CN113125405A - SERS substrate based on nano conical needle structure and preparation method - Google Patents
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Abstract
The invention relates to a SERS substrate based on a nanometer conical needle structure and a preparation method thereof, belonging to the field of spectral analysis. The nano-cone needle structure comprises a base material, wherein the surface of the base material is provided with a nano-cone needle structure which is periodically arranged, the nano-cone needle structure comprises a first layer and a second layer, the first layer is made of a first material, the second layer is made of a second material, the surfaces of the base material and the nano-cone needle structure are coated with a third layer, the third layer is made of a third material, metal nano-particles are deposited on the third layer, and the base material is made of the first material. SiO generation on silicon wafers2Layer, polystyrene colloid ball is adhered to SiO by self-assembly mode2On the layer, the size of the polystyrene colloid ball is regulated and controlled through annealing or reactive ion etching; etching by metal-assisted chemical etching or dry etching; obtaining a nano conical needle structure through chemical corrosion; depositing gold on the silicon chip, and depositing gold nanoparticles by an electrochemical method. The substrate has high sensitivity, good repeatability and low cost, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a SERS substrate based on a nanometer conical needle structure and a preparation method thereof, belonging to the field of spectral analysis.
Background
The surface-enhanced Raman scattering is a spectroscopic technology with single-molecule detection, has the advantages of simple operation, strong specificity, wide application range and the like, is widely applied to the fields of food safety, environmental detection, disease diagnosis and the like, and becomes a powerful rapid detection means.
Surface Enhanced Raman Scattering (SERS) means that raman scattering signals are significantly enhanced when molecules are adsorbed on a rough metal (Au, Ag, Cu, etc.) surface. The currently widely accepted surface-enhanced raman scattering mainly has physical enhancement and chemical enhancement mechanisms, and the physical enhancement is mainly the electromagnetic field enhancement of surface metals. The main cause of the electromagnetic field enhancement is surface plasmon resonance, while the lightning rod effect can also cause the electromagnetic field enhancement. The lightning rod effect often appears on the needle-like structure, and these needle-like structures have very strong local electromagnetic field, and the tip is sharper, and the electromagnetic field of tip department is stronger, and raman signal reinforcing effect is about strong. Therefore, the preparation of the SERS substrate with the tip structure is very important.
Currently, SERS substrates are divided into colloidal substrates and solid substrates. Conventional colloidal substrates, such as gold or silver sols, are mostly spherical particles. With the development of micro-nano communication, electron beam lithography, x-ray lithography and nano-imprinting are frequently used for fabrication. Therefore, the development of a SERS substrate with high sensitivity, low cost, good stability and good repeatability is very meaningful. The invention mainly utilizes a low-cost self-assembly colloidal sphere template to prepare a nano-pillar array and integrates nano-gold particles by combining low-cost electrodeposition.
Patent 201910345971.2 discloses Au @ ZnO nanostructures as SERS substrates, which uses electrodeposition on an anodic alumina template to prepare gold nanoparticles on a nickel base and then grow ZnO nanostructures on the gold particles, which produces SERS substrates at low cost but with poor substrate reproducibility. The patent 201910718767.0 discloses a high-sensitivity SERS substrate, which is prepared by preparing a nano-pillar array by wet etching and combining MOF to perform surface modification.
Disclosure of Invention
Based on the problems in the technology, the invention aims to provide the nano conical needle SERS substrate which is prepared at low cost, has a periodically arranged nano conical needle structure, is simple in preparation process, is suitable for large-scale production, and is high in sensitivity and strong in repeatability.
The utility model provides a SERS base based on nanometer awl needle structure, for reinforcing raman scattering mixed nanostructure, it includes the substrate, the substrate surface has the nanometer awl needle structure of periodic arrangement, nanometer awl needle structure includes the first layer that comprises first material, set up in first layer top and the second layer that comprises the second material, substrate and nanometer awl needle structure surface cladding are by the third layer that the third material constitutes, the metal nanoparticle of deposit on the third layer, the substrate comprises first material.
The first material is a semiconductor, metal or alloy and comprises Si, GaAs, GaN and the like; the thickness of the substrate is 280-450 mu m, and the thickness of the first layer of the nano conical needle structure is 0.2-3 mu m.
The second material is a medium, can be metal oxide and the like, and comprises SiO2、Si3N4Etc.; the thickness of the second layer of the nanometer conical needle structure is 200-500 nm.
The third material is a metal material, including Au, Ag, Cu, and the like; the thickness of the third layer of the nanometer conical needle structure is 10-100 nm.
The metal nano-particles are nano-particles of Au, Ag, Cu and the like.
Preferably, the first material is silicon, the second material is silicon oxide, the third material is gold, and the metal nanoparticles are gold nanoparticles.
Preferably, the second material is grown on the first material by thermal oxidation; the third material is coated on the second material through a physical deposition method, and the metal nano-particles are deposited on the third material through an electrochemical method; the surface with the nanometer conical needle structure is obtained through reactive ion etching, metal auxiliary chemical etching or dry etching and chemical corrosion.
A preparation method of an SERS substrate based on a nano-cone needle structure comprises the following steps:
(1) SiO generation on silicon wafers2A layer;
(2) attaching polymer colloid balls, preferably polystyrene colloid balls, to SiO by self-assembly2On the layer; the self-assembly mode is solvent volatilization self-assembly, active adsorption, electrostatic adsorption, hydrophilic and hydrophobic repulsion or adsorption and the like;
(3) adjusting and controlling the size of the obtained polystyrene colloid ball by annealing or reactive ion etching, and controlling the size of the polystyrene colloid ball by controlling the gas flow and the radio frequency voltage of the reactive ion etching;
(4) by metal-assisted chemical or dry etching of SiO2Etching the dielectric layer;
(5) by metal-assisted chemical or dry etching of SiO2Etching the Si mixed nanostructure;
(6) obtaining a nano conical needle structure through chemical corrosion;
(7) depositing gold on a silicon wafer with a nano structure by adopting a magnetron sputtering method, and then depositing gold nanoparticles by an electrochemical method.
In the step (1), SiO is generated on a silicon wafer by adopting a thermal oxidation method2Layer, the temperature of the thermal oxidation is 1000 ℃, and the time is 25-60 min; SiO 22The thickness of the layer is 200-500 nm. The thickness of the silicon chip is the sum of the thickness of the base material and the thickness of the first layer of the nano conical needle structure.
In the step (2), the self-assembly mode is that a 1L self-assembly container is filled with deionized water, 50-550 μ L of mixed solution of alcohol (with the concentration of 99.5%) and polystyrene microspheres is added along the glass slide, the volume ratio of the alcohol to the polystyrene microspheres is 1/1-3/2, the particle size of the polystyrene microspheres is 100-3000nm, and then ultrasonic treatment is carried out for 5-10 minutes, and the power is 30-50W; and then adding 3-10mL of 2-200mM sodium dodecyl sulfate solution, standing for 1-12h, and finally transferring the polystyrene colloid to the surface of the silicon wafer to form a single-layer film through self-assembly.
In the step (3), the polystyrene colloid is subjected to reactive ion etching, and the etching gas is O2The gas flow is 10-30sccm and 10-30sccm respectively, the pressure is 0.5-1Pa, the power is 40-80W, and the etching time is 1.5-10 min.
In the step (4), the gas flow and the radio frequency voltage of the plasma etching are controlled to control the formation of SiO2A nanostructure; the etching gas is CF4And CHF3The flow rates are 10-15sccm and 35-50sccm respectively, the pressure is 150-300mTorr, the power is 250-500W, and the etching time is 60-200 s.
In the step (5), the gas flow and the radio frequency voltage of the plasma etching are controlled to control the formation of SiO2Mixed with Si and etching gas is Cl2HBr, gas flow rate is 60-120sccm and 10-60sccm respectively, pressure is 200-400mTorr, power is 250-500W, and etching time is 10-180 s.
In the step (6), the nano-cone needle structure is prepared by chemical corrosion. The nanometer conical needle structure is formed by controlling the concentration and the temperature of the KOH solution. The KOH solution has a concentration of 5-30% (w%), a temperature of 30-70 deg.C, and a corrosion time of 10-300 s.
In the step (7), gold is deposited by adopting a magnetron sputtering method, a silicon wafer with a nano structure is placed on a sputtering platform, 10-100nm of gold is sputtered under the conditions that the pressure is 0.5-2Pa, the power is 40-80W, Ar, the gas flow is 10-80sccm and the sputtering rate is 0.3-0.5nm/s, then 10-50mM chloroauric acid prepared by using concentrated sulfuric acid as a solvent is used as an electrolyte, and nano gold particles are deposited through an electrochemical workstation, wherein the prepared substrate is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, the potential is-0.2-0.6V, the pulse is 50-100mV, the number of scanning turns is 15-30, and finally the nano gold particles are formed on the nano structure, the spacing is 10-50nm, and the size is 10-30 nm.
The SERS substrate based on the nano conical needle structure can be applied to the fields of pesticide residue, food safety and disease detection and diagnosis.
Compared with the prior art, the invention has the following advantages:
the method prepares the ordered nano-pillar structure based on the self-assembly colloid ball template at low cost, then prepares the nano-cone needle structure by combining KOH wet corrosion, and finally forms nano-gold particles as an SERS substrate by sputtering on the nano-cone needle, and the substrate has high sensitivity, good repeatability and low cost, and is suitable for large-scale production. The invention can realize the preparation of the nano-column arrays with different intervals and heights by regulating and controlling the size of the polystyrene colloid ball template. The nano conical needle SERS substrate with high enhancement effect is prepared by controlling the concentration of KOH solution.
Drawings
FIG. 1 is a schematic diagram of a self-assembled device (containing deionized water).
FIG. 2 is a schematic view of polystyrene colloidal spheres forming a monolayer film on the surface of deionized water.
FIG. 3 is a schematic view of a polystyrene colloidal sphere monolayer film transferred onto a substrate.
Fig. 4 is a schematic view of a polystyrene monolayer film transferred onto a substrate by self-assembly.
FIG. 5 is a schematic diagram of polystyrene colloidal sphere size control by reactive ion etching.
FIG. 6 is a diagram of the preparation of SiO using colloidal spheres as templates2Schematic diagram of the structure of the nano-pillar.
FIG. 7 is a schematic representation of SiO formation using plasma etching2And Si hybrid nanopillar structure.
Fig. 8 is a schematic diagram after forming a nanocone structure by etching a nanocolumnar structure using KOH.
Fig. 9 is a schematic view after preparing nano gold particles on the nano-cone needle structure by sputtering.
FIG. 10 is an SEM image of a monolayer film of self-assembled polystyrene colloidal spheres according to an embodiment of the invention.
FIG. 11 is an SEM image of the size of a reactive ion etched polystyrene colloidal sphere.
FIG. 12 is SiO2And a Si nanostructure SEM image.
Description of the main reference numerals:
1 deionized water 2 support column
3 rubber band 4 base
5 Syringe 6 slides
7 polystyrene colloidal ball 8 SiO2
9 Si 10 nano-gold particles
Detailed Description
The present invention will now be described in detail with reference to the following examples and the accompanying drawings, which are included by way of illustration only and are not intended to limit the invention to the particular forms disclosed. 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.
In the present invention, the polystyrene colloidal spheres are prepared by a self-assembly method, and embodiments of the self-assembly method include, but are not limited to, solvent volatilization self-assembly, active adsorption, electrostatic adsorption, hydrophilic and hydrophobic repulsion, adsorption, and the like. The size of the polystyrene kickball is regulated and controlled by annealing and reactive ion etching. SiO 22The medium etching is made by metal auxiliary chemical etching and dry etching. SiO 22The etching of the Si-mixed nano structure is prepared by metal-assisted chemical etching and dry etching. The nano conical needle structure is prepared by chemical corrosion. The nano-particles are prepared by magnetron sputtering and electrochemical deposition.
The specific steps of the method of the present invention are described in detail below with reference to an example.
In the preparation method of the SERS substrate based on the nanopyramid structure, a silicon wafer with a thickness of 450 μm is used as a substrate, and SiO with a thickness of 200nm is generated on the silicon wafer by a thermal oxidation method at a temperature of 1000 ℃ for 25min2And (3) a layer.
As shown in fig. 1, a self-assembly apparatus of the present invention is provided with a support column 2 and a rubber ring 3, a substrate 4 is placed in the self-assembly apparatus, and 1L of deionized water 1 is added. As shown in FIG. 2, 550. mu.L of the alcohol/polystyrene sphere mixed solution was added to deionized water along the slide glass 6 at a volume ratio of 3:2 using a syringe 5, and sonicated for 10 minutes at a power of 40W. Then 6mL of 20mM/mM sodium dodecyl sulfate solution was added and allowed to stand for 60 minutes. As shown in fig. 3, the tap in the apparatus was opened so that the self-assembled polystyrene colloidal sphere monolayer film was transferred onto the substrate. As shown in fig. 4, the polystyrene sphere colloid spheres form a single layer film on the substrate.
And then, regulating and controlling the size of the polystyrene colloid sphere by reactive ion etching, as shown in fig. 5, specifically, controlling the size of the polystyrene colloid sphere by controlling the gas flow and the radio frequency voltage of the reactive ion etching. Etching gas is O2The flow rate of gas is 10sccm, the pressure is 1Pa, the power is 40W, and the etching time is 3.5 min.
Then preparing SiO by using polystyrene colloid balls as templates2The nanostructure, as shown in FIG. 6, is controlled by controlling the gas flow and RF voltage of the plasma etching2A nanostructure. The etching gas is CF4And CHF3The flow rates are 10sccm and 50sccm, respectively, the pressure is 200mTorr, the power is 300W, and the etching time is 60 s.
Then plasma etching is used to form SiO2Mixing the nanostructure with Si, as shown in FIG. 7, specifically controlling the gas flow and RF voltage of the plasma to form SiO2And Si mixed nanostructures. The etching gas is Cl2And HBr at a flow rate of 100sccm and 20sccm, respectively, at a pressure of 300mTorr, at a power of 300W, and for an etch time of 60 s.
The nanocolumnar structure was then etched using KOH solution to form the nanocone structure as shown in fig. 8. The KOH solution concentration is 5%, the temperature is 30 ℃, and the corrosion time is 30 s.
Finally, a layer of 20nm Au film is sputtered on the nano structure to make the substrate conductive. And (3) placing the prepared silicon wafer with the nano structure on a sputtering platform, wherein the pressure is 0.6Pa, the power is 50W, Ar, the gas flow is 80sccm, the sputtering rate is 0.3nm/s, and a gold layer with the thickness of 20nm is obtained by sputtering. And then, taking 10mM chloroauric acid prepared by taking concentrated sulfuric acid as a solvent as an electrolyte, depositing the nano-gold particles through an electrochemical workstation, wherein a substrate is taken as a working electrode, an Ag/AgCl electrode is taken as a reference electrode, a platinum electrode is taken as a counter electrode, the potential is-0.2-0.6V, the pulse is 50mV, the number of scanning turns is 15, and finally, the nano-gold particles are formed on the nano-structure, the spacing is 20nm, and the size is 20 nm. As shown in FIG. 9, in SiO2And nano-gold particles on the Si mixed nanostructure.
As shown in fig. 9, the SERS substrate based on the nanopyramid structure in this embodiment includes a substrate Si, where the substrate Si surface has periodically arranged nanopyramid structures, and the nanopyramid structure includes a first layer of Si and a second layer of SiO2The third layer of gold layer is coated on the surfaces of the base material and the nano conical needle structure, and gold nano particles are deposited on the gold layer.
FIG. 10 is a SEM image of a self-assembled polystyrene colloidal sphere monolayer film according to an embodiment of the present invention, wherein the polystyrene colloidal sphere is formed in a close-packed manner by the method of the present invention. FIG. 11 is an SEM image of polystyrene colloidal sphere after size adjustment by reactive ion etching, by adjusting O2The size of the polystyrene colloid sphere can be regulated and controlled by the etching time, and the sphere can be kept in a certain time. FIG. 12 is SiO2And a Si nano-structure SEM picture, and the periodically arranged nano-pillar array can be formed after two times of etching.
Claims (10)
1. The SERS substrate based on the nano conical needle structure comprises a substrate, wherein the surface of the substrate is provided with a nano conical needle structure which is periodically arranged, the nano conical needle structure comprises a first layer and a second layer, the first layer is made of a first material, the second layer is arranged above the first layer and is made of a second material, the surface of the substrate and the surface of the nano conical needle structure are coated with a third layer made of a third material, metal nanoparticles are deposited on the third layer, and the substrate is made of the first material.
2. The SERS substrate based on nanocial needle structures according to claim 1, wherein: the first material is Si, GaAs or GaN, and the second material is SiO2Or Si3N4The third material is Au, Ag or Cu, and the metal nanoparticles are Au, Ag or Cu nanoparticles.
3. The SERS substrate based on nanocial needle structures according to claim 2, wherein: the first material is silicon, the second material is silicon oxide, the third material is gold, and the metal nanoparticles are gold nanoparticles.
4. The nanotaper structure-based SERS substrate of claim 3, wherein: the second material is generated on the first material through thermal oxidation; the third material is coated on the second material through a physical deposition method, and the metal nano-particles are deposited on the third material through an electrochemical method; the surface with the nanometer conical needle structure is obtained through reactive ion etching, metal auxiliary chemical etching or dry etching and chemical corrosion.
5. A preparation method of an SERS substrate based on a nano-cone needle structure comprises the following steps:
(1) SiO generation on silicon wafers2A layer;
(2) polystyrene colloid ball is adhered to SiO by adopting self-assembly mode2On the layer; the self-assembly mode is solvent volatilization self-assembly, active adsorption, electrostatic adsorption, hydrophilic and hydrophobic repulsion or adsorption;
(3) adjusting and controlling the size of the obtained polystyrene colloid ball by annealing or reactive ion etching, and controlling the size of the polystyrene colloid ball by controlling the gas flow and the radio frequency voltage of the reactive ion etching;
(4) by metal-assisted chemical or dry etching of SiO2Etching the dielectric layer;
(5) by metal-assisted chemical or dry etching of SiO2Etching the Si mixed nanostructure;
(6) obtaining a nano conical needle structure through chemical corrosion;
(7) depositing gold on a silicon wafer with a nano structure by adopting a magnetron sputtering method, and then depositing gold nanoparticles by an electrochemical method.
6. The method for preparing the SERS substrate based on the nanocone structure according to claim 5, wherein: the temperature of the thermal oxidation is 1000 ℃, the time is 25-120min, and the SiO is2The thickness of the layer is 200-500 nm; the self-assembly method is in 1LFilling deionized water into a self-assembly container, adding 50-500 mu L of mixed solution of alcohol and polystyrene microspheres along a glass slide, wherein the volume ratio of the alcohol to the polystyrene microspheres is 1/1-3/2, the particle size of the polystyrene microspheres is 100-3000nm, and then carrying out ultrasonic treatment for 5-10 minutes at the power of 30-50W; and then adding 3-10mL of 2-200mM sodium dodecyl sulfate solution, standing for 1-12h, and finally transferring the polystyrene colloid to the surface of the silicon wafer to form a single-layer film through self-assembly.
7. The method for preparing the SERS substrate based on the nanocone structure according to claim 6, wherein: performing reactive ion etching on polystyrene colloid, wherein the etching gas is O2The gas flow is respectively 10-30sccm and 10-30sccm, the pressure is 0.5-1Pa, the power is 40-80W, and the etching time is 1.5-10 min; the formation of SiO is controlled by controlling the gas flow and the radio frequency voltage of the plasma etching2Nano structure with etching gas of CF4And CHF3The gas flow is 10-15sccm and 35-50sccm respectively, the pressure is 150-; the formation of SiO is controlled by controlling the gas flow and the radio frequency voltage of the plasma etching2Mixed with Si and etching gas is Cl2HBr, gas flow rate is 60-120sccm and 10-60sccm respectively, pressure is 200-400mTorr, power is 250-500W, and etching time is 10-180 s.
8. The method for preparing the SERS substrate based on the nanocial needle structure according to claim 7, wherein: the nanometer conical needle structure is formed by controlling the concentration and the temperature of the KOH solution, the concentration of the KOH solution is 5-30 w%, the temperature is 30-70 ℃, and the corrosion time is 10-300 s.
9. The method for preparing the SERS substrate based on the nanocial needle structure according to claim 8, wherein: depositing gold by adopting a magnetron sputtering method, sputtering 10-100nm of gold under the conditions that the pressure is 0.5-2Pa, the power is 40-80W, Ar airflow is 10-80sccm and the sputtering rate is 0.3-0.5nm/s, then depositing nano-gold particles by taking 10-50mM chloroauric acid prepared by taking concentrated sulfuric acid as a solvent as an electrolyte through an electrochemical workstation, taking the prepared substrate as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a platinum electrode as a counter electrode, setting the potential to be-0.2-0.6V, setting the pulse to be 50-100mV and the number of scanning turns to be 15-30, and finally forming the nano-gold particles on the nano-structure, wherein the spacing is 10-50nm and the size is 10-30 nm.
10. Use of the nanopyramid structure-based SERS substrate according to any of claims 1-4 for pesticide residue, food safety and disease detection.
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