CN112708874A - Substrate material with enhancement effect on Raman spectrum - Google Patents

Substrate material with enhancement effect on Raman spectrum Download PDF

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Publication number
CN112708874A
CN112708874A CN202011465178.5A CN202011465178A CN112708874A CN 112708874 A CN112708874 A CN 112708874A CN 202011465178 A CN202011465178 A CN 202011465178A CN 112708874 A CN112708874 A CN 112708874A
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base layer
metal base
substrate material
metal
raman spectroscopy
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曾川
蔡德玲
王梦凡
李珍妮
曾文祥
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Gongbei Customs Technology Center
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Gongbei Customs Technology Center
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/54Contact plating, i.e. electroless electrochemical plating
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention provides a substrate material with enhancement effect on Raman spectrum, which comprises a metal base layer with a roughened surface and a noble metal nanoparticle layer, wherein the noble metal of the noble metal nanoparticle layer is selected from one or more of gold, silver, platinum, palladium, rhodium and ruthenium. At present, the specific detection of target molecules in actual samples by using raman spectroscopy is quite difficult because actual sample systems are often complex in composition, and raman spectroscopy itself is not selective for specific molecules. Particularly, when the content of the target molecules is low or a sample contains structural analogues of the target molecules, the sensitivity and the anti-interference performance of the traditional SERS substrate often cannot meet the detection requirements, and the content detection cannot be carried out. According to the invention, the precious metal nanoparticle layer is arranged on the surface of the metal base layer, and the object to be detected is captured by utilizing the precious metal nanoparticle layer structure, so that quantitative detection is realized.

Description

Substrate material with enhancement effect on Raman spectrum
Technical Field
The present invention relates to a substrate material, and more particularly, to a substrate material having an enhancement effect on raman spectroscopy.
Background
At present, the specific detection of target molecules in actual samples by using raman spectroscopy is quite difficult because actual sample systems are often complex in composition, and raman spectroscopy itself is not selective for specific molecules. Particularly, when the content of the target molecules is low or a sample contains structural analogues of the target molecules, the sensitivity and the anti-interference performance of the traditional SERS substrate often cannot meet the detection requirements, and the content detection cannot be carried out.
Disclosure of Invention
The invention provides a substrate material with an enhancement effect on Raman spectrum, so as to realize content detection on an object to be detected.
The invention provides a substrate material with enhancement effect on Raman spectrum, which comprises a metal base layer with a roughened surface and a noble metal nanoparticle layer, wherein the noble metal of the noble metal nanoparticle layer is selected from one or more of gold, silver, platinum, palladium, rhodium and ruthenium.
Further, the preparation method of the substrate material comprises the following steps:
and (2) placing the metal base layer with the roughened surface in a noble metal ion solution, and performing chemical oxidation-reduction reaction to form a noble metal nanoparticle layer on the surface, wherein the oxidation-reduction point of the metal base layer is lower than the oxidation-reduction potential of the noble metal ion.
Still further, the noble metal ion solution is one or more of chlorate, nitrate and sulfate of the noble metal.
Further, the metal base layer with the roughened surface is a Cu substrate.
Further, the surface of the metal base layer is roughened by the following method:
s2, immersing the metal base layer into a corrosive acid solution with the concentration of 5-30%, standing and preserving heat for 1-20min at the temperature of 20-50 ℃;
s3, cleaning and drying to obtain the metal base layer with the roughened surface.
Further, the corrosive acid solution is one or more of nitric acid, hydrochloric acid and sulfuric acid.
Still further, the surface roughening treatment method for the metal base layer further comprises:
s1, cleaning the surface of the metal base layer to expose the metal surface of the metal base layer.
Further, the surface cleaning of the metal substrate includes:
s11, removing organic matters on the metal surface by using a solvent, and drying.
Further, both of the S1 and S3 are dried under an inert gas.
Still further, the surface roughening treatment method for the metal base layer further comprises:
s4 taking a metal base layer to electrolyze in the solution.
Compared with the prior art, the precious metal nanoparticle layer is arranged on the surface of the metal base layer, and the object to be detected is captured by utilizing the precious metal nanoparticle layer structure, so that quantitative detection is realized.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example 1
Step 1: sequentially taking a Cu metal base layer, cleaning the surface of the Cu metal base layer in pure ethanol and acetone, dissolving grease on the surface of the Cu metal base layer to expose the surface of the Cu metal base layer, soaking the Cu metal base layer in double-pure water, carrying out ultrasonic cleaning, and drying the Cu metal base layer by nitrogen;
step 2: immersing the Cu metal base layer into a nitric acid solution with the concentration of 30%, and standing and preserving heat for 1min at the temperature of 30 ℃;
and step 3: soaking in double-pure water, ultrasonically cleaning, and drying with nitrogen;
and 4, step 4: repeating the step 32-3 times to obtain a Cu metal base layer with the roughened surface, taking the Cu metal base layer in a chloroauric acid solution with the content of 0.01%, standing and preserving heat for 1h at the temperature of 30 ℃, and obtaining the substrate material in the embodiment 1 of the invention.
Example 2
Step 1: sequentially taking a Cu metal base layer, cleaning the surface of the Cu metal base layer in pure ethanol and acetone, dissolving grease on the surface of the Cu metal base layer to expose the surface of the Cu metal base layer, soaking the Cu metal base layer in double-pure water, carrying out ultrasonic cleaning, and drying the Cu metal base layer by nitrogen;
step 2: immersing the Cu metal base layer into a nitric acid solution with the concentration of 30%, and standing and preserving heat for 1min at the temperature of 30 ℃;
and step 3: soaking in double-pure water, ultrasonically cleaning, and drying with nitrogen;
and 4, step 4: repeating the step 32-3 times to obtain a Cu metal base layer with the roughened surface, taking the Cu metal base layer in a solution containing 0.009% chloroauric acid and 0.001% chloroplatinic acid, standing and preserving heat for 1h at 30 ℃ to obtain the substrate material of the embodiment 2 of the invention.
Example 3
Step 1: sequentially taking a Cu metal base layer, cleaning the surface of the Cu metal base layer in pure ethanol and acetone, dissolving grease on the surface of the Cu metal base layer to expose the surface of the Cu metal base layer, soaking the Cu metal base layer in double-pure water, carrying out ultrasonic cleaning, and drying the Cu metal base layer by nitrogen;
step 2: immersing the Cu metal base layer into a nitric acid solution with the concentration of 30%, standing at 30 ℃ and preserving heat for 0.5 min;
and step 3: soaking in double-pure water, ultrasonically cleaning, and drying with nitrogen;
and 4, step 4: repeating the step 32-3 times to obtain a Cu metal base layer with the roughened surface, taking the Cu metal base layer in a chloroplatinic acid solution with the content of 0.001%, standing and preserving heat for 1h at the temperature of 30 ℃ to obtain a substrate material with a platinum layer on the surface;
and 5: immersing the substrate material with the platinum layer into a nitric acid solution with the concentration of 30%, and standing and insulating for 0.5min at the temperature of 30 ℃;
step 6: immersing in double-pure water for ultrasonic cleaning, and drying by nitrogen to obtain a substrate material with a roughened surface and a platinum layer;
and 7: the substrate material with the platinum layer on the roughened surface is taken out and placed in chloroauric acid solution with the content of 0.009 percent, and the substrate material of the embodiment 3 is obtained after standing and heat preservation for 1h at the temperature of 30 ℃.
Comparative example
Step 1: sequentially taking a Cu metal base layer, cleaning the surface of the Cu metal base layer in pure ethanol and acetone, dissolving grease on the surface of the Cu metal base layer to expose the surface of the Cu metal base layer, soaking the Cu metal base layer in double-pure water, carrying out ultrasonic cleaning, and drying the Cu metal base layer by nitrogen;
step 2: immersing the Cu metal base layer into a nitric acid solution with the concentration of 10%, and standing and insulating for 1min at the temperature of 30 ℃;
and step 3: and soaking the substrate in double-pure water for ultrasonic cleaning, and drying the substrate by nitrogen to obtain a Cu metal base layer with a roughened surface, wherein the Cu metal base layer is used as a substrate material of a comparison example of the invention.
The Cu metal base layers of the examples of the present invention and the comparative examples were commercially available inexpensive copper sheets.
Examples 1-3 of the present invention and comparative examples were tested by the following specific methods:
step 1: the concentration of each of the components was 1X 10-8mol/L、1×10-7mol/L、1×10-6mol/L、1×10-5mol/L、1×10-4A rhodamine solution of mol/L;
step 2: examples 1-3 and comparative examples were all prepared carrying 1X 10-8mol/L、1×10-7mol/L、1×10-6mol/L、1×10-5mol/L、1×10-4The specific loading method of the metal base layer of the mol/L rhodamine solution is as follows: dripping 100 mu L of rhodamine solution on the surface of a Cu metal base layer, drying by using nitrogen under the condition of isolated illumination, testing by using a Raman spectrometer, selecting a laser light source with the wavelength of 633nm under the condition of 300mW, integrating once within 10s, and setting the scanning range to be 200-1900 cm-1
And step 3: collecting the characteristic peak intensities of the examples 1-3 and the comparative example, marking by taking the logarithm value of the rhodamine solution as an abscissa and the characteristic peak intensities of the rhodamine solutions with different concentrations on the substrate as an ordinate, establishing a linear regression equation, and calculating R2The results are shown in the following table.
Example 1 Example 2 Example 3 Comparative example
R2 0.995 0.994 0.997
In the embodiment of the invention, the gold nano-layer is formed on the surface of the Cu substrate, so that carriers such as rhodamine and the like can be effectively detected, and the detection limit of the comparative example is low and cannot be used for detecting carriers of 1 multiplied by 10-8mol/L、1×10-7The rhodamine solution with the concentration of mol/L and the like can effectively respond, and the detection effect can not be realized. Meanwhile, the substrate material of the embodiment of the invention has simple preparation and high detection limit, and a linear regression equation R is established by taking the logarithm value of the rhodamine solution as an abscissa and the characteristic peak intensity of the rhodamine solution with different concentrations on the substrate as an ordinate2The characteristic peak intensity of the rhodamine fluorescence detection reagent is larger than 0.99, so that the characteristic peak intensity of the rhodamine fluorescence detection reagent can represent the rhodamine content, and compared with the traditional qualitative detection, the rhodamine fluorescence detection reagent can achieve a quantitative detection effect. Meanwhile, in the embodiment 3 of the invention, the surface roughening and the chemical oxidation-reduction reaction are carried out for multiple times, so that the detection stability is effectively improved, and R2Can reach 0.997.
Finally, it should be noted that the above-mentioned embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the modifications and equivalents of the specific embodiments of the present invention can be made by those skilled in the art after reading the present specification, but these modifications and variations do not depart from the scope of the claims of the present application.

Claims (10)

1. A substrate material with enhancement effect on Raman spectrum is characterized by comprising a metal base layer with a roughened surface and a noble metal nanoparticle layer, wherein the noble metal of the noble metal nanoparticle layer is selected from one or more of gold, silver, platinum, palladium, rhodium and ruthenium.
2. A substrate material having an enhancement effect on raman spectroscopy according to claim 1, characterized in that said substrate material is prepared by the following method:
and (2) placing the metal base layer with the roughened surface in a noble metal ion solution, and performing chemical oxidation-reduction reaction to form a noble metal nanoparticle layer on the surface, wherein the oxidation-reduction point of the metal base layer is lower than the oxidation-reduction potential of the noble metal ion.
3. A substrate material having an enhancing effect on raman spectroscopy according to claim 2, wherein said noble metal ion solution is one or more of chlorate, nitrate, sulfate of said noble metal.
4. The base material with enhanced raman spectroscopy of claim 1, wherein said roughened metal-based layer is a Cu substrate.
5. The base material having an enhancement effect on raman spectroscopy according to claim 1, wherein the surface of said metal base layer is roughened by the following method:
s2, immersing the metal base layer into a corrosive acid solution with the concentration of 5-30%, standing and preserving heat for 1-20min at the temperature of 20-50 ℃;
s3, cleaning and drying to obtain the metal base layer with the roughened surface.
6. The substrate material with enhancement effect on Raman spectroscopy according to claim 5, wherein said corrosive acid solution is one or more of nitric acid, hydrochloric acid, and sulfuric acid.
7. The substrate material with enhanced raman spectroscopy according to claim 5, wherein the surface of said metal base layer is roughened by a roughening treatment method further comprising:
s1, cleaning the surface of the metal base layer to expose the metal surface of the metal base layer.
8. The substrate material with enhanced raman spectroscopy according to claim 7, wherein said surface cleaning of the metal substrate layer comprises:
s11, removing organic matters on the metal surface by using a solvent, and drying.
9. The substrate material having an enhancement effect on Raman spectroscopy according to claim 7, wherein each of the S1 and S3 is dried under an inert gas.
10. The substrate material with enhanced raman spectroscopy according to claim 5, wherein the surface of said metal base layer is roughened by a roughening treatment method further comprising:
s4 taking a metal base layer to electrolyze in the solution.
CN202011465178.5A 2020-12-14 2020-12-14 Substrate material with enhancement effect on Raman spectrum Pending CN112708874A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5255067A (en) * 1990-11-30 1993-10-19 Eic Laboratories, Inc. Substrate and apparatus for surface enhanced Raman spectroscopy
TW201111769A (en) * 2009-09-22 2011-04-01 Univ Vanung Surface-enhanced Raman spectroscopy (SERS) specimen having thermal stability and constancy and its manufacturing method thereof
CN103217410A (en) * 2013-04-02 2013-07-24 南京理工大学 Preparation method of surface enhanced raman spectrum substrate of gold nanoparticle embellished diamond film
US20130242297A1 (en) * 2010-08-24 2013-09-19 Singapore Health Services Pte Ltd Substrate for optical sensing by surface enhanced raman spectroscopy (sers) and methods for forming the same
CN103409734A (en) * 2013-07-25 2013-11-27 苏州大学 Precious metal nanometer particle assembly for SERS base and application of prepared product in detection
CN104060245A (en) * 2014-06-10 2014-09-24 上海交通大学 Super-hydrophobic nano-silver raman-enhanced substrate material and preparation method thereof
CN112481608A (en) * 2020-11-03 2021-03-12 江南大学 Titanium substrate with metal nanoparticles growing on surface in situ and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5255067A (en) * 1990-11-30 1993-10-19 Eic Laboratories, Inc. Substrate and apparatus for surface enhanced Raman spectroscopy
TW201111769A (en) * 2009-09-22 2011-04-01 Univ Vanung Surface-enhanced Raman spectroscopy (SERS) specimen having thermal stability and constancy and its manufacturing method thereof
US20130242297A1 (en) * 2010-08-24 2013-09-19 Singapore Health Services Pte Ltd Substrate for optical sensing by surface enhanced raman spectroscopy (sers) and methods for forming the same
CN103217410A (en) * 2013-04-02 2013-07-24 南京理工大学 Preparation method of surface enhanced raman spectrum substrate of gold nanoparticle embellished diamond film
CN103409734A (en) * 2013-07-25 2013-11-27 苏州大学 Precious metal nanometer particle assembly for SERS base and application of prepared product in detection
CN104060245A (en) * 2014-06-10 2014-09-24 上海交通大学 Super-hydrophobic nano-silver raman-enhanced substrate material and preparation method thereof
CN112481608A (en) * 2020-11-03 2021-03-12 江南大学 Titanium substrate with metal nanoparticles growing on surface in situ and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
邓荻 等: ""不同表面活性剂对Sn基底表面银纳米粒子薄膜的原位生长及其光学性能的影响"", 《四川大学学报(自然科学版)》 *

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Application publication date: 20210427