CN110132935B - Preparation method of enhanced surface Raman scattering substrate - Google Patents
Preparation method of enhanced surface Raman scattering substrate Download PDFInfo
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- CN110132935B CN110132935B CN201910417340.7A CN201910417340A CN110132935B CN 110132935 B CN110132935 B CN 110132935B CN 201910417340 A CN201910417340 A CN 201910417340A CN 110132935 B CN110132935 B CN 110132935B
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Abstract
A preparation method of a surface-enhanced Raman scattering substrate belongs to the technical field of material preparation. The enhanced surface Raman scattering substrate comprises a layer of carbon black nano-particles with a porous structure and noble metal (gold, silver and the like) nano-particles attached to the surfaces of the nano-particles. The porous carbon black nano-particle can be prepared by depositing various combustible non-toxic organic matters on a carrying substrate by a flame method, and a layer of noble metal nano-particles is deposited on the surface of the porous carbon black nano-particle serving as a template by utilizing a physical vapor deposition technology, so that a porous carbon black/noble metal particle composite structure for an SERS detection substrate is constructed. The SERS active substrate with high repeatability, low cost, stable property, large-scale preparation and high sensitivity can be obtained on the carrying substrate by simple flame deposition and physical vapor deposition technology, and a simple, convenient and new way is provided for the preparation and application scientific research of the SERS active substrate.
Description
Technical Field
The invention belongs to the technical field of material preparation, and relates to a preparation method of a surface-enhanced Raman scattering substrate, which is low in cost, good in uniformity, high in repeatability and capable of being prepared in a large scale.
Background
The Surface Enhanced Raman Scattering (SERS) technology realizes the detection of single molecules by using an active substrate with high sensitivity, and is an ultrasensitive spectroscopy technology suitable for low-concentration detection. The method has the advantages of high sensitivity, convenient detection and the like, and becomes a common analysis means in the fields of biology, diagnostics, environmental monitoring, disease diagnosis and the like. The enhancement mechanism of the surface raman-enhanced scattering substrate has two aspects: chemical enhancement and electromagnetic enhancement; the principle of chemical enhancement is: light-induced charge transfer is generated between the noble metal nanoparticles and probe molecules adsorbed on the surface of the substrate, the polarizability of the formed new surface metal complex is increased, and the Raman enhanced scattering effect is achieved under the irradiation of appropriate exciting light. The principle of electromagnetic enhancement is: a local electric field is generated among the noble metal nano particles to form surface plasmon resonance, and the resonance phenomenon causes the enhancement of the local electric field intensity to be multiplied by the Raman scattering intensity. According to the working principle of surface Raman enhanced scattering, the fact that the surface morphology of the substrate is an important influence factor for determining whether the SERS effect can occur and the strength of an SERS signal is known, so that the SERS substrate is always a research hotspot in the field. The purpose of high-sensitivity detection is achieved by preparing a substrate with a special nano structure on the surface and controllable appearance.
The preparation method for preparing the SERS substrate commonly used at present mainly comprises the following steps: chemical vapor deposition, physical vapor deposition, electrochemical oxidation-reduction, chemical etching, metal sol, ordered array printing, and the like. The common preparation method of the SERS substrate has the problems of complex preparation process, high cost, long experimental period and the like, and the popularization and application of the SERS technology are limited to a great extent.
Therefore, it becomes important to develop a high-performance SERS substrate which has excellent performance, is easy to prepare on a large scale, has low cost, is convenient to use, and has high repeatability of detection results.
Disclosure of Invention
The invention aims to solve the problem that the preparation time, the raw material cost, the sensitivity and the like are difficult to coordinate and unify in the existing SERS substrate preparation technology, and provides a rapid, cheap and low-consumption SERS substrate preparation method.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for preparing a surface-enhanced Raman scattering substrate comprises a layer of carbon black nano-particles with a porous structure and noble metal (gold, silver and the like) nano-particles attached to the surfaces of the carbon black nano-particles. The preparation method comprises the following steps:
the method comprises the following steps of firstly, depositing a three-dimensional porous carbon black nano structure on the surface of a carrying substrate by using a flame method to realize the construction of a three-dimensional porous carbon black nano particle structure body, which comprises the following specific steps:
horizontally placing a carrying substrate above the combustible organic matter and aligning the carrying substrate with the center of the flame source; the substrate is defined at a distance d from the flame source as shown in figure 1. Igniting the flame source, and regulating the relative height d of the flame and the carrying substrate to deposit a layer of three-dimensional porous carbon black nanostructure. The thickness of the three-dimensional porous carbon black nanostructure can be regulated and controlled according to the deposition time and the relative position of the supporting substrate and the flame;
the method can also be used for horizontally placing a carrying substrate and a mask plate above the combustible organic matter and aligning the carrying substrate and the mask plate with the center of the flame source, wherein the mask plate is placed on the lower surface of the carrying substrate; igniting the flame source, and regulating the relative height of the flame and the supporting substrate to deposit a layer of modeled three-dimensional porous carbon black nanostructure. The thickness of the patterned three-dimensional porous carbon black nanostructure can be regulated and controlled according to the deposition time and the relative position of the supporting substrate and the flame.
And secondly, taking the three-dimensional porous carbon black nano structure or the modeled three-dimensional porous carbon black nano structure obtained in the first step as a support film of the SERS substrate, and depositing a precious metal nano particle layer with the thickness of 10-500nm on the surface of the support film by adopting a physical vapor deposition method, thereby constructing the composite SERS substrate of carbon black/metal nano particles. The support film is also referred to as a key substrate surface topography manipulation layer. The size of the noble metal nano particles can be regulated and controlled according to related parameters of physical vapor deposition. According to the SERS enhancement characteristic, the size, the morphology and the particle spacing of the metal nanoparticles can be finely adjusted, so that the enhancement of an SERS signal is ensured to reach the optimal strength, and the sensitivity of trace substance detection is improved.
Further, the organic combustible material in the first step is any combustible organic material capable of generating carbon black nano-structure, including alcohol, kerosene, candle and the like.
Further, the carrier substrate described in the first step includes a quartz plate, a silicon wafer, a silicon dioxide plate, stainless steel, an alumina substrate, and the like.
Further, the relative height of the flame and the carrier substrate in the first step is 0< d <7 cm; the deposition time is 10s-180 s.
Further, the noble metal of the second step can form an active hot spot, including gold nanoparticles, silver nanoparticles, or composite nanoparticles of the two.
Furthermore, the physical vapor deposition technique for depositing the metal film in the second step includes a magnetron sputtering method, an ion beam deposition method, an evaporation method, an atomic force deposition method, and a pulse deposition method.
Compared with the prior art, the invention has the beneficial effects that: the SERS active substrate with high repeatability, low cost, stable property, large-scale preparation and high sensitivity can be obtained on the carrying substrate by simple flame deposition and physical vapor deposition technology, and a simple, convenient and new way is provided for the preparation and application scientific research of the SERS active substrate.
Drawings
FIG. 1 is a schematic diagram of a carbon black production process in example 1;
FIG. 2 is a schematic diagram of a carbon black production process in example 2;
FIG. 3 is a top Scanning Electron Micrograph (SEM) of carbon black nanostructures in example 1;
FIG. 4 is a Scanning Electron Micrograph (SEM) of a cross section of a carbon black nanostructure in example 1;
fig. 5 is a top Scanning Electron Micrograph (SEM) of the SERS substrate prepared in example 1;
fig. 6 is a cross-sectional Scanning Electron Micrograph (SEM) of the SERS substrate prepared in example 1;
fig. 7 is a raman signal of R6G measured from the SERS substrate prepared in example 1;
fig. 8 is a raman signal of R6G measured with the SERS substrate prepared in example 2;
fig. 9 is a raman signal of R6G measured with the SERS substrate prepared in example 3;
fig. 10 is a raman signal of R6G measured with the SERS substrate prepared in example 4;
fig. 11 is a raman signal of R6G measured with the SERS substrate prepared in example 6;
fig. 12 is a raman signal of R6G measured with the SERS substrate prepared in example 10;
fig. 13 is a raman signal of R6G measured with the SERS substrate prepared in example 11;
fig. 14 is a raman signal of R6G measured from the SERS substrate prepared in example 14.
Detailed Description
As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source (such as an alcohol burner) and aligned with the center of the flame source, the flame source is ignited to start deposition for 10s-180s, then a three-dimensional porous carbon black nanostructure serving as a supporting film of an SERS substrate is obtained, a layer of noble metal thin film is deposited on the surface of the prepared carbon black structure by utilizing a physical vapor deposition technology, the thickness is 10nm-500nm, and finally the composite SERS substrate of carbon black/metal nanoparticles is obtained.
As shown in the attached figure 2, a carrying substrate and a mask are horizontally placed above a flame source (such as an alcohol burner) and aligned with the center of the flame source, the flame source is ignited and starts to deposit for 10s-180s, so that a three-dimensional porous carbon black nanostructure serving as a support film of an SERS substrate can be obtained, and then a layer of noble metal thin film with the thickness of 10nm-500nm is deposited on the surface of the prepared carbon black structure by utilizing a physical vapor deposition technology, so that the composite SERS substrate of carbon black/metal nanoparticles is finally obtained.
The invention may be understood more readily by reference to the following detailed description of illustrative embodiments and the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are intended to complete the disclosure and to inform those skilled in the art of the invention of the scope of the invention. The macrostructure of the three-dimensional porous carbon black nanometer structure can directly deposit the three-dimensional porous carbon black nanometer structure supporting body on a silicon chip by utilizing a flame source, and can also prepare the three-dimensional porous carbon black nanometer structure supporting body with different modes by utilizing mask plates with various specifications.
Examples 1
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in figure 1, a supporting substrate is horizontally placed above an alcohol lamp and aligned with the center of a flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, and then a three-dimensional porous carbon black nano structure serving as a supporting film of an SERS substrate can be obtained (figure 3 is a Scanning Electron Microscope (SEM) picture of the three-dimensional porous carbon black nano particle layer deposited by using a flame method in the example, as shown in the figure, the size distribution of the carbon black nano structure is uniform, and obvious hole structures are arranged in the carbon black nano structure), silver nano particles are deposited on the carbon black nano structure by using a magnetron sputtering instrument, the working current of the magnetron sputtering instrument is set to be 60mA, the working voltage is 40mV, the working power is 20W, the deposition time is 30min, and then the SERS substrate is obtained (figure 4 is an SEM picture obtained, as shown, the silver nanoparticles are relatively uniform in size and morphology, and also form a three-dimensional pore structure).
FIG. 7 is a Raman spectrum of rhodamine (biological stain, R6G) aqueous solution with different concentrations at a Raman excitation wavelength of 532.8nm by using the SERS substrate prepared in the example, and it can be seen that the detection concentration limit of the SERS substrate prepared in the example is lower than 10-11And the SERS characteristics are excellent.
EXAMPLES example 2
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in figure 2, a supporting substrate and a mask are horizontally placed above an alcohol lamp and aligned with the center of a flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm and starts to be deposited for 10s, and a support film with a modeled three-dimensional porous carbon black nanostructure as an SERS substrate is obtained as shown in the illustration in figure 2 (figure 3 is a Scanning Electron Microscope (SEM) of a three-dimensional porous carbon black nanoparticle layer deposited by using a flame method in the example, as shown in the figure, the size distribution of the carbon black nanostructure is uniform, and an obvious pore structure is formed in the carbon black nanostructure), silver nanoparticles are deposited on the carbon black nanostructure by using a magnetron sputtering instrument, the working current of the magnetron sputtering instrument is set to be 60mA, the working voltage is 40mV, the working power is 20W, and the deposition time is 30min, so as to obtain the SERS substrate (figure 4 is an SEM image obtained after silver nanoparticles are sputtered by using magnetron sputtering, as shown, the silver nanoparticles are relatively uniform in size and morphology, and also form a three-dimensional pore structure).
FIG. 8 is a Raman spectrum of an aqueous solution of rhodamine (biological stain, R6G) with different concentrations at a Raman excitation wavelength of 532.8nm using the SERS substrate prepared in the example, and it can be seen that the detection concentration limit of the SERS substrate prepared in the example is lower than 10-11And the SERS characteristics are excellent.
EXAMPLE 3
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. The carbon black is deposited by using the flame outer flame of kerosene combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position with the flame center d value of 5cm and starts to deposit for 50s, the three-dimensional porous carbon black nano structure is obtained and is used as a support film of an SERS substrate, silver nano particles are deposited on the carbon black nano structure by using a magnetron sputtering instrument, the working current of the magnetron sputtering instrument is set to be 60mA, the working voltage is set to be 40mV, the working power is set to be 20W, the deposition time is set to be 30min, the SERS substrate is obtained, the size and the form of the silver nano particles are uniform, and the three-dimensional hole structure is formed.
FIG. 9 is a Raman spectrum of different concentrations of rhodamine (biological stain, R6G) aqueous solution at a Raman excitation wavelength of 532.8nm with the SERS substrate prepared by the experiment, and it can be seen that the detection concentration limit of the SERS substrate prepared by the example is lower than 10-11And mol/L, the SERS characteristic is very excellent.
EXAMPLE 4
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by the flame envelope of a candle burning. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 1cm, deposition is started for 30s, the three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by using a magnetron sputtering instrument, the working current of the magnetron sputtering instrument is set to be 60mA, the working voltage is set to be 40mV, the working power is set to be 20W, the deposition time is set to be 30min, the SERS substrate is obtained, the size and the form of the silver nanoparticles are uniform, and the three-dimensional hole structure is formed.
FIG. 10 is a Raman spectrum of rhodamine (biological stain, R6G) aqueous solution with different concentrations at a Raman excitation wavelength of 532.8nm by using the SERS substrate prepared in the example, and it can be seen that the detection concentration limit of the SERS substrate prepared in the example is lower than 10-11mol/L, and figure 6 is a Raman spectrogram of different concentrations of rhodamine (biological stain, R6G) aqueous solution prepared by the SERS substrate prepared by the example at the wavelength of 532.8nm of Raman excitation light, and it can be known that the limit of detection concentration of the SERS substrate prepared by the example is lower than 10-11mol/L, and the SERS characteristic is very excellent.
EXAMPLE 5
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above an alcohol lamp and aligned with the center of a flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started for 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by utilizing an ion beam, the SERS substrate is obtained, a three-dimensional hole structure is formed, and excellent SERS characteristics can be shown.
EXAMPLE 6
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. The carbon black is deposited by using the flame outer flame of kerosene combustion. As shown in the attached figure 1, a supporting substrate is horizontally arranged above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 150s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by utilizing an ion beam, the SERS substrate is obtained, and a three-dimensional hole structure is formed.
FIG. 11 is a Raman spectrum of an aqueous solution of rhodamine (biological stain, R6G) with different concentrations at a Raman excitation wavelength of 532.8nm using the SERS substrate prepared in this example, and it can be seen that the detection concentration limit of the SERS substrate prepared in this example is lower than 10-10And mol/L, the SERS characteristic is very excellent.
EXAMPLES example 7
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by the flame envelope of a candle burning. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, the three-dimensional porous carbon black nanometer structure can be obtained and used as a supporting film of an SERS substrate, silver nanoparticles are deposited on the carbon black nanometer structure by utilizing an ion beam, the SERS substrate is obtained, the three-dimensional porous structure is formed, and the excellent SERS characteristics can be shown.
EXAMPLES example 8
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by evaporation, the SERS substrate is obtained, a three-dimensional hole structure is formed, and excellent SERS characteristics can be represented.
EXAMPLES example 9
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. The carbon black is deposited by using the flame outer flame of kerosene combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by evaporation, the SERS substrate is obtained, a three-dimensional hole structure is formed, and excellent SERS characteristics can be shown.
EXAMPLES 10
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by the flame envelope of a candle burning. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started for 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by evaporation, the SERS substrate is obtained, and a three-dimensional hole structure is formed.
FIG. 12 is a Raman spectrum of rhodamine (biological stain, R6G) aqueous solution with different concentrations at a Raman excitation wavelength of 532.8nm, and it can be seen that the detection concentration limit of the SERS substrate prepared by the example is lower than 10-10And mol/L, the SERS characteristic is very excellent.
EXAMPLES example 11
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started for 50s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by utilizing atomic force, the SERS substrate is obtained, and a three-dimensional hole structure is formed.
FIG. 13 is a Raman spectrum of an aqueous solution of rhodamine (biological stain, R6G) with different concentrations at a Raman excitation wavelength of 532.8nm using the SERS substrate prepared in this example, and it can be seen that the limit of detection concentration of the SERS substrate prepared in this example is lower than 10-11And mol/L, the SERS performance is excellent.
EXAMPLE 12
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. The carbon black is deposited by using the flame outer flame of kerosene combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by utilizing atomic force, the SERS substrate is obtained, a three-dimensional hole structure is formed, and excellent SERS characteristics can be shown.
EXAMPLES example 13
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by the flame envelope of a candle burning. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 100s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by utilizing atomic force, the SERS substrate is obtained, a three-dimensional hole structure is formed, and excellent SERS characteristics can be shown.
EXAMPLES example 14
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started for 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by a pulse method, the SERS substrate is obtained, and a three-dimensional hole structure is formed.
FIG. 14 is a Raman spectrum of an aqueous solution of rhodamine (biological stain, R6G) with different concentrations at a Raman excitation wavelength of 532.8nm using the SERS substrate prepared in this example, and it can be seen that the limit of detection concentration of the SERS substrate prepared in this example is lower than 10-11mol/LAnd the SERS characteristics are very excellent.
EXAMPLE 15
And (3) cleaning a supported quartz plate (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. The carbon black is deposited by using the flame outer flame of kerosene combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by a pulse method, the SERS substrate is obtained, a three-dimensional hole structure is formed, and excellent SERS characteristics can be shown.
EXAMPLE 16
And (3) washing a silicon dioxide carrying sheet (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by the flame envelope of a candle burning. As shown in the attached figure 1, a supporting substrate is horizontally placed above a flame source and aligned with the center of the flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, silver nanoparticles are deposited on the carbon black nano structure by a pulse method, the SERS substrate is obtained, a three-dimensional hole structure is formed, and excellent SERS characteristics can be shown.
EXAMPLE 17
The supported stainless steel (1cm x 1cm) is washed by acetone, alcohol and deionized water respectively and then dried for standby. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above an alcohol lamp and aligned with the center of a flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started for 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, gold nanoparticles are deposited on the carbon black nano structure by using a magnetron sputtering instrument, the working current of the magnetron sputtering instrument is set to be 60mA, the working voltage is set to be 40mV, the working power is set to be 20W, the deposition time is set to be 20min, the SERS substrate is obtained, and excellent SERS characteristics can be shown.
EXAMPLES example 18
And (3) cleaning a supported alumina substrate (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above an alcohol lamp and aligned with the center of a flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, gold nanoparticles are deposited on the carbon black nano structure by utilizing an ion beam, the SERS substrate is obtained, and excellent SERS characteristics can be shown.
EXAMPLE 19
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached drawing 1, a supporting substrate is horizontally placed above an alcohol lamp and aligned with the center of a flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, gold nanoparticles are deposited on the carbon black nano structure by evaporation, the SERS substrate is obtained, and excellent SERS characteristics can be shown.
EXAMPLES 20
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above an alcohol lamp and aligned with the center of a flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, gold nanoparticles are deposited on the carbon black nano structure by utilizing atomic force, the SERS substrate is obtained, and excellent SERS characteristics can be shown.
EXAMPLE 21
And (3) cleaning a supported silicon wafer (1cm by 1cm) by using acetone, alcohol and deionized water respectively, and drying for later use. Carbon black is deposited by using the flame out of alcohol combustion. As shown in the attached figure 1, a supporting substrate is horizontally placed above an alcohol lamp and aligned with the center of a flame source, the flame source is ignited, the supporting substrate is placed at the position where the d value of the flame center is 3cm, deposition is started, the time is 10s, a three-dimensional porous carbon black nano structure serving as a support film of an SERS substrate can be obtained, gold nanoparticles are deposited on the carbon black nano structure by a pulse method, the SERS substrate is obtained, and excellent SERS characteristics can be shown.
The above examples demonstrate that: by adopting the technical scheme provided by the invention, the simple and practical SERS substrate is designed and synthesized, the experimental period is obviously reduced, the consumption is low, and the sensitivity is high. While the foregoing examples have been described in order to facilitate a person of ordinary skill in the art to understand and practice the present invention. It will be readily apparent to those skilled in the art that various modifications to these examples can be made, and the generic principles described herein can be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make modifications and alterations to the present invention in light of the present disclosure.
Claims (10)
1. A preparation method of a surface-enhanced Raman scattering substrate is characterized by comprising the following steps:
the method comprises the following steps of firstly, depositing a three-dimensional porous carbon black nano structure on the surface of a carrying substrate by using a flame method to realize the construction of a three-dimensional porous carbon black nano particle structure body, which comprises the following specific steps: horizontally placing a carrying substrate above the combustible organic matter and aligning the carrying substrate with the center of the flame source, and defining the distance between the carrying substrate and the flame source as d; igniting the flame source, and regulating and controlling the distance d between the flame source and the supporting substrate to deposit a layer of three-dimensional porous carbon black nanostructure; the thickness of the three-dimensional porous carbon black nanostructure can be regulated and controlled according to the deposition time and the distance between the supporting substrate and the flame source;
secondly, the three-dimensional porous carbon black nanostructure obtained in the first step is used as a support film of the SERS substrate, and a noble metal nanoparticle layer with the thickness of 10-500nm is deposited on the surface of the three-dimensional porous carbon black nanostructure by adopting a physical vapor deposition method, so that a composite SERS substrate of carbon black/metal nanoparticles is constructed; the size of the noble metal nano particles can be regulated and controlled according to related parameters of physical vapor deposition.
2. A preparation method of a surface-enhanced Raman scattering substrate is characterized by comprising the following steps:
the method comprises the following steps of firstly, depositing a three-dimensional porous carbon black nano structure on the surface of a carrying substrate by using a flame method to realize the construction of a three-dimensional porous carbon black nano particle structure body, which comprises the following specific steps: horizontally placing a carrying substrate and a mask plate above the combustible organic matter and aligning the carrying substrate and the mask plate with the center of the flame source, wherein the mask plate is placed on the lower surface of the carrying substrate; igniting a flame source, and regulating and controlling the distance between the flame source and the supporting substrate to deposit a layer of modeled three-dimensional porous carbon black nanostructure; the thickness of the modeled three-dimensional porous carbon black nanostructure can be regulated and controlled according to the deposition time and the distance between the supporting substrate and the flame source;
secondly, the patterned three-dimensional porous carbon black nanostructure obtained in the first step is used as a support film of the SERS substrate, and a noble metal nanoparticle layer with the thickness of 10-500nm is deposited on the surface of the patterned three-dimensional porous carbon black nanostructure by adopting a physical vapor deposition method, so that a composite SERS substrate of carbon black/metal nanoparticles is constructed; the size of the noble metal nano particles can be regulated and controlled according to related parameters of physical vapor deposition.
3. The method of claim 1 or 2, wherein the distance between the flame source and the supporting substrate is 0< d <7 cm; the deposition time is 10s-180 s.
4. The method of claim 1 or 2, wherein the supporting substrate comprises quartz plate, silicon wafer, silicon dioxide plate, stainless steel and alumina substrate.
5. The method of claim 3, wherein the supporting substrate comprises quartz plate, silicon wafer, silicon dioxide plate, stainless steel and alumina substrate.
6. The method for preparing a substrate for enhancing surface raman scattering according to claim 1, 2 or 5, wherein the noble metal comprises gold nanoparticles, silver nanoparticles or composite nanoparticles of both.
7. The method as claimed in claim 3, wherein the noble metal comprises gold nanoparticles, silver nanoparticles or composite nanoparticles of the two.
8. The method as claimed in claim 4, wherein the noble metal comprises gold nanoparticles, silver nanoparticles or composite nanoparticles of the two.
9. The method for preparing a substrate with enhanced surface raman scattering according to claim 1, 2, 5, 7 or 8, wherein the physical vapor deposition technique for depositing the metal thin film comprises magnetron sputtering, ion beam deposition, evaporation, atomic force deposition, and pulse deposition.
10. The method for preparing a substrate with enhanced surface raman scattering according to claim 3, wherein the physical vapor deposition technique for depositing the metal thin film comprises magnetron sputtering, ion beam deposition, evaporation, atomic force deposition, and pulse deposition.
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