CN113125405B - 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 nano conical needle structure and a preparation method thereof, and belongs to the field of spectrum analysis. The nano-cone needle structure comprises a substrate, wherein the surface of the substrate is provided with a nano-cone needle structure which is periodically arranged, the nano-cone needle structure comprises a first layer made of a first material, a second layer made of a second material, the surfaces of the substrate and the nano-cone needle structure are coated with a third layer made of a third material, metal nano-particles are deposited on the third layer, and the substrate is made of the first material. SiO formation on silicon wafer 2 A layer, wherein polystyrene colloid balls are attached to SiO by adopting a self-assembly mode 2 On the layer, the size of the polystyrene colloid sphere is regulated and controlled by annealing or reactive ion etching; etching by metal-assisted chemical etching or dry etching; obtaining a nano cone needle structure through chemical corrosion; gold is deposited on the silicon wafer, and gold nanoparticles are deposited through an electrochemical method. The substrate has high sensitivity, good repeatability and low cost, and is suitable for mass production.
Description
Technical Field
The invention relates to a SERS substrate based on a nano conical needle structure and a preparation method thereof, and belongs to the field of spectrum analysis.
Background
The surface enhanced Raman scattering is a spectrum technology with single-molecule detection, has the advantages of simple operation, strong specificity, wide application range and the like, and is widely applied to the fields of food safety, environment detection, disease diagnosis and the like, thus becoming a powerful rapid detection means.
Surface Enhanced Raman Scattering (SERS) refers to the significant enhancement of raman scattering signals when molecules adsorb on roughened metal (Au, ag, cu, etc.) surfaces. It is currently widely believed that surface enhanced raman scattering mainly has physical enhancement and chemical enhancement mechanisms, and physical enhancement mainly plays a role, and physical enhancement mainly is electromagnetic field enhancement of surface metals. Mainly causing the electromagnetic field to enhance is surface plasmon resonance, and the lightning rod effect can also cause the electromagnetic field to enhance. The lightning rod effect often appears on needle-like structures, which have strong local electromagnetic fields, the more sharp the tip is, the stronger the electromagnetic field at the tip is, and the stronger the raman signal enhancement effect is. It is therefore important to prepare SERS substrates with tip structures.
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-delivery, e.g. electron beam lithography, x-ray lithography and nanoimprinting, are often used for the preparation. Therefore, it is very significant to develop a SERS substrate with high sensitivity, low cost, good stability, and good repeatability. The invention mainly prepares the nano-pillar array by using a low-cost self-assembled colloid sphere template and integrates nano-gold particles by combining low-cost electrodeposition.
Patent 201910345971.2 discloses au@zno nanostructures as SERS substrates, which use electrodeposition on a nickel base to prepare gold nanoparticles on an anodic alumina template, and then growing ZnO nanostructures on the gold particles, the SERS substrates prepared by this patent are low cost but the substrate is less repeatable. Patent 201910718767.0 discloses a highly sensitive SERS substrate, which uses wet etching to prepare a nano-pillar array and combines MOF to perform surface modification to prepare the SERS substrate, and the nano-pillar array prepared by the method has poor order and low repeatability.
Disclosure of Invention
Based on the problems of the technology, the invention aims to provide the nano taper needle SERS substrate prepared at low cost, and the SERS substrate provided by the invention has the periodically arranged nano taper needle structure, is simple in preparation process, is suitable for large-scale production, and has high sensitivity and strong repeatability.
The SERS substrate based on the nano cone needle structure is a mixed nano structure for enhancing Raman scattering, the SERS substrate comprises a substrate, the surface of the substrate is provided with the nano cone needle structure which is periodically arranged, the nano cone needle structure comprises a first layer made of a first material, a second layer which is arranged above the first layer and is made of a second material, the surfaces of the substrate and the nano cone needle structure are coated with a third layer made of a third material, metal nano particles deposited on the third layer are coated on the surface of the substrate, and the substrate is made of the first material.
The first material is a semiconductor, a metal or an alloy, including Si, gaAs, gaN and the like; the thickness of the base material is 280-450 mu m, and the thickness of the first layer of the nano cone needle structure is 0.2-3 mu m.
The second material is a medium, and can be metal oxide, etc., including SiO 2 、Si 3 N 4 Etc.; the thickness of the second layer of the nanometer taper needle structure is 200-500nm.
The third material is a metal material and comprises Au, ag, cu and the like; the thickness of the third layer of the nanometer taper needle structure is 10-100nm.
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 formed on the first material by thermal oxidation; the third material is coated on the second material by a physical deposition method, and the metal nano particles are deposited on the third material by an electrochemical method; the surface with the nano cone needle structure is obtained through reactive ion etching, metal auxiliary chemical etching or dry etching and chemical etching.
A preparation method of a SERS substrate based on a nanometer taper needle structure comprises the following steps:
(1) SiO formation on silicon wafer 2 A layer;
(2) Attaching polymer colloid spheres, preferably polystyrene colloid spheres, to SiO by self-assembly 2 On 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) The size of the polystyrene colloid ball is regulated and controlled by annealing or reactive ion etching, and the size of the polystyrene ball is controlled by controlling the gas flow and the radio frequency voltage of the reactive ion etching;
(4) SiO is etched by metal auxiliary chemical etching or dry etching 2 Etching the dielectric layer;
(5) General purpose medicineMetal-assisted chemical etching or dry etching of SiO 2 Etching the Si mixed nano structure;
(6) Obtaining a nano cone needle structure through chemical corrosion;
(7) And depositing gold on the silicon wafer with the nanostructure by adopting a magnetron sputtering method, and then depositing gold nanoparticles by adopting an electrochemical method.
In the step (1), siO is generated on the silicon wafer by adopting a thermal oxidation method 2 The temperature of the thermal oxidation is 1000 ℃ and the time is 25-60min; siO (SiO) 2 The thickness of the layer is 200-500nm. The thickness of the silicon wafer is the sum of the thickness of the base material and the thickness of the first layer of the nano cone needle structure.
In the step (2), deionized water is fully filled in a 1L self-assembly container, 50-550 mu L of mixed solution of alcohol (the concentration is 99.5%) and polystyrene microspheres is added along a 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, then ultrasonic treatment is carried out for 5-10 minutes, and the power is 30-50W; and 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 for self-assembly to form a single-layer film.
In the step (3), the polystyrene colloid is subjected to reactive ion etching, and the etching gas is O 2 The air flow is 10-30sccm and 10-30sccm, the pressure is 0.5-1Pa, the power is 40-80W, and the etching time is 1.5-10min.
In the step (4), the formation of SiO is controlled by controlling the gas flow and the radio frequency voltage of the plasma etching 2 A nanostructure; the etching gas being CF 4 And CHF 3 The air flow is 10-15sccm and 35-50sccm, the pressure is 150-300mTorr, the power is 250-500W, and the etching time is 60-200s.
In the step (5), the formation of SiO is controlled by controlling the gas flow and the radio frequency voltage of the plasma etching 2 And Si mixed nano structure, etching gas is Cl 2 And HBr, the air flow is 60-120sccm and 10-60sccm, the pressure is 200-400mTorr, the power is 250-500W, and the etching time is 10-180s.
In the step (6), the nano cone needle structure is prepared by chemical corrosion. The concentration of KOH solution and the temperature are controlled to form the nano cone needle structure. The concentration of KOH solution is 5-30% (w%), the temperature is 30-70 ℃, and the etching time is 10-300s.
In the step (7), gold is deposited by a magnetron sputtering method, a silicon wafer with a nano structure is placed on a sputtering table, gold with the thickness of 10-100nm is sputtered under the conditions that the pressure is 0.5-2Pa, the power is 40-80 and W, ar air flow is 10-80sccm, the sputtering rate is 0.3-0.5nm/s, then gold nanoparticles are deposited by an electrochemical workstation through taking 10-50mM chloroauric acid prepared by concentrated sulfuric acid as a solvent as electrolyte, wherein the prepared 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 50-100mV, the scanning circle number is 15-30, and finally gold nanoparticles are formed on the nano structure, the space is 10-50nm, and the size is 10-30nm.
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:
according to the invention, the ordered nano column structure is prepared based on the self-assembled colloid sphere template at low cost, then the nano cone needle structure is prepared by combining KOH wet corrosion, and finally the nano gold particles are formed on the nano cone needle by sputtering to serve as an SERS substrate, so that the substrate has high sensitivity, good repeatability and low cost, and is suitable for mass production. The invention can realize the preparation of the nano-pillar arrays with different pitches and heights by regulating and controlling the size of the polystyrene colloid sphere template. The nano cone 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-assembly device (filled with deionized water).
Fig. 2 is an illustration of the intent of polystyrene gel spheres to form a monolayer on the surface of deionized water.
FIG. 3 is a schematic representation of the transfer of a polystyrene colloidal sphere monolayer film onto a substrate.
FIG. 4 is a schematic representation of a polystyrene monolayer transferred to a substrate by self-assembly.
FIG. 5 is a schematic diagram of the polystyrene gel ball after the size adjustment by reactive ion etching.
FIG. 6 is a schematic diagram of the preparation of SiO using colloidal spheres as templates 2 Schematic diagram of the structure of the nano column.
FIG. 7 is a schematic diagram of SiO formation using plasma etching 2 And a schematic of Si hybrid nanopillar structure.
Fig. 8 is a schematic diagram of a nanopillar structure etched with KOH to form a nanopyramid needle structure.
Fig. 9 is a schematic diagram after preparation of gold nanoparticles on a nanotaper needle structure by sputtering.
FIG. 10 is an SEM image of a monolayer of self-assembled polystyrene gel spheres according to an embodiment of the present invention.
Fig. 11 is an SEM image after the size adjustment of the reactive ion etched polystyrene colloidal spheres.
FIG. 12 is SiO 2 SEM image of Si nanostructure.
The main reference numerals illustrate:
1. deionized water 2 support column
3. Rubber band 4 base
5. Syringe 6 slide
7. Polystyrene colloid sphere 8 SiO 2
9 Si 10 nano gold particles
Detailed Description
The present invention will now be described in detail with reference to the following examples and figures, which are only a few, but not all, of the non-limiting examples of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the invention, the polystyrene colloid sphere is prepared by a self-assembly mode, and the implementation mode of the self-assembly method comprises but is not limited to solvent volatilization self-assembly, active adsorption,Electrostatic adsorption, hydrophilic-hydrophobic repulsion, adsorption, and the like. The size control of the polystyrene kicking ball is prepared by annealing and reactive ion etching. SiO (SiO) 2 The dielectric etching is prepared by metal auxiliary chemical etching and dry etching. SiO (SiO) 2 And the Si mixed nano structure is prepared by metal auxiliary chemical etching and dry etching. The nano cone 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 will be described in detail below with reference to one example.
In the preparation method of the SERS substrate based on the nano cone needle structure, a silicon wafer with the thickness of 450 μm is adopted as the substrate, and SiO with the thickness of 200nm is generated on the silicon wafer by a thermal oxidation method at the temperature of 1000 ℃ for 25min 2 A layer.
As shown in fig. 1, in the self-assembly device with deionized water according to the embodiment of the present invention, a support column 2 and a rubber ring 3 are provided in a self-assembly container, a substrate 4 is placed in the self-assembly container, and 1L of deionized water 1 is added. As shown in FIG. 2, 550. Mu.L of a mixed solution of alcohol and polystyrene spheres was added to deionized water along slide 6 at a volume ratio of 3:2 using syringe 5 and sonicated for 10 minutes at a power of 40W. Then 6mL of 20mM/mM sodium dodecyl sulfate solution was added and the mixture was allowed to stand for 60 minutes. As shown in fig. 3, the faucet in the device was turned on, so that the self-assembled polystyrene gel sphere monolayer film was transferred to the substrate. As shown in fig. 4, polystyrene sphere colloid spheres form a single layer film on a substrate.
Then, the size of the polystyrene colloid sphere is regulated and controlled by reactive ion etching, as shown in fig. 5, specifically by controlling the gas flow and the radio frequency voltage of the reactive ion etching. The etching gas is O 2 The gas flow rates were 10sccm, the pressure was 1Pa, the power was 40W, and the etching time was 3.5 minutes, respectively.
SiO was then prepared using polystyrene colloid spheres as templates 2 Nanostructure, as shown in FIG. 6, specifically controls the formation of SiO by controlling the gas flow and RF voltage of the plasma etch 2 A nanostructure. EtchingThe gas being CF 4 And CHF 3 The gas flow rates were 10sccm and 50sccm, respectively, the pressure was 200mTorr, the power was 300W, and the etching time was 60s.
Then forming SiO using plasma etching 2 And Si mixed nano structure, as shown in FIG. 7, by controlling the air flow and RF voltage of plasma specifically, siO is formed 2 And Si hybrid nanostructures. The etching gas being Cl 2 And HBr, the gas flow rates are 100sccm and 20sccm, the pressure is 300mTorr, the power is 300W, and the etching time is 60s.
The nanopillar structure is then etched using KOH solution to form a nanotaper needle structure, as shown in fig. 8. The KOH solution had a concentration of 5%, a temperature of 30℃and a corrosion time of 30s.
Finally, sputtering a layer of Au film with the thickness of 20nm on the nano structure to make the substrate conductive. The prepared silicon wafer with the nano structure is placed on a sputtering table, the pressure is 0.6Pa, the power is 50W, ar, the air flow is 80sccm, the sputtering rate is 0.3nm/s, and the gold layer with the thickness of 20nm is obtained through sputtering. And then, taking concentrated sulfuric acid as a solvent to prepare 10mM chloroauric acid as an electrolyte, depositing 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 scanning circle number is 15, and finally, forming the nano gold particles on the nano structure, wherein the distance is 20nm and the size is 20nm. As shown in FIG. 9, in SiO 2 And Si mixed nano-gold particles on the nano-structure.
As shown in fig. 9, the SERS substrate based on the nano taper needle structure of this embodiment includes a substrate Si, and the surface of the substrate Si has periodically arranged nano taper needle structures, and the nano taper needle structures include a first layer Si, a second layer SiO 2 And a third gold layer coated on the surfaces of the base material and the nano cone needle structure, wherein gold nano particles are deposited on the gold layer.
Fig. 10 is an SEM image of a monolayer of self-assembled polystyrene gel spheres according to an embodiment of the present invention, which can be formed into a close-packed monolayer of polystyrene gel spheres by the preparation method of polystyrene gel spheres according to the present invention. FIG. 11 is an SEM image after size adjustment of a reaction ion etched polystyrene colloidal sphere by adjusting O 2 The etching time can regulate and control the size of the polystyrene colloid sphere, and the sphere can be kept for a certain time. FIG. 12 is SiO 2 And an SEM image of the Si nanostructure, it can be seen that the periodically arranged nanopillar array can be formed by two etches.
Claims (5)
1. The SERS substrate based on the nano cone needle structure is an enhanced Raman scattering mixed nano structure, and comprises a substrate, wherein the surface of the substrate is of a nano cone needle structure with periodic arrangement, the nano cone needle structure comprises a first layer made of a first material, a second layer arranged above the first layer and made of a second material, the surfaces of the substrate and the nano cone needle structure are coated with a third layer made of a third material, metal nano particles deposited on the third layer, and the substrate is made of the first material; the first material is Si, and the second material is SiO 2 The third material is Au, and the metal nano-particles are Au nano-particles;
the preparation method comprises the following steps:
(1) SiO formation on silicon wafer 2 A layer; siO is generated on the silicon chip by adopting a thermal oxidation method 2 The layer is thermally oxidized at 1000deg.C for 25-120min, and SiO is formed 2 The thickness of the layer is 200-500nm;
(2) Polystyrene colloid balls are attached to SiO by adopting a self-assembly mode 2 On the layer; the self-assembly mode is solvent volatilization self-assembly, active adsorption, electrostatic adsorption, hydrophilic and hydrophobic repulsion or adsorption;
(3) The size of the polystyrene colloid ball is regulated and controlled by annealing or reactive ion etching, and the size of the polystyrene ball is controlled by controlling the gas flow and the radio frequency voltage of the reactive ion etching; reactive ion etching is carried out on polystyrene colloid, and the etching gas is O 2 The air flow is respectively 10-30sccm and 10-30sccm, the pressure is 0.5-1Pa, the power is 40-80W, and the etching time is 1.5-10min;
(4) SiO is etched by metal auxiliary chemical etching or dry etching 2 Etching the dielectric layer; siO formation is controlled by controlling the gas flow and the radio frequency voltage of plasma etching 2 Nanostructure, etching gas is CF 4 And CHF 3 The air flow is respectively 10-15sccm and 35-50sccm, the pressure is 150-300mTorr, the power is 250-500W, and the etching time is 60-200s;
(5) SiO is etched by metal auxiliary chemical etching or dry etching 2 Etching the Si mixed nano structure; siO formation is controlled by controlling the gas flow and the radio frequency voltage of plasma etching 2 And Si mixed nano structure, etching gas is Cl 2 And HBr, the air flow is 60-120sccm and 10-60sccm, the pressure is 200-400mTorr, the power is 250-500W, the etching time is 10-180s;
(6) Obtaining a nano cone needle structure through chemical corrosion; the nano cone needle structure is formed by controlling the concentration and the temperature of KOH solution, the concentration of KOH solution is 5-30w%, the temperature is 30-70 ℃ and the corrosion time is 10-300s;
(7) And depositing gold on the silicon wafer with the nanostructure by adopting a magnetron sputtering method, and then depositing gold nanoparticles by adopting an electrochemical method.
2. A preparation method of a SERS substrate based on a nanometer taper needle structure comprises the following steps:
(1) SiO formation on silicon wafer 2 A layer; siO is generated on the silicon chip by adopting a thermal oxidation method 2 The layer is thermally oxidized at 1000deg.C for 25-120min, and SiO is formed 2 The thickness of the layer is 200-500nm;
(2) Polystyrene colloid balls are attached to SiO by adopting a self-assembly mode 2 On the layer; the self-assembly mode is solvent volatilization self-assembly, active adsorption, electrostatic adsorption, hydrophilic and hydrophobic repulsion or adsorption;
(3) The size of the polystyrene colloid ball is regulated and controlled by annealing or reactive ion etching, and the size of the polystyrene ball is controlled by controlling the gas flow and the radio frequency voltage of the reactive ion etching; reactive ion etching is carried out on polystyrene colloid, and the etching gas is O 2 The air flow is respectively 10-30sccm and 10-30sccm, the pressure is 0.5-1Pa, the power is 40-80W, and the etching time is 1.5-10min;
(4) By metal-assisted chemical engravingEtching or dry etching SiO 2 Etching the dielectric layer; siO formation is controlled by controlling the gas flow and the radio frequency voltage of plasma etching 2 Nanostructure, etching gas is CF 4 And CHF 3 The air flow is respectively 10-15sccm and 35-50sccm, the pressure is 150-300mTorr, the power is 250-500W, and the etching time is 60-200s;
(5) SiO is etched by metal auxiliary chemical etching or dry etching 2 Etching the Si mixed nano structure; siO formation is controlled by controlling the gas flow and the radio frequency voltage of plasma etching 2 And Si mixed nano structure, etching gas is Cl 2 And HBr, the air flow is 60-120sccm and 10-60sccm, the pressure is 200-400mTorr, the power is 250-500W, the etching time is 10-180s;
(6) Obtaining a nano cone needle structure through chemical corrosion; the nano cone needle structure is formed by controlling the concentration and the temperature of KOH solution, the concentration of KOH solution is 5-30w%, the temperature is 30-70 ℃ and the corrosion time is 10-300s;
(7) And depositing gold on the silicon wafer with the nanostructure by adopting a magnetron sputtering method, and then depositing gold nanoparticles by adopting an electrochemical method.
3. The method for preparing the SERS substrate based on the nano-cone needle structure according to claim 2, wherein the method comprises the following steps of: the self-assembly mode is that deionized water is filled in a 1L self-assembly container, 50-500 mu L of mixed solution of alcohol and polystyrene microspheres is added along a 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, then ultrasonic treatment is carried out for 5-10 minutes, and the power is 30-50W; and 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 for self-assembly to form a single-layer film.
4. The method for preparing the SERS substrate based on the nano-cone needle structure according to claim 2, wherein the method comprises the following steps of: depositing gold by a magnetron sputtering method, sputtering gold with the pressure of 0.5-2Pa, the power of 40-80W, ar, the air flow rate of 10-80sccm and the sputtering rate of 0.3-0.5nm/s, then depositing nano gold particles by using 10-50mM chloroauric acid prepared by concentrated sulfuric acid as a solvent as electrolyte 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 scanning circle number is 15-30, finally nano gold particles are formed on a nano structure, the distance is 10-50nm, and the size is 10-30nm.
5. The use of a SERS substrate based on a nanotaper needle structure according to claim 1 in pesticide residue, food safety and disease detection.
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