CN113702348A - Surface-enhanced Raman substrate with three-dimensional hot spots and preparation method thereof - Google Patents
Surface-enhanced Raman substrate with three-dimensional hot spots and preparation method thereof Download PDFInfo
- Publication number
- CN113702348A CN113702348A CN202110480870.3A CN202110480870A CN113702348A CN 113702348 A CN113702348 A CN 113702348A CN 202110480870 A CN202110480870 A CN 202110480870A CN 113702348 A CN113702348 A CN 113702348A
- Authority
- CN
- China
- Prior art keywords
- solution
- enhanced raman
- silver
- dimensional
- silicon wafer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 57
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 40
- 239000010703 silicon Substances 0.000 claims abstract description 40
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 35
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010931 gold Substances 0.000 claims abstract description 32
- 229910052737 gold Inorganic materials 0.000 claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 32
- 239000004332 silver Substances 0.000 claims abstract description 32
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000005843 Thiram Substances 0.000 claims abstract description 9
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960002447 thiram Drugs 0.000 claims abstract description 9
- 239000000575 pesticide Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 19
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 17
- 239000001509 sodium citrate Substances 0.000 claims description 17
- 241000252506 Characiformes Species 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 8
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 4
- 235000020095 red wine Nutrition 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims description 2
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims description 2
- 235000010703 Modiola caroliniana Nutrition 0.000 claims description 2
- 244000038561 Modiola caroliniana Species 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 13
- 238000001338 self-assembly Methods 0.000 abstract description 7
- 238000001237 Raman spectrum Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004557 single molecule detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Immunology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Biochemistry (AREA)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110480870.3A CN113702348A (en) | 2021-04-30 | 2021-04-30 | Surface-enhanced Raman substrate with three-dimensional hot spots and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110480870.3A CN113702348A (en) | 2021-04-30 | 2021-04-30 | Surface-enhanced Raman substrate with three-dimensional hot spots and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113702348A true CN113702348A (en) | 2021-11-26 |
Family
ID=78647867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110480870.3A Pending CN113702348A (en) | 2021-04-30 | 2021-04-30 | Surface-enhanced Raman substrate with three-dimensional hot spots and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113702348A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115582537A (en) * | 2022-10-08 | 2023-01-10 | 温州医科大学 | Preparation method and application of large-size uniform nano noble metal film |
| CN115815612A (en) * | 2022-10-22 | 2023-03-21 | 上海微淳生物科技有限公司 | Preparation method of annular gold and silver nanoparticles |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608103A (en) * | 2012-03-30 | 2012-07-25 | 中国科学院长春应用化学研究所 | Surface enhanced Raman scattering (SERS) substrate and preparation method thereof |
| CN102944543A (en) * | 2012-11-05 | 2013-02-27 | 中物院成都科学技术发展中心 | Method and device for detecting ultra trace sample based on surface-enhanced Raman spectroscopy |
| CN103357887A (en) * | 2013-07-01 | 2013-10-23 | 西安交通大学 | Sea urchin-shaped hollow gold and silver alloy nano particle and preparation method and application thereof |
| CN103712972A (en) * | 2014-01-07 | 2014-04-09 | 厦门大学 | Preparation method for surface enhanced raman substrate |
| CN104749154A (en) * | 2013-12-27 | 2015-07-01 | 深圳先进技术研究院 | Surface enhanced Raman scattering substrate and preparation method thereof |
| CN106596501A (en) * | 2016-11-23 | 2017-04-26 | 深圳先进技术研究院 | Magnetic movable Raman enhanced chip, and preparation method and application thereof |
| WO2019100231A1 (en) * | 2017-11-22 | 2019-05-31 | 厦门斯贝克科技有限责任公司 | Three dimensional hotspot raman detection chip based on shell isolation nano particles |
| CN110161012A (en) * | 2018-06-14 | 2019-08-23 | 四川大学 | One kind being based on fast-bacteria-detection method associated with Surface enhanced Raman scattering-laser induced breakdown spectroscopy |
| CN111299606A (en) * | 2020-03-19 | 2020-06-19 | 中国科学院高能物理研究所 | Preparation method of nano-gold coffee ring and application of nano-gold coffee ring in SERS detection |
| CN111830005A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院微电子研究所 | Detection method of chip Raman signal |
-
2021
- 2021-04-30 CN CN202110480870.3A patent/CN113702348A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608103A (en) * | 2012-03-30 | 2012-07-25 | 中国科学院长春应用化学研究所 | Surface enhanced Raman scattering (SERS) substrate and preparation method thereof |
| CN102944543A (en) * | 2012-11-05 | 2013-02-27 | 中物院成都科学技术发展中心 | Method and device for detecting ultra trace sample based on surface-enhanced Raman spectroscopy |
| CN103357887A (en) * | 2013-07-01 | 2013-10-23 | 西安交通大学 | Sea urchin-shaped hollow gold and silver alloy nano particle and preparation method and application thereof |
| CN104749154A (en) * | 2013-12-27 | 2015-07-01 | 深圳先进技术研究院 | Surface enhanced Raman scattering substrate and preparation method thereof |
| CN103712972A (en) * | 2014-01-07 | 2014-04-09 | 厦门大学 | Preparation method for surface enhanced raman substrate |
| CN106596501A (en) * | 2016-11-23 | 2017-04-26 | 深圳先进技术研究院 | Magnetic movable Raman enhanced chip, and preparation method and application thereof |
| WO2019100231A1 (en) * | 2017-11-22 | 2019-05-31 | 厦门斯贝克科技有限责任公司 | Three dimensional hotspot raman detection chip based on shell isolation nano particles |
| CN110161012A (en) * | 2018-06-14 | 2019-08-23 | 四川大学 | One kind being based on fast-bacteria-detection method associated with Surface enhanced Raman scattering-laser induced breakdown spectroscopy |
| CN111830005A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院微电子研究所 | Detection method of chip Raman signal |
| CN111299606A (en) * | 2020-03-19 | 2020-06-19 | 中国科学院高能物理研究所 | Preparation method of nano-gold coffee ring and application of nano-gold coffee ring in SERS detection |
Non-Patent Citations (9)
| Title |
|---|
| HONGLIN LIU: "Three-Dimensional and Time-Ordered Surface-Enhanced Raman Scattering Hotspot Matrix", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 136, no. 14, pages 5332 - 5341 * |
| MADHURI MANDAL: "Synthesis of Aucore–Agshelltype bimetallic nanoparticles for single molecule detection in solution by SERS method", JOURNAL OF NANOPARTICLE RESEARCH, pages 53 - 61 * |
| THI THU HA PHAM: "The structural transition of bimetallic Ag–Au from core/shell to alloy and SERS application", ROYAL SOCIETY OF CHEMISTRY, pages 24577 - 24594 * |
| 孙玉蝶: "三维纳米结构热点及其表面增强拉曼散射的研究", 中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑, no. 2014, pages 35 - 40 * |
| 徐抒平: "胶体金光谱性质研究及其在免疫检测方面的应用", 中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑, no. 2006 * |
| 李文鹏;张永良;单妍;: "Au@Ag双金属纳米粒子制备及其SERS性能", 青岛科技大学学报(自然科学版), no. 01, 15 February 2015 (2015-02-15) * |
| 梁营芳;周化岚;王燕;王锋;: "表面增强拉曼光谱技术在食品安全检测中的应用", 理化检验(化学分册), no. 04 * |
| 纪小会, 王连英, 张昕彤, 白玉白, 李铁津, 支壮志, 孔祥贵, 刘益春: "Au/Ag核-壳结构纳米粒子的制备及其SERS效应", 高等学校化学学报, no. 12, 15 January 2003 (2003-01-15) * |
| 裴鹭: "金核银壳双金属表面增强拉曼基底的合成及其在食品痕量危害物质检测中的应用", 万方学术期刊数据库, pages 7 - 25 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115582537A (en) * | 2022-10-08 | 2023-01-10 | 温州医科大学 | Preparation method and application of large-size uniform nano noble metal film |
| CN115582537B (en) * | 2022-10-08 | 2023-05-16 | 温州医科大学 | Preparation method and application of large-size uniform nano noble metal film |
| CN115815612A (en) * | 2022-10-22 | 2023-03-21 | 上海微淳生物科技有限公司 | Preparation method of annular gold and silver nanoparticles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Godoy et al. | Ultrasensitive inkjet-printed based SERS sensor combining a high-performance gold nanosphere ink and hydrophobic paper | |
| CN113702348A (en) | Surface-enhanced Raman substrate with three-dimensional hot spots and preparation method thereof | |
| CN110018148B (en) | Preparation method of surface-enhanced Raman test paper | |
| CN106493381B (en) | A kind of preparation method and applications of silver/cuprous oxide micro-nano structure composite | |
| Jun et al. | Magnetic field induced aggregation of nanoparticles for sensitive molecular detection | |
| CN108279227B (en) | Novel surface-enhanced Raman spectrum substrate material and preparation method and application thereof | |
| Long et al. | Preparation of stable core–shell dye adsorbent Ag-coated silica nanospheres as a highly active surfaced-enhanced Raman scattering substrate for detection of Rhodamine 6G | |
| CN111426741A (en) | Method for performing liquid biopsy based on nano material assisted MA L DI-TOF MS | |
| CN112692298A (en) | Preparation method of core-shell structure nano gold and silver composite material substrate | |
| CN109975271B (en) | High-reproducibility surface-enhanced Raman scattering substrate material and using method thereof | |
| CN109295443B (en) | A kind of nanogold submicron film, its preparation and application | |
| Jagdale et al. | Electrospray deposition for single nanoparticle studies | |
| CN107328750B (en) | High-activity high-uniformity surface enhanced Raman scattering substrate and preparation method thereof | |
| CN110108697B (en) | Surface-enhanced Raman scattering micro-nano chip, preparation method and application thereof, and Raman spectrum testing system | |
| CN113866151B (en) | Thorn-shaped nano gold and silver based triple amplified SERS signal substrate, preparation method and application | |
| Wadekar et al. | A review on gold nanoprticles synthesis and characterization | |
| TWI762811B (en) | Porous substrate with porous nano-particles structure and production method thereof | |
| Sundaram et al. | Stable silver/biopolymer hybrid plasmonic nanostructures for high performance surface enhanced Raman scattering (SERS) | |
| CN112285093A (en) | Spray type surface enhanced Raman scattering substrate and preparation method and application thereof | |
| CN113433111A (en) | Liposome-based core-shell material for Raman spectrum detection and preparation method and application thereof | |
| CN115415539B (en) | Preparation and application methods of hollow ruthenium copper alloy nano-particles | |
| Chu et al. | A novel method for preparing quantum dot nanospheres with narrow size distribution | |
| CN111122544A (en) | Preparation method of enrichment type surface enhanced Raman scattering substrate based on capillary action | |
| TWI669208B (en) | Hollow sphere composite particle and the manufacturing method thereof | |
| CN108872183B (en) | SERS chip preparation, preservation and sample loading method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |