CN113702348A - Surface-enhanced Raman substrate with three-dimensional hot spots and preparation method thereof - Google Patents
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Abstract
A surface enhanced Raman substrate with three-dimensional hot spots and a preparation method thereof belong to the technical field of Raman spectrum detection. The method comprises the following steps: taking a high-concentration silver-coated gold nanoparticle solution with a shell-core structure; taking a hydrophobic silicon wafer; and dropwise adding a micro high-concentration silver-coated gold nanoparticle solution with a shell-core structure on a hydrophobic silicon chip, and naturally drying to obtain thousands of spherical nanoparticles assembled by silver-coated gold nanoparticles, wherein the particles have high-density three-dimensional 'hot spots' and ultrahigh surface-enhanced Raman characteristics. According to the invention, a solvent volatilization self-assembly method is utilized, a high-concentration silver-coated gold nanoparticle solution with a shell-core structure is dripped on a hydrophobic silicon chip, and natural drying is carried out to obtain thousands of spherical nanoparticles stacked by silver-coated gold nanoparticles, wherein the nanoparticles have high-density three-dimensional 'hot spots' and ultrahigh surface enhanced Raman characteristics. The SERS substrate can be used for high-sensitivity detection of thiram pesticide and has practical application value.
Description
Technical Field
The invention belongs to the technical field of Raman spectrum detection, and particularly relates to a surface-enhanced Raman substrate with three-dimensional hot spots and a preparation method thereof.
Background
The surface enhanced raman technology (SERS) uses a plasma metal nanostructure with a gap of less than 10nm, which shows a strong local electromagnetic field under laser excitation, becoming a "hot spot". When molecules enter a hot spot, the Raman signals of the molecules are excited and enhanced by an electromagnetic field, so that the sensitivity is greatly improved, and even the level of single molecule detection is reached. SERS is a short and fast detection time compared to conventional chromatographic and mass spectrometric methods, and detection is usually completed in several seconds. Because the SERS technology has the advantages of simplicity, rapidness, ultrasensitiveness, fingerprint spectrum and the like, the SERS technology is widely applied to the fields of biology, medicine, food safety and the like in recent years. In recent years, in order to achieve higher detection limit and sensitivity, research on three-dimensional SERS substrates having high density of "hot spots" has received increasing attention. Three-dimensional SERS substrates have several advantages over conventional two-dimensional planar platforms. Firstly, three-dimensional SERS hot spots in the laser volume are more than two-dimensional, increasing SERS signals significantly, and compared to conventional two-dimensional platforms, the three-dimensional SERS substrate provides flexibility for constructing plasma materials in spatial directions of different sizes and shapes. In addition, the interaction between the target molecules and the plasma particles can be further enhanced by increasing the surface area of the three-dimensional platform, so that the detection sensitivity is improved. The method for preparing the SERS substrate with the three-dimensional hot spots is generally carried out by the techniques of electron beam lithography, template deposition, electrochemical deposition, chemical vapor deposition and the like. However, the methods have great preparation difficulty and complex process, and the practical application of the methods is greatly limited.
The solvent volatilization self-assembly method is a simple method for obtaining the high-performance SERS substrate. However, after the solvent is evaporated, a famous "coffee ring" phenomenon is often generated, and the distribution of the "hot spot" is not uniform. Researches report that the solvent volatilization rate can be slowed down by controlling the temperature and humidity in the solvent volatilization process, or the coffee ring is inhibited by a method of modifying the surface of the nanoparticle, so that the SERS substrate with a uniform hot spot is obtained. The gold nanorods are most studied, and the vertically arranged gold nanorod substrate (CN 201710158329.4; CN201510354816.9) can be obtained by controlling the concentration of a surfactant, the temperature and the humidity of solvent volatilization. Because only the tips of the vertically arranged gold nanorods have strong SERS enhancement effect, the gold nanorods do not belong to a real three-dimensional hot spot strictly. The polytetrafluoroethylene membrane is immersed into a perfluorinated solution to obtain a smooth hydrophobic surface, the solvent of the nano-gold particle liquid drops on the surface is volatilized, the SERS substrate with a small area is obtained, and the coffee ring effect can be effectively inhibited. As characterized by SEM, the gold nanoparticles did not assemble into structures with three-dimensional "hot spots". It remains a challenge to obtain a uniform SERS substrate with three-dimensional hot spots using a simple solvent-volatilized self-assembly method.
According to the invention, a solvent volatilization self-assembly method is utilized, a high-concentration silver-coated gold nanoparticle solution with a shell-core structure is dripped on a hydrophobic silicon chip, and natural drying is carried out to obtain thousands of spherical nanoparticles stacked by silver-coated gold nanoparticles, wherein the nanoparticles have high-density three-dimensional 'hot spots' and ultrahigh surface enhanced Raman characteristics. The SERS substrate can be used for high-sensitivity detection of thiram pesticide and has practical application value.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a technical scheme of a surface-enhanced Raman substrate with a three-dimensional hot spot and a preparation method thereof. The method utilizes a simple solvent volatilization self-assembly method to obtain the surface enhanced Raman substrate consisting of round super-particles assembled by thousands of silver-coated gold nano-particles. The super-particles can provide high-density three-dimensional 'hot spots', target molecules enter a hot spot region, Raman signals are greatly enhanced, detection sensitivity is improved, and the super-particles are efficient surface enhanced Raman substrates.
The invention is realized by adopting the following technical scheme:
the preparation method of the surface enhanced Raman substrate with the three-dimensional hot spots is characterized by comprising the following steps of:
1) taking a high-concentration silver-coated gold nanoparticle solution with a shell-core structure;
2) taking a hydrophobic silicon wafer;
3) and dropwise adding a micro high-concentration silver-coated gold nanoparticle solution with a shell-core structure on a hydrophobic silicon chip, and naturally drying to obtain thousands of spherical nanoparticles assembled by silver-coated gold nanoparticles, wherein the particles have high-density three-dimensional 'hot spots' and ultrahigh surface-enhanced Raman characteristics.
The preparation method of the surface-enhanced Raman substrate with the three-dimensional hot spots is characterized in that the concentration of the high-concentration silver-coated gold nanoparticle solution with the core-shell structure is as follows: 10 nmol L-1～100 nmol L-1。
The preparation method of the surface-enhanced Raman substrate with the three-dimensional hot spot is characterized in that the high-concentration silver-coated gold nanoparticle solution with the core-shell structure is obtained by the following steps:
heating chloroauric acid solution to reflux at 120-130 ℃ under the condition of magnetic stirring;
after the reflux is stable, quickly adding the sodium citrate solution A into the chloroauric acid solution;
after the solution turns to mauve, reducing the temperature to 100-115 ℃, continuing to heat and stir, adding a sodium citrate solution B, dropwise adding a silver nitrate solution into the mixture, and continuing to heat and stir, wherein the color of the mixture turns to orange from red wine;
after gradually cooling to room temperature under the condition of stirring, filtering the obtained solution by using a 0.22 mu m water system filter membrane, washing and concentrating through multiple steps of centrifugation to obtain a high-concentration silver-coated gold nanoparticle solution with a shell-core structure, and storing at 4 ℃ for later use.
The preparation method of the surface enhanced Raman substrate with the three-dimensional hot spots is characterized in that the contact angle of the hydrophobic silicon wafer is more than 130 degrees.
The preparation method of the surface-enhanced Raman substrate with the three-dimensional hot spots is characterized in that the hydrophobic silicon wafer is obtained by the following steps:
soaking a monocrystalline silicon wafer in a piranha washing liquid, wherein the volume ratio of concentrated sulfuric acid to 30% of hydrogen peroxide in the piranha washing liquid is 3:1, so that the surface of the piranha washing liquid is hydrophilic, and then, washing the piranha washing liquid by using a large amount of ultrapure water and soaking the piranha washing liquid in ultrapure water for later use;
naturally drying a hydrophilic silicon wafer in the air, adding a toluene solution of methyltrichlorosilane to completely immerse the surface of the silicon wafer in the solution, sealing, and standing at room temperature;
and taking the silicon wafer out of the toluene solution of the methyltrichlorosilane, respectively washing the silicon wafer twice with toluene, ethanol, water in a ratio of 1:1 and ultrapure water, and drying to obtain the hydrophobic silicon wafer.
The preparation method of the surface-enhanced Raman substrate with the three-dimensional hot spots is characterized in that the content of the chloroauric acid is 0.1 mmol L-1～0.5 mmol L-1(ii) a The addition amount of the sodium citrate solution A is 0.5 mL-3 mL of 1% sodium citrate solution; the addition amount of the sodium citrate solution B is 3 mL-10 mL of 1% sodium citrate solution; the content of silver nitrate is 0.01 mmol L-1～0.05 mmol L-1。
The preparation method of the surface-enhanced Raman substrate with the three-dimensional hot spots is characterized in that the concentration of the toluene solution of the methyltrichlorosilane is 0.01 mol L-1～0.5 mol L-1。
The surface-enhanced Raman substrate with the three-dimensional hot spots is obtained by the preparation method.
The surface-enhanced Raman substrate with the three-dimensional hot spots is applied to high-sensitivity detection of thiram pesticide.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the surface-enhanced Raman substrate is a solvent volatilization self-assembly method, and has simple process and no need of special equipment.
2. The surface-enhanced Raman substrate prepared by the invention has high-density three-dimensional 'hot spots', and has better enhancement effect compared with a two-dimensional hot spot substrate obtained by traditional solvent volatilization self-assembly.
3. The surface-enhanced Raman substrate prepared by the invention has high sensitivity, good uniformity and good reproducibility when used for detecting trace substances, and has very high application value.
Drawings
FIG. 1 is a high resolution transmission electron micrograph of silver-coated gold nanoparticles.
FIG. 2 is a graph representing the contact angle of a hydrophobic silicon wafer.
FIG. 3 is a left photograph of a surface enhanced Raman substrate obtained by dropping high concentration silver-coated gold nanoparticles onto a hydrophobic silicon wafer and naturally drying; the right picture is a photo of the surface enhanced Raman substrate obtained by dropping low-concentration silver-coated gold nanoparticles on a hydrophobic silicon chip and naturally drying.
FIG. 4 is a scanning electron micrograph of spherical nanoparticles of thousands of silver-coated gold nanoparticles stacked with high density three-dimensional "hot spots".
FIG. 5 is a Raman scattering spectrum of the surface enhanced Raman substrate prepared by the method of the present invention for thiram with different concentrations.
FIG. 6 is a comparison graph of two-dimensional and surface enhanced Raman scattering spectra of a two-dimensional substrate and a surface enhanced Raman substrate prepared according to the present invention.
Detailed Description
The present invention will be further illustrated below by examples for better understanding of the present invention, but the application of the present invention is not limited to only the following specific examples.
Example 1
Take 0.25mmol L-1The chloroauric acid solution of (a) was added to a 500 mL three-necked round bottom flask and heated to reflux at 128 ℃ with magnetic stirring. After the reflux stabilized, 1.5 mL of 1% strength sodium citrate solution was added quickly to the round bottom flask. The temperature is reduced to 115 ℃ after the solution turns to purple red, and the solution is continuously heated and stirred for 30 min. 4 mL of 1% strength sodium citrate solution was added to the round bottom flask and 0.025 mmol L-1AgNO of3The solution was added dropwise to the above mixture, the color of the mixture changed from red wine to orange, and the heating and stirring were continued for 30 min. After gradually cooling to room temperature with stirring, the resulting solution was filtered through a 0.22 μm aqueous membrane,and washing and concentrating by a centrifugation step to obtain a final concentration of 30nmol L-1The Au @ Ag NPs solution is stored at 4 ℃ for later use.
The structure of the nanoparticle is characterized by using a high-resolution transmission electron microscope, and as shown in figure 1, the obtained nanoparticle has a good core-shell structure, gold is in the core, and silver is in the shell. The silver-coated gold nanoparticles with different silver thicknesses can be obtained by regulating the proportion of the chloroauric acid to the silver nitrate.
Example 2
Take 0.40 mmol L-1The chloroauric acid solution of (a) was added to a 500 mL three-necked round bottom flask and heated to reflux at 128 ℃ with magnetic stirring. After the reflux stabilized, 2 mL of 1% strength sodium citrate solution was added quickly to the round bottom flask. The temperature is reduced to 115 ℃ after the solution turns to purple red, and the solution is continuously heated and stirred for 30 min. 6 mL of 1% strength sodium citrate solution was added to the round-bottom flask, and 0.05mmol L of sodium citrate was added-1AgNO of3The solution was added dropwise to the above mixture, the color of the mixture changed from red wine to orange, and the heating and stirring were continued for 30 min. After gradually cooling to room temperature with stirring, the resulting solution was filtered through a 0.22 μm aqueous membrane and washed and concentrated by a centrifugation step to give a final concentration of 45nmol L-1The Au @ Ag NPs solution is stored at 4 ℃ for later use. The silver-coated gold nanoparticles with different silver thicknesses can be obtained by regulating the proportion of the chloroauric acid to the silver nitrate.
Example 3
The monocrystalline silicon piece is soaked in piranha washing liquor (the volume ratio of concentrated sulfuric acid to 30 percent of hydrogen peroxide is 3: 1) for 1 hour to make the surface hydrophilic, and then is washed by a large amount of ultrapure water and then is soaked in the ultrapure water for standby. Naturally drying hydrophilic silicon wafer in air, placing into a beaker, and adding 0.05 mol L-1The surface of the silicon wafer is completely immersed in the methylbenzene solution of the methyltrichlorosilane, the beaker is sealed by a sealing film and then is kept stand for 3 hours at room temperature, then the silicon wafer is taken out, washed twice by methylbenzene, ethanol, water 1:1 (V/V) and ultrapure water respectively, and placed in a clean oven at 120 ℃ for drying for 10 minutes, and the hydrophobic silicon wafer is obtained.
The hydrophilic and hydrophobic properties of the silicon wafer are characterized by a contact angle instrument. As shown in fig. 2, the resulting contact angle was 130 °.
Example 4
The monocrystalline silicon piece is soaked in piranha washing liquor (the volume ratio of concentrated sulfuric acid to 30 percent of hydrogen peroxide is 3: 1) for 1 hour to make the surface hydrophilic, and then is washed by a large amount of ultrapure water and then is soaked in the ultrapure water for standby. Naturally drying hydrophilic silicon wafer in air, placing into a beaker, and adding 0.2 mol L-1The surface of the silicon wafer is completely immersed in the methylbenzene solution of the methyltrichlorosilane, the beaker is sealed by a sealing film and then is kept stand for 3 hours at room temperature, then the silicon wafer is taken out, washed twice by methylbenzene, ethanol, water in a ratio of 1:1 and ultrapure water respectively, and placed in a clean oven at 120 ℃ for drying for 10 minutes, and the hydrophobic silicon wafer is obtained. The contact angle of the hydrophobic silicon wafer is 145 degrees.
Example 5
Using a pipette, 5uL of the product of example 1 was removed to give 30nmol L-1The Au @ Ag NPs solution is dripped on the hydrophobic silicon chip obtained in the embodiment 3, the drying is carried out under the natural condition, the Au @ Ag NPs liquid drops are continuously reduced in the solvent volatilization process, and the surface enhanced Raman substrate shown in the figure 3 is obtained after the drying.
As can be seen from FIG. 3, the Au @ Ag NPs are uniformly distributed on the hydrophobic silicon wafer, and no obvious coffee ring effect appears. Scanning electron microscope analysis is carried out on the substrate, and found that thousands of silver-coated gold nanoparticles are stacked into spherical super particles, and the size of the super particles is 500 nm-1.5 um (figure 4).
Such silver-coated gold nanoparticles with three-dimensional hot spots can also be obtained by dropping Au @ Ag NPs prepared in example 2 on the hydrophobic silicon wafer prepared in example 4.
Example 6
The Au @ Ag solution prepared in example 1 was diluted to a concentration of 1nmol L-1Taking 10 uL of the 1nmol L by using a pipette-1The Au @ Ag NPs solution of (a) was dropped on the hydrophobic silicon wafer obtained in example 3, and dried under natural conditions to obtain a surface enhanced raman substrate as shown in fig. 3 b. It is clear from the figure that at low concentrations, after the solvent has evaporated, the particles at the edges are more and darker, and the particles at the middle are less and lighter, giving a colorThe well-known coffee ring effect causes the enhancement effect of the substrate signal to be different and non-uniform.
Example 7
The surface-enhanced raman substrate prepared in example 5 was used to evaluate the enhancement effect of the surface-enhanced raman substrate using thiram as a probe molecule. The substrate was tested by raman spectroscopy at 532 nm to obtain thiram raman scattering spectra at different concentrations, as shown in fig. 5. Test results show that the surface enhanced Raman substrate with the three-dimensional hot spots has a strong Raman enhancement effect. The lowest detection limit of thiram is 0.005 mg L-1。
Example 8
Using a pipette, 5uL of the product of example 1 was removed to give 30nmol L-1In a solution of Au @ Ag NPs, dropping at a contact angle of 60oThe silicon chip is dried under natural conditions to obtain the surface enhanced Raman substrate, and the silver-coated gold nanoparticles are arranged in a two-dimensional order. Under the same test conditions, the surface enhanced raman substrate of the three-dimensional hot spot enhanced thiram 8 times as much as the two-dimensional surface enhanced raman substrate (fig. 6). Further illustrates the ultrahigh enhancement effect of the surface enhanced Raman substrate with the three-dimensional hot spots prepared by the invention.
Claims (9)
1. A preparation method of a surface enhanced Raman substrate with a three-dimensional hot spot is characterized by comprising the following steps:
1) taking a high-concentration silver-coated gold nanoparticle solution with a shell-core structure;
2) taking a hydrophobic silicon wafer;
3) and dropwise adding a micro high-concentration silver-coated gold nanoparticle solution with a shell-core structure on a hydrophobic silicon chip, and naturally drying to obtain thousands of spherical nanoparticles assembled by silver-coated gold nanoparticles, wherein the particles have high-density three-dimensional 'hot spots' and ultrahigh surface-enhanced Raman characteristics.
2. The method of claim 1, wherein the high concentration is provided by a surface enhanced Raman substrate with three-dimensional hot spotsThe concentration of the silver-coated gold nanoparticle solution with the shell-core structure is as follows: 10 nmol L-1～100 nmol L-1。
3. The method for preparing the surface-enhanced Raman substrate with the three-dimensional hot spot according to claim 1, wherein the high-concentration silver-coated gold nanoparticle solution with the core-shell structure is obtained by the following steps:
heating chloroauric acid solution to reflux at 120-130 ℃ under the condition of magnetic stirring;
after the reflux is stable, quickly adding the sodium citrate solution A into the chloroauric acid solution;
after the solution turns to mauve, reducing the temperature to 100-115 ℃, continuing to heat and stir, adding a sodium citrate solution B, dropwise adding a silver nitrate solution into the mixture, and continuing to heat and stir, wherein the color of the mixture turns to orange from red wine;
after gradually cooling to room temperature under the condition of stirring, filtering the obtained solution by using a 0.22 mu m water system filter membrane, washing and concentrating through multiple steps of centrifugation to obtain a high-concentration silver-coated gold nanoparticle solution with a shell-core structure, and storing at 4 ℃ for later use.
4. The method for preparing a surface-enhanced Raman substrate having three-dimensional hot spots according to claim 1, wherein a contact angle of the hydrophobic silicon wafer is 130 ° or more.
5. The method for preparing the surface-enhanced Raman substrate with the three-dimensional hot spot according to claim 1, wherein the hydrophobic silicon wafer is obtained by the following steps:
soaking a monocrystalline silicon wafer in a piranha washing liquid, wherein the volume ratio of concentrated sulfuric acid to 30% of hydrogen peroxide in the piranha washing liquid is 3:1, so that the surface of the piranha washing liquid is hydrophilic, and then, washing the piranha washing liquid by using a large amount of ultrapure water and soaking the piranha washing liquid in ultrapure water for later use;
naturally drying a hydrophilic silicon wafer in the air, adding a toluene solution of methyltrichlorosilane to completely immerse the surface of the silicon wafer in the solution, sealing, and standing at room temperature;
and taking the silicon wafer out of the toluene solution of the methyltrichlorosilane, respectively washing the silicon wafer twice with toluene, ethanol, water in a ratio of 1:1 and ultrapure water, and drying to obtain the hydrophobic silicon wafer.
6. The method for preparing the surface-enhanced Raman substrate with the three-dimensional hot spots according to claim 3, wherein the content of the chloroauric acid is 0.1 mmol L-1～0.5 mmol L-1(ii) a The addition amount of the sodium citrate solution A is 0.5 mL-3 mL of 1% sodium citrate solution; the addition amount of the sodium citrate solution B is 3 mL-10 mL of 1% sodium citrate solution; the content of silver nitrate is 0.01 mmol L-1～0.05 mmol L-1。
7. The method for preparing a surface-enhanced Raman substrate having three-dimensional hot spots according to claim 5, wherein the concentration of the toluene solution of methyltrichlorosilane is 0.01 mol L-1～0.5 mol L-1。
8. The surface-enhanced Raman substrate with three-dimensional hot spots obtained by the production method according to any one of claims 1 to 7.
9. The application of the surface-enhanced Raman substrate with the three-dimensional hot spots according to claim 8 in high-sensitivity detection of thiram pesticide.
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