WO2023208201A1 - 一种表面具有微纳米光学结构的器件及制备方法 - Google Patents

一种表面具有微纳米光学结构的器件及制备方法 Download PDF

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Publication number
WO2023208201A1
WO2023208201A1 PCT/CN2023/091632 CN2023091632W WO2023208201A1 WO 2023208201 A1 WO2023208201 A1 WO 2023208201A1 CN 2023091632 W CN2023091632 W CN 2023091632W WO 2023208201 A1 WO2023208201 A1 WO 2023208201A1
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Prior art keywords
substrate
micro
nano
metal
optical structure
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English (en)
French (fr)
Inventor
杨天
孙夏清
雷泽雨
钟昊
何晨佳
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Shanghai Jiao Tong University
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Shanghai Jiao Tong University
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/008—Surface plasmon devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/0229—Optical fibres with cladding with or without a coating characterised by nanostructures, i.e. structures of size less than 100 nm, e.g. quantum dots

Definitions

  • the invention belongs to the fields of optics, sensing and micro-nano processing, and relates to a device with a micro-nano optical structure on its surface and a preparation method.
  • SPP Surface plasmon polariton
  • SPP Surface plasmon polariton
  • the resonance conditions of this surface wave such as wavelength, intensity, exit angle, etc., vary with the refractive index of the environment in which it is located. Therefore, Surface Plasmon Resonance (SPR) is used to measure the refractive index of the environment, and has been widely researched and applied in the fields of refractive index, molecules, and acoustic field sensing. How to combine SPR with optical fiber and use fiber-optic waveguide technology to easily excite SPR and perform sensing to obtain new applications including bedside medical diagnosis and agricultural product detection, etc., has been pursued by people for many years.
  • the technology of integrating sensing devices on the end face of optical fiber can give full play to the convenient and fast operation capabilities of optical fiber detection.
  • This type of sensor can be directly inserted into trace biological or medical samples, or read molecules, Optical and acoustic information.
  • the SPP microcavity composed of a nanogroove array on a metal film, and its sensor device integrated into the end face of a single-mode optical fiber, is currently the fiber end face plasmon sensing technology with the highest sensing signal-to-noise ratio. Its refractive index detection The signal-to-noise ratio is 2 orders of magnitude or more higher than that of other fiber end-face plasmon sensing technologies that have been reported.
  • This SPP microcavity can be composed of a middle coupling region and a side reflection region (US 11,022,752 B2), or it can be composed of a periodic structure and an embedded defect structure (ZL201610754423.1, US 11,137,353 B2). These two structures are similar to single-mode
  • the integration of fiber end faces can achieve a noise equivalent detection limit of 10 -6 RIU in refractive index sensing.
  • the purpose of the present invention is to provide a device with a micro-nano optical structure on the surface and a preparation method to solve the problem of plasmon sensing on the fiber end face or other end faces in the prior art.
  • problems such as difficulty in transferring the constituent units from the substrate and performance needs to be improved.
  • the present invention provides a device with a micro-nano optical structure on the surface, including:
  • the support body has a bearing surface
  • Micro-nano optical structure combined with the bearing surface, the micro-nano optical structure includes a surface plasmon resonance structure and a metal nanocap;
  • the surface plasmon resonance structure includes a metal film and nano-openings or an array of nano-openings opened in the metal film, and the nano-openings are filled with a non-metallic medium;
  • the metal nanocap is protruding on a side of the metal film facing away from the support, facing the nano opening, and attached to a side of the non-metallic medium facing away from the support;
  • the non-metallic medium protrudes from the side of the metal film away from the support, and the metal nanocap completely covers or partially covers the protruding part of the non-metallic medium; or the non-metallic medium is recessed in or Flush with the side of the metal film facing away from the support, and the distance between the side of the non-metallic medium facing away from the support and the side of the metal film facing away from the support is less than 10 nm;
  • the nano-openings include at least one of nanopores and nano-grooves, and the side walls of the nano-openings are vertical or inclined.
  • the material of the metal film includes one or more of gold, silver, copper and aluminum
  • the material of the metal nanocap includes one or more of gold, silver, copper and aluminum
  • An adhesion layer is provided at the interface between the metal nanocap and the non-metallic medium.
  • the support body includes an optical fiber
  • the carrying surface is a planar optical fiber end surface
  • the micro-nano optical structure is bonded to the optical fiber end surface
  • the metal film is parallel to the optical fiber end surface
  • the surface plasmon resonance structure includes a middle region and side regions surrounding the middle region, and the array of nano-openings divides the metal film located in the middle region into third a periodic structure, and divides the metal film located in the side area into a second periodic structure, the period of the first periodic structure is different from that of the second periodic structure, the first periodicity
  • the structure is aligned with the fiber core.
  • the surface plasmon resonance structure includes a periodic structure and defects embedded in the periodic structure.
  • a trap structure wherein the array of nano-openings divides the metal film into the periodic structure and the defect structure embedded in the periodic structure, and the defect structure destroys the local period of the periodic structure property, the defect structure is aligned with the optical fiber core layer.
  • the optical fiber is a single-mode optical fiber at the working light wavelength.
  • the micro-nano optical structure further includes a Fabry-Perot microcavity, the Fabry-Perot microcavity is located between the bearing surface and the surface plasmon resonance structure. , the surface plasmon resonant structure and the Fabry-Perot microcavity are coupled to form a Fano resonance, wherein the Fabry-Perot microcavity includes a first substrate, a second substrate and A dielectric layer is located between the first substrate and the second substrate, the first substrate is composed of the surface plasmon resonance structure, and the second substrate is parallel to the first substrate.
  • the Fabry-Perot microcavity includes a first substrate, a second substrate and A dielectric layer is located between the first substrate and the second substrate, the first substrate is composed of the surface plasmon resonance structure, and the second substrate is parallel to the first substrate.
  • the second substrate includes a thin film made of metal material, and an adhesion layer is provided at an interface between the metal thin film and the dielectric layer.
  • the material of the dielectric layer includes one or more of metal oxide, metal nitride, silicon dioxide, semiconductor materials and organic materials, and the thickness of the dielectric layer ranges from 5 nm to 100 ⁇ m.
  • the present invention also provides a method for preparing a device with a micro-nano optical structure on its surface as described in any one of the above, including the following steps:
  • the side of the micro-nano optical structure facing away from the substrate is bonded to the load-bearing surface of the support body through an adhesive;
  • the support body together with the micro-nano optical structure is peeled off from the substrate, so that the micro-nano optical structure is transferred from the substrate to the bearing surface of the support body.
  • forming the micro-nano optical structure on the substrate includes the following steps:
  • a mask layer is formed on the first metal thin film layer and patterned, and the patterned mask layer is used as a mask to etch the first metal thin film layer to obtain nanometer-sized particles penetrating the first metal thin film layer. Opening and etching into the substrate to obtain a recessed structure of a predetermined depth;
  • a non-metallic medium is formed, and the non-metallic medium is filled in the nano-openings.
  • the step of forming an adhesion layer on the surface of the second metal film layer is further included.
  • the material of the substrate includes one or more of metal oxide, metal nitride, silicon dioxide, semiconductor material and organic matter.
  • the invention also provides a method for preparing a device with a micro-nano optical structure on its surface, which includes the following steps:
  • a substrate is provided, and a micro-nano optical structure is formed on the substrate.
  • the micro-nano optical structure includes a surface plasmon resonance structure and a metal nanocap.
  • the surface plasmon resonance structure includes A metal film and a nano-opening or an array of nano-openings opened in the metal film, the nano-openings are filled with a non-metallic medium; the metal nano-cap is protruding on a side of the metal film facing the substrate.
  • the non-metal medium protrudes from the side of the metal film facing the substrate, and the metal nano
  • the cap completely covers or partially covers the protruding part of the non-metallic medium; or the non-metallic medium is recessed or flush with the side of the metal film facing the substrate, and the side of the non-metallic medium faces the substrate.
  • the distance between one side of the substrate and the side of the metal film facing the substrate is less than 10 nm; both the metal film and the metal nanocap are in direct contact with the substrate;
  • the side of the micro-nano optical structure facing away from the substrate is bonded to the bearing surface of the support body through an adhesive;
  • the material of the metal film includes one or more of gold, silver, copper and aluminum
  • the material of the metal nanocap includes one or more of gold, silver, copper and aluminum
  • An adhesion layer is provided at the interface between the metal nanocap and the non-metallic medium
  • the material of the substrate includes one or more of metal oxide, metal nitride, silicon dioxide, semiconductor material and organic matter.
  • the micro-nano optical structure further includes a Fabry-Perot microcavity
  • the Fabry-Perot microcavity includes a first substrate, a second substrate and a second substrate located between the first substrate and the third substrate.
  • a dielectric layer between two substrates, the first substrate is composed of the surface plasmon resonance structure, the second substrate is located on the side of the first substrate away from the substrate and is connected to the The first substrate is parallel, and the surface plasmon resonance structure and the Fabry-Perot microcavity are coupled to form a Fano resonance.
  • the invention also provides a device with a micro-nano optical structure on the surface, including:
  • the support body has a bearing surface
  • Micro-nano optical structure combined with the bearing surface, the micro-nano optical structure includes a surface plasmon resonance structure and a Fabry-Perot microcavity;
  • the surface plasmon resonance structure includes a metal film and nano-openings or an array of nano-openings opened in the metal film;
  • the Fabry-Perot microcavity is located between the bearing surface and the surface plasmon resonance structure, and the surface plasmon resonance structure and the Fabry-Perot
  • the microcavity coupling forms a Fano resonance
  • the Fabry-Perot microcavity includes a first substrate, a second substrate, and a dielectric layer located between the first substrate and the second substrate, and the third substrate
  • a substrate is composed of the surface plasmon resonance structure
  • the second substrate is located on a side of the first substrate facing the support body and parallel to the first substrate;
  • the support body includes optical fiber
  • the optical fiber is a single-mode optical fiber at the working light wavelength.
  • the second substrate includes a thin film made of metal material.
  • the device with a micro-nano optical structure on the surface of the present invention includes a support and a micro-nano optical structure combined with the bearing surface of the support.
  • the micro-nano optical structure includes a surface plasmon resonance structure and a metal nanocap.
  • the surface plasmon resonant structure includes a metal film and nano-openings or an array of nano-openings opened in the metal film, the nano-openings are filled with non-metallic medium; the metal nano-cap is protruding On the side of the metal film facing away from the support, facing the nano opening, and attached to the side of the non-metallic medium facing away from the support; when the light wave passes from the side of the micro-nano optical structure to the One side of the support is incident toward the micro-nano optical structure, which can excite surface plasmon resonance along the side of the metal film away from the support.
  • the present invention combines a metal nanocap with a metal film with nano-openings, and prepares a three-dimensional micro-nano optical structure containing the metal film on a substrate with low binding force to metal, so that the three-dimensional structure can be removed from the substrate.
  • the bottom is peeled off and transferred to the support.
  • the resonant coupling of the incident light wave from the direction of the support with the surface plasmon polaritons on the metal film can also be achieved.
  • the metal nanocaps can be retained or removed as needed. .
  • this three-dimensional micro-nano optical structure may include a Fabry-Perot microcavity disposed between the support and the surface plasmon resonance structure, through which the surface plasmon resonance structure and the Fabry
  • the Fano resonance of the Li-Perot microcavity can improve the coupling efficiency between the incident light wave and the surface plasmon polaritons on the metal film, achieving high signal-to-noise ratio surface plasmon sensing, including refractive index sensing. , molecular sensing and acoustic field sensing, etc.
  • the signal-to-noise ratio of single-mode optical fiber end-face surface plasmon refractive index sensing with a Fabry-Perot microcavity three-dimensional structure can be improved by an order of magnitude.
  • the preparation method of the present invention can also realize various other complex three-dimensional structures. Integration of micro- and nano-optical structures with fiber end faces.
  • Figure 1 shows a schematic structural diagram of a device with micro-nano optical structures on its surface according to the present invention.
  • Figure 2 shows an enlarged view of the area indicated by the dashed box in Figure 1.
  • FIG. 3 shows a schematic diagram of a surface plasmon resonance structure used in the device with a micro-nano optical structure on the surface of the present invention.
  • Figure 4 shows an electron microscope image of the surface plasmon resonance structure shown in Figure 3, showing the junction between the middle region and the side region.
  • FIG. 5 shows a schematic diagram of another surface plasmon resonance structure used in the device with a micro-nano optical structure on the surface of the present invention.
  • FIG. 6 shows a schematic diagram of providing a substrate and forming a first metal thin film layer on the substrate in the method for preparing a device with a micro-nano optical structure on the surface of the present invention.
  • Figure 7 shows that in the preparation method of a device with a micro-nano optical structure on the surface of the present invention, a mask layer is formed on the first metal thin film layer, the mask layer is patterned and the first metal thin film layer and the Schematic diagram of the substrate.
  • FIG. 8 shows a schematic diagram of removing the mask layer in the method for preparing a device with a micro-nano optical structure on its surface according to the present invention.
  • Figure 9 shows a schematic diagram of sequentially forming a second metal film layer and a first adhesion layer in the preparation method of a device with a micro-nano optical structure on the surface of the present invention.
  • Figure 10 shows the formation of a non-metallic medium and a Fabry-Perot microcavity dielectric layer in the preparation method of a device with a micro-nano optical structure on the surface of the present invention, and the formation of a non-metallic dielectric layer on the Fabry-Perot microcavity dielectric layer.
  • Figure 11 shows a schematic diagram of peeling and transferring the micro-nano optical structure from the substrate in the preparation method of a device with a micro-nano optical structure on the surface of the present invention.
  • Figure 12 shows a microscope picture of the micro-nano optical structure transfer process in the preparation method of a device with a micro-nano optical structure on the surface of the present invention.
  • Figure 13 shows an atomic force microscope picture showing the nanocap after the micro-nano optical structure is transferred in the method for preparing a device with a micro-nano optical structure on the surface of the present invention.
  • Figure 14 shows a schematic structural diagram of an experimental device for measuring the refractive index of liquid using the device with a micro-nano optical structure on the surface of the present invention.
  • Figure 15 shows the normalized reflection spectrum of the end surface of the device with micro-nano optical structures of the present invention inserted into methanol, water, acetone, ethanol and isopropyl alcohol.
  • Figure 16 shows the change of each resonant wavelength with respect to the refractive index.
  • Figure 17 shows the results of measuring the change in wavelength of surface plasmon resonance with concentration when the end face of the device with micro-nano optical structures on the surface of the present invention is inserted into phosphate buffer solutions of bovine serum albumin with different concentrations.
  • Figure 18 shows baseline noise
  • Component label description 10 supports 20 Surface plasmon polariton resonance structure 201 metal film layer 2010 The first metal thin film layer 2011 Second metal film layer 202 Non-metallic media 21 middle area 22 side area 23 Periodic Structure 24 defective structure 30 metal nanocaps 40 Fabry-Perot Microcavity 401 first substrate 402 media layer 403 Second substrate 4030 third metal film layer 404 First Adhesion Layer 405 Second Adhesion Layer 50 adhesive layer 60 substrate 70 mask layer
  • This embodiment provides a device with a micro-nano optical structure on the surface, as shown in Figures 1 to 2, which respectively show a schematic structural diagram and a partial enlarged view of the device, including a support 10 and a micro-nano optical structure, where The support 10 has a bearing surface.
  • the micro-nano optical structure is combined with the bearing surface and includes a surface plasmon resonance structure 20 and a metal nanocap 30.
  • the surface plasmon resonance structure 20 includes a metal film 201 and nano-openings or an array of nano-openings opened in the metal film 201.
  • the nano-openings are filled with non-metallic medium 202, and the metal nano-cap 30 is protruding from the metal film 201.
  • the side facing away from the support 10 faces the nano opening and is attached to the side of the non-metallic medium 202 facing away from the support 10.
  • the light wave passes from the side of the micro-nano optical structure to the support
  • One side of the body 10 is incident toward the micro-nano optical structure, which can excite surface plasmon resonance along the side of the metal film 201 away from the support 10 .
  • the non-metallic medium 202 protrudes from the side of the metal film 201 away from the support 10 (as shown in FIG. 2 ), and the metal nanocap 30 completely covers or partially covers the non-metallic medium 202 .
  • the protruding portion of the medium 202 In this embodiment, the distance between the side of the non-metallic medium 202 facing away from the support 10 and the side of the metal film 201 facing away from the support 10 is less than 200 nm. In a preferred example, the distance between the side of the non-metallic medium 202 facing away from the support 10 and the side of the metal film 201 facing away from the support 10 is 8 nm, that is, the metal nanocap 30 The distance from the metal film 201 is 8 nm.
  • the non-metallic medium 202 can also be recessed or flush with the side (not shown) of the metal film away from the support, wherein the non-metallic medium 202 is recessed on the side of the metal film.
  • the side facing away from the support, that is, the nanocap 30 is partially embedded in the nanoopening.
  • the distance between the side of the non-metallic medium 202 facing away from the support 10 and the side of the metal film 201 facing away from the support 10 is less than 10 nm.
  • the nano-openings include at least one of nanopores and nanogrooves.
  • nanopore refers to the The lengths of the longest side and the shortest side of the nano-opening passing through the center of the nano-opening in the plane dimension of the metal film are equal to or close to each other, and their shapes include but are not limited to circles, triangles, squares and hexagons.
  • Nano-grooves It means that the longest side of the nano-opening passing through the center of the nano-opening in the plane dimension of the metal film is much larger than the shortest side, and its shape is such as a long strip.
  • the length of the shortest side of the nano-opening passing through the center of the nano-opening in the plane dimension of the metal film ranges from 5 to 200 nm.
  • the length of the shortest side refers to the diameter of the circular nanopore; if it is a square nanopore, the length of the shortest side refers to the side length of the square nanopore; if it is a rectangular nanochannel, then The length of the shortest side refers to the width of the short side of the rectangular nanogroove.
  • the nano-opening takes a rectangular nano-groove as an example, the width of its short side is 50 nm, and the nano-opening is filled with SiO 2 medium.
  • the sidewalls of the nano-openings are vertical or inclined.
  • the support body 10 includes an optical fiber
  • the carrying surface is a planar optical fiber end face
  • the micro-nano optical structure is bonded to the optical fiber end face
  • the metal film 201 is parallel to the optical fiber end face.
  • the optical fiber is a single-mode optical fiber at the working light wavelength, and the angle between the optical fiber end face and the optical fiber axis ranges from 80° to 100°, further from 82° to 98°, preferably from 88° to 92°.
  • the surface plasmon resonant structure 20 includes a middle region 21 and side regions 22 surrounding the middle region 21 , and the array of nano-openings will be located in the middle.
  • the metal film in the area 21 is divided into a first periodic structure, and the metal film located in the side area 22 is divided into a second periodic structure.
  • the first periodic structure is different from the second periodic structure.
  • the periodicity of the structures is different, and the position of the middle region 21 is aligned with the core layer of the optical fiber.
  • FIG. 4 an electron microscope picture of the surface plasmon polariton resonance structure 20 is shown, showing the interface between the middle region 21 and the side region 22 , and the first part of the middle region 21
  • the period P 1 of the periodic structure is 645 nm, and its period is approximately equal to the wavelength of the surface plasmon resonance on the metal film.
  • the period P 2 of the second periodic structure in the side area 22 is 315 nm, and its period is approximately It is equal to the half-wavelength of the surface plasmon polariton resonance on the metal film.
  • the surface plasmon resonance structure includes a periodic structure 23 and the defect structure 24 embedded in the periodic structure, wherein the nano-opening divides the metal film into the periodic structure 23 and the defect structure 24 embedded in the periodic structure 23, the The defective structure 24 destroys the local periodicity of the periodic structure 23 and is aligned with the optical fiber core.
  • the nano-openings penetrate the upper surface and the lower surface of the metal film, dividing the metal film into a plurality of metal film units, some of which are arranged periodically to form the periodic structure 23.
  • the regularly arranged metal film units are polygonal, including triangles, squares, rectangles, hexagons, etc., and another part of the metal film units are embedded in the periodically arranged metal film units to form the defect structure 24 .
  • the surface plasmon polaritons along the metal film can resonate in the defect structure or in the defect structure and its vicinity, wherein the first-order Fourier transform of the spatial Fourier transform of the periodic structure.
  • the component realizes the coupling of the incident light wave to the surface plasmon polaritons, and restricts the surface plasmon polaritons to oscillate in the space near the defect structure through its second-order Fourier component.
  • the surface plasmon resonant structure 20 may also adopt other layouts of periodic structures or microcavity structures, which are not limited to those shown in FIG. 3 or FIG. 5 .
  • the material of the metal film 201 includes but is not limited to one or more of gold, silver, copper and aluminum, and its thickness ranges from 5 to 200 nm.
  • the material of the metal nanocap includes but is not limited to gold, One or more of silver, copper and aluminum, with a thickness of 5 to 200nm.
  • the metal thin film is a gold film with a thickness of 55 nm
  • the metal nanocap is a gold nanocap with a thickness of 5 nm.
  • an adhesion layer is provided at the interface between the metal nanocap 30 and the non-metallic medium 202.
  • the material of the adhesion layer includes but is not limited to one or more of titanium, chromium and nickel.
  • a titanium layer is used as the adhesion layer, and the thickness of the adhesion layer is 2 nm.
  • the surface plasmon resonance spectrum of the surface plasmon resonance structure 20 moves with the change of the refractive index felt by the surface plasmon resonance structure 20 and is used for sensing. Changes in the refractive index of the environment, the binding of molecules on the structure, and the perception of the sound field through integration with acoustically sensitive materials.
  • the micro-nano optical structure further includes a Fabry-Perot microcavity 40 , which is located between the bearing surface and the surface plasmon resonance structure 20
  • the surface plasmon resonance structure 20 and the Fabry-Perot microcavity 40 are coupled to form a Fano resonance, wherein the Fabry-Perot microcavity includes a first substrate 401 , the second substrate 403 and the dielectric layer 402 located between the first substrate 401 and the second substrate 403.
  • the first substrate 401 is composed of the surface plasmon resonance structure 20, and the The second substrate 403 is parallel to the first substrate 401 .
  • the coupling efficiency between the optical fiber guided wave and the surface plasmon can be improved, so that the refractive index
  • the sensing signal-to-noise ratio is improved.
  • the second substrate 403 includes a thin film made of metal material, such as one or more of a gold film, a silver film, a copper film, and an aluminum film.
  • the thickness of the second substrate 403 ranges from 5 to 200 nm.
  • a gold film with a thickness of 20 nm is selected as the second substrate 403.
  • the material of the dielectric layer 402 includes one or more of metal oxide, metal nitride, silicon dioxide, semiconductor materials, and organic materials.
  • the thickness of the dielectric layer 402 ranges from 5 nm to 100 ⁇ m.
  • the dielectric layer 402 is a SiO 2 layer with a thickness of 230 nm.
  • a first adhesion layer 404 is provided at the interface between the metal film 201 and the dielectric layer 402, and a second adhesion layer 405 is provided at the interface between the second substrate 403 and the dielectric layer 402.
  • the adhesion layer is used to improve the adhesion between the dielectric layer 402 and the first substrate 401 and the second substrate 403.
  • the materials of the adhesion layer include but are not limited to titanium, chromium and nickel. One or several. In this embodiment, a titanium layer is used as the adhesion layer, and the thickness of the adhesion layer is 2 nm.
  • an adhesive layer 50 is provided between the support 10 and the second substrate 403 , and the adhesive layer 50 is used to adhere the support 10 and the micro-nano optical structure.
  • the adhesive layer 50 uses ultraviolet curable glue.
  • the device with a micro-nano optical structure on the surface includes a support body and a micro-nano optical structure combined with the bearing surface of the support body.
  • the micro-nano optical structure includes a surface plasmon resonance structure and Metal nanocap, the surface plasmon resonance structure includes a metal film and a nano opening or an array of nano openings opened in the metal film, the nano openings are filled with a non-metallic medium; the metal nano cap The cap is protruding on the side of the metal film facing away from the support, facing the nano opening, and attached to the side of the non-metallic medium facing away from the support; when the light wave passes from the micro-nano optical structure The side facing the support is incident toward the micro-nano optical structure, which can excite the surface plasmon resonance along the side of the metal film facing away from the support.
  • the micro-nano optical structure may further include a Fabry-Perot microcavity disposed between the support and the surface plasmon resonance structure, through which the surface plasmon resonance structure interacts with the Fabry-Perot microcavity.
  • the Fano resonance of the Perot microcavity can improve the coupling efficiency between the incident light wave and the surface plasmon polaritons on the metal film, achieving high signal-to-noise ratio surface plasmon sensing, including refractive index sensing, molecular Sensing and acoustic field sensing, etc.
  • the signal-to-noise ratio of surface plasmon refractive index sensing of the single-mode optical fiber end face with the Fabry-Perot microcavity three-dimensional structure can be improved up to an order of magnitude.
  • This embodiment provides a method for preparing a device with a micro-nano optical structure on the surface, which is used to prepare the device with a micro-nano optical structure on the surface described in Embodiment 1.
  • the method includes the following steps:
  • S1 Provide a substrate, form the micro-nano optical structure on the substrate, and the metal film and the metal nanocap are in direct contact with the substrate;
  • S2 Provide the support body, and bond the side of the micro-nano optical structure away from the substrate to the load-bearing surface of the support body through an adhesive;
  • S3 Peel the support body together with the micro-nano optical structure from the substrate, and transfer the micro-nano optical structure from the substrate to the bearing surface of the support body.
  • forming the micro-nano optical structure on the substrate includes the following steps:
  • a substrate 60 is provided, and a first metal thin film layer 2010 is formed on the substrate 60 .
  • the substrate 60 material includes one or more of metal oxides, metal nitrides, silicon dioxide, semiconductor materials and organic matter. Considering the rigidity and surface nano-smoothness requirements of the substrate, this embodiment A quartz glass substrate is preferred.
  • the first metal film layer 2010 has low bonding force with the substrate 60 .
  • the material of the first metal film layer 2010 includes but is not limited to one or more of gold, silver, copper and aluminum.
  • the first metal thin film layer 2010 is a gold thin film layer, which can be formed by electron beam evaporation or other suitable methods.
  • a mask layer 70 is formed on the first metal thin film layer 2010 and patterned, and the patterned mask layer 70 is used as a mask to etch the first metal thin film layer. 2010 to obtain nano-openings penetrating the first metal film layer 2010, and etching into the substrate 60 to obtain a recessed structure with a predetermined depth.
  • the mask layer 70 includes but is not limited to a polymer layer and a photoresist layer.
  • the mask layer 70 is made of polymethyl methacrylate (PMMA), which can be formed by spin coating or other suitable methods.
  • PMMA polymethyl methacrylate
  • electron beam lithography is used to etch the mask layer 70 to form an array pattern of nano-openings
  • argon ion beam etching or other suitable methods are used to etch the patterned mask layer 70 into
  • the first metal thin film layer 2010 is etched with a mask, and the speed and time of the argon ion beam etching are controlled.
  • the etching penetrates the first metal thin film layer 2010 and extends into the substrate 60 .
  • a recessed structure with a depth of approximately 15 nm is formed.
  • the side walls of the nano-openings can be made vertical or inclined by adjusting the etching parameters according to actual needs.
  • oxygen plasma cleaning or other suitable methods are used to remove the mask layer 70 .
  • a second metal thin film layer 2011 is formed, and the second metal thin film layer 2011 covers the surface of the first metal thin film layer 2010 and the bottom surface of the recessed structure.
  • the material of the second metal film layer 2011 includes but is not limited to one or more of gold, silver, copper and aluminum.
  • the second metal thin film layer 2011 is a gold thin film layer, which can be formed by electron beam evaporation or other suitable methods.
  • a non-metallic medium 202 is formed, and the non-metallic medium 202 is filled in the nano-openings.
  • the second metal film layer 2011 in the recessed structure of the substrate constitutes the metal nanocap 30 .
  • a step of forming a first adhesion layer 404 on the surface of the second metal film layer 2011 is further included.
  • the first adhesion layer 404 is used to increase the adhesion force between the non-metallic medium 202 and the second metal film layer 2011.
  • the first adhesion layer 404 is formed using an electron beam evaporation method.
  • the micro-nano optical structure further includes the Fabry-Perot microcavity 40
  • the first substrate 401 of the Fabry-Perot microcavity 40 is formed by the surface plasmon polarizer.
  • the metal film 201 of the surface plasmon resonance structure 20 is composed of the first metal film layer 2010 and the third metal film layer located on the surface of the first metal film layer 2010.
  • Composed of two metal thin film layers 2011, forming the Fabry-Perot microcavity 40 also includes the following steps: as shown in Figure 10, forming the dielectric layer 402 of the Fabry-Perot microcavity 40, and A second adhesion layer 405 and a third metal film layer 4030 are sequentially formed on the dielectric layer 402 of the Fabry-Perot microcavity.
  • the third metal film layer 4030 constitutes the Fabry-Perot microcavity 40 the second substrate 403.
  • the dielectric layer 402 may be formed simultaneously with the non-metallic medium 202 or in steps.
  • a plasma enhanced chemical vapor deposition method is used to deposit the dielectric layer 402 at a temperature of 65° C.
  • an electron beam evaporation method is used to form the second adhesion layer 405 .
  • the step S2 of bonding the side of the micro-nano optical structure away from the substrate 60 to the bearing surface of the support 10 through an adhesive includes the following steps:
  • the curing light of the adhesive uses ultraviolet light, and the adhesive is cured under ultraviolet light irradiation.
  • the adhesive is methyl acrylate.
  • This adhesive is transparent to the wavelength of light used for sensing. Its UV curing wavelength range is 100 ⁇ 400nm, and the curing light intensity is 1 ⁇ 2000J/cm 2 .
  • the curing time is 5 to 600 s.
  • the curing wavelength is around 320 nm, the curing light intensity is 100 J/cm 2 , and the curing time is 300 s.
  • an ultraviolet light source is selected, the central wavelength of the curing light is 320nm, and the maximum irradiation power is 2000J/cm 2 .
  • the substrate 60 (quartz glass) is a transparent substrate
  • the support 10 is an optical fiber
  • the method of aligning the optical fiber end face with the micro-nano optical structure includes: One side of the micro-nano optical structure is subjected to microscopic observation, and the position of the optical fiber end face and the micro-nano optical structure is observed and aligned.
  • a lens and an imaging element are used to form a microscopic system to display the magnified image of the optical fiber end face and the micro-nano optical structure. By displaying The image adjusts the position and alignment of the optical fiber end face and the micro-nano optical structure.
  • the method of aligning the optical fiber end face with the micro-nano structure includes: driving broad spectrum light into the optical fiber, the broad spectrum light transmitting along the optical fiber and from the optical fiber end face Ejected, then reflected by the micro-nano structure and then returned to the optical fiber. Move the relative position of the optical fiber and the micro-nano structure and measure the spectrum of the reflected light during the movement. From the perfect alignment of the spectrum of the reflected light Compare the expected reflection spectrum under accurate conditions to determine whether it is aligned. Specifically, broad-spectrum light is injected into the fiber through a broad-spectrum light source (such as a superradiant diode).
  • a broad-spectrum light source such as a superradiant diode
  • the broad-spectrum light is transmitted along the fiber, passes through the fiber directional coupler, and then is emitted from the fiber end face. Then the broad-spectrum light is
  • the micro-nano optical structure reflects and returns to the optical fiber.
  • the reflected light passes through the fiber directional coupler and enters the spectrometer.
  • the relative position of the optical fiber and the micro-nano structure is moved and the spectrum of the reflected light is measured during the movement.
  • the spectrum of the reflected light is measured by the spectrometer.
  • the alignment of the optical fiber end face and the metal micro-nano structure can be judged and adjusted from the comparison of the spectrum of the reflected light with the expected reflection spectrum under perfect alignment.
  • the alignment method of the optical fiber end face and the micro-nano optical structure is operated according to the actual situation and is not limited to this embodiment.
  • the adhesive curing light is irradiated through the substrate to cure the adhesive.
  • step S3 shows that the support 10 and the micro-nano optical structure are peeled off from the substrate 60 to transfer the micro-nano optical structure from the substrate.
  • a schematic view of the bearing surface of the support body 10 is shown in FIG. 11 .
  • FIG 12 it is an optical micrograph during the transfer process of the micro-nano optical structure, where the support is an optical fiber, the bearing surface is the end face of the optical fiber, and the micro-nano optical structure appears It is in the shape of a disk and has been transferred to the end face of the optical fiber.
  • the surface plasmon resonance structure and the nanocap appear as a shadow-like area located in the center of the disk.
  • Figure 12 includes the micro-nano optical structure of the optical fiber and its end face (lower right part of the picture), the mirror reflection of the micro-nano optical structure of the optical fiber and its end face in the substrate (upper right part of the picture), and the disk-shaped deep
  • the color area is the position before the transfer of the micro-nano optical structure on the substrate (middle of the picture).
  • Figure 13 shows an atomic force microscope picture after the micro-nano optical structure is transferred to the bearing surface of the support, showing the nanocap array.
  • the non-metallic medium 202 filled in the nano-openings can prevent the adhesive from entering the nano-openings during the transfer process and thereby affecting the peeling efficiency of the micro-nano optical structure from the substrate 60.
  • the nanocap 30 is the key to forming a low binding force interface between the micro-nano optical structure and the substrate 60 .
  • the nanocap 30 is made of gold, a precious metal material.
  • the binding force between the precious metal and many substrate materials (such as SiO 2 ) largely comes from van der Waals force, which is a low binding force and is conducive to realizing the microstructure.
  • the nano-optical structure is peeled off from the substrate 60 .
  • the nanocap 30 If the nanocap 30 is not provided, the non-metallic medium deposited in the nano opening will be firmly combined with the substrate, making the transfer impossible. Finish.
  • the nanocap 30 of the present invention can effectively reduce the binding force between the micro-nano optical structure and the substrate to facilitate transfer, while still maintaining the surface plasmon polaritons to resonantly tunnel the metal film through the nano-openings. Characteristics, thereby achieving the coupling of surface plasmon resonance and incident light waves from the direction of the support.
  • the three-dimensional structure containing the metal film can be peeled off from the planar substrate and transferred to the fiber end face, and the fiber waveguide and the plasmon polaritons on the other side of the metal film can be realized.
  • Resonance tunneling coupling and at the same time, based on the integration of three-dimensional micro-nano optical structures (such as the Fabry-Perot microcavity 40) on the fiber end face, can enable fiber end face surface plasmon sensing with unprecedented high signal-to-noise Compare.
  • the support body is an optical fiber, which is a single-mode optical fiber at the working light wavelength.
  • the micro-nano optical structure includes a surface plasmon resonance structure, a Fabry-Perot microcavity and a metal nanocap.
  • the surface plasmon resonance structure includes a middle region and is surrounded by the middle region. In the side areas around the area, the position of the middle area is aligned with the optical fiber core layer.
  • the array of nano-openings divides the metal film located in the middle area into a first periodic structure with a period of 645 nm, and The metal film located in the side area is divided into a second periodic structure with a period of 315 nm.
  • the nano opening adopts a rectangular nano groove with a short side width of 50 nm.
  • the nano opening is filled with SiO 2 medium.
  • the medium protrudes from the side of the metal film facing away from the optical fiber, and the distance between the side of the SiO 2 medium facing away from the optical fiber and the side of the metal film 201 facing away from the optical fiber is 8 nm.
  • the metal film adopts 55 nm.
  • the metal nanocap adopts a gold nanocap with a thickness of 5nm
  • a titanium adhesion layer with a thickness of 2nm is provided at the interface between the metal nanocap and the non-metallic medium
  • the second substrate adopts a 20nm thickness
  • the dielectric layer adopts a SiO 2 layer with a thickness of 230 nm
  • a titanium adhesion layer with a thickness of 2 nm is provided between the metal film and the dielectric layer
  • the second substrate and the dielectric layer There is a titanium adhesion layer with a thickness of 2 nm, and the end face of the second substrate and the optical fiber is bonded with ultraviolet curing glue.
  • FIG. 14 a diagram of an experimental device for measuring the refractive index of liquid using the device with a micro-nano optical structure on the surface of the present invention is shown.
  • the working wavelength of the single-mode optical fiber used in the experiment is 780-970nm
  • the light source used is a super-luminescent diode (SLD), which is a broad-spectrum light source.
  • SLD super-luminescent diode
  • the light output from the light source is introduced into the liquid to be measured through a 50%:50% optical fiber directional coupler, and its reflected signal is then introduced into the CCD fiber spectrometer through the directional coupler for analysis.
  • the coupling efficiency of the surface plasmon polariton resonance structure and the Fabry-Perot microcavity is formed.
  • Fano resonance can obtain a resonance valley that is at most about 55% deep, and can also obtain a resonance peak that is about 46% high, indicating that the coupling efficiency of fiber guided waves and surface plasmon resonance has been greatly improved, and their respective resonances have been greatly improved.
  • the wavelength corresponds to the refractive index of each solution, and the scatter plot (experimental value) of the resonant wavelength with respect to the refractive index change as shown in Figure 16 can be obtained. It can be seen that the resonant wavelength changes linearly with the refractive index, and is obtained through linear fitting.
  • the sensitivity is 411nm RIU -1 .
  • the end surface of the device with micro-nano optical structures on the surface of the present invention is also immersed in phosphate buffered saline (PBS) with different concentrations of bovine serum albumin (BSA), and the above method is also used.
  • PBS phosphate buffered saline
  • BSA bovine serum albumin
  • the change of the wavelength of surface plasmon resonance with concentration is measured, and the physical adsorption of BSA molecules on the sensor surface is read in real time through the change of surface plasmon resonance wavelength.
  • the BSA concentration increased from 10ng/mL to 100 ⁇ g/mL, each time increasing 10 times.
  • the sample vibrated back and forth along the direction of the optical fiber at a speed of 80mm/s.
  • the measurement results are shown in Figure 17, which shows that 10ng/ mL concentration.
  • the baseline noise of the surface plasmon resonance wavelength changing with time is shown in Figure 18.
  • the noise equivalent detection limit at 1 second integration is 1.9 ⁇ 10 -7 RIU, which is higher than the highest reported so far.
  • the good level is about an order of magnitude lower.
  • the pressure in the environment where the optical fiber end face is located can also be measured through the refractive index or geometric parameters of the material near the optical fiber end face that change with pressure.
  • the pressure can come from sound waves, ultrasonic waves or infrasound waves
  • the substance can be an adhesive or other substance between the micro-nano optical structure and the fiber end face, or it can be a substance attached to the surface of the metal film or the fiber end face.
  • the nanocap 30 is retained in the micro-nano optical structure.
  • the nanocap can also be removed as needed to more smoothly excite the surface plasmon resonance along the side of the metal film 201 away from the support 10 .
  • the micro-nano optical structure includes a surface plasmon resonance structure and a metal nanocap.
  • the surface plasmon resonance The structure includes a metal film and nano-openings or an array of nano-openings opened in the metal film.
  • the nano-openings are filled with non-metallic medium; the metal nano-cap is protruding on the surface of the metal film facing the substrate.
  • the non-metal medium protrudes from the side of the metal film facing the substrate, and the metal nanocap completely covers or partially covers the protrusion of the non-metal medium part; or the non-metallic medium is recessed or flush with the side of the metal film facing the substrate, and the side of the non-metallic medium facing the substrate is not the same as the side of the metal film facing the substrate.
  • the distance between one side of the substrate is less than 10 nm, and the metal film and the metal nanocap are in direct contact with the substrate;
  • S2 Provide the support body, and bond the side of the micro-nano optical structure away from the substrate to the bearing surface of the support body through an adhesive;
  • S3 Peel the support together with the micro-nano optical structure from the substrate, and transfer the micro-nano optical structure from the substrate to the bearing surface of the support;
  • methods for removing the nanocap may include grinding, ultrasonic vibration, adhesion removal, pulling out and other methods.
  • the material of the metal film includes one or more of gold, silver, copper and aluminum
  • the material of the metal nanocap includes one or more of gold, silver, copper and aluminum
  • an adhesion layer is provided at the interface between the metal nanocap and the non-metallic medium, and the material of the substrate includes one of metal oxides, metal nitrides, silicon dioxide, semiconductor materials and organic matter. or more.
  • the micro-nano optical structure further includes a Fabry-Perot microcavity.
  • the Fabry-Perot microcavity includes a first substrate, a second substrate and a second substrate located between the first substrate and the second substrate.
  • a dielectric layer between substrates, the first substrate is composed of the surface plasmon resonance structure, and the second substrate is located on a side of the first substrate away from the substrate and connected with the The first substrate is parallel, and the surface plasmon resonance structure and the Fabry-Perot microcavity are coupled to form a Fano resonance.
  • an adhesion layer is provided at the interface between the metal film and the dielectric layer, and an adhesion layer is provided at the interface between the second substrate and the dielectric layer.
  • This embodiment provides a device with a micro-nano optical structure on the surface, which can be produced using the manufacturing method in Embodiment 4 or other suitable manufacturing methods.
  • the device with a micro-nano optical structure on the surface includes a support and a micro-nano optical structure. structure, wherein the support body has a bearing surface, and the micro-nano optical structure is combined with the bearing surface, and the micro-nano optical structure includes a surface plasmon resonance structure and a Fabry-Perot microstructure. cavity.
  • the surface plasmon resonance structure includes a metal film and nano-openings or an array of nano-openings opened in the metal film; the Fabry-Perot microcavity is located between the bearing surface and The surface plasmon resonance Between structures, the surface plasmon resonance structure and the Fabry-Perot microcavity are coupled to form a Fano resonance, wherein the Fabry-Perot microcavity includes a first substrate, a first Two substrates and a dielectric layer located between the first substrate and the second substrate, the first substrate is composed of the surface plasmon resonance structure, and the second substrate is located on the first The side of the substrate facing the support is parallel to the first substrate; when the light wave is incident from the side of the micro-nano optical structure facing the support toward the micro-nano optical structure, it can excite along the The surface plasmon resonance of the side of the metal film facing away from the support body resonates.
  • the support includes an optical fiber that is a single-mode optical fiber at the operating light wavelength.
  • the second substrate includes a thin film made of metallic material.
  • the micro-nano optical structure includes a surface plasmon resonance structure and a Fabry-Perot microcavity, but does not include a metal nanocap, which can be smoother. Surface plasmon resonance along a side of the metal film facing away from the support is excited.
  • the device with a micro-nano optical structure on the surface of the present invention includes a support body and a micro-nano optical structure combined with the bearing surface of the support body.
  • the micro-nano optical structure includes a surface plasmon polariton resonance structure and a metal nanostructure.
  • the surface plasmon resonance structure includes a metal film and a nano-opening or an array of nano-openings opened in the metal film, the nano-openings are filled with non-metallic medium; the metal nano-cap protrudes It is provided on the side of the metal film facing away from the support body, facing the nano opening, and attached to the side of the non-metallic medium facing away from the support body; when the light wave passes from the side of the micro-nano optical structure to the One side of the support is incident toward the micro-nano optical structure, which can excite surface plasmon resonance along the side of the metal film away from the support.
  • the present invention combines a metal nanocap with a metal film with nano-openings, and prepares a three-dimensional micro-nano optical structure containing the metal film on a substrate with low binding force to metal, so that the three-dimensional structure can be removed from the substrate.
  • the bottom is peeled off and transferred to the support.
  • the resonant coupling of the incident light wave from the direction of the support with the surface plasmon polaritons on the metal film can also be achieved.
  • the metal nanocaps can be retained or removed as needed. .
  • this three-dimensional micro-nano optical structure may include a Fabry-Perot microcavity disposed between the support and the surface plasmon resonance structure, through which the surface plasmon resonance structure and the Fabry
  • the Fano resonance of the Li-Perot microcavity can improve the coupling efficiency between the incident light wave and the surface plasmon polaritons on the metal film, achieving high signal-to-noise ratio surface plasmon sensing, including refractive index sensing. , molecular sensing and acoustic field sensing, etc.
  • the signal-to-noise ratio of single-mode optical fiber end-face surface plasmon refractive index sensing with a Fabry-Perot microcavity three-dimensional structure can be improved by an order of magnitude.
  • the preparation method of the present invention can also realize the integration of various other complex three-dimensional micro-nano optical structures and optical fiber end faces. Therefore, the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.

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Abstract

本发明提供一种表面具有微纳米光学结构的器件及制备方法，该器件包括支撑体及结合于支撑体的承载面的微纳米光学结构，微纳米光学结构包括由金属薄膜上的纳米开口定义的表面等离极化激元谐振结构及金属纳米帽，当光波从支撑体方向朝微纳米光学结构入射，能够激发沿金属薄膜的背离支撑体的一面的表面等离极化激元谐振。本发明通过金属纳米帽能将微纳米光学结构制备在与金属具有低结合力的衬底上，并剥离转移至支撑体上，其中，金属纳米帽可根据需要保留或去除，另外，微纳米光学结构可进一步包括设置在支撑体与表面等离极化激元谐振结构之间的法布里-珀罗微腔，表面等离极化激元谐振结构与法布里-珀罗微腔耦合，实现高信噪比的表面等离激元传感。

Description

一种表面具有微纳米光学结构的器件及制备方法 技术领域
本发明属于光学、传感和微纳加工领域，涉及一种表面具有微纳米光学结构的器件及制备方法。
背景技术
表面等离极化激元(Surface Plasmon Polariton，SPP)是金属表面电荷与光场耦合形成的表面波。此表面波的谐振条件，如波长、强度、出射角等，随其所处环境的折射率而变化。因此表面等离激元谐振(Surface Plasmon Resonance，SPR)被用于对环境折射率进行测量，在折射率、分子和声场传感领域均得到广泛的研究和应用。如何将SPR与光纤结合，从而利用光纤导波技术来方便的激发SPR并进行传感，以获得包括床旁医疗诊断和农产品检测等在内的新型应用，是人们多年来所追求的。其中，特别地，将传感器件集成在光纤端面的技术能够充分发挥光纤检测的方便、快速操作能力，该类传感器可以被直接插入微量生物或医学样本，或者以微创侵入的方式读取分子、光学和声学信息。金属薄膜上的纳米槽阵列构成的SPP微腔，及其集成在单模光纤端面形成的传感器件，是目前具有最高传感信噪比的光纤端面等离激元传感技术，其折射率检测的信噪比比已报道的其他光纤端面等离激元传感技术高2个数量级或以上。这种SPP微腔可以由中间耦合区域和旁边反射区域构成(US 11,022,752 B2)，也可以由周期性结构及嵌入的缺陷结构构成(ZL201610754423.1，US 11,137,353 B2)，这两种结构与单模光纤端面的集成均可在折射率传感中实现10-6RIU量级的噪声等效检测限。
虽然上述器件已经大幅降低了光纤端面等离激元传感的检测限，但其基础构成单元，即金属薄膜上的纳米槽阵列，属于一种二维结构，限制了检测限的进一步降低。同时，其制备工艺是基于将具有纳米槽的金属薄膜从大面积衬底剥离并精确转移到光纤端面，目前仅局限于二维金属薄膜结构的转移。
因此，如何提供一种新的表面具有微纳米光学结构的器件及制备方法，包括新的端面具有微纳米光学结构的光纤器件及制备方法，以进一步降低该类表面等离激元传感技术的检测限，并发展三维或准三维微纳米结构从衬底到支撑体表面的转移制备工艺，成为本领域技术人员亟待解决的一个重要技术问题。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种表面具有微纳米光学结构的器件及制备方法，用于解决现有技术中光纤端面或其它端面等离激元传感的基础构成单元从衬底上转移难度大、性能有待提高等问题。
为实现上述目的及其他相关目的，本发明提供一种表面具有微纳米光学结构的器件，包括：
支撑体，具有一承载面；
微纳米光学结构，结合于所述承载面，所述微纳米光学结构包括表面等离极化激元谐振结构及金属纳米帽；
其中，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质；
所述金属纳米帽凸设于所述金属薄膜的背离所述支撑体的一侧，正对所述纳米开口，且附着于所述非金属介质的背离所述支撑体的一面；
所述非金属介质突出于所述金属薄膜的背离所述支撑体的一面，所述金属纳米帽完全包覆或部分包覆所述非金属介质的突出部分；或者所述非金属介质凹陷于或齐平于所述金属薄膜的背离所述支撑体的一面，且所述非金属介质的背离所述支撑体的一面与所述金属薄膜的背离所述支撑体的一面之间的距离小于10nm；
当光波从所述微纳米光学结构的面向所述支撑体的一侧朝向所述微纳米光学结构入射，能够激发沿着所述金属薄膜的背离所述支撑体的一面的表面等离极化激元谐振。
可选地，所述纳米开口包括纳米孔及纳米槽中的至少一种，所述纳米开口的侧壁垂直或倾斜。
可选地，所述金属薄膜的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽与所述非金属介质的界面处设有粘附层。
可选地，所述支撑体包括光纤，所述承载面为呈平面状的光纤端面，所述微纳米光学结构粘合于所述光纤端面，所述金属薄膜平行于所述光纤端面。
可选地，所述表面等离极化激元谐振结构包括中间区域及环绕于所述中间区域四周的旁边区域，所述纳米开口的阵列将位于所述中间区域的所述金属薄膜划分为第一周期性结构，并将位于所述旁边区域的所述金属薄膜划分为第二周期性结构，所述第一周期性结构与所述第二周期性结构的周期不同，所述第一周期性结构与光纤芯层对齐。
可选地，所述表面等离极化激元谐振结构包括周期性结构及嵌入所述周期性结构中的缺 陷结构，其中，所述纳米开口的阵列将所述金属薄膜划分为所述周期性结构及嵌入所述周期性结构中的所述缺陷结构，所述缺陷结构破坏所述周期性结构的局部周期性，所述缺陷结构与光纤芯层对齐。
可选地，所述光纤在工作光波长处为单模光纤。
可选地，所述微纳米光学结构还包括法布里-珀罗微腔，所述法布里-珀罗微腔位于所述承载面与所述表面等离极化激元谐振结构之间，所述表面等离极化激元谐振结构和所述法布里-珀罗微腔耦合形成法诺共振，其中，所述法布里-珀罗微腔包括第一基板、第二基板及位于所述第一基板与所述第二基板之间的介质层，所述第一基板由所述表面等离极化激元谐振结构构成，所述第二基板与所述第一基板平行。
可选地，所述第二基板包括由金属材料构成的薄膜，所述金属薄膜与所述介质层的界面处设有粘附层。
可选地，所述介质层的材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机材料中的一种或几种，所述介质层的厚度范围是5nm～100μm。
本发明还提供一种如上任意一项所述的表面具有微纳米光学结构的器件的制备方法，包括以下步骤：
提供一衬底，形成所述微纳米光学结构于所述衬底上，所述金属薄膜及所述金属纳米帽均与所述衬底直接接触；
提供所述支撑体，通过粘合剂将所述微纳米光学结构的背离所述衬底的一面粘合于所述支撑体的所述承载面；
将所述支撑体连同所述微纳米光学结构自所述衬底剥离，使所述微纳米光学结构从所述衬底上转移到所述支撑体的所述承载面。
可选地，形成所述微纳米光学结构于所述衬底上包括以下步骤：
于所述衬底上形成第一金属薄膜层；
于所述第一金属薄膜层上形成掩膜层并图形化，以图形化的所述掩膜层为掩膜刻蚀所述第一金属薄膜层以得到贯穿所述第一金属薄膜层的纳米开口，并刻蚀入所述衬底以得到预设深度的凹陷结构；
去除所述掩膜层；
形成第二金属薄膜层，所述第二金属薄膜层覆盖于所述第一金属薄膜层的表面及所述凹陷结构的底面；
形成非金属介质，所述非金属介质填充于所述纳米开口中。
可选地，形成所述非金属介质之前，还包括形成粘附层于所述第二金属薄膜层表面的步骤。
可选地，所述衬底的材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机物中的一种或多种。
本发明还提供一种表面具有微纳米光学结构的器件的制备方法，包括以下步骤：
提供一衬底，形成微纳米光学结构于所述衬底上，所述微纳米光学结构包括表面等离极化激元谐振结构及金属纳米帽，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质；所述金属纳米帽凸设于所述金属薄膜的面向所述衬底的一侧，正对所述纳米开口，且附着于所述非金属介质的面向所述衬底的一面；所述非金属介质突出于所述金属薄膜的面向所述衬底的一面，所述金属纳米帽完全包覆或部分包覆所述非金属介质的突出部分；或者所述非金属介质凹陷于或齐平于所述金属薄膜的面向所述衬底的一面，且所述非金属介质的面向所述衬底的一面与所述金属薄膜的面向所述衬底的一面之间的距离小于10nm；所述金属薄膜及所述金属纳米帽均与所述衬底直接接触；
提供所述支撑体，通过粘合剂将所述微纳米光学结构的背离所述衬底的一面粘合于所述支撑体的承载面；
将所述支撑体连同所述微纳米光学结构自所述衬底剥离，使所述微纳米光学结构从所述衬底上转移到所述支撑体的承载面；
去除所述纳米帽。
可选地，所述金属薄膜的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽与所述非金属介质的界面处设有粘附层，所述衬底的材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机物中的一种或多种。
可选地，所述微纳米光学结构还包括法布里-珀罗微腔，所述法布里-珀罗微腔包括第一基板、第二基板及位于所述第一基板与所述第二基板之间的介质层，所述第一基板由所述表面等离极化激元谐振结构构成，所述第二基板位于所述第一基板的远离所述衬底的一侧并与所述第一基板平行，所述表面等离极化激元谐振结构和所述法布里-珀罗微腔耦合形成法诺共振。
本发明还提供一种表面具有微纳米光学结构的器件，包括：
支撑体，具有一承载面；
微纳米光学结构，结合于所述承载面，所述微纳米光学结构包括表面等离极化激元谐振结构及法布里-珀罗微腔；
其中，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列；
所述法布里-珀罗微腔位于所述承载面与所述表面等离极化激元谐振结构之间，所述表面等离极化激元谐振结构和所述法布里-珀罗微腔耦合形成法诺共振，其中，所述法布里-珀罗微腔包括第一基板、第二基板及位于所述第一基板与所述第二基板之间的介质层，所述第一基板由所述表面等离极化激元谐振结构构成，所述第二基板位于所述第一基板的面向所述支撑体的一侧并与所述第一基板平行；
当光波从所述微纳米光学结构的面向所述支撑体的一侧朝向所述微纳米光学结构入射，能够激发沿着所述金属薄膜的背离所述支撑体的一面的表面等离极化激元谐振。
可选地，所述支撑体包括光纤；
可选地，所述光纤在工作光波长处为单模光纤。
可选地，所述第二基板包括由金属材料构成的薄膜。
如上所述，本发明的表面具有微纳米光学结构的器件包括支撑体及结合于支撑体的承载面的微纳米光学结构，微纳米光学结构包括表面等离极化激元谐振结构及金属纳米帽，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质；所述金属纳米帽凸设于所述金属薄膜的背离所述支撑体的一侧，正对所述纳米开口，且附着于所述非金属介质的背离所述支撑体的一面；当光波从微纳米光学结构的面向所述支撑体的一侧朝向微纳米光学结构入射，能够激发沿着金属薄膜的背离支撑体的一面的表面等离极化激元谐振。本发明通过金属纳米帽与具有纳米开口的金属薄膜的结合，将包含所述金属薄膜的三维微纳米光学结构制备在与金属具有低结合力的衬底上，能够实现将所述三维结构从衬底剥离并转移到支撑体上，同时，还能够实现从支撑体方向入射的光波与金属薄膜上的表面等离极化激元的共振耦合，其中，转移后金属纳米帽可以根据需要保留或去除。进一步，这种三维微纳米光学结构可包括设置在支撑体与表面等离极化激元谐振结构之间的法布里-珀罗微腔，通过表面等离极化激元谐振结构与法布里-珀罗微腔的法诺共振，能够提高入射光波与金属薄膜上的表面等离极化激元的耦合效率，实现高信噪比的表面等离激元传感，包括折射率传感、分子传感和声场传感等，其中，与二维金属薄膜结构相比，具有法布里-珀罗微腔三维结构的单模光纤端面表面等离激元折射率传感的信噪比可提升达一个量级。再进一步，本发明的制备方法还能够实现其他多种复杂的三维 微纳米光学结构与光纤端面的集成。
附图说明
图1显示为本发明的表面具有微纳米光学结构的器件的结构示意图。
图2显示为图1中虚线框所示区域的放大图。
图3显示为本发明的表面具有微纳米光学结构的器件采用的一种表面等离极化激元谐振结构的示意图。
图4显示为图3所示表面等离极化激元谐振结构的电子显微镜图片，所示为中间区域与旁边区域的交界处。
图5显示为本发明的表面具有微纳米光学结构的器件采用的另外一种表面等离激化激元谐振结构的示意图。
图6显示为本发明的表面具有微纳米光学结构的器件的制备方法中提供衬底并于所述衬底上形成第一金属薄膜层的示意图。
图7显示为本发明的表面具有微纳米光学结构的器件的制备方法中于所述第一金属薄膜层上形成掩膜层，图形化掩膜层并刻蚀所述第一金属薄膜层及所述衬底的示意图。
图8显示为本发明的表面具有微纳米光学结构的器件的制备方法中去除掩膜层的示意图。
图9显示为本发明的表面具有微纳米光学结构的器件的制备方法中依次形成第二金属薄膜层及第一粘附层的示意图。
图10显示为本发明的表面具有微纳米光学结构的器件的制备方法中形成非金属介质及法布里-珀罗微腔介质层，并于所述法布里-珀罗微腔介质层上依次形成第二粘附层及第三金属薄膜层的示意图。
图11显示为本发明的表面具有微纳米光学结构的器件的制备方法中将所述微纳米光学结构从所述衬底剥离转移的示意图。
图12显示为本发明的表面具有微纳米光学结构的器件的制备方法中的所述微纳米光学结构转移过程的显微镜图片。
图13显示为本发明的表面具有微纳米光学结构的器件的制备方法中的所述微纳米光学结构转移后展示所述纳米帽的原子力显微镜图片。
图14显示为采用本发明的表面具有微纳米光学结构的器件测量液体折射率的实验装置结构示意图。
图15显示为本发明的表面具有微纳米光学结构的器件的端面插入甲醇、水、丙酮、乙醇和异丙醇中的归一化反射谱。
图16显示为各谐振波长关于折射率的变化情况。
图17显示为本发明的表面具有微纳米光学结构的器件的端面插入不同浓度牛血清白蛋白的磷酸盐缓冲溶液中测量表面等离激元谐振的波长随浓度的变化的结果。
图18显示为基线噪声。
元件标号说明
10                     支撑体
20                     表面等离极化激元谐振结构
201                    金属薄膜层
2010                   第一金属薄膜层
2011                   第二金属薄膜层
202                    非金属介质
21                     中间区域
22                     旁边区域
23                     周期性结构
24                     缺陷结构
30                     金属纳米帽
40                     法布里-珀罗微腔
401                    第一基板
402                    介质层
403                    第二基板
4030                   第三金属薄膜层
404                    第一粘附层
405                    第二粘附层
50                     粘合层
60                     衬底
70                     掩膜层
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
请参阅图1至图18。需要说明的是，本实施例中所提供的图示仅以示意方式说明本发明的基本构想，遂图式中仅显示与本发明中有关的组件而非按照实际实施时的组件数目、形状及尺寸绘制，其实际实施时各组件的型态、数量及比例可为一种随意的改变，且其组件布局型态也可能更为复杂。
实施例一
本实施例提供一种表面具有微纳米光学结构的器件，如图1至图2所示，分别显示为该器件的结构示意图与局部放大图，包括支撑体10及微纳米光学结构，其中，所述支撑体10具有承载面，所述微纳米光学结构结合于所述承载面，并包括表面等离极化激元谐振结构20及金属纳米帽30，所述表面等离极化激元谐振结构20包括金属薄膜201及开设于所述金属薄膜201中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质202，所述金属纳米帽30凸设于所述金属薄膜201的背离所述支撑体10的一侧，正对所述纳米开口，且附着于所述非金属介质202的背离所述支撑体10的一面，当光波从所述微纳米光学结构的面向所述支撑体10的一侧朝向所述微纳米光学结构入射，能够激发沿着所述金属薄膜201的背离所述支撑体10的一面的表面等离极化激元谐振。
作为示例，所述非金属介质202突出于所述金属薄膜201的背离所述支撑体10的一面(如图2所呈现)，所述金属纳米帽30完全包覆或部分包覆所述非金属介质202的突出部分。本实施例中，所述非金属介质202的背离所述支撑体10的一面与所述金属薄膜201的背离所述支撑体10的一面之间的距离小于200nm。在一优选示例中，所述非金属介质202的背离所述支撑体10的一面与所述金属薄膜201的背离所述支撑体10的一面之间的距离为8nm，即所述金属纳米帽30与所述金属薄膜201的间距为8nm。
作为示例，所述非金属介质202也可以凹陷于或齐平于所述金属薄膜的背离所述支撑体的一面(未图示)，其中，所述非金属介质202凹陷于所述金属薄膜的背离所述支撑体的一面即所述纳米帽30部分嵌入所述纳米开口中。本实施例中，所述非金属介质202的背离所述支撑体10的一面与所述金属薄膜201的背离所述支撑体10的一面之间的距离小于10nm。
作为示例，所述纳米开口包括纳米孔及纳米槽中的至少一种。具体的，纳米孔是指所述 纳米开口在所述金属薄膜平面维度上经过所述纳米开口的中心的最长边与最短边的长度相等或相接近，其形状包括但不限于圆形、三角形、正方形及六边形，纳米槽是指所述纳米开口在所述金属薄膜平面维度上经过所述纳米开口中心的最长边远大于最短边，其形状如长条状等。
作为示例，所述纳米开口在所述金属薄膜平面维度上经过所述纳米开口的中心的最短边的长度范围是5～200nm。例如，若为圆形纳米孔，则最短边的长度是指圆形纳米孔的直径，若为正方形纳米孔，则最短边的长度是指正方形纳米孔的边长，若为长方形纳米槽，则最短边的长度是指长方形纳米槽的短边宽度。本实施例中，所述纳米开口以长方形纳米槽为例，其短边宽度为50nm，所述纳米开口中填充有SiO2介质。
作为示例，所述纳米开口的侧壁垂直或倾斜。
作为示例，所述支撑体10包括光纤，所述承载面为呈平面状的光纤端面，所述微纳米光学结构粘合于所述光纤端面，所述金属薄膜201平行于所述光纤端面。
作为示例，所述光纤在工作光波长处于单模光纤，所述光纤端面与光纤轴线之间的角度范围是80°～100°，进一步可为82°～98°，优选88°～92°。
作为示例，如图3所示，所述表面等离极化激元谐振结构20包括中间区域21及环绕于所述中间区域21四周的旁边区域22，所述纳米开口的阵列将位于所述中间区域21的所述金属薄膜划分为第一周期性结构，并将位于所述旁边区域22的所述金属薄膜划分为第二周期性结构，所述第一周期性结构与所述第二周期性结构的周期不同，所述中间区域21的位置与光纤芯层对准。
作为示例，如图4所示，显示为所述表面等离极化激元谐振结构20的电子显微镜图片，所示为中间区域21与旁边区域22的交界处，所述中间区域21的第一周期性结构的周期P1为645nm，其周期约等于表面等离极化激元谐振在金属薄膜上的波长，所述旁边区域22的第二周期性结构的周期P2为315nm，其周期约等于表面等离极化激元谐振在金属薄膜上的半波长。当光从光纤的芯层入射时，所述中间区域21与入射的光纤导波耦合形成(金薄膜上的)表面等离极化激元，所述旁边区域22反射所述表面等离极化激元。
需要注意的是，图4中所呈现的周期个数与以上描述并不完全相符，仅作为示意用。当上述表面具有微纳米光学结构的器件浸没在水中时，其材料与结构特性使其可产生的一种表面等离极化激元谐振对应约为850nm的自由空间波长，上述光纤在此波长为单模光纤。在具体的实施例中，本发明中的“约等于”表示数值的偏差为±10％以内。
在一些其他实施例中，如图5所示，所述表面等离极化激元谐振结构包括周期性结构23 及嵌入所述周期性结构中的缺陷结构24，其中，所述纳米开口将所述金属薄膜划分为所述周期性结构23及嵌入所述周期性结构23中的所述缺陷结构24，所述缺陷结构24破坏所述周期性结构23的局部周期性，所述缺陷结构与光纤芯层对齐。所述纳米开口贯穿所述金属薄膜的上表面及下表面，将所述金属薄膜划分为多个金属薄膜单元，其中一部分金属薄膜单元呈周期性排列，构成所述周期性结构23，所述周期性排布的金属薄膜单元为多边形，包括三角形、正方形、长方形及六边形等，另一部分金属薄膜单元嵌入呈周期性排列的金属薄膜单元中，构成所述缺陷结构24。沿所述金属薄膜的表面等离极化激元可在所述缺陷结构中或所述缺陷结构及其附近区域进行谐振，其中，通过周期性结构的空间傅里叶变换的一阶傅里叶分量实现入射光波到表面等离极化激元的耦合，通过其二阶傅里叶分量以限制表面等离极化激元在缺陷结构附近的空间进行振荡。
在一些其他实施例中，所述表面等离极化激元谐振结构20还可以采用其它布局的周期性结构或微腔结构，不以图3或图5所呈现的为限。
作为示例，所述金属薄膜201的材料包括但不限于金、银、铜及铝中的一种或几种，其厚度范围为5～200nm，所述金属纳米帽的材料包括但不限于金、银、铜及铝中的一种或几种，其厚度为5～200nm。具体的，本实施例中，所述金属薄膜采用金膜，其厚度为55nm，所述金属纳米帽采用金纳米帽，其厚度为5nm。
作为示例，所述金属纳米帽30与所述非金属介质202的界面处设有粘附层，所述粘附层的材料包括但不限于钛、铬及镍中的一种或几种。本实施例中，所述粘附层选用钛层，所述粘附层的厚度为2nm。
作为示例，所述表面等离极化激元谐振结构20的表面等离激元谐振光谱随所述表面等离极化激元谐振结构20感受到的折射率的变化而移动，被用于感知环境折射率的变化、分子在该结构上的结合以及通过和声学敏感材料的集成来感知声场等。
作为示例，所述微纳米光学结构还包括法布里-珀罗微腔40，所述法布里-珀罗微腔40位于所述承载面与所述表面等离极化激元谐振结构20之间，所述表面等离极化激元谐振结构20和所述法布里-珀罗微腔40耦合形成法诺共振，其中，所述法布里-珀罗微腔包括第一基板401、第二基板403及位于所述第一基板401与所述第二基板403之间的介质层402，所述第一基板401由所述表面等离极化激元谐振结构20构成，所述第二基板403与所述第一基板401平行。
具体的，通过所述表面等离极化激元谐振结构20和所述法布里-珀罗微腔40耦合，能够提升光纤导波与表面等离极化激元的耦合效率，使得折射率传感的信噪比提升。
作为示例，所述第二基板403包括由金属材料构成的薄膜，例如金膜、银膜、铜膜及铝膜中的一种或几种，所述第二基板403的厚度范围是5～200nm，本实施例中，所述第二基板403选用20nm厚度的金膜。
作为示例，所述介质层402的材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机材料中的一种或几种，所述介质层402的厚度范围是5nm～100μm。本实施例中，所述介质层402选用SiO2层，厚度为230nm。
作为示例，所述金属薄膜201与所述介质层402的界面处设有第一粘附层404，所述第二基板403与所述介质层402的界面处设有第二粘附层405，其中，粘附层用于提高所述介质层402与所述第一基板401及所述第二基板403之间的粘附力，粘附层的材料包括但不限于钛、铬及镍中的一种或几种。本实施例中，所述粘附层选用钛层，所述粘附层的厚度为2nm。
作为示例，所述支撑体10与所述第二基板403之间设有粘合层50，所述粘合层50用于粘合所述支撑体10与所述微纳米光学结构。本实施例中，所述粘合层50采用紫外线固化胶。
综上所述，本实施例提供的表面具有微纳米光学结构的器件包括支撑体及结合于支撑体的承载面的微纳米光学结构，微纳米光学结构包括表面等离极化激元谐振结构及金属纳米帽，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质；所述金属纳米帽凸设于所述金属薄膜的背离所述支撑体的一侧，正对所述纳米开口，且附着于所述非金属介质的背离所述支撑体的一面；当光波从微纳米光学结构的面向所述支撑体的一侧朝向微纳米光学结构入射，能够激发沿着金属薄膜的背离支撑体的一面的表面等离极化激元谐振。所述微纳米光学结构可进一步包括设置在支撑体与表面等离极化激元谐振结构之间的法布里-珀罗微腔，通过表面等离极化激元谐振结构与法布里-珀罗微腔的法诺共振，能够提高入射光波与金属薄膜上的表面等离极化激元的耦合效率，实现高信噪比的表面等离激元传感，包括折射率传感、分子传感和声场传感等，其中，与二维金属薄膜结构相比，具有法布里-珀罗微腔三维结构的单模光纤端面表面等离激元折射率传感的信噪比可提升达一个量级。
实施例二
本实施例提供一种表面具有微纳米光学结构的器件的制备方法，用于制备实施例一中所述的表面具有微纳米光学结构的器件，该方法包括以下步骤：
S1：提供一衬底，形成所述微纳米光学结构于所述衬底上，所述金属薄膜及所述金属纳米帽均与所述衬底直接接触；
S2：提供所述支撑体，通过粘合剂将所述微纳米光学结构的背离所述衬底的一面粘合于所述支撑体的所述承载面；
S3：将所述支撑体连同所述微纳米光学结构自所述衬底剥离，使所述微纳米光学结构从所述衬底上转移到所述支撑体的所述承载面。
作为示例，形成所述微纳米光学结构于所述衬底上包括以下步骤：
(1)如图6所示，提供衬底60，于所述衬底60上形成第一金属薄膜层2010。
作为示例，所述衬底60材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机物中的一种或几种，考虑到衬底的刚性及表面纳米光滑度要求，本实施例优选石英玻璃衬底。
作为示例，所述第一金属薄膜层2010与所述衬底60具有低结合力，所述第一金属薄膜层2010的材质包括但不限于金、银、铜及铝中的一种或几种，本实施例中，所述第一金属薄膜层2010为金薄膜层，可以采用电子束蒸发或其他合适的方法形成。
(2)如图7所示，于所述第一金属薄膜层2010上形成掩膜层70并图形化，以图形化的所述掩膜层70为掩膜刻蚀所述第一金属薄膜层2010以得到贯穿所述第一金属薄膜层2010的纳米开口，并刻蚀入所述衬底60以得到预设深度的凹陷结构。
作为示例，所述掩膜层70包括但不限于聚合物层及光刻胶层等。具体的，本实施例中，所述掩膜层70选用聚甲基丙烯酸甲酯层(PMMA)，可以采用旋涂或其他合适方法形成。
作为示例，采用电子束光刻的方法刻蚀所述掩膜层70以形成纳米开口的阵列图案，采用氩离子束刻蚀或其他合适的方法以所述图形化的所述掩膜层70为掩膜刻蚀所述第一金属薄膜层2010，控制氩离子束刻蚀的速度和时间，刻蚀贯穿所述第一金属薄膜层2010并延伸入所述衬底60，于所述衬底60形成约15nm深度的凹陷结构。
作为示例，可根据实际需要并通过调整刻蚀参数使所述纳米开口的侧壁垂直或倾斜。
(3)如图8所示，去除所述掩膜层70。
作为示例，采用氧等离子体清洗或其他合适的方法去除所述掩膜层70。
(4)如图9所示，形成第二金属薄膜层2011，所述第二金属薄膜层2011覆盖于所述第一金属薄膜层2010的表面及所述凹陷结构的底面。
作为示例，所述第二金属薄膜层2011的材质包括但不限于金、银、铜及铝中的一种或几种。本实施例中，所述第二金属薄膜层2011为金薄膜层，可以采用电子束蒸发或其它合适的方法形成。
(5)如图10所示，形成非金属介质202，所述非金属介质202填充于所述纳米开口中。
具体的，所述衬底中凹陷结构内的所述第二金属薄膜层2011构成所述金属纳米帽30。
作为示例，形成所述非金属介质202之前，还包括形成第一粘附层404于所述第二金属薄膜层2011表面的步骤。所述第一粘附层404用于增加所述非金属介质202与所述第二金属薄膜层2011的粘附力。本实施例中，采用电子束蒸发的方法形成所述第一粘附层404。
作为示例，当所述微纳米光学结构还包括所述法布里-珀罗微腔40时，所述法布里-珀罗微腔40的所述第一基板401由所述表面等离极化激元谐振结构20构成，所述表面等离极化激元谐振结构20的所述金属薄膜201由所述第一金属薄膜层2010及位于所述第一金属薄膜层2010表面的所述第二金属薄膜层2011构成，形成所述法布里-珀罗微腔40还包括以下步骤：如图10所示，形成所述法布里-珀罗微腔40的介质层402，并于所述法布里-珀罗微腔的介质层402上依次形成第二粘附层405及第三金属薄膜层4030，所述第三金属薄膜层4030构成所述法布里-珀罗微腔40的所述第二基板403。
作为示例，所述介质层402可以与所述非金属介质202同步形成或分步形成。
作为示例，采用等离子体增强化学气相沉积法在65℃的温度下沉积形成所述介质层402，采用电子束蒸发的方法形成所述第二粘附层405。
作为示例，所述步骤S2通过粘合剂将所述微纳米光学结构的背离所述衬底60的一面粘合于所述支撑体10的所述承载面包括以下步骤：
(1)于所述承载面或所述微纳米光学结构的远离所述衬底60的一面涂敷粘合剂。
作为示例，所述粘合剂的固化光采用紫外光，所述粘合剂在紫外光照射下固化。本实施例中，所述粘合剂为丙烯酸甲酯，此粘合剂同时对传感所用的光波长透明，其紫外固化波长范围为100～400nm，固化光强度为1～2000J/cm2，固化时间为5～600s，优选地，所述固化波长为320nm附近，固化光强度为100J/cm2，固化时间为300s。本实施例中，选用紫外光源，固化光中心波长在320nm，最大照射功率为2000J/cm2。
(2)调整所述支撑体10的位置以使所述承载面与所述微纳米光学结构的位置对准，并通过所述粘合剂相接触。
作为示例，所述衬底60(石英玻璃)为透明衬底，所述支撑体10为光纤，将所述光纤端面与所述微纳米光学结构对准的方法包括：从所述衬底60没有所述微纳米光学结构的一面进行显微观察，观察并对准光纤端面与所述微纳米光学结构的位置。具体的，在所述衬底60没有所述微纳米光学结构的一面，利用透镜和成像元件构成一显微系统，对所述光纤端面与所述微纳米光学结构的放大像进行显示，通过显示的图像调整所述光纤端面与所述微纳米光学结构的位置并对准。
在一些其它示例中，将所述光纤端面与所述微纳米结构对准的方法包括：向所述光纤里打入宽谱光，所述宽谱光沿所述光纤传输并从所述光纤端面射出，之后被所述微纳米结构反射从而返回进入所述光纤，移动所述光纤与所述微纳米结构的相对位置并测量移动过程中反射光的光谱，从所述反射光的光谱与完美对准情形下的预期反射光谱相比较判断是否对准。具体的，通过宽谱光源(例如超辐射二极管)向光纤里打入宽谱光，所述宽谱光沿光纤传输、经过光纤定向耦合器、然后从所述光纤端面射出，接着宽谱光被微纳米光学结构反射从而返回进入光纤，反射光经过光纤定向耦合器并进入光谱仪，移动所述光纤与所述微纳米结构的相对位置并测量移动过程中反射光的光谱，通过光谱仪测量反射光的光谱，从所述反射光的光谱与完美对准情形下的预期反射光谱的比较可以判断与调整光纤端面和金属微纳米结构的对准情况。
具体的，所述光纤端面与所述微纳米光学结构的对准方法根据实际情况进行操作，不以本实施例为限制。
(3)从所述衬底60没有所述微纳米光学结构的一面的方向、透过衬底用粘合剂固化光来照射所述粘合剂以使之固化。
作为示例，如图11所示，显示为所述步骤S3将所述支撑体10连同所述微纳米光学结构自所述衬底60剥离，使所述微纳米光学结构从所述衬底上转移到所述支撑体10的所述承载面的示意图。
作为示例，如图12所示，显示为所述微纳米光学结构转移过程中的光学显微照片，其中所述支撑体为光纤，所述承载面为光纤的端面，所述微纳米光学结构呈现为圆盘状并已被转移到所述光纤端面，所述表面等离极化激元谐振结构及纳米帽呈现为位于圆盘中央的阴影状区域。图12中包括光纤及其端面的微纳米光学结构(图片右下部)，光纤及其端面的微纳米光学结构在所述衬底中的镜像倒影(图片右上部)，以及呈现为圆盘状深色区域的所述衬底上的所述微纳米光学结构转移前在的位置(图片中部)。图13显示为所述微纳米光学结构转移到所述支撑体的承载面后的原子力显微镜图片，展示了纳米帽阵列。
需要强调的是，所述纳米开口中填充的非金属介质202可防止转移过程中粘合剂进入所述纳米开口中从而影响所述微纳米光学结构从所述衬底60上的剥离效率，而所述纳米帽30是所述微纳米光学结构与所述衬底60形成低结合力界面的关键。作为示例，所述纳米帽30由贵金属材质的金构成，贵金属与很多衬底材料(如SiO2)之间的结合力很大程度上来源于范德华力，属于低结合力，利于实现所述微纳米光学结构从所述衬底60上的剥离。而若不设置所述纳米帽30，则纳米开口中沉积的非金属介质会与衬底牢牢地结合在一起，使转移不能 完成。此外，本发明的所述纳米帽30在有效降低微纳米光学结构与衬底的结合力以利转移的同时，仍然能够保有表面等离极化激元通过纳米开孔对金属薄膜进行共振隧穿的特性，从而实现表面等离激元谐振与来自支撑体方向的入射光波的耦合。基于这种微纳米光学结构及制备方法，可以实现将包含金属薄膜的三维结构从平面衬底剥离并转移到光纤端面，且实现光纤导波与金属薄膜另一侧表面等离极化激元的共振隧穿耦合，同时，基于三维微纳米光学结构(例如所述法布里-珀罗微腔40)在光纤端面的集成，能够使光纤端面表面等离激元传感具有前所未有的高信噪比。
实施例三
本实施例采用实施例二制备的表面具有微纳米光学结构的器件进行折射率测量实验，在一具体示例中，所述支撑体以光纤为例，所述光纤在工作光波长处于单模光纤，所述微纳米光学结构包括表面等离极化激元谐振结构、法布里-珀罗微腔及金属纳米帽，所述表面等离极化激元谐振结构包括中间区域及环绕于所述中间区域四周的旁边区域，所述中间区域的位置与光纤芯层对准，所述纳米开口的阵列将位于所述中间区域的所述金属薄膜划分为周期为645nm的第一周期性结构，并将位于所述旁边区域的所述金属薄膜划分为周期为315nm的第二周期性结构，所述纳米开口采用短边宽度为50nm的长方形纳米槽，所述纳米开口中填充有SiO2介质，该SiO2介质突出于所述金属薄膜的背离所述光纤的一面，且该SiO2介质的背离光纤的一面与所述金属薄膜201的背离光纤的一面之间的距离为8nm，所述金属薄膜采用55nm厚度的金膜，所述金属纳米帽采用5nm厚度的金纳米帽，所述金属纳米帽与所述非金属介质的界面处设有厚度为2nm的钛粘附层，所述第二基板采用20nm厚度的金膜，所述介质层采用厚度为230nm的SiO2层，所述金属薄膜与所述介质层之间设有厚度为2nm的钛粘附层，所述第二基板与所述介质层之间设有厚度为2nm的钛粘附层，所述第二基板与光纤的端面采用紫外线固化胶粘合。
作为示例，如图14所示，显示为采用本发明的表面具有微纳米光学结构的器件测量液体折射率的实验装置图。实验所用的单模光纤工作波长为780～970nm，使用的光源为超辐射发光二极管(super-luminescent diode，SLD)，为宽谱光源。光源输出的光经过50％：50％光纤定向耦合器被导入待测液体中，其反射信号再经过该定向耦合器被导入到CCD光纤光谱仪中进行分析。
作为示例，测试了甲醇、水、丙酮、乙醇和异丙醇五种液体，其各自的归一化反射谱如图15所示，如果没有法布里-珀罗微腔，而将表面等离极化激元谐振结构与光纤导波直接耦 合(US 11,022,752B2，ZL201610754423.1，US 11,137,353B2)，则在光纤导波的反射谱里将只能得到较浅的表面等离激元谐振反射谷，即光纤导波和表面等离极化激元微腔的耦合效率很有限，仿真结果表明谷深只有不超过约15％，而在本实施例中，通过表面等离极化激元谐振结构和法布里-珀罗微腔耦合形成法诺共振，得到最多约55％深的谐振谷，且还能得到约46％高的谐振峰，表明光纤导波和表面等离极化激元谐振的耦合效率大幅提高，将其各自的谐振波长和各溶液的折射率对应，可得到如图16所示的谐振波长关于折射率变化的散点(实验值)图，可以看出，谐振波长关于折射率呈线性变化，经过线性拟合得到的灵敏度为411nm RIU-1。
作为示例，本发明的表面具有微纳米光学结构的器件的端面还被浸入不同浓度牛血清白蛋白(bovine serum albumin，BSA)的磷酸盐缓冲溶液(phosphate buffered saline，PBS)中，同样利用上述方法测量表面等离激元谐振的波长随浓度的变化，通过表面等离激元谐振波长的变化实时读取BSA分子在传感器表面的物理吸附。其中，BSA浓度依次从10ng/mL增加到100μg/mL，每次增加10倍，同时，样品以80mm/s的速度沿光纤方向往复振动，测量结果如图17所示，显示可以测到10ng/mL的浓度。表面等离激元谐振波长随时间变化的基线噪音如图18所示，通过信噪比计算，得到1秒积分时的噪声等效检测限为1.9×10-7RIU，比目前已报道的最好水平低了约一个量级。
此外，还可以通过光纤端面附近的物质的折射率或几何参数随压力变化的性质，来测量光纤端面所在环境里的压力。例如，所述压力可以来自声波、超声波或次声波，所述物质可以是微纳米光学结构与光纤端面之间的粘合剂或其他物质，也可以是附着在金属薄膜表面或光纤端面的物质。
实施例四
在实施例二中，当所述微纳米光学结构从所述衬底剥离后，所述纳米帽30被保留于所述微纳米光学结构。然而，也可以根据需要去除所述纳米帽，以更加顺利激发沿着所述金属薄膜201的背离所述支撑体10的一面的表面等离极化激元谐振。本实施例中提供一种表面具有微纳米光学结构的器件的制备方法，包括以下步骤：
S1：提供一衬底，形成微纳米光学结构于所述衬底上，所述微纳米光学结构包括表面等离极化激元谐振结构及金属纳米帽，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质；所述金属纳米帽凸设于所述金属薄膜的面向所述衬底的一侧，正对所述纳米开口，且附着于所述非 金属介质的面向所述衬底的一面；所述非金属介质突出于所述金属薄膜的面向所述衬底的一面，所述金属纳米帽完全包覆或部分包覆所述非金属介质的突出部分；或者所述非金属介质凹陷于或齐平于所述金属薄膜的面向所述衬底的一面，且所述非金属介质的面向所述衬底的一面与所述金属薄膜的面向所述衬底的一面之间的距离小于10nm，所述金属薄膜及所述金属纳米帽均与所述衬底直接接触；
S2：提供所述支撑体，通过粘合剂将所述微纳米光学结构的背离所述衬底的一面粘合于所述支撑体的承载面；
S3：将所述支撑体连同所述微纳米光学结构自所述衬底剥离，使所述微纳米光学结构从所述衬底上转移到所述支撑体的承载面；
S4：去除所述纳米帽。
作为示例，去除所述纳米帽的方法可以包括研磨、超声震荡、粘除、拔除等方法。
作为示例，所述金属薄膜的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽的材料包括金、银、铜及铝中的一种或几种。
作为示例，所述金属纳米帽与所述非金属介质的界面处设有粘附层，所述衬底的材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机物中的一种或多种。
作为示例，所述微纳米光学结构还包括法布里-珀罗微腔，所述法布里-珀罗微腔包括第一基板、第二基板及位于所述第一基板与所述第二基板之间的介质层，所述第一基板由所述表面等离极化激元谐振结构构成，所述第二基板位于所述第一基板的远离所述衬底的一侧并与所述第一基板平行，所述表面等离极化激元谐振结构和所述法布里-珀罗微腔耦合形成法诺共振。
作为示例，所述金属薄膜与所述介质层的界面处设有粘附层，所述第二基板与所述介质层的界面处设有粘附层。
实施例五
本实施例提供一种表面具有微纳米光学结构的器件，其可采用实施例四中的制作方法或其它合适的制作方法制作得到，该表面具有微纳米光学结构的器件包括支撑体及微纳米光学结构，其中，所述支撑体具有一承载面，所述微纳米光学结构结合于所述承载面，所述微纳米光学结构包括表面等离极化激元谐振结构及法布里-珀罗微腔。
具体的，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列；所述法布里-珀罗微腔位于所述承载面与所述表面等离极化激元谐振 结构之间，所述表面等离极化激元谐振结构和所述法布里-珀罗微腔耦合形成法诺共振，其中，所述法布里-珀罗微腔包括第一基板、第二基板及位于所述第一基板与所述第二基板之间的介质层，所述第一基板由所述表面等离极化激元谐振结构构成，所述第二基板位于所述第一基板的面向所述支撑体的一侧并与所述第一基板平行；当光波从所述微纳米光学结构的面向所述支撑体的一侧朝向所述微纳米光学结构入射，能够激发沿着所述金属薄膜的背离所述支撑体的一面的表面等离极化激元谐振。
作为示例，所述支撑体包括光纤，所述光纤在工作光波长处为单模光纤。
作为示例，所述第二基板包括由金属材料构成的薄膜。
本实施例的表面具有微纳米光学结构的器件中，所述微纳米光学结构包括表面等离极化激元谐振结构及法布里-珀罗微腔，但不包括金属纳米帽，可以更加顺利激发沿着所述金属薄膜的背离所述支撑体的一面的表面等离极化激元谐振。
综上所述，本发明的表面具有微纳米光学结构的器件包括支撑体及结合于支撑体的承载面的微纳米光学结构，微纳米光学结构包括表面等离极化激元谐振结构及金属纳米帽，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质；所述金属纳米帽凸设于所述金属薄膜的背离所述支撑体的一侧，正对所述纳米开口，且附着于所述非金属介质的背离所述支撑体的一面；当光波从微纳米光学结构的面向所述支撑体的一侧朝向微纳米光学结构入射，能够激发沿着金属薄膜的背离支撑体的一面的表面等离极化激元谐振。本发明通过金属纳米帽与具有纳米开口的金属薄膜的结合，将包含所述金属薄膜的三维微纳米光学结构制备在与金属具有低结合力的衬底上，能够实现将所述三维结构从衬底剥离并转移到支撑体上，同时，还能够实现从支撑体方向入射的光波与金属薄膜上的表面等离极化激元的共振耦合，其中，转移后金属纳米帽可以根据需要保留或去除。进一步，这种三维微纳米光学结构可包括设置在支撑体与表面等离极化激元谐振结构之间的法布里-珀罗微腔，通过表面等离极化激元谐振结构与法布里-珀罗微腔的法诺共振，能够提高入射光波与金属薄膜上的表面等离极化激元的耦合效率，实现高信噪比的表面等离激元传感，包括折射率传感、分子传感和声场传感等，其中，与二维金属薄膜结构相比，具有法布里-珀罗微腔三维结构的单模光纤端面表面等离激元折射率传感的信噪比可提升达一个量级。再进一步，本发明的制备方法还能够实现其他多种复杂的三维微纳米光学结构与光纤端面的集成。所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (21)

  1. 一种表面具有微纳米光学结构的器件，其特征在于，包括：
    支撑体，具有一承载面；
    微纳米光学结构，结合于所述承载面，所述微纳米光学结构包括表面等离极化激元谐振结构及金属纳米帽；
    其中，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质；
    所述金属纳米帽凸设于所述金属薄膜的背离所述支撑体的一侧，正对所述纳米开口，且附着于所述非金属介质的背离所述支撑体的一面；
    所述非金属介质突出于所述金属薄膜的背离所述支撑体的一面，所述金属纳米帽完全包覆或部分包覆所述非金属介质的突出部分；或者所述非金属介质凹陷于或齐平于所述金属薄膜的背离所述支撑体的一面，且所述非金属介质的背离所述支撑体的一面与所述金属薄膜的背离所述支撑体的一面之间的距离小于10nm；
    当光波从所述微纳米光学结构的面向所述支撑体的一侧朝向所述微纳米光学结构入射，能够激发沿着所述金属薄膜的背离所述支撑体的一面的表面等离极化激元谐振。
  2. 根据权利要求1所述的表面具有微纳米光学结构的器件，其特征在于：所述纳米开口包括纳米孔及纳米槽中的至少一种，所述纳米开口的侧壁垂直或倾斜。
  3. 根据权利要求1所述的表面具有微纳米光学结构的器件，其特征在于：所述金属薄膜的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽与所述非金属介质的界面处设有粘附层。
  4. 根据权利要求1所述的表面具有微纳米光学结构的器件，其特征在于：所述支撑体包括光纤，所述承载面为呈平面状的光纤端面，所述微纳米光学结构粘合于所述光纤端面，所述金属薄膜平行于所述光纤端面。
  5. 根据权利要求4所述的表面具有微纳米光学结构的器件，其特征在于：所述表面等离极化激元谐振结构包括中间区域及环绕于所述中间区域四周的旁边区域，所述纳米开口的阵列将位于所述中间区域的所述金属薄膜划分为第一周期性结构，并将位于所述旁边区域的所述金属薄膜划分为第二周期性结构，所述第一周期性结构与所述第二周期性结构的周期不同，所述第一周期性结构与光纤芯层对齐。
  6. 根据权利要求4所述的表面具有微纳米光学结构的器件，其特征在于：所述表面等离极化激元谐振结构包括周期性结构及嵌入所述周期性结构中的缺陷结构，其中，所述纳米开口的阵列将所述金属薄膜划分为所述周期性结构及嵌入所述周期性结构中的所述缺陷结构，所述缺陷结构破坏所述周期性结构的局部周期性，所述缺陷结构与光纤芯层对齐。
  7. 根据权利要求4所述的表面具有微纳米光学结构的器件，其特征在于：所述光纤在工作光波长处为单模光纤。
  8. 根据权利要求1-7任意一项所述的表面具有微纳米光学结构的器件，其特征在于：所述微纳米光学结构还包括法布里-珀罗微腔，所述法布里-珀罗微腔位于所述承载面与所述表面等离极化激元谐振结构之间，所述表面等离极化激元谐振结构和所述法布里-珀罗微腔耦合形成法诺共振，其中，所述法布里-珀罗微腔包括第一基板、第二基板及位于所述第一基板与所述第二基板之间的介质层，所述第一基板由所述表面等离极化激元谐振结构构成，所述第二基板与所述第一基板平行。
  9. 根据权利要求8所述的表面具有微纳米光学结构的器件，其特征在于：所述第二基板包括由金属材料构成的薄膜，所述金属薄膜与所述介质层的界面处设有粘附层。
  10. 根据权利要求8所述的表面具有微纳米光学结构的器件，其特征在于：所述介质层的材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机材料中的一种或几种，所述介质层的厚度范围是5nm～100μm。
  11. 一种如权利要求1-10任意一项所述的表面具有微纳米光学结构的器件的制备方法，其特征在于，包括以下步骤：
    提供一衬底，形成所述微纳米光学结构于所述衬底上，所述金属薄膜及所述金属纳米帽均与所述衬底直接接触；
    提供所述支撑体，通过粘合剂将所述微纳米光学结构的背离所述衬底的一面粘合于所述支撑体的所述承载面；
    将所述支撑体连同所述微纳米光学结构自所述衬底剥离，使所述微纳米光学结构从所述衬底上转移到所述支撑体的所述承载面。
  12. 根据权利要求11所述的表面具有微纳米光学结构的器件的制备方法，其特征在于，形成所述微纳米光学结构于所述衬底上包括以下步骤：
    于所述衬底上形成第一金属薄膜层；
    于所述第一金属薄膜层上形成掩膜层并图形化，以图形化的所述掩膜层为掩膜刻蚀所述第一金属薄膜层以得到贯穿所述第一金属薄膜层的纳米开口，并刻蚀入所述衬底以得到预设深度的凹陷结构；
    去除所述掩膜层；
    形成第二金属薄膜层，所述第二金属薄膜层覆盖于所述第一金属薄膜层的表面及所述凹陷结构的底面；
    形成非金属介质，所述非金属介质填充于所述纳米开口中。
  13. 根据权利要求12所述的表面具有微纳米光学结构的器件的制备方法，其特征在于：形成所述非金属介质之前，还包括形成粘附层于所述第二金属薄膜层表面的步骤。
  14. 根据权利要求11所述的表面具有微纳米光学结构的器件的制备方法，其特征在于：所述衬底的材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机物中的一种或多种。
  15. 一种表面具有微纳米光学结构的器件的制备方法，其特征在于，包括以下步骤：
    提供一衬底，形成微纳米光学结构于所述衬底上，所述微纳米光学结构包括表面等离极化激元谐振结构及金属纳米帽，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列，所述纳米开口中填充有非金属介质；所述金属纳米帽凸设于所述金属薄膜的面向所述衬底的一侧，正对所述纳米开口，且附着于所述非金属介质的面向所述衬底的一面；所述非金属介质突出于所述金属薄膜的面向所述衬底的一面，所述金属纳米帽完全包覆或部分包覆所述非金属介质的突出部分；或者所述非金属介质凹陷于或齐平于所述金属薄膜的面向所述衬底的一面，且所述非金属介质的面向所述衬底的一面与所述金属薄膜的面向所述衬底的一面之间的距离小于10nm；所述金属薄膜及所述金属纳米帽均与所述衬底直接接触；
    提供所述支撑体，通过粘合剂将所述微纳米光学结构的背离所述衬底的一面粘合于所述支撑体的承载面；
    将所述支撑体连同所述微纳米光学结构自所述衬底剥离，使所述微纳米光学结构从所 述衬底上转移到所述支撑体的承载面；
    去除所述纳米帽。
  16. 根据权利要求15所述的表面具有微纳米光学结构的器件的制备方法，其特征在于：所述金属薄膜的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽的材料包括金、银、铜及铝中的一种或几种，所述金属纳米帽与所述非金属介质的界面处设有粘附层，所述衬底的材料包括金属氧化物、金属氮化物、二氧化硅、半导体材料及有机物中的一种或多种。
  17. 根据权利要求15所述的表面具有微纳米光学结构的器件的制备方法，其特征在于：所述微纳米光学结构还包括法布里-珀罗微腔，所述法布里-珀罗微腔包括第一基板、第二基板及位于所述第一基板与所述第二基板之间的介质层，所述第一基板由所述表面等离极化激元谐振结构构成，所述第二基板位于所述第一基板的远离所述衬底的一侧并与所述第一基板平行，所述表面等离极化激元谐振结构和所述法布里-珀罗微腔耦合形成法诺共振。
  18. 一种表面具有微纳米光学结构的器件，其特征在于，包括：
    支撑体，具有一承载面；
    微纳米光学结构，结合于所述承载面，所述微纳米光学结构包括表面等离极化激元谐振结构及法布里-珀罗微腔；
    其中，所述表面等离极化激元谐振结构包括金属薄膜及开设于所述金属薄膜中的纳米开口或纳米开口的阵列；
    所述法布里-珀罗微腔位于所述承载面与所述表面等离极化激元谐振结构之间，所述表面等离极化激元谐振结构和所述法布里-珀罗微腔耦合形成法诺共振，其中，所述法布里-珀罗微腔包括第一基板、第二基板及位于所述第一基板与所述第二基板之间的介质层，所述第一基板由所述表面等离极化激元谐振结构构成，所述第二基板位于所述第一基板的面向所述支撑体的一侧并与所述第一基板平行；
    当光波从所述微纳米光学结构的面向所述支撑体的一侧朝向所述微纳米光学结构入射，能够激发沿着所述金属薄膜的背离所述支撑体的一面的表面等离极化激元谐振。
  19. 根据权利要求18所述的表面具有微纳米光学结构的器件，其特征在于：所述支撑体包括光纤。
  20. 根据权利要求19所述的表面具有微纳米光学结构的器件，其特征在于：所述光纤在工作光波长处为单模光纤。
  21. 根据权利要求18所述的表面具有微纳米光学结构的器件，其特征在于：所述第二基板包括由金属材料构成的薄膜。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180066307A (ko) * 2016-12-07 2018-06-19 한국기계연구원 플라즈모닉 메타표면 제작방법
CN109437091A (zh) * 2018-10-23 2019-03-08 中山大学 一种在弹性衬底上制备微纳结构的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180066307A (ko) * 2016-12-07 2018-06-19 한국기계연구원 플라즈모닉 메타표면 제작방법
CN109437091A (zh) * 2018-10-23 2019-03-08 中山大学 一种在弹性衬底上制备微纳结构的方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
KOHANDANI, REZA ET AL.: "Self-Referencing Plasmonic Array Sensors", PLASMONICS, vol. 15, 6 April 2020 (2020-04-06), pages 1359 - 1368, XP037236251, DOI: 10.1007/s11468-020-01155-1 *
LEE KUANG-LI, HUANG JHIH-BIN, CHANG JHIH-WEI, WU SHU-HAN, WEI PEI-KUEN: "Ultrasensitive Biosensors Using Enhanced Fano Resonances in Capped Gold Nanoslit Arrays", SCIENTIFIC REPORTS, vol. 5, no. 1, 24 February 2015 (2015-02-24), pages 8547, XP093104797, DOI: 10.1038/srep08547 *
LO SHU-CHENG, YEH CHUN-WEI, WANG SHENG-HANN, KUO CHIA-WEN, LEE KUANG-LI, CHERN RUEY-LIN, WEI PEI-KUEN: "Self-referencing biosensors using Fano resonance in periodic aluminium nanostructures", NANOSCALE, ROYAL SOCIETY OF CHEMISTRY, UNITED KINGDOM, vol. 13, no. 42, 4 November 2021 (2021-11-04), United Kingdom , pages 17775 - 17783, XP093104800, ISSN: 2040-3364, DOI: 10.1039/D1NR03799D *
TIAN YANG, CHEN CHENG, WANG XIAODAN, ZHOU XIN, LEI ZEYU: "Plasmonic Sensingon Fiber Tip", LASER & OPTOELECTRONICS PROGRESS, vol. 56, no. 20, 2 September 2019 (2019-09-02), pages 202404 - 202404-18, XP093104804 *

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