Flexible Transparent Surface-Enhanced Raman Substrate and Its Preparation Method

Abstract

The present invention provides a surface-enhanced Raman substrate and a preparation method thereof. The surface-enhanced Raman substrate comprises: active nanostructures, which are arranged in an array to form an array film; and a substrate, which is formed on one side of the array film; and the substrate is derived from a polymer material, at least a portion of which penetrates into the pores of the active nanostructures and coats the surface of the array film. The flexible, light-transmitting surface-enhanced Raman substrate of the present invention utilizes polymer compounds to partially coat the active nanostructures, thereby slowing down the oxidation and sulfurization of the active nanostructures under atmospheric conditions, thereby improving the temporal stability of the substrate; further, the present invention uses a polymer film formed by a polymer compound as a substrate for the active nanostructure, so that the surface-enhanced Raman substrate has bending and stretching properties, making it easy to obtain samples on surfaces with complex shapes.

Description

Technical Field

[0001] The present invention relates to a flexible light-transmitting surface-enhanced Raman substrate and a preparation method thereof, and particularly to a flexible light-transmitting surface-enhanced Raman substrate capable of in-situ detection and a preparation method thereof, belonging to the technical field of trace organic matter detection. Background Art

[0002] The surface-enhanced Raman effect has been widely used in recent years for trace detection of chemical and biological molecules, offering advantages such as high sensitivity, low cost, and non-destructive analysis. This method primarily uses precious metals such as gold, silver, or copper as surface-enhanced Raman substrates, with silver nanostructures providing the best results. Traditional surface-enhanced Raman substrates typically consist of rigid substrates with silver or gold nanostructures attached to silicon or glass wafers. Flexible surface-enhanced Raman substrates can also be created by combining flexible substrates with silver or gold nanostructures.

[0003] Silver nanostructured substrates are susceptible to oxidation and sulfidation when stored in air and corrosion in solutions. Their poor chemical stability hinders the application of surface-enhanced Raman effects on these substrates. The properties of rigid SERS substrates limit their application on complex, soft surfaces. Most flexible SERS substrates, which attach nanostructures to flexible materials, suffer from complex preparation processes and poor chemical stability.

[0004] Reference 1 discloses a flexible surface-enhanced Raman scattering substrate and its preparation and detection methods. The flexible surface-enhanced Raman scattering substrate includes a flexible transparent substrate and a surface-enhanced Raman-active nanostructure; the surface-enhanced Raman-active nanostructure is a silver nanostructure. The preparation method is as follows: depositing the silver nanostructure on a rigid substrate; transferring the active silver nanostructure from the rigid substrate to the surface of the flexible substrate by a "sticking & peeling" method. The silver nanorod structure on the silicon substrate is prepared by an oblique growth method. The silver nanosphere structure is obtained by adding sodium citrate to a boiling AgNO3 solution. Although this method overcomes the disadvantage of uneven active structure in conventional preparation methods, it cannot solve the problem of silver oxidation and sulfidation under atmospheric conditions.

[0005] Therefore, researching a flexible, light-transmitting surface-enhanced Raman substrate that can solve the problems of silver oxidation and sulfidation under atmospheric conditions has become a technical problem that needs to be solved urgently.

[0006] References:

[0007] Reference 1: CN109916877A Summary of the Invention

[0008] Problems to be solved by the invention

[0009] In view of the technical problems existing in the prior art, the present invention first provides a flexible, light-transmitting surface-enhanced Raman substrate. The flexible, light-transmitting surface-enhanced Raman substrate of the present invention utilizes a polymer compound to partially encapsulate the active nanostructures, thereby slowing down the oxidation and sulfidation of silver under atmospheric conditions, thereby improving the temporal stability of the surface-enhanced Raman substrate. The light-transmitting polymer film substrate allows the penetration of laser light and Raman scattered light, enabling in-situ detection on curved surfaces.

[0010] Furthermore, the present invention also provides a method for preparing a flexible light-transmitting surface-enhanced Raman substrate. The preparation method is simple and easy, the raw materials are easy to obtain, and it is suitable for mass production.

[0011] Solutions for solving problems

[0012] [1] A surface-enhanced Raman substrate comprising:

[0013] Active nanostructures, the active nanostructures are arranged in an array to form an array film; and

[0014] a substrate formed on one side of the array film; and

[0015] The substrate is derived from a polymer material, and at least a portion of the polymer material penetrates into the pores of the active nanostructure and covers the surface of the array film.

[0016] [2] The surface-enhanced Raman substrate according to [1] above, wherein the active nanostructure is derived from a noble metal, preferably comprising gold and / or silver.

[0017] [3] The surface-enhanced Raman substrate according to [1] or [2] above, wherein the length of the active nanostructure is 200-500 nm; and / or the active nanostructure is distributed perpendicular to the substrate or distributed at an inclined angle relative to the substrate, preferably, the inclined angle is 70-75°.

[0018] [4] The surface-enhanced Raman substrate according to any one of [1] to [3] above, wherein the polymer material comprises one or a combination of two or more of a (meth)acrylic polymer or a fluorine-containing polymer; and / or

[0019] The thickness of the surface enhanced Raman substrate is not less than 10 μm.

[0020] [5] A method for preparing a surface-enhanced Raman substrate according to any one of [1] to [4] above, comprising the step of composite-molding the active nanostructure and the substrate.

[0021] [6] The preparation method according to [5] above, comprising the following steps:

[0022] Depositing noble metals on a substrate to form active nanostructures, wherein the active nanostructures are arranged in an array to form an array film;

[0023] Dropping a polymer material solution on the substrate to form a substrate, and allowing part of the polymer material to penetrate into the pores of the active nanostructures and coat the surface of the array film;

[0024] After removing the substrate, the surface enhanced Raman substrate is obtained.

[0025] [7] The preparation method according to [6] above, wherein the steps of preparing the array film include: fixing the substrate on the sample stage of the electron beam evaporation coating machine, adjusting the incident angle to 82° to 88°; -5 ~8×10 -5 In an environment of Pa, using noble metal as a target, active nanostructures are obliquely grown on the substrate to obtain an array film; or,

[0026] The substrate was fixed on the sample stage of the electron beam evaporation coating machine, and the incident angle was adjusted to 82°~88°. At the same time, the sample stage was rotated and the vacuum degree was 3×10 -5 ~8×10 -5 In a Pa environment, noble metals are used as targets to vertically grow active nanostructures on the substrate to obtain an array film.

[0027] [8] The preparation method according to [6] or [7] above, wherein the polymer material solution is prepared by dissolving the polymer material in an organic solvent; preferably, the mass concentration of the polymer material in the polymer material solution is 2%-5%.

[0028] [9] The preparation method according to any one of [6] to [8] above, wherein the polymer material solution is dripped onto the substrate, and the substrate is placed in a ventilated place for 4-6 hours and then naturally dried to form the substrate.

[0029]

[10] The preparation method according to [8] above, wherein the organic solvent comprises one or a combination of two or more of N,N-dimethylformamide, anisole or chlorobenzene.

[0030] Effects of the Invention

[0031] The flexible, light-transmitting surface-enhanced Raman substrate of the present invention utilizes a polymer compound to partially coat the active nanostructure, thereby slowing down the oxidation and sulfurization of the active nanostructure under atmospheric conditions, thereby improving the temporal stability of the substrate.

[0032] Furthermore, the present invention uses a polymer film formed by a polymer compound as a substrate for the active nanostructure, so that the surface-enhanced Raman substrate has bending and stretching properties, making it easy to obtain samples on surfaces with complex shapes.

[0033] Furthermore, the polymer film of the present invention is light-transmitting, and therefore allows laser and Raman scattered light to penetrate, so that the surface-enhanced Raman substrate has the characteristic of in-situ detection on curved surfaces, which can expand the application prospects of surface-enhanced Raman.

[0034] The preparation method of the surface enhanced Raman substrate of the present invention is simple and easy, the raw materials are easy to obtain, and it is suitable for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The scanning electron microscope image of the PVDF-silver nanorod flexible light-transmitting surface-enhanced Raman substrate prepared in Example 1 is shown.

[0036] Figure 2 A scanning electron microscope image of the PVDF-silver nanorod flexible light-transmitting surface-enhanced Raman substrate prepared in Example 2 is shown.

[0037] Figure 3 A scanning electron microscope image of the PMMA-silver nanorod flexible light-transmitting surface-enhanced Raman substrate prepared in Example 3 is shown.

[0038] Figure 4 The trace R6G Raman spectra obtained by incident laser testing on the silver nanorod side and the polymer side using the PMMA-silver nanorod flexible light-transmitting surface-enhanced Raman substrate prepared in Example 3 are shown.

[0039] Figure 5 The trace R6G Raman spectra obtained by incident laser testing on the silver nanorod side and the polymer side using the PVDF-silver nanorod flexible light-transmitting surface-enhanced Raman substrate prepared in Example 2 are shown. DETAILED DESCRIPTION

[0040] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior or preferred over other embodiments.

[0041] In addition, numerous specific details are provided in the following detailed description to better illustrate the present invention. Those skilled in the art will appreciate that the present invention can be practiced without certain specific details. In other instances, methods, means, equipment, and steps well known to those skilled in the art are not described in detail in order to highlight the main points of the present invention.

[0042] Unless otherwise stated, the units used in this specification are international standard units, and the numerical values and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0043] In this specification, the use of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0044] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "embodiments," etc., mean that the specific elements (e.g., features, structures, properties, and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0045] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0046] In this specification, when "normal temperature" or "room temperature" is used, the temperature may be 10-25°C.

[0047] <First Aspect>

[0048] A first aspect of the present invention provides a surface-enhanced Raman substrate comprising:

[0049] Active nanostructures, the active nanostructures are arranged in an array to form an array film; and

[0050] a substrate formed on one side of the array film; and

[0051] The substrate is derived from a polymer material, and at least a portion of the polymer material penetrates into the pores of the active nanostructure and covers the surface of the array film.

[0052] Active nanostructures

[0053] The active nanostructures of the present invention are arranged in an array to form an array film. Using the active nanostructures can produce a surface-enhanced Raman substrate. Using the active nanostructures can achieve excellent surface-enhanced Raman effects.

[0054] Specifically, in the present invention, the active nanostructures are derived from precious metals, preferably gold and / or silver. Silver nanostructures exhibit the best surface-enhanced Raman spectroscopy (SERS) and are relatively cheaper than gold. Therefore, silver is preferred for preparing the active nanostructures. Furthermore, the active nanostructures of the present invention may be active nanorods, preferably silver nanorods.

[0055] Furthermore, in the present invention, the length of the active nanostructure is 200-500 nm, for example: 220 nm, 250 nm, 280 nm, 300 nm, 320 nm, 350 nm, 380 nm, 400 nm, 420 nm, 450 nm, 480 nm, etc.; when the length of the active nanostructure is 200-500 nm, a surface-enhanced Raman substrate with excellent surface-enhanced Raman effect can be prepared.

[0056] Furthermore, in the present invention, the active nanostructure is distributed perpendicularly to the substrate or at an inclined angle relative to the substrate. Preferably, the inclined angle is 70-75°, for example, 71°, 72°, 73°, 74°, etc. This is based on the shadow effect. When the incident angle is 82° to 88°, the inclined angle of the obtained nanostructure to the bottom will not be 82° to 88°, but is calculated to be approximately 70° to 75°. By making the active nanostructure distributed perpendicularly to the substrate or at an inclined angle relative to the substrate, a rod-shaped nanostructure with adjustable length and diameter is obtained by physical vapor deposition, thereby obtaining a surface-enhanced Raman substrate with excellent surface-enhanced Raman effect.

[0057] substrate

[0058] A substrate is formed on one side of the array film; and the substrate is derived from a polymer material, at least a portion of which penetrates into the pores of the active nanostructures and covers the surface of the array film.

[0059] By providing a substrate and partially encapsulating the active nanostructures, the present invention can mitigate oxidation and sulfurization of the active nanostructures under atmospheric conditions, thereby improving the substrate's temporal stability. Furthermore, by using a polymer film formed from a polymer compound as the substrate for the active nanostructures, the present invention imparts bending and stretching properties to the surface-enhanced Raman substrate, facilitating sample acquisition even on complex surfaces.

[0060] Specifically, in the present invention, the polymer material includes one or a combination of two or more of a (meth)acrylic polymer or a fluorine-containing polymer.

[0061] Furthermore, in the present invention, the polymer material is preferably a fluorine-containing polymer material. By using a fluorine-containing polymer material, the polymer film of the present invention is made light-transmissive. Therefore, the polymer film allows laser light and Raman scattered light to penetrate, giving the surface-enhanced Raman substrate the ability to detect in situ on curved surfaces. Specifically, the fluorine-containing polymer material includes one or both of polyvinylidene fluoride and polytetrafluoroethylene.

[0062] In addition, the polymer material of the present invention can also be a (meth) acrylic acid polymer. Specifically, the (meth) acrylic acid polymer can be obtained by polymerization of (meth) acrylic acid monomers. Specifically, the (meth) acrylic acid monomers can be alkyl (meth) acrylic acid esters, cycloalkyl (meth) acrylic acid esters, and aryl (meth) acrylic acid esters. As alkyl (meth) acrylic acid esters, for example, (meth) acrylic acid esters used to form the monomer units of the above-mentioned acrylic acid polymers, that is, (meth) acrylic acid esters as the constituent monomers of the (meth) acrylic acid polymers. Examples include methyl (meth) acrylic acid esters, ethyl (meth) acrylic acid esters, propyl (meth) acrylic acid esters, isopropyl (meth) acrylic acid esters, butyl (meth) acrylic acid esters, isobutyl (meth) acrylic acid esters, sec-butyl (meth) acrylic acid esters, tert-butyl (meth) acrylic acid esters, amyl (meth) acrylic acid esters, isopentyl (meth) acrylic acid esters, heptyl (meth) acrylic acid esters, octyl (meth) acrylic acid esters, 2-ethylhexyl (meth) acrylic acid esters, isooctyl (meth) acrylic acid esters, nonyl (meth) acrylic acid esters, decyl (meth) acrylic acid esters, isodecyl (meth) acrylic acid esters, undecyl (meth) acrylic acid esters, dodecyl (meth) acrylic acid esters, tridecyl (meth) acrylic acid esters, tetradecyl (meth) acrylic acid esters, hexadecyl (meth) acrylic acid esters, octadecyl (meth) acrylic acid esters, and eicosyl (meth) acrylic acid esters. Examples of cycloalkyl (meth)acrylates include cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate. Examples of aryl (meth)acrylates include phenyl (meth)acrylate and benzyl (meth)acrylate. For other acrylic monomers, one (meth)acrylate may be used, or two or more (meth)acrylates may be used.

[0063] Specifically, the (meth)acrylic polymer of the present invention may be polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, or the like.

[0064] Furthermore, in the present invention, the thickness of the surface-enhanced Raman substrate is not less than 10 μm, for example, 10-100 μm, for example, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, etc. When the thickness of the surface-enhanced Raman substrate is not less than 10 μm, a surface-enhanced Raman substrate with excellent performance can be obtained.

[0065] <Second Aspect>

[0066] The second aspect of the present invention provides a method for preparing the surface-enhanced Raman substrate according to the first aspect of the present invention, which comprises the step of composite-forming the active nanostructure and the substrate.

[0067] In some specific embodiments, the preparation method comprises the following steps:

[0068] Depositing noble metals on a substrate to form active nanostructures, wherein the active nanostructures are arranged in an array to form an array film;

[0069] Dropping a polymer material solution onto the substrate to form a substrate, and allowing part of the polymer material to penetrate into the pores of the active nanostructures and coat the surface of the array film;

[0070] After removing the substrate, the surface enhanced Raman substrate is obtained.

[0071] Preferably, in the present invention, the substrate may be pretreated before the precious metal is deposited on the substrate. Specifically, the pretreatment includes washing and / or drying. For washing, the present invention can be performed by washing with acetone, alcohol, deionized water, etc. Specifically, acetone, alcohol, and deionized water can be used for washing in sequence. The present invention does not specifically limit the washing method, and it can be a washing method commonly used in the art, such as ultrasonic cleaning. The present invention does not specifically limit the drying method, and it can be dried by air drying.

[0072] In some specific embodiments, the step of preparing the array film includes: fixing the substrate on the sample stage of the electron beam evaporation coating machine, adjusting the incident angle to 82° to 88°, for example: 83°, 84°, 85°, 86°, 87°, etc., so as to obtain active nanostructures grown obliquely on the substrate; or,

[0073] The substrate is fixed on the sample stage of the electron beam evaporation coating machine, and the incident angle is adjusted to 82° to 88°, for example, 83°, 84°, 85°, 86°, 87°, etc., while the sample stage is rotated, thereby obtaining active nanostructures growing vertically on the substrate. Furthermore, the present invention does not specifically limit the setting conditions of the electron beam evaporation coating machine, but preferably the vacuum degree is 3×10 -5 ~8×10 -5 Pa, for example: 4×10 -5 Pa, 5×10 -5 Pa, 6×10 -5 Pa, 7×10 -5 Under an environment of Pa or the like, noble metals are used as targets to vertically or obliquely grow active nanostructures on the substrate to obtain an array film.

[0074] In some specific embodiments, the polymer solution is prepared by dissolving a polymer in an organic solvent. Preferably, the polymer solution has a mass concentration of 2% to 5%, for example, 2.5%, 3%, 3.5%, 4%, 4.5%, etc. The polymer solution is dripped onto the substrate to form a backing, and a portion of the polymer penetrates into the pores of the active nanostructures, coating the surface of the array film.

[0075] Furthermore, in order to form the substrate, a polymer material solution can be dripped onto the substrate, and then placed in a ventilated place for 4-6 hours and allowed to dry naturally to form the substrate.

[0076] Specifically, in the present invention, the organic solvent for dissolving the polymer material may be one or a combination of two or more of N,N-dimethylformamide, anisole, chlorobenzene, etc.

[0077] Finally, the substrate is removed to obtain a surface-enhanced Raman substrate. The present invention does not impose any particular limitation on the method of removing the substrate, as long as it can be removed without affecting the substrate.

[0078] Example

[0079] The embodiments of the present invention will be described in detail below with reference to the examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention. Where specific conditions are not specified in the examples, the methods were performed according to conventional conditions or the conditions recommended by the manufacturer. Where the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be obtained commercially.

[0080] Example 1

[0081] 1. Ultrasonic clean the silicon substrate with acetone, alcohol, and deionized water in sequence and dry it;

[0082] 2. Fix the cleaned substrate on the sample stage of the electron beam evaporation coating machine;

[0083] 3. Using metallic silver as the target material at room temperature, pump the deposition chamber of the e-book evaporation coating machine to 5×10 -5 High vacuum of Pa;

[0084] 4. Adjust the tilt angle of the sample stage so that the evaporation angle is 86°, and keep the sample stage still. On the base of the sample stage, grow an apparent thickness of Silver thin film;

[0085] 5. Slowly add polyvinylidene fluoride powder (PVDF) (weight average molecular weight of about 400,000 Da) to N,N-dimethylformamide (DMF) to make the mass concentration of PVDF 5%. Stir continuously during the addition process until the PVDF is completely dissolved to obtain a uniform translucent solution.

[0086] 6. Place the surface-enhanced Raman substrate prepared in steps 1 to 4 on a flat surface, and evenly drop the polyvinylidene fluoride solution prepared in step 5 onto the substrate to form a uniform thin layer. Then, let it stand in air for 6 hours to form a polymer film. The amount of polyvinylidene fluoride solution added should be sufficient to completely cover the substrate without forming a noticeable convex liquid surface.

[0087] 7. Use tweezers to peel off the polymer film from the silicon substrate to obtain a PVDF-silver nanorod flexible and transparent surface-enhanced Raman substrate.

[0088] The scanning electron microscope photos of the prepared substrate are as follows Figure 1 As shown, it can be seen that the silver nanorods obtained by electron beam deposition are attached to the surface of the film composed of polyvinylidene fluoride, making the substrate flexible and bendable; and the surface of each silver nanorod is also covered with a polymer layer, thereby reducing contact with oxygen and improving the performance stability of the substrate.

[0089] Example 2

[0090] 1. Ultrasonic clean the silicon substrate with acetone, alcohol, and deionized water in sequence and dry it;

[0091] 2. Fix the cleaned substrate on the sample stage of the electron beam evaporation coating machine;

[0092] 3. Using metallic silver as the target material at room temperature, pump the deposition chamber of the electron beam evaporation coating machine to 5×10 -5 High vacuum of Pa;

[0093] 4. Adjust the tilt angle of the sample stage to make the evaporation angle 86°, and keep the sample stage still. On the base of the sample stage, grow the apparent thickness of Silver thin film;

[0094] 5. Slowly add polyvinylidene fluoride powder (weight average molecular weight of about 400,000 Da) to N,N-dimethylformamide (DMF) to make the mass concentration of polyvinylidene fluoride 2%. Stir continuously during the addition process until the polyvinylidene fluoride is completely dissolved to obtain a uniform translucent solution;

[0095] 6. Place the surface-enhanced Raman substrate prepared in steps 1 to 4 on a flat surface, and evenly drop the polyvinylidene fluoride solution prepared in step 5 onto the substrate to form a uniform thin layer. Then, let it stand in air for 6 hours to form a polymer film. The amount of polyvinylidene fluoride solution added should be sufficient to completely cover the substrate without forming a noticeable convex liquid surface.

[0096] 7. Use tweezers to peel off the polymer film from the silicon substrate to obtain a PVDF-silver nanorod flexible and transparent surface-enhanced Raman substrate.

[0097] The scanning electron microscope photos of the prepared substrate are as follows Figure 2 As shown, based on the silver nanorods deposited by electron beam attached to the surface of the polymer film, the distribution of the silver nanorods is more uniform, and the polymer layer attached to each silver nanorod is thinner, which effectively isolates the silver nanorods from contact with oxygen while ensuring their surface enhanced Raman effect.

[0098] Example 3

[0099] 1. Ultrasonic clean the silicon substrate with acetone, alcohol, and deionized water in sequence and dry it;

[0100] 2. Fix the cleaned substrate on the sample stage of the electron beam evaporation coating machine;

[0101] 3. Using metallic silver as the target material at room temperature, pump the deposition chamber of the electron beam evaporation coating machine to 5×10 -5 High vacuum of Pa;

[0102] 4. Adjust the tilt angle of the sample stage to make the evaporation angle 86°, and keep the sample stage still. On the base of the sample stage, grow the apparent thickness of Silver thin film;

[0103] 5. Place the surface-enhanced Raman substrate prepared in steps 1 to 4 on a flat surface, and add a polymethyl methacrylate (PMMA) photoresist (model PMMA 950A4, weight-average molecular weight 950,000 Da, solvent anisole, so that the mass concentration of polymethyl methacrylate is 4%) produced by MicroChem, USA. Then, evenly drop the polymethyl methacrylate solution onto the substrate to form a uniform thin layer. Then, let it stand in air for 12 hours to form a polymer film. The amount of polymethyl methacrylate solution added should be sufficient to completely cover the substrate without forming a noticeable convex meniscus.

[0104] 6. Use tweezers to peel off the polymer film from the silicon substrate to obtain a PMMA-silver nanorod flexible and transparent surface-enhanced Raman substrate.

[0105] The scanning electron microscope photos of the prepared substrate are as follows Figure 3As shown, the silver nanorods deposited by electron beam are covered by polymers, which effectively isolates the silver nanorods from oxygen while ensuring their surface enhanced Raman effect.

[0106] Performance Test 1

[0107] Preparation 10 -4 mol / L Rhodamine 6G solution, 10 -5 mol / L Rhodamine 6G solution;

[0108] 20 μL of the above-prepared solution was extracted using a pipette and dropped onto one side of the silver nanorods of the surface-enhanced Raman substrate of Example 3, and then dried in air to attach a trace amount of rhodamine 6G to the surface-enhanced Raman substrate;

[0109] The surface enhanced Raman substrate with trace amount of Rhodamine 6G was placed into the Raman spectrometer, and the light source with wavelength of 785nm was selected to measure the Raman spectrum. The results are as follows: Figure 4 shown.

[0110] Depend on Figure 4 It can be seen that by measuring the Raman spectra on different sides of the surface-enhanced Raman substrate, it was found that the characteristic Raman spectra of Rhodamine 6G appeared in the Raman spectra on both sides, indicating that the substrate has a certain enhancement effect on Rhodamine 6G; the polymer layer has good transmittance to laser and has the ability of in-situ adsorption-testing.

[0111] Performance Test 2

[0112] Preparation 10 -4 mol / L Rhodamine 6G solution, 10 -6 mol / L Rhodamine 6G solution;

[0113] 20 μL of the above-prepared solution was extracted using a pipette and dropped onto one side of the silver nanorods of the surface-enhanced Raman substrate of Example 2, and then dried in air to attach a trace amount of rhodamine 6G to the surface-enhanced Raman substrate;

[0114] The surface enhanced Raman substrate with trace amount of Rhodamine 6G was placed into the Raman spectrometer, and the light source with wavelength of 785nm was selected to measure the Raman spectrum. The results are as follows: Figure 5 shown.

[0115] Depend on Figure 5It can be seen that by measuring the Raman spectra on two different sides of the surface-enhanced Raman substrate, the Raman spectral intensity on both sides is almost unchanged and the spectral peak shape does not change significantly, indicating that the polymer layer has good transmittance to laser light and is capable of in-situ adsorption and testing. The effect is better than the surface-enhanced Raman substrate of Example 3.

[0116] It should be noted that, although the technical solutions of the present invention are described with specific examples, those skilled in the art will appreciate that the present invention should not be limited thereto.

[0117] While various embodiments of the present invention have been described above, the above descriptions are intended to be illustrative, non-exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is selected to best explain the principles of the embodiments, their practical applications, or technological improvements in the marketplace, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A surface-enhanced Raman substrate, characterized in that: include: Active nanostructures, wherein the active nanostructures are arranged in an array to form an array film; as well as a substrate formed on one side of the array film; and The substrate is derived from a polymer material, and at least a portion of the polymer material penetrates into the pores of the active nanostructures and covers the surface of the array film; The length of the active nanostructure is 200-500 nm; the active nanostructure is distributed perpendicular to the substrate or distributed at an inclined angle relative to the substrate; The polymer material includes one or a combination of two or more fluorine-containing polymer materials.

2. The surface-enhanced Raman substrate according to claim 1, characterized in that The active nanostructures are derived from noble metals.

3. The surface-enhanced Raman substrate according to claim 2, characterized in that The precious metals include gold and / or silver.

4. The surface-enhanced Raman substrate according to any one of claims 1 to 3, characterized in that The inclination angle is 70-75°.

5. The surface-enhanced Raman substrate according to any one of claims 1 to 3, characterized in that: The thickness of the surface enhanced Raman substrate is not less than 10 μm.

6. A method for preparing a surface-enhanced Raman substrate according to any one of claims 1 to 5, characterized in that: The method comprises the steps of composite-forming the active nanostructure and the substrate.

7. The preparation method according to claim 6, characterized in that The following steps are involved: Depositing noble metals on a substrate to form active nanostructures, wherein the active nanostructures are arranged in an array to form an array film; Dropping a polymer material solution on the substrate to form a substrate, and allowing part of the polymer material to penetrate into the pores of the active nanostructures and coat the surface of the array film; After removing the substrate, the surface enhanced Raman substrate is obtained.

8. The preparation method according to claim 7, characterized in that The steps of preparing the array film include: fixing the substrate on the sample stage of the electron beam evaporation coating machine, adjusting the incident angle to 82° to 88°; -5 ~8×10 - 5 In an environment of Pa, using noble metal as a target, active nanostructures are obliquely grown on the substrate to obtain an array film; or, The substrate was fixed on the sample stage of the electron beam evaporation coating machine, and the incident angle was adjusted to 82°~88°. At the same time, the sample stage was rotated and the vacuum degree was 3×10 -5 ~8×10 -5 In a Pa environment, noble metals are used as targets to vertically grow active nanostructures on the substrate to obtain an array film.

9. The preparation method according to claim 7 or 8, characterized in that The polymer material solution is prepared by dissolving the polymer material in an organic solvent.

10. The preparation method according to claim 9, characterized in that In the polymer material solution, the mass concentration of the polymer material is 2%-5%.

11. The preparation method according to claim 7 or 8, characterized in that: After the polymer material solution is dripped onto the substrate, the substrate is placed in a ventilated place for 4-6 hours and then dried naturally to form the substrate.

12. The preparation method according to claim 9, characterized in that The organic solvent includes one or a combination of two or more of N,N-dimethylformamide, anisole or chlorobenzene.

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