CN113720826A - Application of controllable electroplating method based on V-shaped cavity array surface in preparation of high-sensitivity SERS substrate - Google Patents
Application of controllable electroplating method based on V-shaped cavity array surface in preparation of high-sensitivity SERS substrate Download PDFInfo
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 29
- 238000009713 electroplating Methods 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010931 gold Substances 0.000 claims abstract description 15
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 238000007747 plating Methods 0.000 claims description 11
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- 238000004769 chrono-potentiometry Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 11
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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
-
- 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
- C23C14/04—Coating on selected surface areas, e.g. using masks
- C23C14/042—Coating on selected surface areas, e.g. using masks using masks
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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
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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
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Abstract
The invention provides an application of a controllable electroplating method based on a V-shaped cavity array surface in preparation of a high-sensitivity SERS substrate, which comprises the following steps: 1) preparing electroplating template by adopting an AAO template with a V-shaped cavity structure at a fixed angle and constant speedEvaporating 10nm chromium and 120nm silver to form a layer of tightly combined AAO silver film electroplated layer; 2) preparing electroplating solution, namely preparing a mixed solution of 3.3mM chloroauric acid and 0.1M hydrofluoric acid; 3) electrochemical controllable assembly, adopting three-electrode electrochemical workstation, electroplating template as working electrode, platinum sheet electrode as counter electrode, Ag/AgCl2As a reference electrode, at 0.1mA/cm2The deposition growth was carried out at constant current density and recorded. The gold nanoparticles can realize directional controllable deposition on the surface of a V-shaped cavity array, the obtained high-sensitivity SERS substrate can reach the single-molecule detection level, and the detection limit of R6G can be as low as 10‑18M。
Description
Technical Field
The invention relates to the technical field of electrochemical directional controllable deposition, and Au is utilized+The nano-gold multilevel aggregate with the high chemical stability structure and the gap below 10 nanometers greatly enhances the Raman signal of probe molecules, and particularly relates to a structural design, a preparation method and application of nano-gold attached to the surface of a V-shaped cavity array.
Background
Surface Enhanced Raman Scattering (SERS) is an extremely sensitive molecular fingerprint technique, is widely used for trace monitoring of various molecules, can detect chemical substances down to a single-molecule level, and has important applications in the fields of biology, medicine, virus detection, and the like. High performance SERS substrates depend on the intensity and size of the "hot spot" in the substrate, which is mainly generated at the tip and small gap (< 10nm) of the metal nanostructure. The SERS substrate generally adopts nano gold and nano silver as a nano structure of the substrate, and has good biocompatibility. Based on the remarkable advantages, the kit has good prospect in the aspect of specifically detecting various molecules.
However, the cost of the current high-performance SERS enhancing substrate is high, and a regular periodic array in morphology is generally required to be prepared by a fine micro-nano processing means to ensure the uniformity and reproducibility of the substrate, but the fine nano processing apparatus is very expensive and has poor cost benefit. Therefore, developing a cost-effective method to fabricate large-area, topographically uniform nanostructured surfaces is the ultimate goal pursued by SERS.
The electrodeposition technology is widely applied to the growth of metal such as a nano column and a nano ring, and the nano-scale growth of the metal can be realized by controlling the deposition potential and the charge density, however, most of the work is electrodeposition and limited deposition of metal nanoparticles, most of the deposited morphology is accumulation of metal particles, and the arrangement of the metal particles with nano gaps is difficult to realize. Therefore, the development of an assembly of directionally controllable gold nanoparticles is also the final goal pursued by electroplating.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems, the gold nanoparticles are assembled by controlling the charge density through an electroplating method in electrochemistry, a silver film with a hierarchical structure in a V-shaped cavity body is obtained by carrying out vacuum evaporation on a V-shaped AAO template, and the charge density in the electroplating process is further controlled. The controllable deposition of gold nanoparticles is realized by utilizing the difference of charge densities of different sites on the surface of the cavity array, and a plasmon V-shaped cavity body membrane with a gap smaller than 10 nanometers is formed. The Ag and Au composite nano structure is utilized to generate huge electromagnetic enhancement, and Au particles in the shape of a 'hierarchical ring' with nano gaps form multiple 'hot spots', so that the adsorption capacity of the SERS substrate is greatly improved, and the high-sensitivity detection of the substrate is realized.
The technical scheme is as follows: in order to achieve the purpose, the invention provides the following scheme:
1. an application of a controllable electroplating method based on a V-shaped cavity array surface in preparation of a high-sensitivity SERS substrate comprises the following steps:
step (1) preparing an electroplating template: selecting a cleaned AAO template with a V-shaped aperture, wherein the model parameters are as follows: the top is a hexagonal hole with the aperture of 450nm, the bottom is a circular pocket bottom with the aperture of 100nm, and the hole depth is 400 nm; firstly, evaporating a layer of metal chromium with the thickness of 10nm on the surface of AAO by using a vacuum film plating machine, wherein the constant evaporation rate is 0.2 angstrom/second; then, continuously evaporating a layer of 120nm silver film at the same evaporation rate to form a layer of thin electro-silver film, and covering the inner wall and the surface of the V-shaped cavity of the whole AAO to obtain the electroplating template with the V-shaped cavity body structure;
preparing electroplating solution in step (2): preparing a mixed solution of 3.3mM chloroauric acid and 0.1M hydrofluoric acid, wherein the used water is deionized water with EW-I standard;
and (3) electrochemical controllable assembly: adopting a three-electrode electrochemical workstation, taking the electroplating template obtained in the step (1) as a working electrode, taking a platinum sheet electrode as a counter electrode, and taking Ag/AgCl2As a reference electrode, at 0.1mA/cm2The current density is deposited for different time to obtain the high-sensitivity SERS substrate with uniform appearance.
Further, in the step (3), the electrochemical deposition method is chronopotentiometry and is constant at 0.1mA/cm2The current density of (a) is deposited.
Further, in step (3), the electrochemical deposition is optimal for 400s, the SERS signal is strongest and the detection limit for R6G can be as low as 10-18M。
Has the advantages that: compared with the prior art, the invention has the following specific advantages:
1. the preparation method can rapidly prepare a large amount of high-performance SERS substrates, and can reach the level of single molecule detection;
2. the preparation method is electroplating assembly of directionally controllable nano gold particles, and has high social market value and application prospect;
3. the preparation method provided by the invention considers cost benefits, integrates low cost, high performance, high sensitivity and the like, is a final target pursued by the SERS substrate, and has important significance in the aspect of low-concentration trace detection.
Drawings
Fig. 1 is a flow chart of an application of the controllable electroplating method based on the V-cavity array surface in the preparation of a high-sensitivity SERS substrate according to the present invention.
Fig. 2 is a high resolution image of a plating stencil of the present invention.
FIG. 3 shows the plating solution of the present invention at 0.1mA/cm2A planar high resolution image of 400s was deposited at a current density of (1).
FIG. 4 shows the plating solution of the present invention at a rate of 0.1mA/cm2A lateral high resolution image of 400s was deposited at a current density of (a).
FIG. 5 shows the plating solution of the present invention at a rate of 0.1mA/cm2A planar high resolution image of 100s was deposited at a current density of (a).
FIG. 6 shows the plating solution of the present invention at a rate of 0.1mA/cm2A planar high resolution image of 200s was deposited at a current density of (1).
FIG. 7 shows the plating solution of the present invention at 0.1mA/cm2A flat high resolution image of 300s was deposited at a current density of (a).
FIG. 8 shows the plating solution of the present invention at a rate of 0.1mA/cm2A planar high resolution image of 500s was deposited at a current density of (a).
FIG. 9 shows the plating solution of the present invention at a rate of 0.1mA/cm2A planar high resolution image of 600s was deposited at a current density of (a).
FIG. 10 is a graph of R6G10 detection after different times of constant current density deposition in accordance with the present invention-6SERS spectrum of M.
FIG. 11 shows SERS spectra of different R6G concentrations detected during constant current density deposition for 400s according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the following description, taken in conjunction with the accompanying drawings, provides specific embodiments of the present invention, which is based on the application of the controllable electroplating method for V-cavity array surface in the preparation of the high-sensitivity SERS substrate. Of course, the specific examples described herein are merely illustrative of the invention and are not intended to be limiting.
Example 1
The invention discloses a method for using a V-shaped thin electro-silver film as an electric template (see figure 2), which comprises the following steps:
1) the AAO template with the aperture of V-type 450-100 is adopted, the upper end of the aperture is a hexagonal hole with the aperture of 450nm, the bottom is a circular pocket bottom with the aperture of 100nm, and the depth of the hole is 400 nm. Ultrasonically cleaning in deionized water, ethanol, acetone and deionized water for 10 minutes according to the steps, cleaning the surface and the holes of the AAO template, and then blowing the AAO template by nitrogen for later use.
2) Firstly, a layer of metal chromium with the thickness of 10nm is evaporated on the surface of the AAO by using a vacuum film plating machine, so that a subsequently evaporated silver film is uniformly and tightly combined with the AAO.
3) And (3) evaporating a 120nm silver film at a constant rate of 0.2 angstrom/second, and finally forming an AAO electroplating template covered by the silver film, wherein the average value of the hole wall thickness is 60nm, the upper end of the hole diameter is a hexagonal hole with the diameter of 360nm, the bottom of the hole diameter is a circular pocket bottom with the diameter of 100nm, and the depth of the hole is 400nm, as shown in figure 2.
Example 2
The invention discloses a method for preparing a high-performance uniform SERS substrate by directionally and controllably assembling electrodeposited gold nanoparticles, which comprises the following steps of:
1) preparing electroplating solution, preparing a mixed solution of 3.3mM chloroauric acid and 0.1M hydrofluoric acid, wherein the used water is EW-I standard deionized water.
2) Adopting a three-electrode electrochemical workstation, taking an electroplating template as a working electrode, taking a platinum sheet electrode as a counter electrode, and taking Ag/AgCl2As a reference electrode, at 0.1mA/cm2The different shapes and SERS performances are obtained by depositing the particles at different times under the current density.
3) Referring to fig. 3-9, the deposition growth process is detailed for different profiles of deposition 100s-600s, respectively.
4) SERS detection is carried out aiming at different morphologies, and R6G10 is used-6For example, referring to fig. 10, the deposition time of 400s is found to be the optimum profile, and the SERS intensity is significantly higher than for samples with other profiles.
The invention reports a method for assembling gold nanoparticles by directional controllable electrodeposition, and a funnel-type cascade structure with nanoscale gaps (less than 10nm) can be formed and is uniform and controllable, the appearance has a large number of nanoscale gaps, and the funnel-type cascade structure is provided with a uniform and regular three-dimensional funnel cavity, the gold nanoparticles with nanoscale gaps are assembled in the funnel cavity, and the adsorption capacity on probe molecules is greatly enhanced by the rough-surface cascade structure and the concave-convex cascade cavity wall. The unique structure not only forms an electromagnetic field with high intensity and enhances the SERS excitation efficiency, but also provides a large number of molecular binding sites with the detection limit as low as 10-18The R6G concentration of M (see figure 11) can realize single-molecule detection, and the developed low-cost, high-performance and high-sensitivity solid membrane substrate has great significance in SERS detection.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made for different situations without departing from the manufacturing method of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. The application of a controllable electroplating method based on a V-shaped cavity array surface in preparation of a high-sensitivity SERS substrate is characterized in that: the method comprises the following steps:
step (1) preparing an electroplating template: selecting a cleaned AAO template with a V-shaped aperture, wherein the model parameters are as follows: the top is a hexagonal hole with the aperture of 450nm, the bottom is a circular pocket bottom with the aperture of 100nm, and the hole depth is 400 nm; firstly, evaporating a layer of metal chromium with the thickness of 10nm on the surface of AAO by using a vacuum film plating machine, wherein the constant evaporation rate is 0.2 angstrom/second; then, continuously evaporating a layer of 120nm silver film at the same evaporation rate to form a layer of thin electro-silver film, and covering the inner wall and the surface of the V-shaped cavity of the whole AAO to obtain the electroplating template with the V-shaped cavity body structure;
preparing electroplating solution in step (2): preparing a mixed solution of 3.3mM chloroauric acid and 0.1M hydrofluoric acid, wherein the used water is deionized water with EW-I standard;
and (3) electrochemical controllable assembly: adopting a three-electrode electrochemical workstation, taking the electroplating template obtained in the step (1) as a working electrode, taking a platinum sheet electrode as a counter electrode, and taking Ag/AgCl2As a reference electrode, at 0.1mA/cm2The current density is deposited for different time to obtain the high-sensitivity SERS substrate with uniform appearance.
2. The method for controllably assembling the high-performance uniform SERS substrate of the electrodeposited gold nanoparticles of the V-shaped thin electrodeposited silver film according to claim 1, which is characterized in that: in the step (3), the electrochemical deposition method is a chronopotentiometry method, and the constant rate is 0.1mA/cm2The current density of (a) is deposited.
3. The application of the controllable electroplating method based on the V-shaped cavity array surface in the preparation of the high-sensitivity SERS substrate according to claim 1 is characterized in that: in the step (3), the electrochemical deposition is optimal for 400s, the SERS signal is strongest at the time, and the detection limit for R6G can be as low as 10-18M。
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