different thicknesses to obtain SERS substrates with composite gold and silver nano array structures with different appearances. The method has simple process and low preparation cost, and is suitable for large-scale batch production.
Description
Technical Field
The invention relates to preparation and application of a patterned nano material, in particular to a preparation method of a SERS substrate with a composite gold-silver nano array structure, and belongs to the field of nanotechnology.
Background
The development of nano science and technology provides a new visual angle for the human to know the substance world, becomes a relatively independent subject, uses an advanced analytical instrument as a technical means, explores and develops a new detection means in a nano scale, and the preparation of nano materials becomes a research hotspot in the field of nano technology.
The Surface Enhanced Raman Spectroscopy (SERS) has the characteristics of high sensitivity, high selectivity and the like, and plays an important role in the fields of chemical analysis, biomolecular structure identification, environmental pollutant, explosive, drug detection and the like. Among them, the SERS activity of noble metal materials such as gold and silver is most prominent, and the effect thereof mainly exists in gaps (<10nm) of metal nanostructures, i.e., "hot spots" (hotspots). The 'hot spot' has a great enhancement effect on the Raman signal of the substance to be detected, and can realize the trace detection of the detected substance.
From the application perspective, the gold and silver materials have advantages and disadvantages, the gold nanoparticles have better chemical stability and biocompatibility, and the silver particles have better SPR refractive index sensitivity and SERS activity, i.e. the composite bimetallic nanoparticles have better application prospect. The composite gold and silver nano material mainly comprises zero-dimensional nano materials such as nano spherical particles and nano cubes or one-dimensional materials such as nano rods and nano wires or two-dimensional materials such as nano sheets and nano belts at present, the preparation method mainly comprises a co-reduction method, the method is simple, and the preparation of high-monodispersity nano particles with uniform appearance is difficult; the size of the seed growing method is uniform; the hollow alloy structure is prepared by a Galvanic substitution method, and the gold-silver composite nano substrate prepared by the methods is mainly granular and has a single appearance.
Disclosure of Invention
In view of the above, the present invention provides a composite gold and silver SERS substrate with a periodic metal array structure and a preparation method thereof. The periodic metal array structure nano structure prepared by the invention is a novel plasma structure, and adjacent gold and silver structure units and gold nano particles among gaps can form a hot spot structure, so that abundant hot spot types are provided for electromagnetic field enhancement, and the periodic metal array structure nano structure has the advantages of simple and convenient preparation process, good uniformity, good repeatability and low cost.
The invention provides a preparation method of the SERS substrate, which comprises the following steps:
(1) a double-pass porous alumina (AAO) template is prepared by taking a single-pass AAO as a template and carrying out reactions such as coating, replacement and the like.
(2) Placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation silver plating to obtain a periodic silver circular table array structure;
(3) and further evaporating gold with different thicknesses to obtain SERS substrates with composite gold and silver nano array structures with different appearances.
Preferably, the preparation of the template of the two-pass porous alumina (AAO) by the reaction of coating, displacement and the like in the step (1) comprises the following steps: performing ultrasonic treatment on the AAO in ethanol for 30s, washing with a large amount of water, and drying with nitrogen; uniformly coating nail polish with proper thickness on the single-pass AAO to serve as a protective layer; under the ice-bath condition, the sample is floated on a mixed solution of CuCl2 and HCl, and the displacement reaction is carried out until the reaction of the aluminum substrate is complete; floating the sample on the liquid surface of 5 wt% phosphoric acid solution at 35 ℃, and removing the alumina barrier layer after 65 min; after repeated washing with water, the samples were placed in acetone to remove nail polish. Finally obtaining the bi-pass porous AAO template.
Preferably, the obtaining of the periodic silver circular platform array structure in the step (2) includes the following steps: putting the bi-pass AAO on a silicon chip, and performing vacuum thermal evaporation on silver with the thickness of 200nm (the vacuum degree is 2 multiplied by 10 < -4 > Pa, and the plating rate is 0.15 nm/s); and (3) adhering the bi-pass AAO by using an adhesive tape to obtain a periodic silver circular table array structure on the silicon chip.
Preferably, the deposition thickness of gold evaporated with different thicknesses in the step (3) is 5-100 nm.
The invention also provides the SERS substrate with the composite gold-silver nano array structure or the SERS substrate with the composite gold-silver nano array structure obtained by the preparation method, which can be applied to detection of dye molecules.
Compared with the prior art, the invention has the following beneficial effects:
(1) the technical scheme for preparing the composite gold-silver nano array structure is obtained according to a plurality of links such as coating, replacement, evaporation and the like, and the obtained nano column arrays are uniform and ordered in arrangement and show good detection uniformity.
(2) The SERS substrate provided by the invention is based on a composite gold-silver nano array structure on a silicon wafer, has better chemical stability and higher SERS activity, has detection advantages compared with single metal, and has high controllability, good repeatability and low cost in an operation mode related to the invention, and can be prepared on a large scale.
(3) By using the composite gold-silver nano array structure provided by the invention as an SERS substrate, the measured Raman signal of the crystal violet probe molecule has a relative standard deviation value of less than 15%, the good detection uniformity is shown, the probe molecule with lower concentration can be detected, and the higher sensitivity is shown.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a SERS substrate with a composite gold-silver nano array structure by using an AOO template.
Fig. 2 is a characterization result of a scanning electron microscope performed on the composite gold and silver nano array structure according to the embodiment of the present invention. Wherein, the silver round table array (size: the diameter of the round table is 400nm, the distance between adjacent layers is 50nm) in the embodiment of the figure (a), the silver round table array mentioned in the embodiment 1-4 of the figure (b-e) is respectively evaporated with a composite gold-silver nano array structure SERS substrate of gold with different sizes (5, 30, 50, 100nm), and the upper right corner is a high-magnification enlarged view;
FIG. 3 shows the results of Raman spectroscopy on the target product containing the probe molecule crystal violet according to the present invention. The silver circular table array in the embodiment and the silver circular table arrays mentioned in the embodiments 1 to 4 are respectively evaporated with gold composite gold-silver nano array structure SERS substrates with different sizes (5 nm, 30nm, 50nm and 100 nm);
FIG. 4 shows the results of Raman spectroscopy on the target product containing different concentrations of the probe molecule crystal violet according to the present invention. The sensitivity of the SERS substrate with the composite gold-silver nano array structure in the embodiment 4 to crystal violet with different concentrations is determined;
FIG. 5 shows the results of Raman spectroscopy on the target product containing the probe molecule crystal violet at different locations on the substrate. In the embodiment, a 3D surface enhanced Raman spectrum of the crystal violet molecule is obtained by randomly selecting 50 detection points on the surface of the SERS substrate with the composite gold-silver nano array structure.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings and embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a periodic metal array nanostructure SERS substrate which comprises a composite gold-silver nanomaterial and a uniform array nanostructure, namely noble metal gold-silver composite nanoparticles are uniformly distributed on the structure.
As shown in fig. 1, the present invention further provides a method for preparing the SERS substrate, including the following steps:
(1) a double-pass porous alumina (AAO) template is prepared by taking a single-pass AAO as a template and carrying out reactions such as coating, replacement and the like.
(2) Placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation silver plating to obtain a periodic silver circular table array structure;
(3) and further evaporating gold with different thicknesses to obtain SERS substrates with composite gold and silver nano array structures with different appearances.
The preparation of the template of the bi-pass porous alumina (AAO) through the reactions of coating, replacement and the like in the step (1) comprises the following steps: performing ultrasonic treatment on the AAO in ethanol for 30s, washing with a large amount of water, and drying with nitrogen; uniformly coating nail polish with proper thickness on the single-pass AAO to serve as a protective layer; under the ice-bath condition, the sample is floated on a mixed solution of CuCl2 and HCl, and the displacement reaction is carried out until the reaction of the aluminum substrate is complete; floating the sample on the liquid surface of 5 wt% phosphoric acid solution at 35 ℃, and removing the alumina barrier layer after 65 min; after repeated washing with water, the samples were placed in acetone to remove nail polish. Finally obtaining the bi-pass porous AAO template.
The step (2) of obtaining the periodic silver circular table array structure comprises the following steps: putting the bi-pass AAO on a silicon chip, and performing vacuum thermal evaporation on silver with the thickness of 200nm (the vacuum degree is 2 multiplied by 10 < -4 > Pa, and the plating rate is 0.15 nm/s); and (3) adhering the bi-pass AAO by using an adhesive tape to obtain a periodic silver circular table array structure on the silicon chip.
The deposition thickness of gold evaporated in different thicknesses in the step (3) is 5-100 nm.
The invention also provides the SERS substrate with the composite gold-silver nano array structure or the SERS substrate with the composite gold-silver nano array structure obtained by the preparation method, which can be applied to detection of dye molecules.
Example 1
The preparation method comprises the following specific steps:
Step 2, placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation on silver with the thickness of 200nm (the vacuum degree is 2 multiplied by 10 < -4 > Pa, and the plating rate is 0.15 nm/s); and (3) adhering double-pass AAO by using an adhesive tape to obtain a periodic silver film structure on the silicon wafer, namely a silver circular table array structure shown in figure 2(a), wherein the diameter of a circular table is 400nm, and the inter-adjacent distance is 50 nm.
And 3, evaporating gold with the deposition thickness of 5nm to obtain the SERS substrate with the composite gold-silver nano array structure, namely the composite gold-silver nano array structure shown in the figure 3 (b).
And 4, titrating a certain amount of crystal violet solution on the surface of the SERS active substrate by taking the target product as the SERS active substrate, standing and adsorbing for 20min, then washing with ultrapure water, drying with nitrogen, and carrying out SERS performance test by using a Raman spectrometer, as shown in fig. 3 (a).
Example 2
Example 2 differs from example 1 in that step 3 is prepared with the specific steps of: the deposition thickness of the evaporated gold was 30 nm. As shown in fig. 1, the specific preparation process is as follows:
Step 2, placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation on silver with the thickness of 200nm (the vacuum degree is 2 multiplied by 10 < -4 > Pa, and the plating rate is 0.15 nm/s); and (3) adhering double-pass AAO by using an adhesive tape to obtain a periodic silver film structure on the silicon wafer, namely a silver circular table array structure shown in figure 2(a), wherein the diameter of a circular table is 400nm, and the inter-adjacent distance is 50 nm.
And 3, evaporating gold with the deposition thickness of 30nm to obtain the SERS substrate with the composite gold-silver nano array structure, namely the composite gold-silver nano array structure shown in the figure 2 (c).
And 4, titrating a certain amount of crystal violet solution on the surface of the SERS active substrate by taking the target product as the SERS active substrate, standing and adsorbing for 20min, then washing with ultrapure water, drying with nitrogen, and carrying out SERS performance test by using a Raman spectrometer, as shown in figure 3.
Example 3
Example 3 differs from example 1 in that step 3 is prepared by the following specific steps: the deposition thickness of the evaporated gold was 50 nm. As shown in fig. 1, the specific preparation process is as follows:
Step 2, placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation on silver with the thickness of 200nm (the vacuum degree is 2 multiplied by 10 < -4 > Pa, and the plating rate is 0.15 nm/s); and (3) adhering double-pass AAO by using an adhesive tape to obtain a periodic silver film structure on the silicon wafer, namely a silver circular table array structure shown in figure 2(a), wherein the diameter of a circular table is 400nm, and the inter-adjacent distance is 50 nm.
And 3, evaporating gold with the deposition thickness of 50nm to obtain the SERS substrate with the composite gold-silver nano array structure, namely the composite gold-silver nano array structure shown in the figure 2 (d).
And 4, titrating a certain amount of crystal violet solution on the surface of the SERS active substrate by taking the target product as the SERS active substrate, standing and adsorbing for 20min, then washing with ultrapure water, drying with nitrogen, and carrying out SERS performance test by using a Raman spectrometer, as shown in figure 3.
Example 4
Example 4 differs from example 1 in that step 3 is prepared with the specific steps of: the deposited thickness of the evaporated gold was 100nm, and different concentrations of crystal violet solution were titrated to the substrate surface in the step 4 assay. As shown in fig. 1, the specific preparation process is as follows:
Step 2, placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation on silver with the thickness of 200nm (the vacuum degree is 2 multiplied by 10 < -4 > Pa, and the plating rate is 0.15 nm/s); and (3) adhering double-pass AAO by using an adhesive tape to obtain a periodic silver film structure on the silicon wafer, namely a silver circular table array structure shown in figure 2(a), wherein the diameter of a circular table is 400nm, and the inter-adjacent distance is 50 nm.
And 3, evaporating gold with the deposition thickness of 30nm to obtain the SERS substrate with the composite gold-silver nano array structure, namely the composite gold-silver nano array structure shown in fig. 2 (e).
And 4, titrating the crystal violet solution with different concentrations on the surface of the SERS active substrate by taking the target product as the SERS active substrate, standing and adsorbing for 20min, then washing with ultrapure water, drying with nitrogen, and carrying out SERS performance test by using a Raman spectrometer, as shown in FIG. 4.
Test example 1: scanning by electron microscope
Scanning the SERS substrate with the composite gold-silver nano array structure obtained in examples 1-4 by an electron microscope to obtain a characterization result shown in FIG. 2. Wherein, the figure (a) is a silver round platform array (the size is 400nm of the diameter of the round platform and 50nm of the distance between adjacent layers), and the silver round platform array (b-e) is a composite nano array structure formed by evaporating 5nm, 30nm, 50nm and 100nm of gold on the examples 1-4 respectively. It can be seen that each structure exhibited a high degree of uniformity and stability. When the thickness of the evaporated gold film is changed, the distribution form of the array is not changed, which shows that the method is a reliable technical means in the field of preparing micro-nano structures; in addition, as the thickness of gold increases, the inter-adjacent spacing of the array gradually decreases; and the gold nanoparticles at the gap are firstly enlarged and then reduced, namely, the adjacent gold @ silver structural units and the gold nanoparticles at the gap form a hot spot structure.
Test example 2: applied analysis for crystal violet detection
Adding a certain amount of the mixture with the concentration of 10-4Dripping M crystal violet solution on the surface of the SERS substrate with the composite gold-silver nano array structure obtained in the embodiment 1-4, standing and adsorbing for 20min, then washing with ultrapure water, drying with nitrogen, and carrying out SERS performance test by using a Raman spectrometer to obtain a Raman spectrometer characterization result shown in the figure 3-5. Wherein the silver circular platform array in the embodiment of FIG. 3 and the silver circular platform arrays mentioned in the embodiments 1-4 are respectively evaporated with different sizes (5, 30, 5)0. 100nm) gold-silver composite nano array structure SERS substrate. FIG. 4 shows the sensitivity of the SERS substrate with the composite gold and silver nano array structure to crystal violet with different concentrations; fig. 5 is a 3D surface enhanced raman spectrum of the crystal violet molecule obtained by randomly selecting 50 detection points on the surface of the SERS substrate with the composite gold-silver nano array structure. The black circle is represented at 1160cm-1And calculating the relative standard deviation value of the Raman signals at the characteristic peak. As can be seen from the figure 3, with the increase of the thickness of the gold evaporation plating, the SERS signal is enhanced, the number of visible hot spot structures is increased, and the effect is obvious; the graph 4 has good signal-to-noise ratio, which indicates that the sensitivity of the composite gold-silver nanoarray SERS substrate is high, and 10 can be detected-10MCrystal violet; the signal intensities of the graph 5 at different points are basically consistent, which shows that the SERS substrate with the composite gold-silver nano array structure has good structural uniformity, and the crystal violet is 1161cm-1At the characteristic peak, the RSD of the SERS signal is 3.00 percent, which particularly shows that the substrate prepared by the invention has uniform and good SERS performance.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (6)
1. The SERS substrate with the composite gold and silver nano array structure is characterized in that: comprises a columnar nano array structure with gold-silver composite material and uniform distribution on the surface. The method takes single-pass AAO as a template, and prepares a template of bi-pass porous alumina (AAO) through reactions such as coating, replacement and the like; then placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation silver plating to obtain a periodic silver circular table array structure; and finally, evaporating gold with different thicknesses to obtain SERS substrates with composite gold and silver nano array structures with different appearances.
2. A method for preparing the SERS substrate with the composite gold and silver nano array structure according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) a double-pass porous alumina (AAO) template is prepared by taking a single-pass AAO as a template and carrying out reactions such as coating, replacement and the like.
(2) Placing the bi-pass AAO on a silicon wafer, and performing vacuum thermal evaporation silver plating to obtain a periodic silver circular table array structure;
(3) and further evaporating gold with different thicknesses to obtain SERS substrates with composite gold and silver nano array structures with different appearances.
3. The preparation method of the SERS substrate with the composite gold-silver nano array structure according to claim 2, characterized in that: the preparation of the template of the bi-pass porous alumina (AAO) through the reactions of coating, replacement and the like in the step (1) comprises the following steps: performing ultrasonic treatment on the AAO in ethanol for 30s, washing with a large amount of water, and drying with nitrogen; uniformly coating nail polish with proper thickness on the single-pass AAO to serve as a protective layer; under the ice-bath condition, the sample is floated on a mixed solution of CuCl2 and HCl, and the displacement reaction is carried out until the reaction of the aluminum substrate is complete; floating the sample on the liquid surface of 5 wt% phosphoric acid solution at 35 ℃, and removing the alumina barrier layer after 65 min; after repeated washing with water, the samples were placed in acetone to remove nail polish. Finally obtaining the bi-pass porous AAO template.
4. The preparation method of the SERS substrate with the composite gold-silver nano array structure according to claim 2, characterized in that: the step (2) of obtaining the periodic silver circular table array structure comprises the following steps: putting the bi-pass AAO on a silicon chip, and performing vacuum thermal evaporation on silver with the thickness of 200nm (the vacuum degree is 2 multiplied by 10 < -4 > Pa, and the plating rate is 0.15 nm/s); and (3) adhering the bi-pass AAO by using an adhesive tape to obtain a periodic silver circular table array structure on the silicon chip.
5. The preparation method of the SERS substrate with the composite gold-silver nano array structure according to claim 2, characterized in that: the deposition thickness of gold evaporated in different thicknesses in the step (3) is 5-100 nm.
6. The composite gold-silver nano-array structure SERS substrate of claim 1 or the composite gold-silver nano-array structure SERS substrate prepared by the preparation method of any one of claims 2 to 5, characterized in that: can be applied to detecting dye molecules with low concentration.
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| CN111781188A (en) * | 2020-07-02 | 2020-10-16 | 南通大学 | Preparation method of SERS substrate with aluminum-based flower-shaped composite nanostructure and SERS substrate |
| CN112903655A (en) * | 2021-01-24 | 2021-06-04 | 复旦大学 | Single micro/nano plastic detection method based on Raman spectrum technology |
| CN113702352A (en) * | 2021-08-25 | 2021-11-26 | 山东智微检测科技有限公司 | SERS detection chip suitable for gas-phase erosive toxicant and preparation method thereof |
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