CN106290296B - SERS substrate based on metal dot matrix, preparation method thereof and method for performing Raman detection by using substrate - Google Patents
SERS substrate based on metal dot matrix, preparation method thereof and method for performing Raman detection by using substrate Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
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- General Physics & Mathematics (AREA)
- Immunology (AREA)
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention provides a SERS substrate based on a metal dot matrix, which comprises a silicon-based substrate, the metal dot matrix formed on the silicon-based substrate and a hydrophobic layer arranged in an area outside the metal dot matrix, wherein a metal layer forming the metal dot matrix is made of gold, silver or copper. The region outside the metal lattice on the substrate has hydrophobicity, and the metal point position of the metal lattice is relatively hydrophilic, so that the substance to be detected can be better enriched on the metal point, and the enhancement of Raman signals is facilitated. The invention also provides a preparation method of the substrate, a method for carrying out Raman detection by using the substrate, and a SERS chip based on the metal dot matrix.
Description
Technical Field
The invention relates to the field of analysis and detection, in particular to a SERS substrate based on a metal dot matrix, a preparation method thereof and a method for carrying out Raman detection by using the substrate.
Background
Surface-enhanced Raman scattering (SERS) has the advantages of high sensitivity, nondestructive detection, in-situ measurement and the like, and is widely applied to various fields such as food safety detection, medical diagnosis, material characterization, archaeology, criminal investigation and the like. In particular, SERS is a very important analytical tool in the field of hazardous substance detection and material characterization.
The advantages of SERS technology are very clear, but when the SERS technology is pushed out of laboratory levels, the practical popularization of SERS technology is limited due to the absence of SERS active substrates suitable for practical application. The existing SERS active substrates comprise two types, namely solid and liquid, although the solid active substrate has a controllable periodic hot spot position, which can ensure the reproducibility of SERS measurement, the substrates cannot be stored for a long time and are prepared when in use, thereby increasing the difficulty of part of processes; the liquid active substrate can be stored for a long time and is used in the SERS analysis, but the reproducibility of the SERS analysis is poor due to the uncontrollable aggregation of the nanoparticles in the liquid substrate in the SERS analysis. Moreover, most of the existing SERS technologies simply use metal nanoparticles on a substrate to construct a 'hot spot', and the gain effect on Raman signals is limited.
The problems prevent the SERS technology from stepping to market application from research level, and restrict the development of practical application of the SERS technology. There is therefore an urgent need to develop a SERS-active substrate that can be stored for a long period of time, be used on demand, and has high detection sensitivity.
Disclosure of Invention
In view of this, the first aspect of the present invention provides a SERS substrate based on a metal dot matrix, where an area outside the metal dot matrix of the substrate has hydrophobicity, and a metal point position of the metal dot matrix is relatively hydrophilic, so that a substance to be detected can be better enriched on the metal point, which is beneficial to enhancing a raman signal, and improves detection sensitivity.
In a first aspect, the invention provides a SERS substrate based on a metal dot matrix, which includes a silicon-based substrate, a metal dot matrix formed on the silicon-based substrate, and a hydrophobic layer disposed in an area other than the metal dot matrix, wherein a material of a metal layer constituting the metal dot matrix is gold, silver, or copper.
In the first aspect of the present invention, the thickness of the metal layer of the metal lattice is 0.1 to 1 μm, and the diameter of each metal dot in the metal lattice is 0.2 to 2 mm. Preferably, the metal layer has a thickness of 0.1 to 0.5 μm and the metal dots have a diameter of 0.8 to 1.5 mm. The metal dots may be circular.
In the first aspect of the present invention, the hydrophobic layer is made of a hydrophobic silane coupling agent, such as n-propyl Trimethoxysilane (TMPS), methyl trimethoxysilane, and methyl triethoxysilane, and the thickness of the hydrophobic layer is substantially equal to the thickness of the gold layer and is 0.1 to 1 μm.
In the first aspect of the present invention, a polymer protective film is further disposed on the surface of the metal layer of the metal lattice, and the material constituting the polymer protective film is a polymer which is water-soluble and cannot form a strong bonding force with the metal material of the metal lattice. The SERS substrate provided with the polymer protective film can be stored for a long time, can be taken and used at any time, is simple to operate, is rapid and convenient, saves the detection time and simplifies the detection process. The polymer used for the polymer protective film of the present invention is required to have water solubility and not to generate strong functional groups such as carboxyl, amino, mercapto and hydroxyl groups with the metal layer. Specifically, the material of the polymer protective film may be polyethylene glycol (PEG), or other polymers meeting the requirements of the present invention. The polymer protective film can be directly washed clean by deionized water without residue.
In the first aspect of the present invention, adhesion layers are disposed between the silicon-based substrate and the metal lattice, and between the silicon-based substrate and the hydrophobic layer, the adhesion layers are titanium metal layers or chromium metal layers, and the thickness of the adhesion layers is 10 to 1000 nm.
In the first aspect of the present invention, the silicon-based substrate may be a glass wafer, a silicon wafer, or a silicon nitride wafer.
According to the SERS substrate based on the metal dot matrix, the metal dot positions of the metal dot matrix are relatively hydrophilic, and the regions outside the metal dot matrix are hydrophobic, so that a series of hydrophilic and hydrophobic periodic structures are formed, and therefore, a substance to be detected can be better enriched on the metal dots, so that the enhancement of Raman signals is facilitated, and the detection sensitivity is improved; the invention further arranges the polymer protective film on the metal layer of the metal lattice, so that the SERS substrate based on the metal lattice can be stored for a long time and used at any time, thereby finally saving the detection time and simplifying the detection process.
In a second aspect, the present invention provides a method for preparing a SERS substrate based on a metal dot matrix, including the following steps:
(1) providing a clean silicon-based substrate, and evaporating a metal layer on the silicon-based substrate in an evaporation mode, wherein the metal layer is made of gold, silver or copper;
(2) coating a layer of photoresist on the metal layer, covering the photoresist by adopting a pre-designed mask plate, and then forming a metal dot matrix on the silicon-based substrate by an etching process;
(3) carrying out hydrophobic treatment on the silicon-based substrate with the metal dot matrix formed on the surface so as to form a hydrophobic layer in an area except the metal dot matrix, then ultrasonically cleaning the silicon-based substrate by adopting an organic solvent to remove the photoresist, cleaning the silicon-based substrate by using deionized water, and drying the silicon-based substrate by using nitrogen to obtain the SERS substrate based on the metal dot matrix.
In the second aspect of the present invention, after the step (3), a polymer protective film is further disposed on the surface of the metal layer of the metal lattice, and a material constituting the polymer protective film is a polymer which is water-soluble and cannot form a strong bonding force with the metal material of the metal lattice. Specifically, the material of the polymer protective film may be polyethylene glycol (PEG), or other polymers meeting the requirements of the present invention. The operation of disposing the polymer protective film on the surface of the metal layer of the metal lattice may specifically be: and (3) dropwise adding a polymer solution on the surface of the metal layer of the metal dot matrix or soaking the SERS substrate obtained in the step (2) in the polymer solution, and drying to form a polymer protective film. The drying operation may be: drying in a constant temperature drying oven at 50-80 deg.C for 5-60 min.
In the second aspect of the present invention, in the step (1), the silicon-based substrate may be a glass plate, a silicon wafer or a silicon nitride wafer. The clean silicon-based substrate may be obtained by a pretreatment process as follows: and (3) taking the silicon-based substrate, cleaning the silicon-based substrate with deionized water, drying the silicon-based substrate with nitrogen, putting the silicon-based substrate into acetone for ultrasonic treatment for 1-30 minutes, taking the silicon-based substrate out, cleaning the silicon-based substrate with deionized water, and drying the silicon-based substrate with nitrogen. The thickness of the evaporated metal layer is 0.1-1 micron.
In the step (2), the photoresist can be MMA and PMMA mixed photoresist, and the etching solution adopted in the etching process is an acid solution obtained by mixing aqua regia and water in a volume ratio of 1: 1-10, and is etched for 10-600 seconds. The diameter of each metal point in the metal lattice is 0.2-2 mm. The metal dots may be circular.
In the step (3), the specific operation of performing the hydrophobic treatment on the silicon-based substrate with the metal lattice formed on the surface thereof may be: taking a silicon-based substrate with a metal lattice formed on the surface and 0.01-20 ml of hydrophobic silane coupling agent, placing the silicon-based substrate and the hydrophobic silane coupling agent in a container, and keeping the silicon-based substrate and the hydrophobic silane coupling agent at 90-200 ℃ for 20-300 minutes. The hydrophobic silane coupling agent can be n-propyl trimethoxy silane (TMPS), methyl trimethoxy silane and methyl triethoxy silane. The organic solvent may be acetone, and the ultrasonic cleaning may be performed for 1 to 30 minutes.
In the second aspect of the present invention, before the step (1), an adhesion layer is prepared on the silicon-based substrate by evaporation, where the adhesion layer may be a titanium metal layer or a chromium metal layer, and the thickness of the adhesion layer is 10 to 1000 nanometers.
The preparation method provided by the second aspect of the invention has the advantages of simple process and convenient operation.
In a third aspect, the present invention provides a method for performing raman detection by using a SERS substrate based on a metal dot matrix, including the following steps:
taking the SERS substrate which is not provided with the polymer protective film and is based on the metal dot matrix, dripping a fluid object to be detected on the metal dot of the metal dot matrix, drying, and performing SERS detection by adopting a Raman spectrometer; or
The SERS substrate provided with the polymer protective film and based on the metal dot matrix is taken, the polymer protective film is firstly cleaned and removed by deionized water, a fluid object to be detected is dropped on the metal dots of the metal dot matrix after being dried by nitrogen, and after drying, a Raman spectrometer is adopted for SERS detection.
The detection method can be used for preparing the SERS substrate which is not provided with the polymer protective film and is based on the metal dot matrix for SERS detection. The SERS substrate which is provided with the polymer protective film and is based on the metal dot matrix can be directly taken for SERS detection. The latter is more convenient and faster, and saves detection time.
The method for raman detection according to the third aspect of the present invention further includes, before performing SERS detection: and dripping metal nanoparticle sol on the surface of the object to be detected, wherein the metal nanoparticles in the metal nanoparticle sol are gold, silver or copper nanoparticles. Size of the metal nanoparticlesThe nano-meter can be 10-1000 nanometers, and the shape can be spherical, conical, cylindrical, rod-shaped and other shapes. The detection method of the invention utilizes the principle that the active metal lattice and the metal nano particles jointly construct a 'hot spot', and further dropwise adds the metal nano particle sol on the surface of the object to be detected, so that the active metal lattice, the substance to be detected and the metal nano particles construct a 'sandwich structure', and the structure has the advantages of good reproducibility and good enhancement effect. The detection method has ultrahigh sensitivity, and the detection limit can reach 10-9mol/L。
The substance to be measured in the third aspect of the present invention may be malachite green, rhodamine 6G, melamine, sudan red, furazolidone, ciprofloxacin, enrofloxacin, chloramphenicol and other harmful substances in foods, medicines and environments.
In the third aspect of the present invention, the drying operation may be: drying in a constant temperature drying oven at 50-80 deg.C for 1-5 min.
In the third aspect of the present invention, the raman spectrometer used is a confocal raman spectrometer, and specifically, the substrate on which the object to be measured is dropped is placed on an XYZ automatic platform of the confocal raman spectrometer, and the microscope objective of the raman spectrometer is used to focus the substrate.
The XYZ stage parameters may be X75 mm, Y50 mm, XY 0.1 micron minimum step size, and Z0.1 micron minimum step size. The wavelength of a laser light source adopted by the confocal stretched surface spectrometer is set according to a specific metal lattice, for example, the gold and silver lattice can be 633 nanometers and 532 nanometers respectively, and the multiplying power of a microscope objective can be 20, 50 and 100 times.
The invention provides a SERS chip based on a metal dot matrix, which comprises a silicon-based substrate, the metal dot matrix formed on the silicon-based substrate, a hydrophobic layer arranged in an area except the metal dot matrix, a layer to be detected arranged on a metal point of the metal dot matrix and a metal nanoparticle layer arranged on the layer to be detected, wherein the metal dot matrix is made of gold, silver or copper, and the metal nanoparticle layer is made of gold, silver or copper nanoparticles.
In the fourth aspect of the invention, the thickness of the metal layer of the metal lattice is 0.1-1 micron, and the diameter of each metal point in the metal lattice is 0.2-2 mm. The metal dots may be circular.
In the fourth aspect of the present invention, the hydrophobic layer is made of a hydrophobic silane coupling agent, such as n-propyl Trimethoxysilane (TMPS), methyl trimethoxysilane, and methyl triethoxysilane, and the thickness of the hydrophobic layer is substantially equal to the thickness of the gold layer and is 0.1 to 1 μm.
In the fourth aspect of the present invention, a polymer protective film is further disposed on the surface of the metal layer of the metal lattice, and the material constituting the polymer protective film is a polymer which is water-soluble and cannot form a strong bonding force with the metal material of the metal lattice. Specifically, the material of the polymer protective film may be polyethylene glycol (PEG), or other polymers meeting the requirements of the present invention.
In the fourth aspect of the present invention, adhesion layers are disposed between the silicon-based substrate and the metal lattice, and between the silicon-based substrate and the hydrophobic layer, the adhesion layers are titanium metal layers or chromium metal layers, and the thickness of the adhesion layers is 10 to 1000 nm.
In the fourth aspect of the present invention, the silicon-based substrate may be a glass wafer, a silicon wafer, or a silicon nitride wafer.
In the fourth aspect of the present invention, the size of the metal nanoparticles may be 10 to 1000 nm, and the shape may be spherical, conical, cylindrical, rod-like, or other shapes.
According to the SERS chip based on the metal dot matrix provided by the fourth aspect of the invention, by utilizing the principle that the active metal dot matrix and the metal nanoparticles jointly construct a 'hot spot', and by further arranging the metal nanoparticle layer on the surface of the object to be detected, the active metal dot, the substance to be detected and the metal nanoparticles construct a 'sandwich structure', and the structure has the advantages of good reproducibility and good enhancement effect. The chip structure is used for SERS detection, has ultrahigh sensitivity, and the detection limit can reach 10-9mol/L。
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
FIG. 1 is a diagram of a gold dot matrix based SERS substrate according to an embodiment of the present invention;
FIG. 2 is a flow chart of a process for preparing a gold-lattice-based SERS substrate according to an embodiment of the present invention;
FIG. 3 is a flow chart of Raman detection using a gold-lattice-based SERS substrate according to an embodiment of the present invention;
fig. 4 shows the detection result of malachite green by using the SERS substrate based on gold lattice according to the embodiment of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
Example 1
A preparation method of a SERS substrate based on a gold dot matrix comprises the following steps:
(1) taking a glass sheet, firstly cleaning the glass sheet by using deionized water, then drying the glass sheet by using nitrogen, then placing the glass sheet in acetone for ultrasonic treatment for 10 minutes, then taking the glass sheet out, cleaning the glass sheet by using the deionized water, and finally drying the glass sheet by using the nitrogen for standby; evaporating a titanium metal layer with the thickness of 10 nanometers on a glass sheet in an evaporation mode, and then evaporating and preparing a gold layer with the thickness of 100 nanometers on the titanium metal layer;
(2) designing a series of 4 multiplied by 4 dot matrix masks by using CAD, wherein the diameter of each gold dot is 1 mm, spin-coating photoresist on a gold layer, covering the designed masks on the gold layer, placing the masks in a photoetching machine, and corroding the gold layer for 300 seconds by using aqua regia which is prepared in a volume ratio of 1: 3 to water, namely forming a series of gold dots on a titanium metal layer to obtain a gold dot matrix; as shown in fig. 1, 1 is a glass plate to which a titanium metal layer is attached, and 2 is a gold lattice.
(3) Hydrophobization treatment is carried out on the titanium metal part except the gold dot matrix, namely the substrate obtained in the step (2) and 5 ml of n-propyl trimethoxy silane (TMPS) are placed in a container, heated for 100 minutes at 134 ℃, then taken out, placed in acetone for water bath ultrasound for 5 minutes, repeatedly cleaned by deionized water, dried by nitrogen and washed away photoresist; thus, a hydrophobic layer with the thickness of 0.2 micrometer is formed on the titanium metal layer outside the gold dot matrix, and the SERS substrate based on the gold dot matrix is obtained, wherein the area ratio of the gold dot matrix to the hydrophobic layer on the substrate is about 1: 7.
Example 2
A preparation method of a SERS substrate based on a gold dot matrix comprises the following steps:
(1) taking a glass sheet, firstly cleaning the glass sheet by using deionized water, then drying the glass sheet by using nitrogen, then placing the glass sheet in acetone for ultrasonic treatment for 10 minutes, then taking the glass sheet out, cleaning the glass sheet by using the deionized water, and finally drying the glass sheet by using the nitrogen for standby; evaporating a titanium metal layer with the thickness of 100 nanometers on a glass sheet in an evaporation mode, and then evaporating and preparing a gold layer with the thickness of 500 nanometers on the titanium metal layer;
(2) designing a series of 4 multiplied by 4 dot matrix masks by using CAD, wherein the diameter of each gold dot is 0.6 mm, spinning and coating photoresist on a gold layer, covering the designed masks on the gold layer, placing the masks in a photoetching machine, and corroding the gold layer for 600 seconds by using aqua regia which is prepared in a volume ratio of 1: 3 to water, namely forming a series of gold dots on a titanium metal layer to obtain a gold dot matrix;
(3) hydrophobization treatment is carried out on the titanium metal part except the gold dot array, namely the substrate obtained in the step (2) and 10 ml of n-propyl trimethoxy silane (TMPS) are placed in a container, heated for 200 minutes at 130 ℃, then taken out, placed in acetone for water bath ultrasound for 5 minutes, repeatedly washed by deionized water, dried by nitrogen and washed away photoresist, and thus a hydrophobic layer with the thickness of 500 nanometers is formed on the titanium metal layer except the gold dot array;
(4) and (4) dripping polyethylene glycol liquid on the substrate obtained in the step (3), then placing the substrate in a constant-temperature drying box for 30 minutes, drying and taking out the substrate to obtain the SERS substrate based on the gold dot matrix, wherein the area ratio of the gold dot matrix to the hydrophobic layer on the substrate is about 1: 7.
Fig. 2 is a flow chart of a preparation process of the SERS substrate based on the gold dot matrix in this embodiment, in which 101 is a glass substrate, 102 is a titanium metal layer, 103 is a gold layer, 104 is a photoresist layer, 105 is a hydrophobic layer, and 106 is a polyethylene glycol layer.
Example 3
A preparation method of a SERS substrate based on a silver dot matrix comprises the following steps:
(1) taking a glass sheet, firstly cleaning the glass sheet by using deionized water, then drying the glass sheet by using nitrogen, then placing the glass sheet in acetone for ultrasonic treatment for 10 minutes, then taking the glass sheet out, cleaning the glass sheet by using the deionized water, and finally drying the glass sheet by using the nitrogen for standby; evaporating a titanium metal layer with the thickness of 10 nanometers on a glass sheet by adopting an evaporation method, and then evaporating and preparing a silver layer with the thickness of 100 nanometers on the titanium metal layer;
(2) designing a series of 4 multiplied by 4 dot matrix masks by using CAD, wherein the diameter of each silver dot is 0.2 mm, spinning and coating photoresist on a gold layer, covering the designed masks on a silver layer, placing the silver layer in a photoetching machine, and corroding the silver layer for 200 seconds by using aqua regia which is prepared in a volume ratio of 1: 3 to water, namely forming a series of silver dots on a titanium metal layer to obtain a silver dot matrix;
(3) hydrophobization treatment is carried out on the titanium metal part except the silver dot array, namely the substrate obtained in the step (2) and 1 ml of n-propyl trimethoxy silane (TMPS) are placed in a container, heated for 100 minutes at 134 ℃, then taken out, placed in acetone for water bath ultrasound for 5 minutes, repeatedly washed by deionized water, dried by nitrogen and washed away photoresist, and thus a hydrophobic layer with the thickness of 200 nanometers is formed on the titanium metal layer except the silver dot array;
(4) and (3) soaking the silver dot matrix substrate obtained in the step (3) in polyethylene glycol (PEG) for 30 minutes, taking out, placing in a constant-temperature drying oven for 30 minutes, drying and taking out to obtain the SERS substrate based on the silver dot matrix.
Example 4
A preparation method of a SERS substrate based on a copper dot matrix comprises the following steps:
(1) taking a glass sheet, firstly cleaning the glass sheet by using deionized water, then drying the glass sheet by using nitrogen, then placing the glass sheet in acetone for ultrasonic treatment for 10 minutes, then taking the glass sheet out, cleaning the glass sheet by using the deionized water, and finally drying the glass sheet by using the nitrogen for standby; evaporating a titanium metal layer with the thickness of 10 nanometers on a glass sheet in an evaporation mode, and then evaporating and preparing a copper layer with the thickness of 1 micrometer on the titanium metal layer;
(2) designing a series of 4 multiplied by 4 dot matrix masks by using CAD, wherein the diameter of each silver dot is 1 mm, spin-coating photoresist on a gold layer, covering the designed masks on a copper layer, placing the masks in a photoetching machine, and corroding the copper layer for 300 seconds by using aqua regia which is prepared in a volume ratio of 1: 3 to water, namely forming a series of copper dots on a titanium metal layer to obtain a copper dot matrix;
(3) hydrophobization treatment is carried out on the titanium metal part outside the copper dot matrix, namely the substrate obtained in the step (2) and 20 ml of n-propyl trimethoxy silane (TMPS) are placed in a container, heated for 300 minutes at 134 ℃, then taken out, placed in acetone for water bath ultrasound for 5 minutes, repeatedly washed by deionized water, dried by nitrogen and washed away photoresist, and thus a hydrophobic layer with the thickness of 1 micron is formed on the titanium metal layer outside the copper dot matrix;
(4) and (3) soaking the copper dot matrix substrate obtained in the step (3) in polyethylene glycol (PEG) for 5-30 minutes, taking out, placing in a constant-temperature drying oven for 30 minutes, and taking out after drying to obtain the SERS substrate based on the copper dot matrix.
Example 5
A method for carrying out Raman detection by utilizing a SERS substrate based on a gold dot matrix comprises the following steps:
ready 10-4～10-7malachite green solution with mol/L concentration;
taking the SERS substrate based on the gold dot matrix prepared in example 1, respectively dropping 0.5 microliter of malachite green solution with different concentrations on a gold dot by using a liquid transfer device, placing the gold dot in a constant-temperature drying box for 10 minutes, drying the gold dot, placing the dried gold dot on an XYZ moving platform of a Raman spectrometer, focusing by using a Raman microscope objective with 20 multiplying powers, and performing Raman scattering detection by using laser with a wavelength of 633 nanometers as a light source, wherein the Raman detection result shows that: the SERS substrate based on the gold dot matrix has high sensitivity, and the detection limit of the SERS substrate reaches 10-7mol/L。
Example 6
A method for carrying out Raman detection by utilizing a SERS substrate based on a gold dot matrix comprises the following steps:
ready 10-5～10-9malachite green solution with mol/L concentration;
taking the SERS substrate based on the gold dot matrix prepared in the embodiment 2, washing with deionized water to remove a PEG protective film, drying with nitrogen, then respectively dropping 0.5 microliter of malachite green solution with different concentrations on a gold dot by using a liquid transfer device, placing the gold dot in a constant-temperature drying box for 10 minutes, drying, then dropping the prepared gold nanoparticle sol on the gold dot, placing the gold dot in the constant-temperature drying box for 10 minutes, drying, placing the dried gold nanoparticle sol on an XYZ moving platform of a Raman spectrometer, selecting a Raman microscope objective with a magnification of 20 times for focusing, selecting laser with a wavelength of 633 nanometers as a light source, and carrying out Raman scattering detection. Fig. 3 is a flow chart of raman detection using the SERS substrate based on gold dot matrix in embodiment 1 of the present invention, in which 107 is a malachite green solution to be detected, and 108 is gold nanoparticles. FIG. 4 shows the results of Raman scattering detection.
Example 7
A method for carrying out Raman detection by utilizing an SERS substrate based on a silver dot matrix comprises the following steps:
ready 10-5～10-9malachite green solution with mol/L concentration;
taking the SERS substrate based on the silver dot matrix prepared in the embodiment 3, washing with deionized water to remove a PEG protective film, drying with nitrogen, then respectively taking 0.5 microliter of malachite green solution with different concentrations to drip on a silver spot by using a pipettor, placing the silver spot in a constant-temperature drying box for 10 minutes, drying, dripping the prepared silver nanoparticle sol on the silver spot, placing the silver nanoparticle sol on the constant-temperature drying box for 10 minutes, drying, placing the silver nanoparticle sol on an XYZ moving platform of a Raman spectrometer, selecting a Raman microscope objective with 20 multiplying powers for focusing, selecting laser with 532-nanometer wavelength as a light source, and performing Raman scattering detection, wherein a Raman detection result shows that: the SERS substrate based on the silver dot matrix has ultrahigh sensitivity, and the detection limit of the SERS substrate can reach 10-10mol/L。
Claims (7)
1. The utility model provides a SERS basement based on metal dot matrix, its characterized in that, includes silicon-based basement, and forms metal dot matrix on the silicon-based basement is in with the setting hydrophobic layer in the region outside the metal dot matrix constitutes the material of the metal layer of metal dot matrix is gold, silver or copper, the metal layer surface of metal dot matrix further is provided with the polyethylene glycol protection film, the polyethylene glycol protection film have water-solubility, and can not with form strong cohesion between the metal material of metal dot matrix.
2. The SERS substrate of claim 1, wherein the metal layer of the metal lattice has a thickness of 0.1 to 1 micron and each metal dot of the metal lattice has a diameter of 0.2 to 2 mm.
3. The SERS substrate according to claim 1, wherein the hydrophobic layer is made of a hydrophobic silane coupling agent, and the hydrophobic layer has a thickness of 0.1 to 1 μm.
4. A preparation method of a SERS substrate based on a metal dot matrix is characterized by comprising the following steps:
(1) providing a clean silicon-based substrate, and evaporating a metal layer on the silicon-based substrate in an evaporation mode, wherein the metal layer is made of gold, silver or copper;
(2) coating a layer of photoresist on the metal layer, covering the photoresist by adopting a pre-designed mask plate, and then forming a metal dot matrix on the silicon-based substrate by an etching process;
(3) carrying out hydrophobic treatment on the silicon-based substrate with the metal dot matrix formed on the surface so as to form a hydrophobic layer in an area except the metal dot matrix, then ultrasonically cleaning the silicon-based substrate by adopting an organic solvent to remove the photoresist, cleaning the silicon-based substrate by using deionized water, then drying the silicon-based substrate by using nitrogen, and then arranging a polyethylene glycol protective film on the surface of the metal layer of the metal dot matrix to obtain the SERS substrate based on the metal dot matrix.
5. A method for carrying out Raman detection by utilizing a SERS substrate based on a metal dot matrix is characterized by comprising the following steps:
taking the SERS substrate based on the metal dot matrix as claimed in any one of claims 1 to 3, firstly cleaning with deionized water to remove the polyethylene glycol protective film, drying with nitrogen, dripping the fluid object to be measured on the metal dots of the metal dot matrix, drying, and performing SERS detection by using a Raman spectrometer.
6. The method of raman detection according to claim 5, further comprising, prior to performing the SERS detection: and dripping metal nanoparticle sol on the surface of the object to be detected, wherein the metal nanoparticles in the metal nanoparticle sol are gold, silver or copper nanoparticles.
7. The method of raman detection according to claim 6, wherein the metal nanoparticles have a size of 10 to 1000 nanometers.
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| CN107064107B (en) * | 2017-04-11 | 2019-11-19 | 中山大学 | A kind of super hydrophobic surface enhancing Raman substrate and preparation method thereof using the preparation of silicon nanometer dielectric material |
| CN107290331B (en) * | 2017-06-08 | 2019-10-25 | 北京航空航天大学 | A kind of method that hydrophobicity composite high-molecular film is used for Raman detection |
| CN108872183B (en) * | 2018-03-22 | 2024-05-07 | 苏州纳微生命科技有限公司 | SERS chip preparation, preservation and sample loading method |
| CN109342398A (en) * | 2018-11-27 | 2019-02-15 | 浙江工业大学 | The SERS detection method of trace Ciprofloxacin in a kind of flesh of fish |
| CN109975271B (en) * | 2019-04-24 | 2020-11-24 | 西南交通大学 | High-reproducibility surface-enhanced Raman scattering substrate material and using method thereof |
| CN111299606B (en) * | 2020-03-19 | 2021-08-13 | 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 |
| CN113281324A (en) * | 2021-06-29 | 2021-08-20 | 江苏大学 | Characteristic information extraction method of small molecule volatile matter and portable detection system |
| CN114377736B (en) * | 2022-01-11 | 2023-06-16 | 中科新芯纳米技术(常州)有限公司 | Hydrophilic and hydrophobic patterned array chip, preparation method and application thereof |
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