CN110320198B - Array SERS substrate integrated with convex lens and preparation method thereof - Google Patents

Array SERS substrate integrated with convex lens and preparation method thereof Download PDF

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Publication number
CN110320198B
CN110320198B CN201910603310.5A CN201910603310A CN110320198B CN 110320198 B CN110320198 B CN 110320198B CN 201910603310 A CN201910603310 A CN 201910603310A CN 110320198 B CN110320198 B CN 110320198B
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substrate
convex lens
array
integrated
holes
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CN110320198A (en
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陈李
杨峰
李丹阳
徐溢
李顺波
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Chongqing University
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Chongqing University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B3/0006Arrays
    • G02B3/0037Arrays characterized by the distribution or form of lenses
    • G02B3/0056Arrays characterized by the distribution or form of lenses arranged along two different directions in a plane, e.g. honeycomb arrangement of lenses

Abstract

The invention discloses an array SERS substrate integrated with convex lenses, which comprises a substrate, wherein a plurality of through holes distributed in an array manner are arranged on the substrate, double-sided convex lenses are arranged in the through holes, and metal nanoparticles are attached to one sides of the convex lenses. The Raman scattering collection efficiency and the Raman scattering intensity can be improved, high-flux multi-parameter detection is realized, and the cost is low. The invention also discloses a preparation method of the array SERS substrate integrated with the convex lens, which has simple preparation process flow and is convenient for batch manufacturing.

Description

Array SERS substrate integrated with convex lens and preparation method thereof
Technical Field
The invention relates to the technical field of surface enhanced Raman spectroscopy, in particular to an array SERS substrate integrated with a convex lens and a preparation method thereof.
Background
The Surface Enhanced Raman Spectroscopy (SERS) technology has many advantages such as high sensitivity, small water-based interference, and nondestructive detection, and is widely used in the detection fields of biomedicine, environmental pollution, food safety, and the like.
The SERS substrate plays a key role in SERS detection applications, and therefore, a great deal of research is devoted to developing SERS substrates with high sensitivity and good repeatability and uniformity. Various high-quality SERS substrates are prepared by various methods such as a chemical method, a physical method, an electrochemical method, a self-assembly method and the like. However, most of the current researches are to construct more and more uniformly distributed "hot spots" by adjusting and controlling the metal nano-structures so as to improve the performance of the SERS substrate, and the SERS substrate is rarely designed from the aspect of improving the collection efficiency of raman scattered light.
Disclosure of Invention
The invention aims to provide an array SERS substrate integrated with a convex lens and a preparation method thereof, which can improve the collection efficiency and Raman scattering intensity of Raman scattering, realize high-flux multi-parameter detection, and have the advantages of low cost and simple and feasible preparation process.
The array SERS substrate integrated with the convex lens comprises a substrate, wherein a plurality of through holes distributed in an array mode are formed in the substrate, double-sided convex lenses are arranged in the through holes, and metal nanoparticles are attached to one sides of the convex lenses.
Further, the substrate is a stainless steel plate, a copper plate or an aluminum plate.
Further, the convex lens is formed by drying and curing a transparent medium in the through hole, wherein the transparent medium is one of PMMA, PDMS and transparent resin.
Furthermore, the through hole is a circular through hole, and the diameter of the through hole is 0.15-2 mm.
Further, the metal nanoparticles are made of gold, silver, a silver core gold shell or a gold core silver shell.
A preparation method of an array SERS substrate integrated with a convex lens comprises the following steps:
s1, machining the substrate to obtain through holes distributed in an array manner, and performing hydrophobic treatment on the substrate by adopting a surfactant;
s2, preparing a transparent medium solution;
s3, dropwise adding the transparent medium solution on a substrate, spin-coating for 40-60 min at a rotating speed of 2000-3000 r/min, and then drying for 2-3 h at a temperature of 60-100 ℃ to obtain a convex lens in a through hole of the substrate;
s4, preparing metal nano sol, dropwise adding the metal nano sol to one side of the convex lens, and drying in a dark place to obtain the array SERS substrate integrated with the convex lens.
Compared with the prior art, the invention has the following beneficial effects.
1. According to the invention, the convex lens is arranged in the through hole of the substrate, and the Raman scattering light is converged by utilizing the principle that the convex lens converges light, so that the collection efficiency and the Raman scattering intensity of Raman scattering are improved. The through holes are distributed in an array mode, and the consistency and the stability of the SERS substrate are guaranteed.
2. The SERS substrate has high integration level, simple preparation process flow and convenient batch manufacturing.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a schematic structural view of a substrate of the present invention;
in the figure, 1-substrate, 2-via, 3-convex lens, 4-metal nanoparticle.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
In a first embodiment, referring to fig. 1 and 2, the shown array SERS substrate integrated with a convex lens includes a substrate 1, the substrate 1 is made of a 304 stainless steel plate with a thickness of 0.5-2 mm, a plurality of circular through holes 2 distributed in an array manner are formed in the substrate by stamping, the diameter of each circular through hole is 1mm, a double-sided convex lens 3 is arranged in each through hole 2, each convex lens 3 is formed by drying and curing PDMS in each through hole, a metal nanoparticle 4 is attached to one side of each convex lens 3, and the metal nanoparticle is made of silver.
The preparation method of the array SERS substrate integrated with the convex lens comprises the following steps:
s1, selecting a 304 stainless steel plate with the thickness of 0.5mm as a substrate, punching and processing a plurality of through holes distributed in an array form on the substrate, wherein the diameter of each through hole is 1mm, sequentially performing ultrasonic cleaning for 30min by using ethanol and deionized water respectively, performing hydrophobic treatment on the substrate by using a surfactant, and drying to enable the substrate to be hydrophobic.
S2, uniformly mixing the PDMS main agent and the hardening agent according to the mass ratio of 10:1 to obtain a mixed solution A, and removing air bubbles in the mixed solution A by adopting a vacuumizing mode to obtain a mixed solution B.
S3, dripping 500 mu L of the mixed solution B on a substrate, spin-coating for 40min at the rotation speed of 2500r/min, drying for 2.5h at the temperature of 80 ℃, forming convex lenses in the through holes of the substrate under the actions of capillary force of the through holes, self gravity of the transparent medium and surface tension, and adjusting the focal length of the convex lenses by changing the size of the through holes and the surface tension of the transparent medium.
S4, preparing nano silver sol by reducing silver nitrate with sodium citrate, dripping the nano silver sol on one side of the convex lens, drying in the dark to obtain the array SERS substrate integrated with the convex lens, and converging Raman scattering light by utilizing the principle of converging light of the convex lens, thereby improving the collection efficiency and Raman scattering intensity of Raman scattering.
An embodiment two, integrated convex lens's array SERS base, including the substrate, the material of substrate is the copper that 2mm is thick, and the punching press is formed with a plurality of circular through-holes that are array distribution on it, the diameter of circular through-hole is 0.15mm, is equipped with convex lens in this through-hole, convex lens is formed by transparent resin after the drying and solidification in the through-hole, is attached to gold nanoparticle in one side of convex lens.
The preparation method of the array SERS substrate integrated with the convex lens is similar to that of the first embodiment.
Third, integrated convex lens's array SERS base, including the substrate, the material of substrate is the aluminum plate that 1.5mm is thick, and the punching press is formed with a plurality of circular through-holes that are array distribution on it, the diameter of circular through-hole is 2mm, is equipped with convex lens in this through-hole, convex lens is formed by PMMA drying and solidification back in the through-hole, is attached to silver nanoparticle in one side of convex lens.
The preparation method of the array SERS substrate integrated with the convex lens is similar to that of the first embodiment.
The fourth embodiment, integrated convex lens's array SERS base, including the substrate, the material of substrate is the aluminum plate of 1mm thickness, and the punching press is formed with a plurality of circular through-holes that are array distribution on it, the diameter of circular through-hole is 0.5mm, is equipped with convex lens in this through-hole, convex lens is formed by PDMS drying and solidification back in the through-hole, is attached to silver nanoparticle in one side of convex lens.
The preparation method of the array SERS substrate integrated with the convex lens is similar to that of the first embodiment.
The fifth embodiment, integrated convex lens's array SERS base, including the substrate, the material of substrate is the thick 304 stainless steel board of 0.75 mm, and the punching press is formed with a plurality of circular through-holes that are array distribution on it, the diameter of circular through-hole is 1.5mm, is equipped with convex lens in this through-hole, convex lens is formed by PDMS drying and solidification back in the through-hole, is attached with silver-core gold shell nanoparticle in one side of convex lens.
The preparation method of the array SERS substrate integrated with the convex lens is similar to that of the first embodiment.
The sixth embodiment, integrated convex lens's array SERS base, including the substrate, the material of substrate is the aluminum plate that 1.5mm is thick, and the punching press is formed with a plurality of circular through-holes that are array distribution on it, the diameter of circular through-hole is 1mm, is equipped with convex lens in this through-hole, convex lens is formed by PDMS drying and solidification back in the through-hole, is attached to gold core silver-shell nanoparticle in one side of convex lens.
The preparation method of the array SERS substrate integrated with the convex lens is similar to that of the first embodiment.
Technical solution of the invention is described above with reference to the accompanying drawings, it is obvious that the specific implementation of the invention is not limited by the above-mentioned manner, and it is within the scope of the invention to adopt various insubstantial modifications of the inventive method concept and technical solution, or to apply the inventive concept and technical solution to other occasions without modification.

Claims (4)

1. An array SERS substrate integrated with convex lens comprises a substrate (1), and is characterized in that: the substrate (1) is provided with a plurality of through holes (2) distributed in an array manner, double-sided convex lenses (3) are arranged in the through holes (2), and metal nano particles (4) are attached to one sides of the convex lenses (3);
the preparation method of the array SERS substrate integrated with the convex lens comprises the following steps:
s1, machining the substrate to obtain through holes distributed in an array manner, and performing hydrophobic treatment on the substrate by adopting a surfactant;
s2, preparing a transparent medium solution, wherein the transparent medium is one of PMMA, PDMS and transparent resin;
s3, dropwise adding the transparent medium solution on a substrate, spin-coating for 40-60 min at a rotating speed of 2000-3000 r/min, and then drying for 2-3 h at a temperature of 60-100 ℃ to obtain a convex lens in a through hole of the substrate;
s4, preparing metal nano sol, dropwise adding the metal nano sol to one side of the convex lens, and drying in a dark place to obtain the array SERS substrate integrated with the convex lens.
2. The convex lens integrated array SERS substrate of claim 1, wherein: the substrate (1) is a stainless steel plate, a copper plate or an aluminum plate.
3. The convex lens integrated array SERS substrate according to claim 1 or 2, wherein: the through holes (2) are round through holes, and the diameter of each through hole is 0.15-2 mm.
4. The convex lens integrated array SERS substrate according to claim 1 or 2, wherein: the metal nanoparticles (4) are made of gold, silver, a silver core gold shell or a gold core silver shell.
CN201910603310.5A 2019-07-05 2019-07-05 Array SERS substrate integrated with convex lens and preparation method thereof Active CN110320198B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103060878A (en) * 2013-01-31 2013-04-24 中国科学院合肥物质科学研究院 Silver nanometer column array erected on orifice of porous alumina template and preparation method and application thereof
CN104498881A (en) * 2014-12-09 2015-04-08 中国科学院合肥物质科学研究院 Method for preparing silver nano particle modified polyacrylonitrile nano-structure array flexible substrate
CN106567119A (en) * 2016-10-19 2017-04-19 华中科技大学 Polymer based nanometer cone structure SERS substrate and preparation method
CN109467043A (en) * 2018-11-14 2019-03-15 重庆大学 A kind of SERS substrate of integrated micro-concave mirror and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8786852B2 (en) * 2009-12-02 2014-07-22 Lawrence Livermore National Security, Llc Nanoscale array structures suitable for surface enhanced raman scattering and methods related thereto
US8358407B2 (en) * 2010-04-30 2013-01-22 Hewlett-Packard Development Company, L.P. Enhancing signals in Surface Enhanced Raman Spectroscopy (SERS)
CN104502323A (en) * 2014-12-22 2015-04-08 安徽师范大学 Transparent flexible surface enhanced Raman active substrate and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103060878A (en) * 2013-01-31 2013-04-24 中国科学院合肥物质科学研究院 Silver nanometer column array erected on orifice of porous alumina template and preparation method and application thereof
CN104498881A (en) * 2014-12-09 2015-04-08 中国科学院合肥物质科学研究院 Method for preparing silver nano particle modified polyacrylonitrile nano-structure array flexible substrate
CN106567119A (en) * 2016-10-19 2017-04-19 华中科技大学 Polymer based nanometer cone structure SERS substrate and preparation method
CN109467043A (en) * 2018-11-14 2019-03-15 重庆大学 A kind of SERS substrate of integrated micro-concave mirror and preparation method thereof

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