CN111830004A - Method for detecting Raman signal - Google Patents
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- CN111830004A CN111830004A CN201910313500.3A CN201910313500A CN111830004A CN 111830004 A CN111830004 A CN 111830004A CN 201910313500 A CN201910313500 A CN 201910313500A CN 111830004 A CN111830004 A CN 111830004A
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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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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
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- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to the technical field of laser Raman detection, in particular to a method for detecting Raman signals, which comprises the following steps: dripping the mixed solution on a chip to be detected, wherein metal nano particles or metal nano wires are deposited on a substrate of the chip to be detected, and the mixed solution is specifically an electrolyte solution containing molecules to be detected; placing the chip to be detected dropwise with the mixed solution on a lower electrode plate between an upper electrode plate and a lower electrode plate, and applying voltage to the upper electrode plate and the lower electrode plate; the chip to be detected is detected through the Raman detector, the Raman signal of the chip to be detected is obtained, molecules in an acidic or alkaline solution in the dropwise added mixed solution are ionized under the action of an electrolyte solution to carry charges, and under the action of an electric field, the molecules can move along the opposite direction of an electric field line or an electric field line, so that a large number of molecules to be detected are closer to the chip to be detected, the number of the molecules is larger, the Raman signal is stronger, and the Raman detector can detect the enhanced Raman signal.
Description
Technical Field
The invention relates to the technical field of laser Raman detection, in particular to a method for detecting Raman signals
Background
Surface Enhanced Raman Scattering (SERS) amplifies inherently weak raman signals by preparing plasma nanostructures, and identification of material components is usually performed by raman spectroscopy, but since many chemical substances cannot directly detect signals by raman spectroscopy, the signal-to-noise ratio of raman signals needs to be improved by raman enhancement, thereby detecting the raman signals of the substances to be detected.
Because the surface enhanced raman scattering technology has extremely high sensitivity, unique fingerprint spectrum, non-destructive data collection and other characteristics become one of the most promising analysis means at present. At present, the surface enhanced Raman scattering technology realizes the enhancement of Raman signals by preparing various substrate structures, but the preparation of the highly sensitive substrate structure has the disadvantages of complex process, poor uniformity, high cost and difficult batch production.
Therefore, how to enhance the raman signal by a simple method is a technical problem to be solved urgently at present.
Disclosure of Invention
In view of the above, the present invention has been made to provide a method of detecting raman signals that overcomes or at least partially solves the above mentioned problems.
The embodiment of the invention provides a method for detecting Raman signals, which comprises the following steps:
dripping the mixed solution on a chip to be detected, wherein metal nano particles or metal nano wires are deposited on a substrate of the chip to be detected, and the mixed solution is specifically an electrolyte solution containing molecules to be detected;
placing the chip to be detected dropwise with the mixed solution on a lower electrode plate between an upper electrode plate and a lower electrode plate, and applying voltage to the upper electrode plate and the lower electrode plate;
and detecting the chip to be detected by a Raman detector to obtain a Raman signal of the chip to be detected.
Further, the detecting the chip to be detected by a raman detector to obtain a raman signal of the chip to be detected specifically includes:
and after the voltages are applied to the upper electrode plate and the lower electrode plate, detecting the chip to be detected by a Raman detector to obtain a Raman signal of the chip to be detected.
Further, the detecting the chip to be detected by a raman detector to obtain a raman signal of the chip to be detected specifically includes:
and in the process of applying voltage to the upper electrode plate and the lower electrode plate, detecting the chip to be detected by a Raman detector to obtain a Raman signal of the chip to be detected.
Further, the substrate is made of any one of the following materials:
silicon, silicon dioxide, black silicon, a porous alumina template, titanium dioxide, graphene, non-woven fabric, polymethyl methacrylate and adhesive tape.
Further, the metal nanoparticles are specifically single metal nanoparticles and/or alloy nanoparticles:
the single metal nano particle is specifically a gold nano particle, a silver nano particle or a copper nano particle;
the alloy nano-particles comprise at least two metals of gold, silver and copper;
the metal nanowire is specifically a gold nanowire, a copper nanowire or a silver nanowire.
Further, the shape of the metal nanoparticles is specifically any one of the following:
star, hexagon, and circle.
Further, the molecule to be detected is specifically a molecule of any one of the following substances:
R6G, malachite green and methylene blue.
Further, the electrolyte solution is specifically any one of the following:
dilute hydrochloric acid, dilute sulfuric acid, dilute phosphoric acid and sodium chloride.
Further, the voltage applied when the voltage is applied to the upper and lower electrode plates ranges from 1V to 3V, and the time length of the voltage application ranges from 10min to 30 min.
Further, the upper and lower electrode plates are made of any one of the following materials:
copper, iron, aluminum, and titanium oxide.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides a method for detecting Raman signals, which comprises dripping a mixed solution on a chip to be detected, depositing metal nano particles or metal nano wires on a substrate of the chip to be detected, wherein the mixed solution is an electrolyte solution containing molecules to be detected, then placing the chip to be detected with the dripped mixed solution on a lower electrode plate between an upper electrode plate and a lower electrode plate, applying voltage on the upper electrode plate and the lower electrode plate, detecting the chip to be detected through a Raman detector to obtain the Raman signals of the chip to be detected, applying voltage on the upper electrode plate and the lower electrode plate to generate an electric field, so that the molecules to be detected are ionized under the action of the electrolyte solution to carry charges, and under the action of the electric field of the upper electrode plate and the electric field of the lower electrode plate, the molecules can move along the electric field lines or the opposite directions of the electric field lines, the distance between the molecules to be detected and the chip to be detected is reduced through the action of an electric field, a large number of molecules to be detected are gathered in the preset distance range of the chip to be detected, the Raman signal is enhanced through a physical enhancement mechanism, meanwhile, the distance between the molecules to be detected and the chip to be detected is reduced under the action of the electric field, the molecules to be detected and the metal nano particles on the substrate of the chip to be detected form bonds or generate charge transfer, the Raman signal is enhanced through a chemical enhancement mechanism, and the Raman detector can detect the enhanced Raman signal of the chip to be detected.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 is a schematic flow chart illustrating steps of a method for detecting a raman signal according to a first embodiment of the present invention;
fig. 2 is a schematic structural diagram of an apparatus for detecting a raman signal according to a first embodiment of the present invention;
fig. 3 is a flow chart illustrating steps of a method for detecting a raman signal according to a second embodiment of the present invention;
fig. 4 is a schematic structural diagram of an apparatus for detecting a raman signal according to a second embodiment of the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The raman scattering effect is a very weak process, typically with an intensity of only about 10 of the incident intensity-10Therefore, the raman signal is weak and cannot be directly detected by the raman detector.
The embodiment of the invention provides a method for detecting Raman signals, which comprises the following steps: dripping the mixed solution on a chip to be detected, wherein metal nano particles or metal nano wires are deposited on a substrate of the chip to be detected, and the mixed solution is specifically an electrolyte solution containing molecules to be detected; placing the chip to be detected dropwise with the mixed solution on a lower electrode plate between an upper electrode plate and a lower electrode plate, and applying voltage to the upper electrode plate and the lower electrode plate; and detecting the chip to be detected by a Raman detector to obtain a Raman signal of the chip to be detected.
The method for detecting the Raman signal comprises two implementation modes, wherein the first mode is that the chip to be detected is detected through a Raman detector to obtain the Raman signal of the chip to be detected, and the method specifically comprises the following steps:
after voltage is applied to the upper electrode plate and the lower electrode plate, the chip to be detected is detected through a Raman detector, and a Raman signal of the chip to be detected is obtained.
The other method is to detect the chip to be detected through a raman detector to obtain a raman signal of the chip to be detected, and specifically comprises the following steps:
and in the process of applying voltage to the upper electrode plate and the lower electrode plate, detecting the chip to be detected by a Raman detector to obtain a Raman signal of the chip to be detected.
The details are described in detail by the following examples.
Example one
An embodiment of the present invention provides a method for detecting a raman signal, as shown in fig. 1, including: s101, dripping a mixed solution on a chip to be detected, wherein metal nano particles or metal nano wires are deposited on a substrate of the chip to be detected, and the mixed solution is an electrolyte solution containing molecules to be detected; s102, placing the chip to be detected, in which the mixed solution is dripped, on a lower electrode plate between an upper electrode plate and a lower electrode plate, and applying voltage to the upper electrode plate and the lower electrode plate; s103, after the upper electrode plate and the lower electrode plate are applied with voltage, the chip to be detected is detected through a Raman detector, and a Raman signal of the chip to be detected is obtained.
In an alternative embodiment, metal nanoparticles or metal nanowires are deposited on the substrate of the chip to be detected.
The substrate is made of any one of the following materials: silicon, silicon dioxide, black silicon, a porous alumina template, titanium dioxide, graphene, non-woven fabric, polymethyl methacrylate and adhesive tape. The embodiments of the present invention are not limited to the above materials.
The metal nanoparticles are specifically single metal nanoparticles and/or alloy nanoparticles. Wherein the single metal nanoparticle is specifically a gold nanoparticle, a silver nanoparticle, or a copper nanoparticle; the alloy nano-particle comprises at least two metals of gold, silver and copper. The alloy nanoparticles include gold and silver alloy nanoparticles, gold and copper alloy nanoparticles, silver and copper alloy nanoparticles, and gold, silver and copper alloy nanoparticles.
For example, gold nanoparticles, or gold and copper alloy nanoparticles, or both gold and copper alloy nanoparticles may be deposited on the substrate.
In addition, the metal nanowire is any one of a gold nanowire, a silver nanowire and a copper nanowire. Therefore, any one of gold nanowires, silver nanowires, and copper nanowires may also be deposited on the substrate.
The shape of the metal nano-particle is specifically any one of the following: star, flower, hexagon, and circle. Wherein, the star can be a pentagram, a hexagram and the like. The pattern can be a shape with uniform edge angles.
In an alternative embodiment, the molecule to be detected is specifically a molecule of any one of the following substances: R6G, malachite green and methylene blue. Preferred is R6G, the R6G can be adjusted to a solution, wherein the concentration of the solution is 10-5M, the concentration is not particularly limited.
In the embodiment of the present invention, the electrolyte solution is specifically any one of the following: dilute hydrochloric acid, dilute sulfuric acid, and sodium chloride in dilute phosphoric acid. Dilute hydrochloric acid is preferred.
After dropping the mixed solution onto the chip to be tested in S101, S102 is performed, and the chip to be tested with the mixed solution dropped thereon is placed on the lower electrode plate between the upper and lower electrode plates, and a voltage is applied to the upper and lower electrode plates. As shown in FIG. 2, the chip A to be tested to which the mixed solution was added was placed between the upper and lower electrode plates L1 and L2, and a voltage was applied to the upper and lower electrode plates L1 and L2 by a power source.
Specifically, the upper and lower electrode plates are made of conductive materials such as copper, aluminum, iron or titanium oxide. Copper is preferably used.
The molecules to be detected are ionized under the action of the electrolyte solution and carry charges, the molecules can move along the electric field line or the opposite direction of the electric field line under the action of the electric fields of the upper electrode plate and the lower electrode plate, so that a large number of molecules are gathered on the chip to be detected.
Therefore, in the process of S103, after applying a voltage to the upper and lower electrode plates, the chip to be detected is detected by the raman detector, so as to obtain a raman signal of the chip to be detected. After a preset duration of voltage is applied, the Raman signal enhanced by the chip to be detected can be detected and obtained by the Raman detector.
In an optional embodiment, the voltage applied to the upper and lower electrode plates ranges from 1V to 3V, specifically 1V, 2V, and 3V, and the time duration of the applied voltage ranges from 10min to 30min, specifically 10min, 20min, and 30 min. Preferably, 3V voltage is applied to the upper electrode plate and the lower electrode plate for 30min, after the voltage is applied for 30min, the chip to be detected is taken out from between the upper electrode plate and the lower electrode plate and dried by blowing, specifically, the drying mode can be natural air drying or nitrogen drying, and then the chip to be detected is detected by the Raman detector, so that the enhanced Raman signal is obtained.
When the Raman detector detects a Raman signal, laser with the incident wavelength of 532nm is adopted to irradiate the surface of the chip to be detected, a scattered Raman spectrum is detected, and an enhanced Raman signal is obtained.
Example two
An embodiment of the present invention further provides a method for detecting a raman signal, as shown in fig. 3, including:
s301, dripping the mixed solution on a chip to be detected, wherein metal nano particles or metal nano wires are deposited on a substrate of the chip to be detected, and the mixed solution is specifically an electrolyte solution containing molecules to be detected
S302, placing the chip to be detected dropwise with the mixed solution on a lower electrode plate between an upper electrode plate and a lower electrode plate, and applying voltage to the upper electrode plate and the lower electrode plate;
and S303, detecting the chip to be detected by a Raman detector in the process of applying voltage to the upper electrode plate and the lower electrode plate to obtain a Raman signal of the chip to be detected.
The method is characterized in that a Raman detector is adopted to carry out real-time online detection while voltage is applied. Therefore, the upper electrode plate in the upper electrode plate and the lower electrode plate is provided with the light transmission area, so that laser emitted by the laser emitting end can penetrate through the light transmission area to reach the chip to be detected, meanwhile, scattered light of the chip to be detected can reach the receiver through the light transmission area, detection of the chip to be detected by the Raman detector is achieved, and an enhanced Raman signal is obtained.
The transparent area of the upper electrode plate is formed by forming an opening in the upper electrode plate or directly using a transparent conductive material for the upper electrode plate, the upper and lower electrode plates are formed by using a conductive material such as copper, aluminum, iron, titanium oxide, preferably titanium oxide, the entire upper electrode plate can be made of a transparent titanium oxide material, the upper electrode plate can be made of a conductive material such as copper, aluminum, iron, etc., the upper electrode plate is formed with an opening, and a transparent conductive plate, for example, titanium oxide (TiO) is used in the opening2). As shown in fig. 4, in order to provide an opening in the upper electrode plate L1, a transparent conductive plate is used in the opening, and a chip a to be tested is placed on the lower electrode plate L2 between the upper and lower electrode plates L1 and L2.
In an alternative embodiment, the substrate of the chip to be detected is made of any one of the following materials:
silicon, silicon dioxide, black silicon, a porous alumina template, titanium dioxide, graphene, non-woven fabric, polymethyl methacrylate and adhesive tape.
In an alternative embodiment, the metal nanoparticles are in particular single metal nanoparticles and/or alloy nanoparticles:
the single metal nano particle is specifically a gold nano particle, a silver nano particle or a copper nano particle;
the alloy nano-particles comprise at least two metals of gold, silver and copper;
the metal nanowire is specifically a gold nanowire, a copper nanowire or a silver nanowire.
In an alternative embodiment, the metal nanoparticles are specifically in the shape of any one of the following:
star, hexagon, and circle. Patterns, particularly shapes with uniform edge angles, can also be adopted.
In an alternative embodiment, the molecule to be detected is specifically a molecule of any one of the following substances:
R6G, malachite green and methylene blue.
In an alternative embodiment, the electrolyte solution is specifically any one of the following:
dilute hydrochloric acid, dilute sulfuric acid, dilute phosphoric acid and sodium chloride.
In an optional embodiment, the voltage applied to the upper and lower electrode plates ranges from 1V to 3V, and the voltage is applied for 10min to 30 min.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the invention provides a method for detecting Raman signals, which comprises dripping a mixed solution on a chip to be detected, depositing metal nano particles or metal nano wires on a substrate of the chip to be detected, wherein the mixed solution is an electrolyte solution containing molecules to be detected, then placing the chip to be detected with the dripped mixed solution on a lower electrode plate between an upper electrode plate and a lower electrode plate, applying voltage on the upper electrode plate and the lower electrode plate, detecting the chip to be detected through a Raman detector to obtain the Raman signals of the chip to be detected, applying voltage on the upper electrode plate and the lower electrode plate to generate an electric field, so that the molecules to be detected are ionized under the action of the electrolyte solution to carry charges, and under the action of the electric field of the upper electrode plate and the electric field of the lower electrode plate, the molecules can move along the electric field lines or the opposite directions of the electric field lines, the distance between the molecules to be detected and the chip to be detected is reduced through the action of an electric field, a large number of molecules to be detected are gathered in the preset distance range of the chip to be detected, the Raman signal is enhanced through a physical enhancement mechanism, meanwhile, the distance between the molecules to be detected and the chip to be detected is reduced under the action of the electric field, the molecules to be detected and the metal nano particles on the substrate of the chip to be detected form bonds or generate charge transfer, the Raman signal is enhanced through a chemical enhancement mechanism, and the Raman detector can detect the enhanced Raman signal of the chip to be detected.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method of detecting raman signals, comprising:
dripping the mixed solution on a chip to be detected, wherein metal nano particles or metal nano wires are deposited on a substrate of the chip to be detected, and the mixed solution is specifically an electrolyte solution containing molecules to be detected;
placing the chip to be detected dropwise with the mixed solution on a lower electrode plate between an upper electrode plate and a lower electrode plate, and applying voltage to the upper electrode plate and the lower electrode plate;
and detecting the chip to be detected by a Raman detector to obtain a Raman signal of the chip to be detected.
2. The method according to claim 1, wherein the detecting the chip to be detected by a raman detector to obtain the raman signal of the chip to be detected specifically comprises:
and after the voltages are applied to the upper electrode plate and the lower electrode plate, detecting the chip to be detected by a Raman detector to obtain a Raman signal of the chip to be detected.
3. The method according to claim 1, wherein the detecting the chip to be detected by a raman detector to obtain the raman signal of the chip to be detected specifically comprises:
and in the process of applying voltage to the upper electrode plate and the lower electrode plate, detecting the chip to be detected by a Raman detector to obtain a Raman signal of the chip to be detected.
4. The method of claim 1, wherein the substrate is made of any one of the following materials:
silicon, silicon dioxide, black silicon, a porous alumina template, titanium dioxide, graphene, non-woven fabric, polymethyl methacrylate and adhesive tape.
5. The method according to claim 1, wherein the metal nanoparticles are in particular single metal nanoparticles and/or alloy nanoparticles:
the single metal nano particle is specifically a gold nano particle, a silver nano particle or a copper nano particle;
the alloy nano-particles comprise at least two metals of gold, silver and copper;
the metal nanowire is specifically a gold nanowire, a copper nanowire or a silver nanowire.
6. The method of claim 1, wherein the metal nanoparticles are shaped specifically as any one of:
star, hexagon, and circle.
7. The method of claim 1, wherein the molecule to be detected is a molecule of any one of the following:
R6G, malachite green and methylene blue.
8. The method of claim 1, wherein the electrolyte solution is specifically any one of:
dilute hydrochloric acid, dilute sulfuric acid, dilute phosphoric acid and sodium chloride.
9. The method according to claim 1, wherein the voltage is applied to the upper and lower electrode plates in a range of 1V to 3V for a period of 10min to 30 min.
10. The method of claim 1, wherein the upper and lower electrode plates are made of any one of the following materials:
copper, iron, aluminum, and titanium oxide.
Priority Applications (1)
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