CN110082341B - Preparation of SERS substrate based on nanosphere etching and application of SERS substrate in explosive TNT detection - Google Patents
Preparation of SERS substrate based on nanosphere etching and application of SERS substrate in explosive TNT detection Download PDFInfo
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Abstract
The invention discloses preparation of an SERS substrate based on nanosphere etching and application of the SERS substrate in explosive TNT detection, relates to the field of surface enhanced Raman spectroscopy detection, and solves the problem that direct trace detection is difficult to perform due to small Raman scattering cross section of explosive TNT, and the following scheme is provided, and comprises the following steps: s1, spin coating of a monolayer polystyrene microsphere on a PET film: the PET film is first hydrophilized, and then the PS ball stock solution is centrifuged and transferred to a container containing the components in a volume ratio of 2: 1, and finally adjusting the PS solution concentration to 2.5 w/v%, the surfactant TX-100 was added to the final mixture at 0.5 vol%, and then a drop of PS solution having a volume of about 8 μ l was spin-coated on a pure PET film. The invention realizes rapid, high-efficiency and nondestructive detection, does not need professional operation, has simple detection operation process, adopts an indirect detection mode and can reach lower detection limit.
Description
Technical Field
The invention relates to the field of surface-enhanced Raman spectrum detection, in particular to preparation of a SERS substrate based on nanosphere etching and application of the SERS substrate in explosive TNT detection.
Background
Surface-Enhanced Raman Spectroscopy (Surface-Enhanced Raman Spectroscopy) is used as a high-sensitivity detection material tool, and Fleischmann et al firstly obtains a high-quality Raman spectrum of a monomolecular layer pyridine molecule adsorbed on the Surface of a silver electrode after roughening the Surface of the smooth silver electrode in 1974. Fleishmann, however, believes that this is due to the roughening of the electrode surface, the increase in the actual surface area of the electrode and the increase in the amount of adsorbed pyridine molecules, without realizing the Raman spectra of the adsorbed molecules by the roughened surfaceEnhancement of the signal. Until 1977, the two research groups of Van Duyne and Creighton independently found that the Raman signal of each pyridine molecule adsorbed on the surface of the rough silver electrode is about 10 times stronger than that of a single pyridine molecule in the solution6It is pointed out that this is a surface enhancing effect associated with rough surfaces, known as SERS effect. The SERS detection mode overcomes the contact detection of the traditional chemical detection mode, realizes the detection of harmless and trace substances, and has the advantages of rapid detection speed, simplified sample pretreatment operation, realization of on-site timely detection, obvious spectrogram reaction information and the like. With the further development of science and technology, the new generation of raman spectroscopy detection device is diversified, portable and intelligent, has become a powerful means for analyzing and detecting substances, and is widely introduced in various industrial fields.
Trinitrotoluene (TNT) is a colorless or light yellow crystal, odorless, hygroscopic, has a melting point of 354K (80.9 ℃), is explosive and is one of the common explosive components. Trinitrotoluene is moderately toxic and can invade through the skin, respiratory tract and digestive tract, and the main harm is chronic poisoning and dermatitis caused by local skin irritation. TNT is also an important component of various explosives, and the main explosive in our country is still TNT at present, so that the detection of TNT is the main direction for detecting explosives. Because the production, preparation, transportation and use of TNT all cause that a small amount of TNT exists in the natural environment, the TNT can cause serious pollution to the environment, in particular to soil and water resources.
Trace explosives detection techniques are primarily intended to detect traces of explosives particles remaining in vapor emitted by explosives and traces remaining on persons or objects that have come into contact with the explosives. At present, the detection methods of trace explosives mainly comprise ion mobility spectrometry, chemiluminescence, gas chromatography, infrared spectrometry, mass spectrometry and the like. Because the detection technology is not suitable for field detection, a large amount of pretreatment preparation needs to be carried out on a test sample, and a sample for nondestructive detection cannot be realized; or the detection equipment is expensive and is not suitable for comprehensive popularization. The Raman detection technology is an ideal detection technology due to the characteristics of quick detection and nondestructive detection. Due to the fact that the Raman scattering cross section of the TNT molecule is small, a spectrogram with low concentration is difficult to detect through direct detection, and the TNT molecule cannot be effectively connected with the gold and silver nanoparticles, a direct detection mode cannot be adopted, a Raman substrate for detection needs to be modified, so that the Raman substrate can effectively adsorb more TNT molecules, and the level of trace detection is achieved. Commonly used modifying reagents comprise cysteine, polydiacetylene, p-mercaptoaniline and the like, and the modifying reagents form a complex with TNT molecules so as to facilitate detection and determination.
The reactive ion etching technology is a dry etching technology with strong anisotropy and high selectivity. The method is characterized in that molecular gas plasma is utilized to etch in a vacuum system, ion-induced chemical reaction is utilized to realize anisotropic etching, namely ion energy is utilized to form an easily etched damage layer on the surface of an etched layer and promote chemical reaction, and ions can also remove surface products to expose a clean etched surface.
Disclosure of Invention
The invention aims to solve the problem that direct trace detection is difficult to carry out due to a small Raman scattering cross section of explosive TNT, and provides preparation of a SERS substrate based on nanosphere etching and application of the SERS substrate in explosive TNT detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
preparation of SERS substrate based on nanosphere etching and application of SERS substrate in explosive TNT detection comprise the following steps:
s1, spin coating of a monolayer polystyrene microsphere on a PET film: the PET film is first hydrophilized, and then the PS ball stock solution is centrifuged and transferred to a container containing the components in a volume ratio of 2: 1, and finally adjusting the PS solution concentration to 2.5 w/v%, adding the surfactant TX-100 to the final mixture at 0.5 vol%, then spin-coating a drop of PS solution having a volume of about 8 μ l on a pure PET film, spinning at 650 rpm for 15 seconds, followed by 1000 rpm for 1 second to remove excess liquid, and keeping the film in a heater for several minutes to dry the solvent, thus obtaining a PET film having a monolayer of PS spheres;
s2, reactive ion etching: placing the PET film with the single-layer PS balls in an etching cavity of a reactive ion etching machine for etching, adjusting the etching time to be 5min, and finally obtaining a periodic array containing the nanocones on the surface of the PET film to obtain a periodic nanocone array film substrate;
s3, electron beam deposition of gold nanoparticles: performing gold plating on the obtained periodic nanocone array film substrate in an electron beam deposition system at the speed of 0.02-0.03nm/s to finally obtain a Raman substrate with the thickness of gold nanoparticles of 30 nm;
s4, modification of PET film substrate: dissolving 4-aminothiophenol in an ethanol solution with the concentration of 10-5mol/L to serve as a 4-aminothiophenol original solution, taking a certain amount of the 4-aminothiophenol original solution, using ethanol as a solvent to dilute the solution to 10-7mol/L, completely immersing the gold-plated Raman substrate in the 10-7 mol/L4-aminothiophenol solution, soaking the solution for 10 hours at normal temperature, taking the solution out, continuously washing the solution for three times by using deionized water to wash away 4-aminothiophenol molecules which are not connected to the Raman substrate, washing the molecules for 10 seconds each time, and drying the molecules at room temperature;
s5, synthesis of silver nanoparticles: firstly, adding 10ml of 9mg/ml silver nitrate solution into 490ml of deionized water, boiling at the speed of 550r/min of magneton rotation speed, then slowly dropwise adding 10ml of 1% sodium citrate solution by mass fraction, and continuously keeping the boiling state for 1 hour after the solution turns to grey brown;
s6, surface modification of silver nanoparticles: adding 100ul of 10-4 mol/L4-aminothiophenol solution into 900ul of silver colloid, oscillating for one hour in an oscillator to achieve the effect of fully adsorbing 4-aminothiophenol molecules and silver nanoparticles, wherein the 4-aminothiophenol molecules and the silver nanoparticles form S-Ag bonds with strong interaction;
s7, linkage of TNT molecule: soaking the Raman substrate soaked in 10-7 mol/L4-aminothiophenol solution in TNT ethanol solution with different concentrations for 10h, taking out and drying at room temperature;
and S8, Raman detection.
Preferably, the raman detection in step S8 includes the following steps:
s81, verifying the substrate effect, namely dissolving R6G molecules in ethanol to prepare a mother solution, diluting the mother solution into solutions to be detected with different concentrations by using the ethanol, soaking the gold-plated Raman substrate in R6G solutions with different concentrations to connect the molecules R6G of the substance to be detected on the surface of the Raman substrate, and verifying the Raman effect of the prepared substrate by using Raman spectrum obtained by Raman measurement;
s82, verifying the TNT effect, namely respectively detecting three samples, namely soaking the samples in 10-7 mol/L4-aminothiophenol solution for 10h to obtain a Raman substrate, soaking the samples in 10-7 mol/L4-aminothiophenol solution for 10h to obtain a Raman substrate, taking out the Raman substrate and washing the Raman substrate for 3 times, soaking the Raman substrate in 4-aminothiophenol modified silver colloid for 10h, taking out the Raman substrate and washing the Raman substrate, drying the Raman substrate at room temperature to be tested, soaking the Raman substrate in 10-7 mol/L4-aminothiophenol solution for 10h, taking out the Raman substrate and washing the Raman substrate for 3 times, soaking the Raman substrate in 10-5mol/L TNT solution for 10h, taking out the Raman substrate and washing the Raman substrate for 3 times, finally soaking the Raman substrate in 4-aminothiophenol modified silver colloid for 10h, taking out and washing the Raman substrate for 3 times, and drying the Raman substrate at room temperature to be tested;
s83, TNT gradient concentration, namely soaking the Raman substrate in 10-7 mol/L4-aminothiophenol solution for 10h, taking out and washing, then respectively soaking in 10-8-10-13 mol/L TNT solution for 10h, taking out and drying, finally soaking in 4-aminothiophenol modified silver colloid for 10h, taking out and washing for 3 times, removing free molecules, and drying at room temperature to be tested;
and S84, verifying the effect of the substrate and the TNT by using a Raman spectrometer to control the Raman spectrum of the sample.
Preferably, the hydrophilic treatment of the PET film in the step S1 includes cutting the PET film into a square of 2.0 × 2.0 cm, then ultrasonically cleaning the surface with ethanol and deionized water in sequence, taking out the surface after fifteen minutes, then blow-drying the surface with nitrogen, then putting the surface into a plasma cleaner to clean for 3 minutes to make the surface of the PET film hydrophilic, and performing plasma cleaning for 3 minutes after the PET film is dried at room temperature.
Preferably, the raman spectrometer is a confocal raman spectrometer LabRAM HR Evolution type confocal raman spectrometer, the parameter of the spectrometer is set to be 633nm of excitation light source, the laser power is 2.5-5mW, the integration time is 10s, and the integration times is 3 times.
Preferably, the model of the reactive ion etcher is ME-3A.
The invention has the beneficial effects that:
1. the invention realizes rapid, high-efficiency and nondestructive detection, does not need professional operation and has simple detection operation process.
2. And a lower detection limit can be reached by adopting an indirect detection mode.
Drawings
FIG. 1 is a schematic representation of the TNT molecule junction.
Fig. 2 is an SEM image of a flexible substrate.
Fig. 3 is a raman spectrum of R6G measured on a flexible substrate.
FIG. 4 is a graph of the uniformity and reproducibility of the flexible substrate.
Fig. 5 is a TNT concentration gradient raman spectrum and a corresponding linear regression curve thereof.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1-5, preparation of a SERS substrate based on nanosphere etching and application thereof in explosive TNT detection include the following steps:
s1, spin coating of a monolayer polystyrene microsphere on a PET film: the PET film is first hydrophilized, and then the PS ball stock solution is centrifuged and transferred to a container containing the components in a volume ratio of 2: 1, and finally adjusting the PS solution concentration to 2.5 w/v%, adding the surfactant TX-100 to the final mixture at 0.5 vol%, then spin-coating a drop of PS solution having a volume of about 8 μ l on a pure PET film, spinning at 650 rpm for 15 seconds, followed by 1000 rpm for 1 second to remove excess liquid, and keeping the film in a heater for several minutes to dry the solvent, thus obtaining a PET film having a monolayer of PS spheres;
s2, reactive ion etching: placing the PET film with the single-layer PS balls in an etching cavity of a reactive ion etching machine for etching, adjusting the etching time to be 5min, and finally obtaining a periodic array containing the nanocones on the surface of the PET film to obtain a periodic nanocone array film substrate;
s3, electron beam deposition of gold nanoparticles: performing gold plating on the obtained periodic nanocone array film substrate in an electron beam deposition system at the speed of 0.02-0.03nm/s to finally obtain a Raman substrate with the thickness of gold nanoparticles of 30 nm;
s4, modification of PET film substrate: dissolving 4-aminothiophenol in an ethanol solution with the concentration of 10-5mol/L to serve as a 4-aminothiophenol original solution, taking a certain amount of the 4-aminothiophenol original solution, using ethanol as a solvent to dilute the solution to 10-7mol/L, completely immersing the gold-plated Raman substrate in the 10-7 mol/L4-aminothiophenol solution, soaking the solution for 10 hours at normal temperature, taking the solution out, continuously washing the solution for three times by using deionized water to wash away 4-aminothiophenol molecules which are not connected to the Raman substrate, washing the molecules for 10 seconds each time, and drying the molecules at room temperature;
s5, synthesis of silver nanoparticles: firstly, adding 10ml of 9mg/ml silver nitrate solution into 490ml of deionized water, boiling at the speed of 550r/min of magneton rotation speed, then slowly dropwise adding 10ml of 1% sodium citrate solution by mass fraction, and continuously keeping the boiling state for 1 hour after the solution turns to grey brown;
s6, surface modification of silver nanoparticles: adding 100ul of 10-4 mol/L4-aminothiophenol solution into 900ul of silver colloid, oscillating for one hour in an oscillator to achieve the effect of fully adsorbing 4-aminothiophenol molecules and silver nanoparticles, wherein the 4-aminothiophenol molecules and the silver nanoparticles form S-Ag bonds with strong interaction;
s7, linkage of TNT molecule: soaking the Raman substrate soaked in 10-7 mol/L4-aminothiophenol solution in TNT ethanol solution with different concentrations for 10h, taking out and drying at room temperature;
and S8, Raman detection.
In this embodiment, the raman detection in step S8 includes the steps of:
s81, verifying the substrate effect, namely dissolving R6G molecules in ethanol to prepare a mother solution, diluting the mother solution into solutions to be detected with different concentrations by using the ethanol, soaking the gold-plated Raman substrate in R6G solutions with different concentrations to connect the molecules R6G of the substance to be detected on the surface of the Raman substrate, and verifying the Raman effect of the prepared substrate by using Raman spectrum obtained by Raman measurement;
s82, verifying the TNT effect, namely respectively detecting three samples, namely soaking the samples in 10-7 mol/L4-aminothiophenol solution for 10h to obtain a Raman substrate, soaking the samples in 10-7 mol/L4-aminothiophenol solution for 10h to obtain a Raman substrate, taking out the Raman substrate and washing the Raman substrate for 3 times, soaking the Raman substrate in 4-aminothiophenol modified silver colloid for 10h, taking out the Raman substrate and washing the Raman substrate, drying the Raman substrate at room temperature to be tested, soaking the Raman substrate in 10-7 mol/L4-aminothiophenol solution for 10h, taking out the Raman substrate and washing the Raman substrate for 3 times, soaking the Raman substrate in 10-5mol/L TNT solution for 10h, taking out the Raman substrate and washing the Raman substrate for 3 times, finally soaking the Raman substrate in 4-aminothiophenol modified silver colloid for 10h, taking out and washing the Raman substrate for 3 times, and drying the Raman substrate at room temperature to be tested;
s83, TNT gradient concentration, namely soaking the Raman substrate in 10-7 mol/L4-aminothiophenol solution for 10h, taking out and washing, then respectively soaking in 10-8-10-13 mol/L TNT solution for 10h, taking out and drying, finally soaking in 4-aminothiophenol modified silver colloid for 10h, taking out and washing for 3 times, removing free molecules, and drying at room temperature to be tested;
and S84, verifying the effect of the substrate and the TNT by using a Raman spectrometer to control the Raman spectrum of the sample.
In this embodiment, the step S1 of hydrophilizing the PET film includes cutting the PET film into 2.0 × 2.0 cm squares, ultrasonically cleaning the surface with ethanol and deionized water sequentially, taking out the PET film after fifteen minutes, blow-drying the PET film with nitrogen, cleaning the PET film in a plasma cleaner for 3 minutes to hydrophilize the surface of the PET film, and plasma cleaning the PET film after drying the PET film at room temperature for 3 minutes.
In this embodiment, the raman spectrometer is a confocal raman spectrometer LabRAM HR Evolution type confocal raman spectrometer, the parameters of the spectrometer are set to be 633nm of excitation light source, the laser power is 2.5-5mW, the integration time is 10s, and the integration times is 3 times.
In this embodiment, the type of the reactive ion etcher is ME-3A.
In the invention, the modification principle of the Raman substrate is as follows: the 4-aminothiophenol molecules and the gold nanoparticles on the Raman substrate form strongly interacting S-Au bonds, and the Raman spectrum of the 10-7 mol/L4-aminothiophenol-modified Raman substrate does not allow the measurement of the characteristic peak of 4-aminothiophenol, which has no effect on the subsequent detection. The connection principle of the TNT molecule is as follows: the TNT molecule and the 4-amino thiophenol molecule form stronger pi-pi acceptor interaction, namely, the interaction exists between the amino of the electron-donating 4-amino thiophenol molecule as a ligand and the TNT benzene ring with electron deletion, which is also the basis for the subsequent connection of the silver nano-particles modified by the 4-amino thiophenol molecule.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the equipment or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. The application of the SERS substrate based on nanosphere etching in explosive TNT detection is characterized by comprising the following steps:
s1, spin coating of a monolayer polystyrene microsphere on a PET film: the PET film is first hydrophilized, and then the PS ball stock solution is centrifuged and transferred to a container containing the components in a volume ratio of 2: 1, and finally adjusting the PS solution concentration to 2.5 w/v%, adding a surfactant TX-100 to the final mixture at 0.5% by volume, and then spin-coating a drop of PS solution having a volume of about 8 μ l on a pure PET film for 15 seconds at 650 rpm, followed by 1 second at 1000 rpm to remove excess liquid, and holding the film in a heater for several minutes to dry the solvent, thus obtaining a PET film having a monolayer of PS spheres;
s2, reactive ion etching: placing the PET film with the single-layer PS balls in an etching cavity of a reactive ion etching machine for etching, adjusting the etching time to be 5min, and finally obtaining a periodic array containing the nanocones on the surface of the PET film to obtain a periodic nanocone array film substrate;
s3, electron beam deposition of gold nanoparticles: performing gold plating on the obtained periodic nanocone array film substrate in an electron beam deposition system at the speed of 0.02-0.03nm/s to finally obtain a Raman substrate with the thickness of gold nanoparticles of 30 nm;
s4, modification of PET film substrate: 4-aminothiophenol in a concentration of 10-5Dissolving in ethanol solution at mol/L to obtain 4-aminothiophenol original solution, and diluting 4-aminothiophenol original solution with ethanol to 10% concentration- 7mol/L, and completely immersing the Raman substrate after gold plating in 10 DEG-7Soaking in mol/L4-aminothiophenol solution at normal temperature for 10h, taking out, continuously washing with deionized water for three times to wash away 4-aminothiophenol molecules which are not connected to the Raman substrate, washing for 10s each time, and drying at room temperature;
s5, synthesis of silver nanoparticles: firstly, adding 10ml of 9mg/ml silver nitrate solution into 490ml of deionized water, boiling at the speed of 550r/min of magneton rotation speed, then slowly dropwise adding 10ml of 1% sodium citrate solution by mass fraction, and continuously keeping the boiling state for 1 hour after the solution turns to grey brown;
s6, surface modification of silver nanoparticles: taking 100ul of 10-4Adding a mol/L4-aminothiophenol solution into 900ul of silver colloid, oscillating for one hour in an oscillator to achieve the effect of fully adsorbing 4-aminothiophenol molecules and silver nanoparticles, wherein the 4-aminothiophenol molecules and the silver nanoparticles form S-Ag bonds with strong interaction;
s7, linkage of TNT molecule: will be soaked in 10-7Soaking the Raman substrate in the 4-aminothiophenol solution of mol/L in TNT ethanol solutions of different concentrations for 10h, taking out and drying at room temperature;
s8, Raman detection, comprising the following steps:
s81, substrate effect verification: dissolving R6G molecules in ethanol to prepare a mother solution, diluting the mother solution into solutions to be detected with different concentrations by using the ethanol, soaking the gold-plated Raman substrate in the solutions R6G with different concentrations to connect the surface of the Raman substrate with molecules R6G of the substance to be detected;
s82, verification of TNT effect: three samples were tested separately, one being soaked in 10-7Soaking the Raman substrate in a 4-aminothiophenol solution of mol/L for 10h, and soaking the Raman substrate in the solution for 10h-7Taking out and washing a Raman substrate for 10h in a 4-aminothiophenol solution of mol/L for 3 times, soaking the Raman substrate in 4-aminothiophenol modified silver colloid for 10h, taking out and washing, drying at room temperature to be tested, and soaking the Raman substrate in 10h- 7Taking out the Raman substrate of 10h in mol/L4-aminothiophenol solution, washing for 3 times, and soaking in 10-5Taking out the TNT solution of mol/L for 10 hours to be dried, finally soaking the TNT solution of mol/L in 4-amino thiophenol modified silver colloid for 10 hours, taking out and washing the silver colloid for 3 times, and drying the silver colloid at room temperature to be tested;
s83, verification of TNT gradient concentration: soaking the Raman substrate in 10-7Soaking in mol/L4-aminothiophenol solution for 10 hr, washing, and soaking in 10-8mol/L、10-9mol/L、10-10mol/L、10-11mol/L、10-12mol/L、10-13Soaking in TNT solution of mol/L for 10 hr, taking out, drying, and soaking in 4-aminothiophenol modified silver colloidTaking out and washing for 3 times after neutralization for 10 hours, removing free molecules, and drying at room temperature to be detected;
s84, effect verification: and (3) verifying the effects of the substrate and the TNT by using a Raman spectrometer to control the Raman spectrum of the sample.
2. The application of the SERS substrate based on nanosphere etching in explosive TNT detection is characterized in that the PET film hydrophilic treatment in S1 comprises cutting the PET film into squares of 2.0 x 2.0 cm, then ultrasonically cleaning the surface with ethanol and deionized water in sequence, taking out the PET film after fifteen minutes, then drying the PET film by using nitrogen, then cleaning the PET film in a plasma cleaner for 3 minutes to make the surface of the PET film hydrophilic, and performing plasma cleaning on the PET film after the PET film is dried at room temperature for 3 minutes.
3. The application of the SERS substrate based on nanosphere etching in explosive TNT detection is characterized in that the Raman spectrometer is a confocal Raman spectrometer LabRAM HR Evolution type confocal Raman spectrometer, the parameter of the spectrometer is set to be 633nm of excitation light source, the laser power is 2.5-5mW, the integration time is 10s, and the integration times are 3 times.
4. The application of the SERS substrate based on nanosphere etching in explosive TNT detection is characterized in that the model of the reactive ion etching machine is ME-3A.
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| CN113702354A (en) * | 2021-09-02 | 2021-11-26 | 电子科技大学 | Flexible SERS substrate based on array type microstructure and preparation method thereof |
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