CN114624222A - Preparation method of Ag/Cu/PET double-nanoparticle flexible SERS substrate - Google Patents

Preparation method of Ag/Cu/PET double-nanoparticle flexible SERS substrate Download PDF

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CN114624222A
CN114624222A CN202210247234.0A CN202210247234A CN114624222A CN 114624222 A CN114624222 A CN 114624222A CN 202210247234 A CN202210247234 A CN 202210247234A CN 114624222 A CN114624222 A CN 114624222A
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pet
sers substrate
nanoparticle
substrate
preparation
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宁金妍
华承志
潘登
张玲
刘瑾
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals

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Abstract

The invention discloses a preparation method of an Ag/Cu/PET double-nanoparticle flexible SERS substrate, which comprises the steps of coating Cu nanoparticle ink on a PET substrate, drying, and immersing a Cu/PET composite film into AgNO3Oxidation and reduction in solution. The Ag/Cu/PET SERS substrate prepared by the method contains two kinds of nanoparticles of Ag and Cu, and the minimum detection limits of the Ag/Cu/PET SERS substrate to a rhodamine 6G solution and a crystal violet solution can respectively reach 10‑18M and 10‑10And M. The invention has simple process, flexible operation and low cost, can realize the batch production of the substrate, and can change the pattern shape of the substrate according to the actual requirement at any time. The SERS substrate prepared by the invention has the advantages of high detection sensitivity, high uniformity, good flexibility, good mechanical stability and good flexibility, and can be widely applied to the field of trace detection of various substances.

Description

Preparation method of Ag/Cu/PET double-nanoparticle flexible SERS substrate
Technical Field
The invention belongs to the technical field of Raman detection, and particularly relates to a preparation method of an Ag/Cu/PET double-nanoparticle flexible SERS substrate.
Background
Surface Enhanced Raman Scattering (SERS), which was first discovered by Fleischman in 1974, is a technology developed on the basis of ordinary raman scattering, overcomes the disadvantage of low signal of the conventional raman spectrum, can obtain structural information that is not easily obtained by the conventional raman spectrum, and is currently widely applied in the fields of biomedicine, surface science, biosensing, food safety, trace analysis and detection, and the like. As for the enhancement mechanism of SERS, an electromagnetic Enhancement Mechanism (EM) is dominant, which is considered to be mainly related to noble metal nanostructures and surface plasmons. The interaction between the metal localized surface plasmon and the incident photon can generate coupling resonance, i.e. localized surface plasmon resonance, which has strong localized electromagnetic field enhancement effect, especially in the specific position of the nanostructure, such as the tip, and the nano-gap between particles: (<10nm) etc (referred to as "hot spot" locations) produce stronger localized electromagnetic field enhancement. As the local electric field near the surface of the metal substrate is greatly enhanced, the Raman signal of the molecules to be detected adsorbed on the SERS substrate is also greatly improved, and the enhancement factor of the electromagnetic enhancement can reach 108As described above. Currently, the commonly used SERS substrates are mainly gold, silver, copper, and the like. The preparation of the gold and silver flexible SERS substrate tends to be mature, but the cost of gold and silver is high, the preparation process is complex, the required equipment is high, the price of copper is low, and the enhancement factor of copper is inferior to that of gold and silver. Therefore, a simple new process is developed to improve the surface Raman enhancement performance of copper, so that the copper is always a leading-edge hot spot problem compared with gold and silver.
The displacement reaction is the simplest and most effective method in the method for modifying the Raman enhancement performance of the copper surface. In 2017, Hu et al take a copper foil as a substrate, and obtain an Ag-Cu alloy SERS substrate through a displacement reaction, wherein the detection limit of the SERS substrate on a rhodamine 6G (R6G) solution can be 10 at most-13And M. Tzeng and the like firstly carry out gas-phase deposition on graphene on copper foil, then prepare an Ag/G/Cu SERS substrate through a displacement reaction, and the minimum detection limit of R6G solution can reach 10-16And M. Xun et al, by combining laser-induced selective metallization of polymer surfaces with improved electrowinning reactionsAnd preparing the Ag-Cu alloy SERS substrate, wherein the minimum detection limit of the Ag-Cu alloy SERS substrate to the R6G solution can reach 10-17And M. In reported work, the preparation cost of the copper layer is high, the pattern shape of the SERS substrate cannot be flexibly adjusted, and the current flexible and variable production requirements cannot be met.
Nanoparticle ink deposition is used as a novel additive manufacturing method, and plays an important role in the field of SERS substrate preparation by virtue of free and flexible deposition pattern selectivity and load substrate selectivity. Dune et al prepared highly reproducible surface-enhanced raman spectroscopy arrays (6 x 10 printed spots) by screen printing silver nanoparticles onto a background. The detection limit of the material on rhodamine 6G can reach 1.6 multiplied by 10-13And M. Godoy et al prepared the SERS substrate by printing gold nanosphere ink of 70nm on hydrophobic paper using ink jet technology. The detection limit of the Crystal Violet (CV) can reach 10-11And M. And the cost of each SERS pattern only needs $ 0.01, so that the preparation cost of the SERS substrate is greatly reduced. At present, gold and silver ink is widely applied, but few reports are reported on the preparation of a high-sensitivity SERS substrate by using copper ink.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of the Ag/Cu/PET double-nanoparticle flexible SERS substrate, which is simple and rapid, low in cost, flexible in modeling, high in detection sensitivity of the prepared substrate, uniform in SERS performance and high in bending stability.
The invention is realized by the following technical scheme:
preparing Cu nano particle ink, ultrasonically cleaning a PET film, coating the Cu nano particle ink on the PET film into corresponding patterns according to actual requirements, drying in vacuum, and immersing the Cu/PET composite film into AgNO3And (3) performing oxidation reduction in the solution, and cleaning and drying with deionized water to obtain the Ag/Cu/PET double-nanoparticle flexible SERS substrate.
Wherein the Cu content in the Cu nanoparticle ink is 30-80 wt%.
Wherein the ultrasonic cleaning time of the PET film is 10-30 min.
Wherein the size of the Cu nanoparticles in the Cu nanoparticle ink is 5-300 nm.
Wherein said immersion AgNO3Solution of AgNO3The concentration of the solution is 0.005-0.05M, and the immersion time is 0.5-2 min. The invention has the following beneficial effects:
according to the preparation method of the Ag/Cu/PET double-nanoparticle flexible SERS substrate, the substrate prepared by the method is used for detecting R6G solution, and the lowest detection limit can reach 10-18M; the detection limit of the CV solution can reach 10-10M, the SERS performance of the substrate is distributed uniformly, 10 points are randomly selected for testing, the minimum relative standard deviation value between the characteristic peak intensities at the same peak position is as low as 0.131, in addition, the bending stability is also excellent, and after the substrate is bent for 15 times at a bending angle of 180 degrees with a bending radius of 3mm, the SERS performance is basically unchanged. The substrate has high sensitivity, low cost and simple preparation method, and can flexibly adjust the pattern shape of the substrate according to the requirements.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is an experimental flow chart for preparing an Ag/Cu/PET dual-nanoparticle flexible SERS substrate.
FIG. 2 is a scanning electron microscope image of a Cu/PET composite film.
FIG. 3 is a diagram showing the distribution of copper element and carbon element at the position corresponding to FIG. 2 in the Cu/PET composite film
FIG. 4 is a scanning electron microscope image of a Ag/Cu/PET dual-nanoparticle flexible SERS substrate
FIG. 5 is a distribution diagram of copper element and silver element of the Ag/Cu/PET double-nanoparticle flexible SERS substrate corresponding to the position in FIG. 4
FIG. 6 shows a pair of Ag/Cu/PET dual-nanoparticle flexible SERS substrates 10-8-10-18M R6 Raman Spectroscopy of solution 6G
FIG. 7 shows a pair of Ag/Cu/PET dual-nanoparticle flexible SERS substrates 10-7-10-10Raman spectra obtained from M CV solutions
FIG. 8 is 10-8M R6G solution testing condition, 612cm-1Raman scanning imaging picture obtained by peak position
FIG. 9 shows SERS performance changes of the Ag/Cu/PET dual-nanoparticle flexible SERS substrate after being bent for 0, 5, 10 and 15 times at a bending angle of 180 degrees with a bending radius of 3mm
Detailed Description
In order to make the technical content of the invention more comprehensible to those skilled in the art, specific embodiments accompanied with the figures are described below.
Example 1
The preparation method of the Ag/Cu/PET double-nanoparticle flexible SERS substrate comprises the following steps:
(1) and preparing Cu nano particle ink with corresponding volume according to the area of the PET film. This example is a 1cm × 1cm PET film. Preparing a mixed solution of 4ml of ethylene glycol and 1.7ml of lactic acid, and adding 1g of NaH2PO2Fully dissolving the powder to obtain a mixed solution A; taking 0.2g of Cu (OH)2The powder was dissolved in 2ml of ethylene glycol solution sufficiently to obtain a mixed solution B. Mixing A and B, heating in 95 deg.C water bath for 10min, centrifuging at 4000 rpm for 5min to obtain copper nanoparticles, dissolving the particles in anhydrous ethanol, centrifuging at 4000 rpm for 5min, repeating twice, and washing to remove impurities. 0.006g of ethyl cellulose was dissolved in 0.1ml of terpineol to prepare an ink, and then 0.1g of pure copper nanoparticles were added to disperse to obtain a copper nanoparticle ink having a Cu content of 50.25 wt%.
(2) Ultrasonically cleaning the PET film for 15min, then coating the copper nanoparticle ink on the PET film according to actual requirements to form a corresponding pattern, and performing vacuum drying to obtain the Cu/PET composite film. The copper layer on the PET film was surface roughened (fig. 2) with copper nanoparticles ranging in size from 5-300 nm. The copper and carbon elements are uniformly distributed in the copper ink (fig. 3).
(3) Immersing Cu/PET composite film into 0.02M AgNO3And carrying out oxidation reduction for 1 minute in the solution, taking out, washing with deionized water, and carrying out vacuum drying to obtain the Ag/Cu/PET double-nanoparticle flexible SERS substrate. The SEM image of the base is shown in fig. 4, the white irregular particles are silver nanoparticles with an average size of 254nm, and the grey substrate is a copper nanoparticle layer. Further testing of the elemental distribution of the substrate surfaceThe copper element is now distributed mainly in the grey substrate and the silver element is distributed mainly in the white particles, as shown in fig. 5
Example 2
Preparation 10-8-10-18M in a solution of R6G, the Ag/Cu/PET double-nanoparticle flexible SERS substrate is soaked in the solution of R6G for 3 hours and then dried, and the Raman spectrum of the substrate is tested, and the result is shown in figure 6. The flexible substrate has a wider detection range for R6G molecules, and the detection limit can reach 10 at most-18And M. And the main characteristic peak of R6G is still clearly and clearly obvious, which indicates that the substrate has extremely high sensitivity.
Preparation 10-7-10-10M CV solution, soaking the Ag/Cu/PET double-nanoparticle flexible SERS substrate in the CV solution for 3h, drying, and performing SERS characterization, wherein the Raman spectrum is shown in figure 7, and the lowest detection limit of CV molecules can reach 10-10And M. The substrate is proved to have higher sensitivity to various organic matters.
Example 3
Soaking Ag/Cu/PET double-nanoparticle flexible SERS substrate in 10-8M R6G, which were dried, were subjected to raman scan imaging tests, the results of which are shown in fig. 8. The numerical value in the color bar represents the relative intensity of the Raman characteristic peak, the intensity is from low to high, and the color correspondingly transits from blue to red. It can be seen from the figure that the green color occupies most of the green color in the test range, and only a small part of the green color is blue or red, which proves that in the test region, the intensity of the characteristic peak of most of the region is about moderate, and the intensity of the small part is higher or lower, which accords with the natural law of normal distribution, further showing that the SERS performance of the substrate is uniformly distributed.
Example 4
Soaking Ag/Cu/PET double-nanoparticle flexible SERS substrate in 10-12M R6G, after drying, were bent a total of 15 times back and forth at a bending angle of 180 ° with a bending radius of 3mm, and after 0, 5, 10, 15 times of bending, respectively, the SERS performance of the substrate was tested, as shown in fig. 9. The SERS performance of the substrate does not fluctuate obviously, and the substrate is further proved to have good bending stability and practicability.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, which is intended to cover any variations, equivalents, or improvements made within the spirit and scope of the invention.

Claims (6)

1. A preparation method of an Ag/Cu/PET double-nanoparticle flexible SERS substrate is characterized by comprising the following steps:
preparing Cu nano particle ink, ultrasonically cleaning a PET film, coating the Cu nano particle ink on the PET film into corresponding patterns according to actual requirements, drying in vacuum, and immersing the Cu/PET composite film into AgNO3And (3) carrying out oxidation reduction in the solution, washing with deionized water and drying to obtain the Ag/Cu/PET double-nanoparticle flexible SERS substrate.
2. The method for preparing the Ag/Cu/PET double-nanoparticle flexible SERS substrate according to claim 1, wherein the Cu content of the Cu nanoparticle ink is 30-80 wt%.
3. The preparation method of the Ag/Cu/PET double-nanoparticle flexible SERS substrate according to claim 1, wherein the ultrasonic cleaning time of the PET film is 10-30 min.
4. The preparation method of the Ag/Cu/PET dual-nanoparticle flexible SERS substrate according to claim 1, wherein the size of the Cu nanoparticles in the Cu nanoparticle ink is 5-300 nm.
5. The method for preparing the Ag/Cu/PET double-nanoparticle flexible SERS substrate according to claim 1, wherein the AgNO is3The concentration of the solution is 0.005-0.05M.
6. The preparation method of the Ag/Cu/PET double-nanoparticle flexible SERS substrate according to claim 1, wherein the redox time is 0.5-2 min.
CN202210247234.0A 2022-03-14 2022-03-14 Preparation method of Ag/Cu/PET double-nanoparticle flexible SERS substrate Pending CN114624222A (en)

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