Nondestructive fitting type self-powered SERS (Surface Enhanced Raman Scattering) flexible substrate and use method thereof
By leveraging the multilayer composite structure and biomimetic adhesion properties of flexible substrates, combined with self-powered modules and intelligent algorithms, the problem of non-destructive bonding and efficient detection of flexible SERS substrates on curved samples was solved, enabling high-sensitivity trace substance analysis in complex environments.
Patent Information
- Application Number
- CN202510723878.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-01
- Publication Date
- 2025-11-07
AI Technical Summary
Existing flexible SERS substrates are difficult to adapt to biological tissues and curved surface samples, leading to substrate breakage or sample damage. Furthermore, their signal stability and ease of operation are insufficient, limiting their application in complex scenarios.
A sandwich structure composed of polydimethylsiloxane and polyimide is adopted, combined with a PDMS nanopillar array with a biomimetic gecko foot structure and a self-powered module. Through the conductive network of graphene and carbon nanotubes and the noble metal nanostructure layer, non-destructive bonding and efficient charge transfer are achieved. Spectral feature recognition is performed by combining convolutional neural network algorithm.
It achieves adaptive bonding of the substrate to complex surfaces, allows for multiple non-destructive reuses, enhances Raman signal enhancement and detection sensitivity, supports rapid identification of trace substances and is applicable to multiple scenarios, meeting the needs of biomedicine and environmental monitoring.
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Figure CN120908160A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of SERS detection, in particular to a nondestructive fitting type self-powered SERS flexible substrate and a use method. BACKGROUND
[0002] A surface-enhanced Raman spectroscopy (SERS) flexible substrate is a core component for trace substance detection, and can enhance the Raman signal of a to-be-detected substance by millions of times through the localized plasmon resonance effect of a noble metal nanostructure. In recent years, with the development of flexible electronics and wearable technology, the SERS substrate gradually evolves towards flexibility and self-powering to meet the demand for in-situ analysis of non-planar samples in biomedical detection, environmental on-site monitoring and the like. However, the mechanical adaptability, signal stability and operation convenience of the existing flexible SERS substrate still have significant limitations, which restrict the practical application of the flexible SERS substrate in complex scenes.
[0003] Traditional SERS substrates are mostly made of rigid materials or simple polymer films, and are difficult to adapt to surfaces with curvature changes such as biological tissues and microfluidic devices, and forced fitting may easily lead to substrate fracture or sample damage. SUMMARY
[0004] In view of the deficiencies of the prior art, the application provides a nondestructive fitting type self-powered SERS flexible substrate and a use method, which solve the problem that the prior art cannot meet the requirement for nondestructive fitting in the scenes of in-vivo detection and curved surface trace analysis.
[0005] To achieve the above object, the application is implemented by the following technical scheme: a nondestructive fitting type self-powered SERS flexible substrate, comprising:
[0006] A flexible substrate layer in a sandwich structure formed by polydimethylsiloxane and polyimide, with a total thickness of 50-200 mu m;
[0007] A conductive interdigital electrode layer arranged on the surface of the flexible substrate layer and comprising a mesh structure interwoven by graphene and carbon nanotubes, with an electrode spacing of 50-200 nm and a thickness of 10-50 nm;
[0008] A noble metal nanostructure layer covering the surface of the conductive interdigital electrode layer and comprising a three-dimensional nano-gap array formed by periodic arrangement of silver nanowires and gold nanotapers, with a gap size of 5-20 nm and a 2-5 nm thick SiO2 protective layer deposited on the surface;
[0009] A self-powered module electrically connected to the conductive interdigital electrode layer through a wire and comprising an integrated unit of a friction nanogenerator and a micro super capacitor, with an output current of 10-100 mu A and a continuous power supply time of greater than or equal to 30 minutes;
[0010] Reversible adhesive surface, set in the outermost layer of the substrate, is a PDMS nanorod array with a biomimetic gecko footpad structure, with a rod diameter of 200-500 nm and an adjustable adhesion range of 0.1-5 N / cm 2 .
[0011] By the above technical solution: the composite network structure of graphene and carbon nanotubes forms a high-transmittance conductive network, the electrode spacing matches the plasmonic coupling distance of the noble metal nanostructure, and the surface electric field distribution is optimized. The nanoscale thickness design reduces light scattering loss while maintaining a low sheet resistance (<10 Ω / sq), providing an efficient charge transport channel for self-powered modules;
[0012] The polydimethylsiloxane nanorod array with a gecko footpad structure realizes controllable adhesion through van der Waals force, and the diameter gradient design adapts to different roughness surfaces. When peeling vertically, the nanorod elastic deformation releases the adhesion force, avoiding damage to the sample or residual pollutants, and supporting more than 50 times of repeated use.
[0013] Preferably, the middle layer of the flexible substrate layer is a shape memory polymer with a glass transition temperature of 30-60℃, and the thickness of the polyimide protective layer on both sides is 10-50μm. The substrate can withstand bending deformation with a radius of curvature ≥50μm and the resistance change rate is <5% after 1000 bending cycles.
[0014] By the above technical solution: through the sandwich composite design of polydimethylsiloxane and polyimide, the flexible and rigid requirements are balanced. The middle shape memory polymer layer can restore the original shape when heated or mechanically stimulated, enhancing the adaptive fitting ability of the substrate to curved surfaces and avoiding structural fatigue after multiple bending. The two-sided polyimide protective layer blocks environmental moisture and chemical corrosion, ensuring the long-term stability of the substrate in complex environments.
[0015] Preferably, the noble metal nanostructure layer is prepared by electrochemical self-assembly method, including the following steps:
[0016] Spin coating an ethanol solution containing 0.1-1wt% polyvinylpyrrolidone on the surface of the conductive interdigital electrode;
[0017] Applying a direct current voltage of 1-5V to induce the directional arrangement of silver nanowires along the electrode direction;
[0018] Using magnetron sputtering to deposit gold nanotapers in the gap of silver nanowires, with a sputtering power of 50-200W and a time of 10-60 seconds;
[0019] Atomic layer deposition method generates a 2-5nm thick SiO2 protective layer on the surface.
[0020] Through the technical scheme, the directional arrangement of the silver nanowires and the gap filling of the gold nanotapers form a three-dimensional electromagnetic field hot spot, and the Raman signal is enhanced by 8-11 orders of magnitude through surface plasmon resonance. The silica protective layer inhibits the oxidation of noble metals and fixes the nano structure, avoiding the instability of the hot spot during detection.
[0021] Preferably, the friction nanogenerator of the self-powered module comprises the following steps:
[0022] The upper and lower laminated fluorinated ethylene-propylene copolymer film and copper electrode pair, the film thickness is 20-100 μm;
[0023] The micro super capacitor is composed of MXene / graphene composite electrode and ionic liquid electrolyte, and the capacitance value is 0.1-1 mF;
[0024] The energy conversion efficiency is ≥40%, and the maximum output power density is 10-100 mW / cm 2 .
[0025] Through the technical scheme, the friction nanogenerator generates pulse current through mechanical deformation, and the micro super capacitor converts it into stable direct current output, which is free from dependence on external power supply. The high electron affinity of the fluorinated ethylene-propylene copolymer film and the copper electrode pair improve the charge density, and the pseudo-capacitive characteristics of the MXene / graphene composite electrode prolong the power supply time.
[0026] Preferably, the silver nanowires and gold nanotapers of the noble metal nano structure layer are arranged in three-dimensional orthogonal arrangement, wherein the silver nanowires are arranged along the extension direction of the electrode, the gold nanotapers are inserted into the gap between the silver nanowires at an inclination angle of 45°-90°, forming a periodic nanocavity array, and the equivalent electromagnetic field enhancement factor gradient of the nanocavity is 10 8 -10 11 / cm 2 .
[0027] Through the technical scheme: the inclined gold nanotapers and silver nanowires form cross electromagnetic field coupling, and the enhancement factor gradient covers the detection requirements of different molecular sizes.
[0028] A use method of a non-destructive conformable self-powered SERS flexible substrate, the use method comprising the following steps:
[0029] Step one, by applying a negative pressure of 0.1-0.5 atm, the reversible adhesive surface of the substrate is self-adapted to the surface of the object to be measured with a curvature radius of ≥50 μm;
[0030] Step two, apply mechanical excitation to the substrate with a frequency of 1-100 Hz and a strain rate of ≤5% / s, to trigger the self-powered module to generate stable current;
[0031] Step three, use laser with wavelength of 532nm or 785nm to irradiate the substrate surface with power density of 10 4 -10 6 W / cm 2 The substrate surface is irradiated with power density, and the Raman signal is collected by a fiber spectrometer with a collection time of 10-300ms.
[0032] Step four, non-destructively peel the substrate with a vertical tensile force of ≤5N / cm 2 , and repeat the use for ≥50 times.
[0033] Step five, combine convolutional neural network algorithm to identify characteristic peaks of Raman spectrum, and the detection sensitivity reaches 10 - 12 mol / L.
[0034] Through the above technical solutions: negative pressure fitting combined with shape memory effect, the substrate self-adapts to the curvature of the concave-convex surface with a curvature of ≥50μm, eliminating the edge warping problem of traditional hard substrate, bending excitation mode preferentially activates the piezoelectric effect of the friction nanogenerator, matching the mechanical deformation characteristics of curved surface detection, improving the energy conversion efficiency, laser incidence angle adjustment matches the sample surface reflection characteristics, 30°-90° adjustable range covers the detection needs of mirror surface to diffuse reflection surface, vertical peeling strategy controls the direction of adhesion force, avoiding the damage of nanometer structure caused by shear force, convolutional neural network algorithm quickly identifies characteristic peaks through transfer learning, solving the small sample spectrum data training problem, and improving the detection versatility.
[0035] Preferably, the fitting process in step one includes pre-stretching the substrate to 5-15% strain rate and then releasing, using shape memory effect to realize curved surface self-adaptation, and fitting error <5μm.
[0036] Through the above technical solutions: the glass transition temperature of shape memory polymer (30-60℃) can be softened by body temperature or local heating during fitting, and the shape is locked after cooling, realizing <5μm level fitting precision.
[0037] Preferably, in step three, the adjustable range of laser incidence angle is 30°-90°, which cooperates with the plasmonic resonance effect of conductive interdigital electrode to make the electromagnetic field enhancement factor reach 10 8 -10 10 .
[0038] Through the above technical solutions: polyvinylpyrrolidone in electrochemical self-assembly controls the spacing of silver nanowires, and the sputtering time of magnetic control is controlled to control the density of gold nanotaper, forming uniform distributed plasmonic hot spots.
[0039] Preferably, in the fourth step, the mechanical excitation includes bending, stretching or vibration mode, and the bending excitation is preferred when detecting the curved sample, the bending angle is 5-30 degrees, and the frequency is 10-50 Hz.
[0040] Preferably, in the third step, the adjustment of the laser power density and the acquisition time satisfies the following relationship:
[0041]
[0042] wherein P is the laser power density (W / cm 2 ), M is the molecular weight of the to-be-detected substance, t is the acquisition time (ms), k is the adjustment coefficient and is 0.1-1.0, and the optimization detection with a signal-to-noise ratio of greater than or equal to 25 dB is realized.
[0043] By the above technical solution: the mathematical relationship of the laser power density, the molecular weight and the acquisition time realizes the adaptive detection, and damage of the low-molecular-weight sample by high-power laser is avoided.
[0044] The application provides a non-destructive fitting type self-powered SERS flexible substrate and a use method.
[0045] 1. The flexible substrate of the application has a multi-layer composite structure and a biomimetic adhesion property, so that the substrate can be self-adapted to surfaces with different curvatures, and the non-destructive peeling is realized through controllable adhesion, so that the substrate is better adapted to the shape of the detection object, especially for in-situ analysis of biological tissues and micro-nano devices on non-flat surfaces, the deformation recovery ability and mechanical stability of the substrate support repeated use, avoid material loss or performance degradation caused by fitting operation, realize self-adaptive fitting and non-destructive detection of complex surfaces.
[0046] 2. The three-dimensional arrangement and gap regulation of the noble metal nano unit greatly improve the surface plasmon resonance effect, effectively enhance the Raman signal intensity, and the self-powered module provides continuous and stable power supply for the detection process through the combination of mechanical energy conversion and energy storage, and breaks away from the dependence on traditional power supply. The synergistic effect of the two can still maintain high detection sensitivity of the substrate in complex environments, meet the rapid identification demand of trace substances, and provide technical support for real-time analysis on site.
[0047] 3. The application is based on a dynamic regulation model of detection conditions, which can autonomously optimize laser parameters and signal acquisition strategies, thereby improving the detection efficiency of different molecular characteristic substances, combining with the intelligent analysis of spectral characteristics by deep learning algorithm, realizing the rapid determination of substance types and concentrations, and automatically matching the optimal detection scheme in diversified scenes, greatly expanding the applicability of the substrate in the fields of biomedicine and environmental monitoring. Through the combination of dynamic parameter adjustment and intelligent algorithm, multi-scene adaptive rapid analysis is realized. Attached Figure Description
[0048] Figure 1 This is a flowchart illustrating a method for using a non-destructive bonding type self-powered SERS flexible substrate according to the present invention. Detailed Implementation
[0049] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0050] Please see the appendix Figure 1 This invention provides a non-destructive bonding type self-powered SERS flexible substrate, comprising:
[0051] The flexible substrate layer is a sandwich structure formed by polydimethylsiloxane and polyimide, with a total thickness of 50-200μm.
[0052] The conductive interdigitated electrode layer is disposed on the surface of the flexible substrate layer and contains a mesh structure of interwoven graphene and carbon nanotubes. The electrode spacing is 50-200nm and the thickness is 10-50nm.
[0053] A noble metal nanostructure layer covers the surface of the conductive interdigitated electrode layer. It is formed by a three-dimensional nano-gap array of silver nanowires and gold nanocones arranged periodically, with a gap size of 5-20 nm. A 2-5 nm thick SiO2 protective layer is deposited on the surface.
[0054] The self-powered module is electrically connected to the conductive interdigital electrode layer via wires. It includes an integrated unit of a triboelectric nanogenerator and a micro supercapacitor, with an output current of 10-100μA and a continuous power supply time of ≥30 minutes.
[0055] A reversible adhesive surface, located on the outermost layer of the substrate, is a PDMS nanopillar array with a biomimetic gecko foot structure. The pillars have a diameter of 200-500 nm, and the adhesion force is adjustable from 0.1-5 N / cm. 2 .
[0056] Graphene provides in-plane conductive pathways, carbon nanotubes fill interlayer gaps to reduce contact resistance, and the 50-200 nanometer spacing matches the plasmon coupling distance of noble metal nanostructures to avoid electromagnetic shielding effects. The 10-50 nanometer thickness is achieved through a combination of chemical vapor deposition and spraying processes to balance light transmittance and conductivity.
[0057] The polydimethylsiloxane nanocolumn array is adhered by van der Waals force, the diameter gradient design is adapted to different surface roughness, the adhesion force is adjusted by the aspect ratio of the nanocolumn, the high aspect ratio provides a larger contact area and elastic deformation capacity, the low surface energy characteristics of polydimethylsiloxane avoid the adhesion of pollutants, and the reusability is ensured.
[0058] The middle layer of the flexible substrate layer is a shape memory polymer with a glass transition temperature of 30-60℃, and the thickness of the polyimide protective layer on both sides is 10-50μm. The substrate can withstand bending deformation with a radius of curvature ≥50μm and the resistance change rate is <5% after 1000 bending cycles.
[0059] The polydimethylsiloxane provides flexibility and biocompatibility, the polyimide layer enhances mechanical strength and high temperature resistance, the shape memory polymer middle layer endows shape memory characteristics, the total thickness range is optimized by finite element simulation to ensure uniform stress distribution when the substrate is bent, avoiding the risk of delamination, and the glass transition temperature range of the shape memory polymer is suitable for human body temperature to high temperature detection scenarios (such as industrial equipment surface).
[0060] The noble metal nanostructure layer is prepared by electrochemical self-assembly method, including the following steps:
[0061] Spin coating an ethanol solution containing 0.1-1wt% polyvinylpyrrolidone on the surface of the conductive interdigital electrode;
[0062] Apply a direct current voltage of 1-5V to induce the directional arrangement of silver nanowires along the electrode direction;
[0063] Gold nanotapers are deposited in the gap between silver nanowires using magnetron sputtering, with a sputtering power of 50-200W and a time of 10-60 seconds;
[0064] A 2-5nm thick SiO2 protective layer is generated on the surface by atomic layer deposition method.
[0065] The high conductivity of silver nanowires and the tip enhancement effect of gold nanotapers synergistically enhance the local electric field strength, the silver nanowire spacing is controlled by the voltage in the electrochemical self-assembly, the gold nanotaper density is adjusted by the magnetron sputtering time, and the silicon dioxide layer is uniformly coated by the atomic layer deposition process to prevent oxidation of the noble metal and fix the position of the nanostructure.
[0066] The friction nanogenerator of the self-powered module includes the following steps:
[0067] The upper and lower layers of fluorinated ethylene propylene copolymer film and copper electrode pairs, with a film thickness of 20-100μm;
[0068] The micro super capacitor is composed of MXene / graphene composite electrode and ionic liquid electrolyte, with a capacitance of 0.1-1mF;
[0069] Energy conversion efficiency ≥ 40%, maximum output power density 10-100 mW / cm 2 .
[0070] The friction nanogenerator converts mechanical energy into pulsed electrical energy, the supercapacitor filters and stores, outputs smooth direct current, fluorinated ethylene propylene copolymer film (negative material) and copper electrode pair to improve the friction charge density, two-dimensional transition metal carbide or nitride / graphene composite electrode increases the specific surface area of supercapacitor, and the energy conversion efficiency is realized through impedance matching circuit to avoid energy transmission loss.
[0071] The silver nanowires and gold nanotapers of the noble metal nanostructure layer are arranged in three-dimensional orthogonal arrangement, wherein the silver nanowires are arranged in the direction of the electrode extension, and the gold nanotapers are inserted into the gaps between the silver nanowires at an inclination angle of 45°-90°, forming a periodic nanocavity array, and the equivalent electromagnetic field enhancement factor gradient of the nanocavity is 10 8 -10 11 / cm 2 .
[0072] The silver nanowires guide the propagation of surface plasmons, and the inclined gold nanotapers produce cross-coupling hot spots. The inclination angle of 45°-90° is optimized by multi-physical field simulation software, so that the electric field enhancement factor gradient covers a specific range, and the nanocavity array period matches the visible light to near-infrared laser wavelength.
[0073] A use method of a lossless attached self-powered SERS flexible substrate, the use method comprising the following steps:
[0074] Step one, by applying a negative pressure of 0.1-0.5 atm, the reversible adhesive surface of the substrate is self-adapted to the surface of the object to be measured with a curvature radius of ≥50 μm;
[0075] Step two, apply mechanical excitation to the substrate with a frequency of 1-100 Hz and a strain rate of ≤5% / s to trigger the self-powered module to generate a stable current;
[0076] Step three, irradiate the surface of the substrate with a laser with a wavelength of 532 nm or 785 nm at a power density of 10 4 -10 6 W / cm 2 , collect the Raman signal by an optical fiber spectrometer, and the collection time is 10-300 ms;
[0077] Step four, peel off the substrate without damage with a vertical tensile force of ≤5 N / cm 2 , and the number of repeated uses is ≥50 times;
[0078] Step five, combine the convolutional neural network algorithm to identify the characteristic peaks of the Raman spectrum, and the detection sensitivity reaches 10 - 12 mol / L.
[0079] The negative pressure is uniformly applied through the micro-channel, eliminating the interference of bubbles; the pre-stretching activates the shape memory effect of the shape memory polymer; the bending excitation is preferentially used for curved surface detection, as the bending angle can maximize the output current density of the friction nanogenerator; the 532 nm laser is suitable for biological samples, and the 785 nm laser is suitable for dark background samples; the convolutional neural network model is pre-trained through transfer learning, supporting high-precision identification of small sample spectral data.
[0080] In step one, the lamination process includes pre-stretching the substrate to a strain rate of 5-15% and then releasing, and the shape memory effect is used to realize self-adaptation of the curved surface, with a lamination error of <5 μm.
[0081] In step three, the laser incidence angle can be adjusted in the range of 30°-90°, and the plasmonic resonance effect of the conductive interdigital electrode makes the electromagnetic field enhancement factor reach 10 8 -10 10 .
[0082] In step four, the mechanical excitation includes bending, stretching or vibration modes, and the bending excitation is preferentially used when detecting curved surface samples, with a bending angle of 5°-30° and a frequency of 10-50 Hz.
[0083] In step three, the adjustment of laser power density and acquisition time satisfies the following relationship:
[0084]
[0085] where P is the laser power density (W / cm 2 ), M is the molecular weight of the substance to be detected, t is the acquisition time (ms), k is the adjustment coefficient and takes a value of 0.1-1.0, and the optimization detection with a signal-to-noise ratio ≥25 dB is realized.
[0086] The molecular weight is positively correlated with the Raman scattering cross section, and higher power density is required to excite effective signals for high molecular weight substances; the adjustment coefficient covers the light loss difference in different detection environments; and the signal-to-noise ratio is realized through an adaptive filtering algorithm to filter out environmental vibration and thermal noise interference.
[0087] Although embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and alterations can be made thereto without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.
Claims
1. A lossless conformal self-powered SERS flexible substrate, characterized in that, Comprise: A flexible substrate layer, a sandwich structure composed of polydimethylsiloxane and polyimide, total thickness of 50-200 μm; A conductive interdigital electrode layer, disposed on the surface of the flexible substrate layer, containing a mesh structure of graphene and carbon nanotube interweaving, electrode spacing of 50-200 nm, thickness of 10-50 nm; A noble metal nanostructure layer, covering the surface of the conductive interdigital electrode layer, a three-dimensional nano-gap array formed by periodic arrangement of silver nanowires and gold nanotapers, gap size of 5-20 nm, with a 2-5 nm thick SiO2 protective layer deposited on the surface; A self-powered module, electrically connected to the conductive interdigital electrode layer through a wire, containing an integrated unit of triboelectric nanogenerator and micro-supercapacitor, output current of 10-100 μA, continuous power supply time ≥ 30 minutes; Reversible adhesive surface, set in the outermost layer of the substrate, is a PDMS nano-pillar array of biomimetic gecko footpads structure, pillar diameter 200-500 nm, adhesive force adjustable range 0.1-5 N / cm 2 .
2. The lossless conformal self-powered SERS flexible substrate according to claim 1, characterized in that: The middle layer of the flexible substrate layer is a shape memory polymer with a glass transition temperature of 30-60 ℃, and the polyimide protective layer on both sides has a thickness of 10-50 μm, the substrate can withstand bending deformation with a radius of curvature ≥ 50 μm and the resistance change rate is < 5% after 1000 bending cycles.
3. The lossless conformal self-powered SERS flexible substrate according to claim 1, wherein: The noble metal nanostructure layer is prepared by electrochemical self-assembly method, comprising the following steps: Spin coating 0.1-1 wt% polyvinylpyrrolidone ethanol solution on the surface of the conductive interdigital electrode; Apply a direct current voltage of 1-5 V to induce silver nanowires to align along the electrode direction; Depositing gold nanotapers in the gap of silver nanowires by magnetron sputtering, sputtering power of 50-200 W, time of 10-60 seconds; Atomic layer deposition method to generate a 2-5 nm thick SiO2 protective layer on the surface.
4. The lossless conformal self-powered SERS flexible substrate according to claim 1, wherein: The triboelectric nanogenerator of the self-powered module comprises the following steps: A pair of upper and lower stacked fluorinated ethylene-propylene copolymer films and copper electrodes, film thickness of 20-100 μm; The micro-supercapacitor is composed of MXene / graphene composite electrode and ionic liquid electrolyte, with a capacitance of 0.1-1 mF; Energy conversion efficiency > 40%, maximum output power density 10-100 mW / cm 2 .
5. The lossless conformal self-powered SERS flexible substrate according to claim 1, wherein: The silver nanowires and gold nanotapers of the noble metal nanostructure layer are arranged in three-dimensional orthogonal arrangement, wherein the silver nanowires are arranged in the direction of the electrode extension, and the gold nanotapers are inserted into the gaps between the silver nanowires at an inclination angle of 45°-90° to form a periodic nanocavity array, and the equivalent electromagnetic field enhancement factor gradient of the nanocavity is 10 8 -10 11 / cm 2 .
6. A method of using a lossless conformal self-powered SERS flexible substrate, comprising: A non-destructive conformable self-powered SERS flexible substrate according to any one of claims 1-5, the use method comprising the following steps: Step one, by applying a negative pressure of 0.1-0.5 atm, the reversible adhesive surface of the substrate is self-adapted to the surface of the object to be measured with a radius of curvature ≥ 50 μm; Step two, apply mechanical excitation to the substrate with a frequency of 1-100 Hz and a strain rate of ≤ 5% / s to trigger the self-powered module to generate a stable current; Step three, the laser with wavelength of 532nm or 785nm is used to irradiate the surface of the substrate with power density of 10 4 -10 6 W / cm 2 Power density irradiates the surface of the substrate, and the Raman signal is collected by the fiber spectrometer, and the collection time is 10-300ms; Step four, non-destructively peel the substrate with a vertical pull force of < 5 N / cm 2 ≥ 50 times. Step five, the convolutional neural network algorithm is combined to identify the characteristic peaks of the Raman spectrum, and the detection sensitivity reaches 10 -12 mol / L.
7. The non-destructive conformal self-powered SERS flexible substrate and method of use of claim 6, wherein: In step one, the conforming process includes pre-stretching the substrate to 5-15% strain rate and then releasing it, which realizes the self-adaptation of the curved surface by using the shape memory effect, with a conforming error of < 5 μm.
8. The non-destructive conformal self-powered SERS flexible substrate and method of use of claim 6, wherein: In the third step, the laser incidence angle can be adjusted in the range of 30°-90°, and the plasmonic resonance effect of the conductive interdigital electrode can make the electromagnetic field enhancement factor reach 10 8 -10 10 .
9. The non-destructive conformal self-powered SERS flexible substrate and method of use of claim 6, wherein: In step four, the mechanical excitation includes bending, stretching or vibration modes, when detecting curved surface samples, bending excitation is preferred, with a bending angle of 5°-30° and a frequency of 10-50 Hz.
10. The non-destructive conformal self-powered SERS flexible substrate and method of use of claim 6, wherein: In step three, the adjustment of laser power density and collection time satisfies the following relationship: wherein P is the laser power density (W / cm2), M is the molecular weight of the substance to be measured, t is the acquisition time (ms), and k is a correction factor and has a value of 0.1-1.0, achieving an optimized detection with a signal-to-noise ratio > 25 dB. 2 wherein P is the laser power density (W / cm2), M is the molecular weight of the substance to be measured, t is the acquisition time (ms), and k is a correction factor and has a value of 0.1-1.0, achieving an optimized detection with
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