A high-performance surface-enhanced Raman detection substrate based on a honeycomb structure, a processing method, and a detection method

By building a honeycomb structure on a SERS substrate, the improvement of the substrate surface roughness and uniformity of hot spot distribution are achieved, the problem of uneven detection signals of traditional SERS substrates is solved, and the detection sensitivity is improved, especially the detection effect of biological macromolecules.

CN117107194BActive Publication Date: 2025-07-11DALIAN MARITIME UNIVERSITY
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Patent Information

Application Number
CN202310960030.6
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2023-08-01
Publication Date
2025-07-11
Estimated Expiration
2043-08-01

AI Technical Summary

Technical Problem

The surface roughness of traditional SERS substrates is low, and the metal nanoparticles are disordered, resulting in uneven distribution of hot spots, insignificant enhancement of detection signals, and insufficient contact between the molecules to be tested and the substrate, affecting the consistency of detection.

Method used

A high-performance surface-enhanced Raman detection substrate is adopted with a honeycomb structure. By preparing a mixed liquid and assembling nanometer microspheres in an orderly manner on the surface of the substrate, a honeycomb-like silica nanostructure is formed, and conductive metal nanofilms are sprayed on its surface to enrich the substances to be tested using an electric field.

Benefits of technology

It improves the surface roughness of the substrate, uniformly distributes hot spots, enhances the sensitivity of Raman signal detection, and is particularly effective in detecting biological macromolecules.

✦ Generated by Eureka AI based on patent content.

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Patent Text Reader

Abstract

The present invention provides a high-performance surface-enhanced Raman detection substrate based on a honeycomb structure, a processing method and a detection method. The method of the present invention includes: preparing a mixed solution, which is obtained by adding nanospheres to a tetraethyl orthosilicate precursor solution; performing a hydrophobic treatment on the surface of the substrate, orderly assembling the prepared mixed solution on the surface of the substrate, and performing high-temperature calcination on the assembled thin film plate to remove the nanospheres and obtain a honeycomb-shaped silica nanostructure, and uniformly spraying a layer of conductive metal nanofilm on the surface of the honeycomb-shaped silica nanostructure to prepare a surface Raman enhanced scattering substrate with a honeycomb structure. Compared with traditional substrates, the surface of this substrate has high roughness, can trap laser light in the pores, has a more uniform distribution of hot spots, high sensitivity, and is particularly more efficient in detecting substances such as biological macromolecules, with great application prospects.
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Description

Technical Field

[0001] The present invention relates to the technical field of surface enhanced Raman scattering detection, and in particular, to a high-performance surface enhanced Raman detection substrate based on a honeycomb structure, a processing method and a detection method. Background Art

[0002] Surface Enhanced Raman Scattering (SERS) is a phenomenon in which a molecule to be detected is adsorbed on a rough metal surface or a metal nanostructure, causing it to undergo surface plasmon resonance with the metal surface, thereby enhancing the Raman scattering signal. It has a wide range of applications in food safety, environmental protection, medical detection, etc. Research shows that the detection intensity of the signal of traditional SERS substrates is affected by many factors. For example, factors such as the material of the SERS active substrate, the shape and size of the nanoparticles, the adsorption amount and distance of the analyte on the active substrate, etc. will all affect the enhancement effect of SERS. Among them, the surface roughness of the SERS substrate has a greater impact on its signal intensity. This is because there are quasi-free electrons on the surface of a metal substrate with a certain roughness, which greatly enhances the electromagnetic field generated by the incident laser on the substrate surface, thereby increasing the probability of the molecules adsorbed on the surface generating Raman scattering and improving the intensity of the Raman signal.

[0003] Most traditional SERS substrates can only effectively detect small molecules as their sensitive sites (referred to as "hot spots", usually less than 10 nm). They have a relatively low surface roughness, the metal nanoparticles are disordered, and the distribution of hot spots is uneven, resulting in an unclear enhancement of the SERS signal; moreover, the contact between the analyte molecule and the SERS substrate is not sufficient, making the enhancement consistency of the substrate poor. Summary of the Invention

[0004] In view of the above-mentioned technical problems, a high-performance surface enhanced Raman detection substrate based on a honeycomb structure, a processing method and a detection method are provided.

[0005] The technical means adopted by the present invention are as follows:

[0006] A processing method for a high-performance surface enhanced Raman detection substrate based on a honeycomb structure, comprising the following steps:

[0007] Step 1. Prepare a mixed solution, which is prepared by adding nanospheres to a tetraethyl orthosilicate precursor solution;

[0008] Step 2. Perform hydrophobic treatment on the surface of the substrate, specifically as follows: paste a polyimide film with circular holes on the surface of the conductive film glass to construct a circular hydrophilic region on the surface of the conductive film glass;

[0009] Step 3. Assemble the mixture prepared in Step 1 on the substrate surface in an orderly manner as follows: Drop the mixture prepared in Step 1 into the circular holes on the surface of the conductive film glass prepared in Step 2. The volume of the dropped mixture can be adjusted according to the size of the circular holes. Place the conductive film glass on a heating plate and heat it while applying an electric field between the surface of the conductive film glass and the dropped liquid droplet. After the solvent has completely evaporated, an orderly assembled microsphere thin film plate can be obtained.

[0010] Step 4. Calcinate the thin film plate assembled in Step 3 at a high temperature to remove the nanospheres and obtain a honeycomb-shaped silica nanostructure, and uniformly spray a layer of conductive metal nanofilms on the surface of the honeycomb-shaped silica nanostructure to prepare a surface Raman enhanced scattering substrate with a honeycomb structure.

[0011] Further, the material of the nanospheres includes polystyrene and polymethyl methacrylate.

[0012] Further, in Step 1, use a pipette to sequentially add a quantified amount of tetraethyl orthosilicate, ethanol, and HCl into a beaker, and stir at room temperature for 1 to 1.5 hours to form a tetraethyl orthosilicate precursor solution. Dilute the nanospheres, and then add a quantified amount of the tetraethyl orthosilicate precursor solution. Place the mixed solution in an ultrasonic cleaner and dissolve it thoroughly by ultrasonic waves.

[0013] Further, in Step 2, perform a hydrophobic treatment on the substrate surface as follows: Use a cutting machine to print circular holes on a polyimide film. Ultrasonically clean the conductive film glass sequentially with acetone, absolute ethanol, and ultrapure water. After drying the surface with a nitrogen gun to keep it dry, paste the PI film with circular holes on the surface of the conductive film glass to construct a circular hydrophilic region on the surface of the conductive film glass.

[0014] Further, in Step 3, the heating temperature of the heating plate is 85 - 90 °C, apply an electric field with a voltage of 0.5 - 1 V between the surface of the conductive film glass and the dropped liquid droplet, and turn off the power after 30 - 40 s of power-on.

[0015] Further, in Step 4, the high-temperature calcination is specifically as follows: Place it in a muffle furnace and heat it to 500 - 510 °C at a heating rate of 4 - 5 °C / min and calcine for 3 - 3.5 h.

[0016] Further, the conductive metal in Step 4 includes gold, silver, platinum, and chromium.

[0017] Further, the thickness of the conductive metal nanofilms is 8 - 10 nm.

[0018] The present invention discloses a high-performance surface-enhanced Raman detection substrate with a honeycomb structure prepared based on the above method.

[0019] The present invention also provides a detection method for a high-performance surface-enhanced Raman detection substrate based on a honeycomb structure, comprising the following steps: adding a sample to a surface Raman-enhanced scattering substrate having a honeycomb structure and performing enrichment and detection analysis of the analyte, specifically as follows: dropping the analyte solution onto the surface Raman-enhanced substrate, applying an electric field between the solution and the conductive film glass to enrich the analyte onto the surface of the surface Raman-enhanced scattering substrate having a honeycomb structure under the action of the electric field force, and after the solvent has completely evaporated, quantitatively analyzing the sample using a Raman spectrometer.

[0020] Compared with the prior art, the present invention has the following advantages: the present invention realizes particle self-assembly by applying an electric field to the mixture, and forms an orderly arranged honeycomb-like silica (SiO2) inverse opal photonic crystal (IOPCs) nanostructure on the substrate surface by calcination, and uniformly sprays a layer of gold nanofilms on the top thereof, which can be used as an active substrate for surface-enhanced Raman scattering. Compared with the traditional substrate, the surface of this substrate has a high roughness, can trap the laser in the pores, has a more uniform hot spot distribution, high sensitivity, and is particularly more efficient in detecting substances such as biological macromolecules, and has great application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0022] Figure 1 It is a schematic flow chart of constructing a Raman detection substrate based on a honeycomb structure according to the present invention. In the figure: (a) Preparation of a PI-ITO conductive film glass substrate; (b) Dropwise adding a mixture into the circular holes; (c) Applying an electric field to the liquid droplets; (d) Self-assembly of the mixture; (e) Calcination to form an orderly porous SiO2 IOPCs structure; (f) Spraying a layer of gold nanofilms on the top of the SiO2 IOPCs structure; (g) Applying an electric field to the target detection molecule probe to enrich it onto the substrate; (h) Raman detection; wherein 1. Glass sheet; 2. ITO conductive film; 3. PI film; 4. Mixture; 5. Electric field; 6. SiO2 IOPCs structure; 7. Metal nanoparticles; 8. Target detection molecule probe; 9. Raman detector.

[0023] Figure 2 It is a scanning electron microscope image of the honeycomb structure-based substrate of the present invention and a fluorescence microscope image of the traditional substrate, wherein, (a) Scanning electron microscope image of the honeycomb Raman substrate; (b) Fluorescence microscope image of the traditional Au / PDMS Raman substrate.

[0024] Figure 3 Raman detection result graph of 4-aminothiophenol based on a honeycomb structure SERS substrate modified with gold nanoparticles.

[0025] Figure 4 For the characteristic peak of 4-aminothiophenol at 1072 cm -1 The linear relationship between the Raman signal intensity and its concentration. Detailed implementation manners

[0026] It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0027] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way limits the present invention and its application or use. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0028] It should be noted that the terms used herein are only for describing specific implementation manners and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular forms are also intended to include the plural forms. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or their combinations.

[0029] Unless otherwise specifically stated, the relative arrangements of the components and steps, numerical expressions and values set forth in these embodiments do not limit the scope of the present invention. At the same time, it should be clear that, for the convenience of description, the dimensions of the various parts shown in the drawings are not drawn according to the actual proportional relationship. Technologies, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods and devices should be regarded as part of the authorized specification. In all the examples shown and discussed herein, any specific values should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values. It should be noted that: similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, it does not need to be further discussed in the subsequent drawings.

[0030] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by orientation words such as "front, rear, upper, lower, left, right", "lateral, vertical, perpendicular, horizontal" and "top, bottom", etc. is usually based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description. Without contrary description, these orientation words do not indicate and imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation on the protection scope of the present invention: the orientation words "inside, outside" refer to the inside and outside relative to the contour of each component itself.

[0031] For convenience of description, spatial relative terms such as "above...", "over...", "on the upper surface of...", "above-mentioned" etc. can be used here to describe the spatial positional relationship between a device or feature shown in the drawings and other devices or features. It should be understood that the spatial relative terms are intended to cover different orientations in use or operation in addition to the orientation described in the drawings for the device. For example, if the device in the drawing is inverted, the device described as "above other devices or structures" or "over other devices or structures" will then be positioned as "below other devices or structures" or "under other devices or structures". Thus, the exemplary term "above..." can include both the orientations of "above..." and "below...". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the corresponding explanations should be made for the spatial relative descriptions used here.

[0032] In addition, it should be noted that using words such as "first", "second", etc. to limit components is only for the convenience of distinguishing the corresponding components. Without additional statement, the above words have no special meaning. Therefore, it should not be construed as a limitation on the protection scope of the present invention.

[0033] Inspired by the excellent sound absorption performance of natural beehives, the present invention discloses a gold (Au)-coated silica (SiO2) inverse opal photonic crystal (IOPCs) structure, which can increase the roughness of the detection substrate, perfectly coordinate the interaction of laser, sample and SERS substrate, and effectively improve the detection sensitivity of SERS. The SiO2-IOPCs calcined at high temperature can be firmly adhered to the surface of the substrate glass, improving the stability of the sensor. The honeycomb structure can increase the roughness of the substrate surface. Secondly, the interconnected nano-porous network macroporous structure helps to capture large molecular targets. The honeycomb structure can effectively absorb sound waves through multiple scattering processes. Similarly, the SiO2-IOPCs structure has an optical stop band depending on the pore size. The SiO2-IOPCs structure with an appropriate stop band can trap the laser in the pores, known as the "slow light effect", which can be used to enhance the Raman signal of the analyte. A thin layer of Au film is attached to the top of the SiO2-IOPCs structure. The Au layer on the SiO2-IOPCs structure can further enhance the Raman signal of the analyte through the SERS effect. Therefore, the development of a substrate with a honeycomb structure is expected to provide an excellent method and platform for high-precision SERS detection.

[0034] The present invention proposes a method for developing a high-performance surface-enhanced Raman detection substrate based on a honeycomb structure. The SiO2-IOPCs structure can effectively increase the roughness of the substrate surface, trap the laser in the pores, and large molecular targets, especially macromolecules, can be easily captured by the orderly interconnected macroporous structure. This substrate can effectively improve the hot spot distribution and the detection sensitivity of SERS. This invention is of great significance for improving the sensitivity and application promotion of surface-enhanced Raman detection technology.

[0035] For the specific preparation method, please refer to Example 1.

[0036] Example 1

[0037] Figure 1 The following is a schematic flow chart of the processing method of the high-performance surface-enhanced Raman detection substrate based on the honeycomb structure of the present invention. The specific operation steps of this solution are as follows:

[0038] Step 1. Prepare a mixed solution, which is prepared by adding monodisperse polystyrene (PS) colloidal nanospheres into a tetraethyl orthosilicate (TEOS) precursor solution. Specifically as follows: Use a pipette to sequentially add 1 mL of TEOS (>99%), 2 mL of ethanol (≥99.5%), and 1 mL of HCl (0.1 M) into a beaker, and stir at room temperature for 1 - 1.5 hours to form a TEOS precursor solution; Dilute the PS colloidal microspheres into an 8 mL - 0.2 wt% solution and pour it into a 10 mL beaker, then add 40 μL of the TEOS precursor solution, and place the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 15 min for sufficient dissolution. The microspheres are not limited to polystyrene materials, and can also be materials such as polymethyl methacrylate (PMMA).

[0039] Step 2. Hydrophobically treat the surface of the substrate. Specifically as follows: Paste a polyimide film (PI) with circular holes on the surface of indium tin oxide (ITO) transparent conductive film glass to construct a circular hydrophilic region on the ITO conductive film glass surface. Use a cutting machine to print a circular hole with a diameter of 5 mm on a PI film with a size of 4 mm × 5 mm. Ultrasonically clean the ITO conductive film glass with acetone, absolute ethanol, and ultrapure water in sequence for 20 min. After drying the surface with a nitrogen gun to keep it dry, paste the PI film with circular holes on the surface of the ITO conductive film glass to construct a circular hydrophilic region on the ITO conductive film glass surface. It should be noted that the PI film with circular holes is punched by a cutting machine according to the set size, and the pore size can be adjusted according to actual needs. The protective film material and processing method are not limited to PI and the cutting machine punching method.

[0040] Step 3. Orderly assemble the PS colloidal microspheres and TEOS mixture on the surface of the circular hole of the PI-ITO conductive film glass to form a uniform PS close-packed substrate. Specifically as follows: Use a pipette to drop 30 μL of the mixed solution into the circular hole on the surface of the PI-ITO conductive film glass, and then place it on a hot plate at 85 - 90 °C. At the same time, apply an electric field with a voltage of 0.5 - 1 V between the surface of the ITO conductive film glass and the dropped liquid droplet. After powering on for 30 - 40 s, turn off the power and remove the wire in the liquid droplet. Applying an electric field can effectively weaken the "coffee ring" effect during the self-assembly process of PS microspheres. The heating process enables the solvent to evaporate quickly. After the solvent has completely volatilized, an orderly assembled PS microsphere thin film plate can be obtained. It should be noted that the volume of the dropped mixed solution can be adjusted according to the size of the circular hole, and the applied electric field and heating temperature can both be adjusted according to the self-assembly effect. The embodiment only gives an optional implementation method.

[0041] Step 4. High-temperature calcination is carried out on the self-assembled PS thin film plate to remove PS microspheres and obtain a honeycomb-like silica nanostructure, and a gold nanometer film is uniformly sprayed on the surface of the honeycomb-like silica nanostructure to prepare a surface Raman enhanced scattering substrate with a honeycomb structure, specifically as follows: The thin film plate with the PI film removed is horizontally placed in a muffle furnace and heated to 500-510°C at a heating rate of 4-5°C / min and calcined for 3-3.5 h. After the muffle furnace is slowly cooled to room temperature, the thin film plate is taken out. The PS microsphere structure is removed to obtain a solidified IOPCs framework, and an orderly arranged honeycomb-like silica (SiO2) inverse opal photonic crystal (IOPCs) nanostructure is obtained; A gold nanometer film with a thickness of 8-10 nm is uniformly sprayed on its surface to obtain a surface Raman enhanced scattering substrate with a honeycomb structure. The spraying material is not limited to gold, and other metals with good conductivity such as silver, platinum, and chromium can also be selected. The spraying method includes evaporation coating.

[0042] The present invention also provides a detection method for a high-performance surface-enhanced Raman detection substrate based on a honeycomb structure, including the following steps:

[0043] A sample is added to the surface Raman enhanced scattering substrate with a honeycomb structure and enrichment and detection analysis of the analyte are carried out, specifically as follows: The analyte solution is dropped on the surface Raman enhanced substrate, and an electric field is applied between the solution and the ITO to enrich the analyte to the surface of the surface Raman enhanced scattering substrate with a honeycomb structure under the action of the electric field force. After the solvent is completely volatilized, Raman spectrometer is used to quantitatively analyze the sample. Among them, the analyte solution is dropped on the surface Raman enhanced substrate with a honeycomb structure, and an electric field is applied between the solution and the ITO layer to enrich the analyte to the surface Raman enhanced scattering substrate under the action of the electric field.

[0044] The time, voltage, and polarity can be adjusted according to the charged characteristics of the analyte. Finally, Raman spectrometer is used to quantitatively analyze the sample. The wavelength of the Raman detection excitation light source and the detection process parameters adopted can be adjusted accordingly according to the size of the honeycomb nanostructure. The analyte solution is dropped on the surface Raman enhanced substrate with a honeycomb structure, and an electrode is applied to the solution to enrich it to the surface Raman enhanced scattering substrate. After the solvent is completely volatilized, the analyte target molecules are uniformly distributed on the honeycomb structure.

[0045] Specifically, a sample is added to a surface Raman enhanced scattering substrate with a honeycomb structure for enrichment and detection analysis of the analyte as follows: Finally, a Raman spectrometer is used to perform quantitative analysis on the sample; the excitation wavelength of the Raman spectrum used is 785 nm. A pipette is used to drop 5 μL of 4-aminothiophenol (4-ATP) with a concentration of 10 μM onto the sample. An electric field with a voltage of 1 V is also applied between the solution and the ITO layer, and the power is turned on for 30 s to enrich the analyte onto the surface Raman enhanced scattering substrate under the action of the electric field. After the solvent has completely evaporated, the target analyte molecules are evenly distributed on the honeycomb structure. The integration time used for detection is 5 s, and the excitation intensity used is 200 mW.

[0046] Test Example 1: Scanning Electron Microscope

[0047] The SiO2 IOPCs honeycomb structure modified with gold nanoparticles in Example 1 was scanned by an electron microscope, and the results are as Figure 2 (a) shown. It can be seen that a structure similar to a honeycomb morphology is formed on the substrate surface. Compared with the traditional SERS substrate Figure 2 (b), spherical pits with a diameter of 200 nm are evenly and closely arranged on the substrate surface (the size of the spherical pits depends on the size of the PS microspheres), which makes the surface roughness of the substrate reach a very good effect.

[0048] Test Example 2: Monitoring and Analysis of 4-Aminothiophenol

[0049] Taking 4-aminothiophenol as the probe molecule to monitor the activity of the SERS substrate, the specific steps are as follows: The 4-aminothiophenol solution is dropped onto the surface Raman enhanced substrate, and an electric field is applied between the solution and the ITO layer to enrich the analyte onto the surface Raman enhanced scattering substrate under the action of the electric field. After the solvent has completely evaporated, the target analyte molecules are evenly distributed on the honeycomb structure; finally, a Raman spectrometer is used to perform quantitative analysis on the sample; the excitation wavelength of the Raman spectrum used is 785 nm. 5 μL of 4-aminothiophenol with a concentration of 10 μM is dropped onto the sample. The integration time used for detection is 5 s, and the excitation intensity used is 200 mW. The test results of the Raman spectrometer are as shown in Figure 3 . Each peak corresponds to a specific functional group. It can be seen from the figure that the substrate with a honeycomb structure has a very strong enhancement effect on the Raman signal. Figure 4 The linear relationship between the Raman signal intensity at the characteristic peak of 4-aminothiophenol at 1072 cm -1 is shown, indicating that the invented SERS substrate has good detection sensitivity.

[0050] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A processing method for a high-performance surface-enhanced Raman detection substrate based on a honeycomb structure, characterized in that It includes the following steps: Step 1. Prepare a mixed solution, which is obtained by adding nanospheres into a tetraethyl orthosilicate precursor solution; Step 2. Perform hydrophobic treatment on the substrate surface as follows: Paste a polyimide film with circular holes on the surface of the conductive film glass to construct a circular hydrophilic region on the surface of the conductive film glass; Step 3. Orderly assemble the mixed solution prepared in Step 1 on the substrate surface as follows: Drop the mixed solution prepared in Step 1 into the circular holes on the surface of the conductive film glass prepared in Step 2. The volume of the dropped mixed solution can be adjusted according to the size of the circular holes; Place the conductive film glass on a heating plate for heating, and apply an electric field between the surface of the conductive film glass and the dropped liquid droplet at the same time. After the solvent has completely volatilized, an orderly assembled microsphere thin film plate can be obtained; Step 4. Horizontally place the thin film plate after removing the polyimide film into a muffle furnace and heat it up to 500 - 510 °C at a heating rate of 4 - 5 °C / min for calcination for 3 - 3.5 h, then remove the nanospheres and obtain a honeycomb-like silica nanostructure, and evenly spray a layer of conductive metal nanofilms on the surface of the honeycomb-like silica nanostructure to prepare a surface Raman enhanced scattering substrate with a honeycomb structure.

2. The processing method of the high-performance surface-enhanced Raman detection substrate based on the honeycomb structure according to claim 1, wherein The materials of the nanospheres include polystyrene and polymethyl methacrylate.

3. The processing method of the high-performance surface-enhanced Raman detection substrate based on the honeycomb structure according to claim 1, characterized in that, In Step 1, use a pipette to sequentially add a quantitative amount of tetraethyl orthosilicate, ethanol, and HCl into a beaker, and stir at room temperature for 1 - 1.5 hours to form a tetraethyl orthosilicate precursor solution; Dilute the nanospheres, and then add a quantitative amount of the tetraethyl orthosilicate precursor solution. Put the mixed solution into an ultrasonic cleaner and dissolve it thoroughly by ultrasonic waves.

4. The processing method of the high-performance surface-enhanced Raman detection substrate based on the honeycomb structure according to claim 1, wherein, In Step 2, perform hydrophobic treatment on the substrate surface as follows: Use a cutting machine to print circular holes on the polyimide film. Ultrasonically clean the conductive film glass successively with acetone, absolute ethanol, and ultrapure water. After drying the surface with a nitrogen gun to keep it dry, paste the PI film with circular holes on the surface of the conductive film glass to construct a circular hydrophilic region on the surface of the conductive film glass.

5. The processing method of the high-performance surface-enhanced Raman detection substrate based on the honeycomb structure according to claim 1, wherein, In Step 3, the heating temperature of the heating plate is 85 - 90 °C, apply an electric field with a voltage of 0.5 - 1 V between the surface of the conductive film glass and the dropped liquid droplet, and turn off the power supply after 30 - 40 s of power on.

6. The processing method of the high-performance surface-enhanced Raman detection substrate based on the honeycomb structure according to claim 1, characterized in that, The conductive metal in Step 4 includes gold, silver, platinum, and chromium.

7. The processing method of the high-performance surface-enhanced Raman detection substrate based on the honeycomb structure according to claim 1, wherein The thickness of the conductive metal nanofilms is 8 - 10 nm.

8. A high-performance surface-enhanced Raman detection substrate with a honeycomb structure prepared by the processing method according to any one of claims 1 - 7.

9. A detection method for a high-performance surface-enhanced Raman detection substrate with a honeycomb structure prepared by the processing method according to any one of claims 1 to 7, characterized in that, It includes the following steps: Add a sample on the surface Raman enhanced scattering substrate with a honeycomb structure and perform enrichment and detection analysis of the analyte as follows: Drop the analyte solution on the surface Raman enhanced substrate, apply an electric field between the solution and the conductive film glass to enrich the analyte to the surface of the surface Raman enhanced scattering substrate with a honeycomb structure under the action of the electric field force. After the solvent has completely volatilized, use a Raman spectrometer to perform quantitative analysis on the sample.

Citation Information

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