LU101707B1 - Flexible sers substrate based on nano-structures and ordered nano-particles, and preparation method and application thereof - Google Patents

Flexible sers substrate based on nano-structures and ordered nano-particles, and preparation method and application thereof Download PDF

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LU101707B1
LU101707B1 LU101707A LU101707A LU101707B1 LU 101707 B1 LU101707 B1 LU 101707B1 LU 101707 A LU101707 A LU 101707A LU 101707 A LU101707 A LU 101707A LU 101707 B1 LU101707 B1 LU 101707B1
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nano
particles
grooves
structures
photo
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LU101707A
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Chengpeng Zhang
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Univ Shandong
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
    • B81B7/04—Networks or arrays of similar microstructural devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
    • B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00349—Creating layers of material on a substrate
    • B81C1/00373—Selective deposition, e.g. printing or microcontact printing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • G—PHYSICS
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/02—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a matt or rough surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
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    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
    • B81B2207/00—Microstructural systems or auxiliary parts thereof
    • B81B2207/05—Arrays
    • B81B2207/056—Arrays of static structures
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    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N2021/653—Coherent methods [CARS]
    • G01N2021/655—Stimulated Raman

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Abstract

The present invention belongs to the technical field of flexible electronic films, and particularly relates to a flexible SERS substrate based on nano-structures and ordered nano-particles, and a preparation method and application thereof. The SERS substrate comprises: a flexible film base material, a photo-curable resin layer, grooves, a metal film layer and nano-particles, wherein: the photo-curable resin layer is disposed on the surface of the flexible film base material, the grooves are distributed in an array on the photo-curable resin layer and integrally formed with the photo-curable resin layer, the metal film layer covers the surface of the photo-curable resin layer and the grooves, and the nano-particles are orderly filled in the grooves. The photo-curable resin layer and the grooves are metallized, and Raman signals are enhanced by through the synergistic effect of the nano-structures and the ordered nano-particles, so that the flexible SERS substrate has the advantages of high precision, high sensitivity, good stability, strong signal reproducibility, etc.

Description

1 | FLEXIBLE SERS SUBSTRATE BASED ON NANO-STRUCTURES AND ORDERED LU101707 NANO-PARTICLES, AND PREPARATION METHOD AND APPLICATION THEREOF ] Field of the Invention Ë The present invention belongs to the technical field of flexible electronic films, and particularly | relates to a flexible SERS substrate based on nano-structures and ordered nano-particles, and a ; preparation method and application thereof. à Background of the Invention . The information disclosed in the background of the invention is merely intended to increase the 7 understanding on the general background of the present invention, and should not be construed as } acknowledgment or hint in any form that the information constitutes the prior art known by those . ] skilled in the art.
Surface-enhanced Raman scattering (SERS) can amplify molecular signals adsorbed on a metal É surface to 106-1015 times, can even achieve single-molecule detection, and is a highly sensitive | spectroscopic technology widely used in the fields of materials science, surface science, analytical ; chemistry, biology, diagnostics, etc. | Surface-enhanced Raman spectroscopy test requires signals to have stability and reproducibility, ) which mainly depends on the orderliness and uniformity of nano-structures and nano-particles of ! a surface-enhanced substrate.
Quick preparation of SERS substrates with high precision, high ; sensitivity, good stability, and strong signal reproducibility has become an urgent problem.
Patent document CN 109187487 A discloses a silver nano-cluster surface-enhanced Raman ) | scattering substrate and a preparation method and application thereof.
This patent prepares | nano-silver particle clusters through electrochemical displacement reaction to achieve Raman | signal enhancement.
However, the inventors believe that this patent document only realizes an : SERS function through nano-silver particles, and the nano-silver particles are randomly ; distributed, which cannot guarantee the signal reproducibility of multiple detections. ! Patent document CN 109239051 A discloses a flexible transferable surface-enhanced Raman | detection substrate, where thiolated polystyrene is modified onto noble metal nano-particles / through ligand exchange, and then the noble metal nano-particles are assembled by self-assembly Ë of a gas-liquid interface on a porous substrate into an ordered, substrate-free and self-supported |two-dimensional noble metal nano-superlattice film, thus obtaining the flexible transferable SER§Y101707 | substrate.
However, the inventors believe that this patent document has the disadvantages of | complicated manufacturing process, low efficiency, high cost, etc, and the self-assembly process | can only achieve two-dimensional assembly of a single layer of metal particles, but cannot achieve ordered arrangement of multiple layers of metal particles, which weakens the Raman | signal enhancement effect. ; Summary of the Invention ; In view of the above problems in the prior art, the present invention aims to provide a flexible } SERS substrate based on nano-structures and ordered nano-particles, and a preparation method ] and application thereof.
The method of the present invention is not only low in cost, efficient and | suitable for large-scale batch processing, but also the prepared SERS substrate can realize à high-precision, high-sensitivity, stability, and reproducibility test of Raman signals. / A first object of the present invention is to provide a flexible SERS substrate based on / nano-structures and ordered nano-particles. 1 A second object of the present invention is to provide a preparation method of the flexible SERS ] substrate based on nano-structures and ordered nano-particles. | A third object of the present invention is to provide application of the flexible SERS substrate E based on nano-structures and ordered nano-particles and the preparation method thereof.
J In order to achieve the above objects, the present invention discloses the following technical | solutions: ] First, the present invention discloses a flexible SERS substrate based on nano-structures and | ordered nano-particles, including: a flexible film base material, a photo-curable resin layer, ; grooves, a metal film layer and nano-particles, wherein: the photo-curable resin layer is disposed | on the surface of the flexible film base material, the grooves are distributed in an array on the ] photo-curable resin layer and integrally formed with the photo-curable resin layer, the metal film layer covers the surface of the photo-curable resin layer and the grooves, and the nano-particles are orderly filled in the grooves. | As a further technical solution, the flexible film base material includes: any one of polyethylene | terephthalate (PET), polycarbonate (PC), polypropylene (PP), polyvinyl chloride (PVC), ; polymethyl methacrylate (PMMA) and the like. |
As a further technical solution, the metal film layer and the nano-particles are made of materials" 01707 having a Raman signal enhancing function, for example, gold, silver, copper, platinum, or the : like.
J As a further technical solution, the shape of the grooves includes any one or more of cylindrical ı structures, rectangular structures, cubic structures, prismatic structures, etc. ! As a further technical solution, the shape of the array composed of the grooves includes a | rectangular array, a square array, a hexagonal array, a circular array, a rhombic array, or a | triangular array. ] As a further technical solution, the thickness of the metal film layer is 3 to 100 nm. | As a further technical solution, the diameter of the nano-particles is 1 to 200 nm. | As a further technical solution, the diameter or side length of the grooves is larger than the À diameter of the nano-particles and less than 1.4 times the diameter of the nano-particles; the ' diameter of the grooves is slightly larger than that of the nano-particles, which can ensure smooth filling of the nano-particles; however, the diameter of the grooves should not be too large, which | can ensure that each layer can only accommodate one nano-particle in the longitudinal direction, | limit the positions of the nano-particles to the greatest extent, and ensure the orderliness of the | nano-particles in the longitudinal direction. | As a further technical solution, the depth of the grooves is 1.5 to 500 nm. | As a further technical solution, the spacing between the grooves is 5 to 1000 nm. / Second, the present invention discloses a preparation method of the flexible SERS substrate based ; on nano-structures and ordered nano-particles, including the following steps: ; (1) coating the surface of a flexible film base material with ‘ | a photo-curable resin material to form a photo-curable resin layer, and embossing the ' photo-curable resin layer through a roll-to-roll ultraviolet curing process to obtain grooves | integrally formed with the photo-curable resin layer, wherein the grooves are distributed in an ; array on the photo-curable resin layer; : (2) depositing a metal film layer on the surface of the photo-curable resin layer and the grooves } by using an evaporation coating technology to metallize the surface so as to have an SERS | function; and Ë (3) filling the grooves with nano-particles in a way that the nano-particles are orderly distributed É in the grooves, thus obtaining the flexible SERS substrate.
Ë
As a further technical solution, in the roll-to-roll ultraviolet curing process, the embossing speed!’ 01707 ; is 0.5-60 m/min, the extrusion force is 1 to 9 kg/cm?, and the mold temperature is 10 to 100°C. : As a further technical solution, in the evaporation coating process, the degree of vacuum is 1x107 | to 4x10° Pa. | As a further technical solution, the nano-particles are filled by a blade coating process, including: | coating the gaps between the grooves with a nano-particle solution, and then wiping off the excess 1 nano-particle solution on the surface with alcohol. Optionally, the blade coating speed is 0.1 to ] Finally, the present invention discloses an application of the flexible SERS substrate based on | nano-structures and ordered nano-particles in electronic equipment; and an application of the ; preparation method of the flexible SERS substrate in preparation of flexible electronic materials. | Compared with the prior art, the present invention achieves the following beneficial effects: (1) The method of the present invention is not only low in cost, efficient and suitable for / large-scale batch processing, but also the prepared SERS substrate can realize high-precision, ‘ high-sensitivity, stability, and reproducibility test of Raman signals. ; (2) The present invention metallizes the photo-curable resin layer and the grooves, so that the ; structure array has a triple function: the metallized grooves can generate "hot spots” and excite ; plasma resonance to realize the function of enhancing the intensity of Raman signals; in addition, ] the grooves can also limit the nano-particles, so that the nano-particles are kept orderly and .
consistent over a large area to realize stability and reproducibility tests of the Raman signals; : moreover, on the basis of "hot spots" generated between the grooves, a lot of "hot spots" can also be generated between the metallized grooves and the nano-particles, which further improves the precision and sensitivity of Raman signal detection. ; (3) The present invention controls the uniformity and orderliness of the nano-particles through the ] array structure formed by the grooves, enhances the Raman signals through the synergistic effect ; of the nano-structures and the ordered nano-particles, and has the advantages of high precision, : high sensitivity, good stability, strong signal reproducibility, etc. Brief Description of the Drawings : The accompanying drawings constituting a part of the present invention are used for providing a ] further understanding on the present invention, and the schematic embodiments of the present |invention and the descriptions thereof are used for interpreting the present invention, rather thant 101707 ; constituting improper limitations to the present invention. | Fig. 1 is a cross-sectional view of a flexible SERS substrate based on nano-structures and ordered ] nano-particles in Embodiment 1 of the present invention. 2 Fig. 2 is a top view of the flexible SERS substrate based on nano-structures and ordered | nano-particles in Embodiment 1 of the present invention. | Fig. 3 is a process flowchart of preparing the flexible SERS substrate based on nano-structures ; and ordered nano-particles in Embodiment 2 of the present invention. | Signs in the drawings represent: 1-flexible film base material, 2-photo-curable resin layer, | 3-groove, 4-metal film layer, 5-nano-particle. | Detailed Description of Embodiments à It should be pointed out that the following detailed descriptions are all exemplary and aim to further | illustrate the present application.
Unless otherwise specified, all technical and scientific terms used ; in the descriptions have the same meanings generally understood by those of ordinary skill in the art | of the present application. ] It should be noted that the terms used herein are merely for describing specific embodiments, but ; are not intended to limit exemplary embodiments according to the present application.
As used | herein, unless otherwise explicitly pointed out by the context, the singular form is also intended to j include the plural form.
In addition, it should also be understood that when the terms “include” a and/or “comprise” are used in the specification, they indicate features, steps, operations, devices, | components and/or their combination. | As mentioned in the background, surface-enhanced Raman spectroscopy test requires signals to : have stability and reproducibility, which mainly depends on the orderliness and uniformity of ' nano-structures and nano-particles of a surface-enhanced substrate.
Quick preparation of SERS ; substrates with high precision, high sensitivity, good stability, and strong signal reproducibility ; has become an urgent problem.
Therefore, the present invention proposes a flexible SERS / substrate based on nano-structures and ordered nano-particles and a preparation method thereof. ; The present invention will be further described with reference to the drawings and specific | embodiments. | Embodiment 1 }
A flexible SERS substrate based on nano-structures and ordered nano-particles, referring to Figs)! 01707 ' 1 and 2, includes: a flexible film base material 1, a photo-curable resin layer 2, grooves 3, a metal | film layer 4 and nano-particles 5, wherein: the photo-curable resin layer 2 is disposed on the ; surface of the flexible film base material 1, the grooves 3 have cylindrical structures and are | distributed in a square array on the photo-curable resin layer 2 and integrally formed with the ; photo-curable resin layer 2, the metal film layer 4 covers the surface of the photo-curable resin Ë layer 2 and the grooves 3, and the nano-particles 5 are orderly filled in the grooves 3; the material ; of the flexible film base material 1 is polyethylene terephthalate (PET); the metal film layer 4 and a the nano-particles 5 are both silver nano-particles; the thickness of the metal film layer 4 is 15 ; nm; the diameter of the nano-particles 5 is 20 nm; the depth of the grooves 3 is 100 nm, and the | diameter thereof is 25 nm; and the spacing between the grooves 3 is 60 nm. | Embodiment 2 l A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that ] in Embodiment 1, except that the grooves 3 have rectangular structures and are distributed in a | rectangular array on the photo-curable resin layer 2; the material of the flexible film base material | 1 is polycarbonate (PC); the thickness of the metal film layer 4 is 30 nm; the metal film layer 4 ; and the nano-particles 5 are both gold nano-particles; the diameter of the nano-particles is 10 nm; | | the depth of the grooves 3 is 20 nm, and the diameter thereof is 10.5 nm; and the spacing between | the grooves 3 is 10 nm. } Embodiment 3 ; A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that ] in Embodiment 1, except that the grooves 3 have cubic structures and are distributed in a ) hexagonal array on the photo-curable resin layer 2; the material of the flexible film base material Ë 1 is polyvinyl chloride (PVC); the thickness of the metal film layer 4 is 50 nm; the metal film i layer 4 and the nano-particles 5 are both copper nano-particles; the diameter of the nano-particles ] is 15 nm; the depth of the grooves 3 is 20 nm, and the diameter thereof is 15.5 nm; and the : spacing between the grooves 3 is 60 nm. | Embodiment 4 | A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that a in Embodiment 1, except that the grooves 3 have prismatic structures and are distributed in a } circular array on the photo-curable resin layer 2; the material of the flexible film base material 1 is °polymethyl methacrylate (PMMA); the thickness of the metal film layer 4 is 60 nm; the metdi "101707 ' film layer 4 and the nano-particles 5 are both silver nano-particles; the diameter of the ; nano-particles is 50 nm; the depth of the grooves 3 is 150 nm, and the diameter thereof is 70 nm; ] and the spacing between the grooves 3 is 150 nm. | Embodiment 5 ; | A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that } in Embodiment 1, except that the material of the flexible film base material 1 is polypropylene . (PP); the thickness of the metal film layer 4 is 3 nm; the metal film layer 4 and the nano-particles Ë 5 are both platinum nano-particles; the diameter of the nano-particles is 1 nm; the depth of the } grooves 3 is 1.5 nm, and the diameter thereof is 1.4 nm; and the spacing between the grooves 3 is Ë Embodiment 6 ; A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that in Embodiment 2, except that the grooves 3 are distributed in a rhombic array on the | photo-curable resin layer 2; the thickness of the metal film layer is 100 nm; the diameter of the | nano-particles is 80 nm; the depth of the grooves 3 is 200 nm, and the diameter thereof is 100 nm; | and the spacing between the grooves 3 is 200 nm. ' Embodiment 7 ; A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that f in Embodiment 3, except that the grooves 3 are distributed in a triangular array on the ; photo-curable resin layer 2; the thickness of the metal film layer is 20 nm; the diameter of the nano-particles is 200 nm; the depth of the grooves 3 is 300 nm, and the diameter thereof is 250 : | nm; and the spacing between the grooves 3 is 500 nm. | Embodiment 8 | A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that | in Embodiment 5, except that the thickness of the metal film layer 4 is 50 nm; the diameter of the } nano-particles is 120 nm; the depth of the grooves 3 is 500 nm, and the diameter thereof is 150 } nm; and the spacing between the grooves 3 is 1000 nm. | Embodiment 9 | A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that | in Embodiment 1, except that the thickness of the metal film layer 4 is 25 nm; the diameter of the Ënano-particles is 45 nm; the depth of the grooves 3 is 300 nm, and the diameter thereof is 50 nh:101707 and the spacing between the grooves 3 is 600 nm. Embodiment 10 A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that in Embodiment 1, except that the photo-curable resin layer 2, the grooves 3, and the metal film layer 4 are not provided. Embodiment 11 A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that in Embodiment 1, except that no nano-particles are provided.
Embodiment 12 A flexible SERS substrate based on nano-structures and ordered nano-particles is the same as that in Embodiment 1, except that the photo-curable resin layer 2, the grooves 3, the metal film layer 4 | and the nano-particles 5 are not provided, that is, only the flexible film base material 1 is | provided. | Embodiment 13 | A preparation method of the flexible SERS substrate based on nano-structures and ordered | nano-particles described in Embodiment 1 includes the following steps: | (1) coating the surface of a flexible film base material with a photo-curable resin material to form a photo-curable resin layer, and embossing the photo-curable resin layer through a roll-to-roll ultraviolet curing process to obtain grooves integrally formed with the photo-curable resin layer, wherein the grooves are distributed in an array on the photo-curable resin layer; wherein in the roll-to-roll ultraviolet curing process, the embossing speed is 20 m/min, the extrusion force is 5 kg/em”, and the mold temperature is 50°C; (2) depositing a metal film layer on the surface of the photo-curable resin layer and the grooves by using an evaporation coating technology, wherein in the evaporation coating process, the degree of vacuum is 3.5%10 Pa; and (3) coating the gaps between the grooves 3 with a nano-particle solution, and then wiping off the excess nano-particle solution on the surface with alcohol such that the nano-particles are orderly distributed between the grooves, thus obtaining the flexible SERS substrate, wherein the coating speed is 20 mm/s. Signal enhancement factors of the flexible SERS substrates prepared in Embodiments 1-12 and Pm pe aaa]
relative standard deviations of multi-point tests are shown in a statistical table. During the testd, (4101707 rhodamine 6G solution is used as a marker, the wavelength of laser is 785 nm, the power is 1 mW, the integration time is 10 s, and Raman signal enhancement factors at the 1366-1 peak are calculated. The calculation of the relative standard deviations is to randomly select 9 positions from sample surfaces to characterize Raman signals, the relative standard deviations of the Raman signal enhancement factors measured at different positions are calculated, and the results are as shown in Table 1. Table 1 | ole eee fee 1 2 3 4 5 7 10 11 | 12 ent Raman signal enhancem | 6.4x | 4.3x | 1.6x | 52x | 3.2x | 49% | 2.8% | 5.1x | 58x | 7.6x | 9.2x ent factor | 10! | 10! | 10! | 10° | 10"! | 10 | 10" | 10"! | 10!! | 107 | 108 at 1366"! peak | Relative | standard deviation | 6.7 | 6.2 | 7.3 7.1 | 7.5
6.9% | 6.5% | 7.2% | 5.8% | 6.8% | 5.9% | 18% of test % % % % | % values at 9 points Described above are merely preferred embodiments of the present application, and the present application is not limited thereto. Various modifications and variations may be made to the present application for those skilled in the art. Any modification, equivalent substitution, improvement or the like made within the spirit and principle of the present application shall fall into the protection scope of the present application.
Tle i a aa a

Claims (11)

  1. | Claims LU101707 }
    1. A flexible SERS substrate based on nano-structures and ordered nano-particles, comprising: a | flexible film base material, a photo-curable resin layer, grooves, a metal film layer and | nano-particles, wherein: the photo-curable resin layer is disposed on the surface of the flexible i film base material, the grooves are distributed in an array on the photo-curable resin layer and : integrally formed with the photo-curable resin layer, the metal film layer covers the surface of the ] photo-curable resin layer and the grooves, and the nano-particles are orderly filled in the grooves. |
    2. The flexible SERS substrate based on nano-structures and ordered nano-particles according to Ë claim 1, wherein the flexible film base material comprises any one of polyethylene terephthalate | (PET), polycarbonate (PC), polypropylene (PP), polyvinyl chloride (PVC), and polymethyl ! methacrylate (PMMA). À
    3. The flexible SERS substrate based on nano-structures and ordered nano-particles according to ] claim 1, wherein the metal film layer and the nano-particles are made of a material having a 4 Raman signal enhancing function, preferably one or more of gold, silver, copper, and platinum. |
    4. The flexible SERS substrate based on nano-structures and ordered nano-particles according to ) claim 1, wherein the shape of the grooves comprises any one or more of cylindrical structures, | rectangular structures, cubic structures, and prismatic structures. |
    5. The flexible SERS substrate based on nano-structures and ordered nano-particles according to | claim 1, wherein the shape of the array composed of the grooves comprises a rectangular array, a | square array, a hexagonal array, a circular array, a rhombic array, or a triangular array. )
    6. The flexible SERS substrate based on nano-structures and ordered nano-particles according to ] any one of claims 1-4, wherein the thickness of the metal film layer is 3 to 100 nm; and | preferably, the diameter of the nano-particles is 1 to 200 nm. |
    6. The flexible SERS substrate based on nano-structures and ordered nano-particles according to | any one of claims 1-4, wherein the diameter or side length of the grooves is larger than the | diameter of the nano-particles and less than 1.4 times the diameter of the nano-particles. |
    7. The flexible SERS substrate based on nano-structures and ordered nano-particles according to | any one of claims 1-4, wherein the depth of the grooves is 1.5 to 500 nm; and | preferably, the spacing between the grooves is 5 to 1000 nm. |
    38. A preparation method of the flexible SERS substrate based on nano-structures and ordered } nano-particles, comprising the following steps: |
    EEE ET
    (1) coating the surface of a flexible film base material with a photo-curable resin material to forrh/101707 É a photo-curable resin layer, and embossing the photo-curable resin layer through a roll-to-roll / ultraviolet curing process to obtain grooves integrally formed with the photo-curable resin layer, ] wherein the grooves are distributed in an array on the photo-curable resin layer; à (2) depositing a metal film layer on the surface of the photo-curable resin layer and the grooves | by using an evaporation coating technology; and ] (3) filling the gaps between the grooves with nano-particles in a way that the nano-particles are i orderly distributed in the grooves, thus obtaining the flexible SERS substrate. |
    9. The preparation method according to claim 8, wherein in the roll-to-roll ultraviolet curing Ë process, the embossing speed is 0.5-60 m/min, the extrusion force is 1 to 9 kg/cm?, and the mold Ë temperature is 10 to 100°C; ] preferably, in the evaporation coating process, the degree of vacuum is 1x107 to 4x10 Pa; | preferably, the nano-particles are filled by a blade coating process, comprising: coating the gaps ; between the grooves with a nano-particle solution, and then wiping off the excess nano-particle : solution on the surface with alcohol; and ; preferably, the blade coating speed is 0.1 to 100 mm/s. . :
    10. An application of the flexible SERS substrate based on nano-structures and ordered | nano-particles according to any one of claims 1-7 in electronic equipment and/or an application of ; the preparation method according to claim 8 or 9 in preparation of flexible electronic materials. |
LU101707A 2019-05-08 2020-03-27 Flexible sers substrate based on nano-structures and ordered nano-particles, and preparation method and application thereof LU101707B1 (en)

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