WO2019169747A1 - 表面等离激元-光-电混合传导纳米异质结构及制备方法 - Google Patents

表面等离激元-光-电混合传导纳米异质结构及制备方法 Download PDF

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WO2019169747A1
WO2019169747A1 PCT/CN2018/088737 CN2018088737W WO2019169747A1 WO 2019169747 A1 WO2019169747 A1 WO 2019169747A1 CN 2018088737 W CN2018088737 W CN 2018088737W WO 2019169747 A1 WO2019169747 A1 WO 2019169747A1
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surface plasmon
nano
micro
semiconductor
dimensional
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PCT/CN2018/088737
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French (fr)
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张晓阳
张彤
王善江
薛小枚
周桓立
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东南大学
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Priority to US16/978,717 priority Critical patent/US11099323B2/en
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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
    • 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
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/1226—Basic optical elements, e.g. light-guiding paths involving surface plasmon interaction
    • 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
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/124—Geodesic lenses or integrated gratings
    • 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
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • 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
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13—Integrated optical circuits characterised by the manufacturing method
    • G02B6/132—Integrated optical circuits characterised by the manufacturing method by deposition of thin films
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
    • G01Q60/38—Probes, their manufacture, or their related instrumentation, e.g. holders
    • G01Q60/40—Conductive probes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q80/00—Applications, other than SPM, of scanning-probe techniques
    • 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
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/107—Subwavelength-diameter waveguides, e.g. nanowires

Definitions

  • the invention relates to the fields of nano optics, nano materials and integrated optoelectronic devices, in particular to a surface plasmon-photo-electric hybrid conducting nano-heterostructure platform and a preparation method thereof.
  • the surface plasmon signal can be excited by the optical signal, but how to effectively convert the optical signal into a surface plasmon signal, thereby achieving efficient coupling transmission of the optical signal and the surface plasmon signal, is still a problem.
  • Experimental studies have shown that the efficiency of plasmon signal excitation on metal surface by lens alone is less than 2%. Therefore, it is necessary to introduce some auxiliary means to improve the wave vector of incident light, thereby improving the efficiency of light wave conversion into plasmon. method. So far, these auxiliary means, which can realize the mutual coupling and transmission of the optical signal and the surface plasmon signal, mainly manufacture the optical waveguide device and the metal surface plasmon waveguide device separately, and bring the two devices close to each other.
  • the optical waveguide and surface plasmon waveguide devices prepared by these methods must introduce a large insertion loss when implementing signal coupling.
  • the causes of loss include: scattering loss due to roughness at the coupling interface between the optical medium and the metal structure, scattering loss of the waveguide sidewall caused by material defects caused by various coating processes such as various coating, photolithography, and etching. End surface scattering, etc., can not achieve effective transmission of optical signals or electrical signals, greatly reducing the optical transmission efficiency of the device.
  • this patent proposes a surface plasmon-photo-electric hybrid conducting nano-heterostructure platform, which utilizes a single crystal, atomic-level plasmon and semiconductor material directly, to utilize effective materials between materials. Lattice matching, realizing zero contact in the true sense, greatly reducing the transmission loss at the coupling interface, and providing a new nano-optical platform for studying various novel effects caused by the interaction of light and matter.
  • the object of the present invention is to overcome the deficiencies of the prior art, and to provide a surface plasmon-photo-electric hybrid conducting nano-heterostructure and a preparation method thereof, which control the crystal by adding a water wheel number
  • the size and density of the species enable a highly consistent control of the seed crystal.
  • the length to diameter ratio and distribution of the semiconductor structure are strictly controlled by continuous growth.
  • This kind of surface plasmon-photo-electric hybrid conducting nano-heterostructure platform directly on the surface plasmon metal micro/nano structure grows dense and controllable, long-ratio ratio controllable semiconductor structure in nanomaterials, integrated optoelectronics
  • the device field has important applications.
  • a surface plasmon-photo-electric hybrid conducting nano-heterostructure of the present invention comprises: an excitation light source, a semiconductor nanostructure array, a two-dimensional surface plasmon micro/nano structure, subwavelength plasmon polarization Excimer guided wave, outgoing light wave, one-dimensional surface plasmon micro/nano structure, wire, metal electrode, conductive substrate, probe molecule, atomic force microscopic conductive probe and voltage source; wherein semiconductor nanostructure array is located in two dimensions The upper surface of the surface plasmon micro-nano structure or the outer surface of the one-dimensional surface plasmon micro-nano structure, and form a tight Schottky contact, the excitation light source is vertically irradiated on the two-dimensional surface plasmon micro-nano The outer surface of the structure or the one-dimensional surface of the outer surface of the plasmon micro/nano structure; the probe molecules are located on the surface of the semiconductor nanostructure array, and the subwavelength plasmon polaris guided waves
  • the conductive substrate is made of a chemically active metal material such as aluminum, tin, copper, iron or zinc which is easily oxidized with external water and oxygen, and the rate of chemical reaction between different metals and water and oxygen is different, and The physical and chemical properties of the resulting metal oxide semiconductor seed crystals are different, so that the distribution density and morphology of the semiconductor seed crystals on the surface plasmon micro/nano structure can be accurately controlled, and then the semiconductor crystals can be optimized.
  • Surface plasmon-photo-electric hybrid conducting nano-heterostructure platform with different morphology, structure and function.
  • the semiconductor nanostructure array wherein the semiconductor nanostructure is a one-dimensional semiconductor nanostructure of nanorods, nanometer cones or nanotubes, having a length of 1-1000 ⁇ m, a diameter of 0.1-1000 ⁇ m, a pitch of 1-1000 nm, or It is a zero-dimensional, two-dimensional or complex spiral crystal structure; the alternative material is zinc oxide, titanium dioxide or aluminum oxide.
  • the metal electrode is made of gold, silver or platinum;
  • the conductive substrate is made of a conductive carrier such as indium tin oxide ITO, fluorine-doped tin oxide FTO or graphite, and has a thickness of 100 nm to 10000 ⁇ m.
  • the probe molecule is selected from the group consisting of rhodamine 6G, p-nonylaniline 4-ATP or 4-mercaptopyridine 4-MPY.
  • the excitation light source is a single-wavelength light source or a broad-spectrum light source, and the wavelength range is from 300 nm to 3000 nm covering the ultraviolet to mid-infrared band.
  • the method for preparing the surface plasmon-photo-electric hybrid conducting nanoheterostructure of the present invention is as follows:
  • Step 1 Preparation of single crystal, density-controlled semiconductor seed crystals
  • the surface plasmon micro-nano structure solution is uniformly coated on a clean metal active substrate and naturally dried in the air to obtain a uniformly distributed surface plasmon micro-nano structure; the deionized water is uniformly coated on the metal active On the substrate, it is naturally dried in the air to obtain a semiconductor seed crystal structure uniformly distributed on the surface plasmon micro/nano structure; the semiconductor seed crystal is controlled by selecting a metal active substrate having different activities and coating the amount of deionized water. Distribution density and morphology of surface plasmon micro/nano structures;
  • Step 2 Growing semiconductor nanowires on a surface plasmon micro/nano structure
  • the semiconductor nanocrystals with the semiconductor seed crystal as the core on the surface of the surface plasmon micro/nano structure are oriented by gas phase method or solution method.
  • the semiconductor nanowires with adjustable density and adjustable aspect ratio are formed by metal and semiconductor heterostructures.
  • the metal salt is weighed into a porcelain boat, the metal active substrate is placed in the center of the tube furnace, high-purity N 2 is introduced , and the temperature of the deposition chamber of the tube furnace is adjusted to 100-700 ° C, and the temperature is constant.
  • the reaction is carried out for 0.5-10 h, and finally naturally cooled to room temperature to obtain a sample;
  • the surface plasmon-photo-electric hybrid conducting nano-heterostructures are respectively operated as two types of integrated optoelectronic devices: the first type is a passive one-dimensional, two-dimensional surface plasmon integrated nano-transmission platform, A subwavelength surface plasmon signal transmission waveguide is formed on the surface of the one-dimensional surface plasmon micro-nano structure and the two-dimensional surface plasmon micro-nano structure, and the semiconductor nanowire is used as an optical waveguide for transmitting light waves to realize a surface or the like.
  • the interconnection of the excimer signal and the optical signal, the grating structure formed by the density controllable semiconductor nanowire array 2 is used to enhance the incident light wave vector, enhance the coupling excitation and emission efficiency between the optical signal and the surface plasmon signal, or further pass Metal particles and other modifications are introduced into the "hot spot" to form a zero-dimensional scattering point source, and a certain function of the optical signal and surface plasmon signal is constructed on the surface plasmon-photo-electric hybrid conducting nano-heterostructure platform.
  • Devices and systems; the second type is a heterogeneous integrated active device composed of a semiconductor nanocrystal source with optical gain characteristics and a surface plasmon waveguide.
  • the surface plasmon micro-nano structure and the two-dimensional surface plasmon micro-nano structure edge form a one-dimensional sub-wavelength scattering light source, and the plasmon-photo-electrical effective coupling and energy conversion are realized at the nanometer scale.
  • the photoelectric conversion effect of the semiconductor nanowire to convert the optical signal incident on the surface of the semiconductor nanowire into an electrical signal, and transmit the electrical signal through the surface plasmon micro-nano structure having the conductive property to realize the surface plasmon - On-chip interconnection of three signals of light and electricity.
  • the metal salt is selected from the group consisting of aluminum trichloride, tin tetrachloride, iron nitrate or zinc acetate.
  • the weak reducing agent solution the alternative material is ascorbic acid AA, hydrogen peroxide aqueous solution H 2 O 2 or urotropine HMTA; the surface capping agent, the alternative material is polyethyleneimine PEI, curve Pass X-100 or sodium di-ethylhexyl succinate sulfonate AOT.
  • the present invention has the following advantages over the prior art:
  • the present invention first proposed a surface plasmon-optical-electric hybrid conducting nano-heterostructure platform, which provides a mixture of surface plasmons, light and electricity signals, interconnection and low scattering loss conduction.
  • a new medium that can be widely used in the future development of high-density integrated optoelectronic devices and systems.
  • the nano-platform Compared with the internationally reported integrated photoelectric devices using near-field coupling and physical contact, the nano-platform not only effectively avoids the above problems, but also has many advantages. Wavelength, wide spectrum simultaneous excitation, low loss transmission, and the transmission direction can be extended to multiple dimensions.
  • the electronic chip technology of the CMOS process can be directly interconnected with the nano platform to realize photoelectric multiplexing and play a powerful information processing function.
  • Plasmon metal-semiconductor optoelectronic devices based on traditional coating technology and micro-nano pattern processing technology have problems of poor crystal quality and many interface defects, resulting in large optical loss.
  • the invention provides a surface plasmon-semiconductor heterojunction structure, and the atomic-planar surface plasmon micro-nano structure is used as a processing platform to grow a one-dimensional single crystal semiconductor nanostructure with controllable aspect ratio, which avoids Impurity defects, surface roughness and other problems, to achieve crystal lattice matching of single crystal to single crystal, greatly reducing surface and interface loss, can achieve effective coupling, transmission and resonance of light at nanometer size.
  • the invention proposes a novel preparation method of semiconductor seed crystals with adjustable density and controllable distribution. Based on traditional methods of synthesizing seed crystals such as vapor deposition, magnetron sputtering, and chemical reduction, the results are based on the uncontrollable size, morphology, and distribution of semiconductors.
  • the invention realizes the strict controllability of the density and distribution of the semiconductor seed crystal by adjusting the free metal ions provided by the water, the oxygen, the temperature and the metal substrate, and is a process for controlling the growth of the semiconductor seed crystal on the surface plasmon micro/nano structure. Breakthrough.
  • the method of constructing the seed crystal is generally applicable to the subsequent chemical method for continuously growing the one-dimensional semiconductor nanostructure, and the practicality is greatly improved.
  • the wave vector of the surface plasmon wave is larger than the wave vector of the light wave under normal conditions, it is impossible to directly excite the surface plasmon wave with the light wave, that is, the wave vector matching condition is not satisfied.
  • Traditional ways of implementing wave vector matching such as prism coupling, grating coupling, and near-field coupling, require the introduction of additional special structures, which increase the volume of the device, the scattering loss caused by the roughness at the coupling interface, and nano-machining.
  • the scattering loss and the end face scattering of the waveguide sidewall caused by the material defects caused by the process, etc. result in the inability of the optical signal and the electrical signal to be effectively transmitted.
  • the grating structure formed by the density-controlled semiconductor nanowire array is used as the scattering center.
  • Figure 1 is a plasmon-optical signal transmission diagram of a two-dimensional surface plasmon micro/nanostructure-sparse semiconductor hybrid integrated nano-platform structure.
  • Figure 2 is a plasmon-electrical signal transmission and acquisition diagram of a two-dimensional surface plasmon micro/nanostructure-sparse semiconductor hybrid integrated nano-platform structure.
  • Fig. 3 SEM image of a two-dimensional surface plasmon micro/nano structure-sparse semiconductor hybrid integrated nano-platform structure scanning electron microscope.
  • Figure 4 is a plasmon-electrical signal transmission and acquisition diagram of a two-dimensional surface plasmon micro/nano structure-dense semiconductor hybrid integrated nano-platform structure.
  • FIG. 5 is a plasmon-optical signal transmission diagram of a two-dimensional surface plasmon micro/nano structure-dense semiconductor hybrid integrated nano-platform structure.
  • Figure 6 is a scanning electron microscope SEM image of a two-dimensional surface plasmon micro/nano structure-dense semiconductor hybrid integrated nano-platform structure.
  • plasmon-photo-electric heterogeneous integrated photocatalytic reaction device composed of a one-dimensional surface plasmon micro/nano structure-dense semiconductor heterojunction and a metal electrode.
  • Figure 8 is an in-situ remote sensing Raman optoelectronic integrated device composed of a one-dimensional surface plasmon micro/nanostructure-sparse semiconductor heterojunction and probe molecules.
  • excitation light source 1 semiconductor nanostructure array 2, two-dimensional surface plasmon micro/nano structure 3, subwavelength plasmon polariton guide wave 4, outgoing light wave 5, one-dimensional surface plasmon micro Nanostructure 6, conductor 7, metal electrode 8, conductive substrate 9, probe molecule 10, AFM conductive probe 11, voltage source 12.
  • the invention provides a surface plasmon-photo-electric hybrid conducting nano-heterostructure, the structure comprises: an excitation light source, a semiconductor nanostructure array, a two-dimensional surface plasmon micro-nano structure, a sub-wavelength plasmon The oscillating guided wave, the outgoing light wave, the one-dimensional surface plasmon micro-nano structure, the wire, the metal electrode, the conductive substrate, the probe molecule, the atomic force microscopic conductive probe and the voltage source.
  • the positional relationship is that the semiconductor nanostructure array is on the upper surface or side of the two-dimensional surface plasmon micro/nano structure or the one-dimensional surface plasmon micro-nano structure, and forms a tight Schottky contact, and the excitation light is vertically irradiated.
  • the probe molecules are on the surface of the semiconductor nanostructure array, and the subwavelength plasmon polaritons are guided by two
  • the surface surface plasmon micro-nano structure or the one-dimensional surface plasmon micro-nano structure surface propagates, the outgoing light wave is located at the tip of the semiconductor nano-structure array, and the wire is connected to the conductive substrate or metal electrode or atomic force micro-conductive probe or voltage source.
  • the atomic force microscopic conductive probe is located on the semiconductor nanostructure array.
  • the surface plasmon-photo-electric hybrid conducting nano-heterostructure platform is prepared according to the following steps:
  • Step 1 Preparation of single crystal, density-controlled semiconductor seed crystals
  • a certain amount of surface plasmon micro-nanostructure solution is uniformly coated on a clean metal active substrate and naturally dried in the air to obtain a uniformly distributed surface plasmon micro-nano structure.
  • a certain amount of deionized water is uniformly coated on the metal active substrate and naturally dried in the air to obtain a semiconductor seed crystal structure uniformly distributed on the surface plasmon micro/nano structure.
  • the distribution density and morphology of the semiconductor seed crystals on the surface plasmon micro/nanostructures are controlled by selecting metal active substrates having different activities, and the amount of deionized water applied.
  • Step 2 Growing semiconductor nanowires on a surface plasmon micro/nano structure
  • the semiconductor nanocrystals with the semiconductor seed crystal as the core on the surface of the surface plasmon micro/nano structure are oriented by gas phase method or solution method.
  • the semiconductor nanowires with adjustable density and adjustable aspect ratio are formed by metal and semiconductor heterostructures.
  • the surface of the plasmon-photo-electric hybrid conducting nano-heterostructure platform In the gas phase method, a certain amount of metal salt is weighed into a porcelain boat, and the above metal active substrate is placed in the center of the tube furnace, and high purity N 2 is introduced .
  • the temperature of the deposition chamber of the tube furnace is adjusted to 100-700 ° C, and the temperature is reacted for 0.5-10 h. Finally, it was naturally cooled to room temperature to obtain a sample.
  • the surface plasmon-optical-electric hybrid conducting nano-heterostructure platform is respectively used as an operation method of two types of integrated optoelectronic devices: the first type is a passive one-dimensional, two-dimensional plasmon integrated nano-transmission platform, A subwavelength surface plasmon signal transmission waveguide is formed on the surface of the one-dimensional surface plasmon micro-nano structure and the two-dimensional surface plasmon micro-nano structure, and the semiconductor nanowire is used as an optical waveguide for transmitting light waves to realize a surface or the like.
  • the interconnection of the excimer signal and the optical signal, the grating structure formed by the density-controlled semiconductor nanowire array is used to enhance the incident light wave vector, enhance the coupling excitation and emission efficiency between the optical signal and the surface plasmon signal, or further pass the metal Particles and other modifications are introduced into the "hot spot" to form a zero-dimensional scattering point source, and a certain function of optical signal and surface plasmon signal device is constructed on the surface plasmon-optical-electric hybrid conducting nano-heterostructure platform.
  • the second type is a heterogeneous integrated active device composed of a semiconductor nanocrystal source with optical gain characteristics and a surface plasmon waveguide.
  • Two-dimensional plasmon micro-nanostructures form a one-dimensional sub-wavelength scattering source, and achieve plasmon-photo-electrical effective coupling and energy conversion at the nanoscale, or use
  • the photoelectric conversion effect of the semiconductor nanowire converts the optical signal incident on the surface of the semiconductor nanowire into an electrical signal, and transmits the electrical signal through the surface plasmon micro/nano structure having the conductive property to realize surface plasmon-light. - On-chip interconnection of three signals.
  • the surface plasmon micro-nano structure has an anisotropic structure such as a triangular plate, a line or a polyhedron, and has a size of 1-1000 ⁇ m, and the selection material is one-dimensional or two-dimensional such as gold, silver, copper, aluminum or platinum.
  • a metal crystal material having a surface plasmon effect is one-dimensional or two-dimensional such as gold, silver, copper, aluminum or platinum.
  • the metal active substrate is made of a chemically active metal material such as aluminum, tin, copper, iron or zinc which is easily oxidized with external water and oxygen. Since different metals react with water and oxygen at different rates, Moreover, the physical and chemical properties of the generated metal oxide semiconductor seed crystals are different, so that the distribution density and morphology of the semiconductor seed crystals on the surface plasmon micro/nano structure can be accurately controlled, and then the optimized design of the semiconductor seed crystal is obtained.
  • Surface plasmon-photo-electric hybrid conducting nano-heterostructure platform with different morphology, structure and function for subsequent growth.
  • the semiconductor nanostructure has a one-dimensional semiconductor nanostructure such as a nanorod, a nanometer cone or a nanotube, and has a length of 1-1000 ⁇ m, a diameter of 0.1-1000 ⁇ m, a spacing of 1-1000 nm, or other zero-dimensional and two-dimensional structures. Dimensional or complex spiral crystal structure.
  • the material to be selected is a semiconductor material having different energy band structures such as zinc oxide, titanium dioxide or aluminum oxide.
  • the amount of deionized water is 0-1000 ⁇ l, and the number of water additions is 0-15 times.
  • the metal salt is selected from the group consisting of metal elements such as aluminum trichloride, tin tetrachloride, iron nitrate or zinc acetate and metal salts in the semiconductor nanostructure seed crystal.
  • a weak reducing agent solution which is a less reactive reagent such as ascorbic acid AA, hydrogen peroxide aqueous solution H 2 O 2 or urotropine HMTA.
  • the surface capping agent is made of polyethyleneimine PEI, Triton X-100 or sodium di-ethylhexyl succinate sulfonate AOT, which can promote the growth of semiconductor nanostructures in a specific direction.
  • the metal electrode is made of a metal material such as gold, silver or platinum; and the conductive substrate is made of a conductive carrier such as indium tin oxide ITO, fluorine-doped tin oxide FTO or graphite, and has a thickness of 100 nm to 10000 ⁇ m. .
  • the probe molecule is made of a common Raman probe molecule such as rhodamine 6G, p-nonylaniline 4-ATP or 4-mercaptopyridine 4-MPY.
  • the excitation light source may be a single-wavelength light source or a broad-spectrum light source, and the wavelength range is from 300 nm to 3000 nm covering the ultraviolet to mid-infrared band.
  • the two-dimensional surface plasmon micro/nano structure-sparse semiconductor hybrid integrated nano-platform includes: the excitation light source is a single-wavelength light source with a wavelength of 532 nm; and the semiconductor nano-structure array is oxidized.
  • the zinc nano-cone array has a length of 10 ⁇ m, a diameter of 1 ⁇ m and a pitch of 1000 nm;
  • the two-dimensional surface plasmon micro-nano structure is a silver triangle plate with a size of 30 ⁇ m.
  • the positional relationship is that the zinc oxide nanocone array is located on the side of the silver triangle and forms a tight Schottky contact.
  • the excitation light source When the excitation light source is vertically irradiated on the side of the silver triangle plate, the sub-wavelength plasmon excitation wave guided along the surface of the silver triangle plate is excited, and the guided wave is again converted into an outgoing light wave at the tip of the zinc oxide nano-cone array to realize light- The plasmon-light mode transition. Due to the reversibility of the optical path, this process can be reversed.
  • high-energy photogenerated electrons (ie, "hot electrons”) excited by metal plasmons will cross the barrier due to the existence of the Schottky barrier.
  • the platform can be used as a light-plasmon-electric hybrid integrated nano-platform.
  • Step 1 Preparation of single crystal, density-controlled semiconductor seed crystals
  • a certain amount of silver triangle plate solution is uniformly coated on a clean active metal substrate and naturally dried in the air to obtain a uniformly distributed silver triangle plate nanostructure.
  • 100 ⁇ l of deionized water was uniformly coated on the active metal substrate and naturally dried in the air to obtain a semiconductor seed crystal structure uniformly distributed on the silver triangle.
  • Step 2 Continued growth of semiconductor seeds
  • vapor deposition is used to achieve continuous growth.
  • a certain amount of zinc nitrate is weighed into a porcelain boat, and the metal zinc substrate is placed.
  • high purity N 2 is introduced .
  • the temperature of the deposition chamber of the tube furnace was adjusted to 300 ° C, and the temperature was reacted for 2 h. Finally, it was naturally cooled to room temperature and the sample was taken out.
  • the two-dimensional surface plasmon micro/nano structure-dense semiconductor hybrid integrated nano-platform structure comprises: the excitation light source is a single-wavelength light source with a wavelength of 785 nm; and the semiconductor nano-structure array is The zinc oxide nanorod array has a length of 1 ⁇ m, a diameter of 0.5 ⁇ m, and a pitch of 1 nm; the two-dimensional surface plasmon micro/nano structure is a silver triangle plate having a size of 10 ⁇ m. The positional relationship is that the zinc oxide nanorod array is located on the surface and sides of the silver triangle and forms a tight Schottky contact.
  • the wave-wavelength matching excites the sub-wavelength plasmon polarization guided wave propagating along the surface of the silver triangle plate, and the guided wave is on the surface of the silver triangle plate.
  • the tip is again transformed into an outgoing light wave to achieve a light-plasmon-light mode transition. Due to the reversibility of the optical path, this process can be reversed.
  • high-energy photogenerated electrons ie, "hot electrons" excited by metal plasmons will cross the barrier due to the existence of the Schottky barrier.
  • the platform can be used as a light-plasmon-electric hybrid integrated nano-platform.
  • Step 1 Preparation of single crystal, density-controlled semiconductor seed crystals
  • a certain amount of silver triangle plate solution is uniformly coated on a clean active metal substrate and naturally dried in the air to obtain a uniformly distributed silver triangle plate nanostructure.
  • 200 ⁇ l of deionized water was uniformly coated on the active metal substrate and naturally dried in the air to obtain a zinc oxide seed crystal structure uniformly distributed on the silver triangle.
  • Step 2 Continued growth of semiconductor seeds
  • the solution method is used to achieve continuous growth.
  • a certain amount of ascorbic acid AA, polyethyleneimine PEI and zinc oxide are respectively weighed into corresponding ones.
  • the mixture was heated at a low speed of 80 ° C to dissolve it sufficiently.
  • Stirring was stopped and the active metal substrate was placed in the continuous growth solution. Keep this temperature constant for 8 hours.
  • the substrate is taken out, the surface debris is rinsed out, and it is naturally dried in the air.
  • Embodiment 3 As shown in FIG. 7, a one-dimensional surface plasmon micro/nano structure-dense semiconductor heterojunction and a metal electrode constitute a plasmon-photo-electric heterogeneous integrated photocatalytic reaction device structure including:
  • the excitation light source is a wide-spectrum light source of 400 nm to 2000 nm;
  • the semiconductor nanostructure array is a zinc oxide nanorod array having a length of 2 ⁇ m, a diameter of 1 ⁇ m, and a pitch of 100 nm;
  • the one-dimensional surface plasmon micro-nano structure is a silver nanorod, and the size It is 80 ⁇ m.
  • the positional relationship is that the zinc oxide nanorod array is located on the side of the silver nanorods and forms a tight Schottky contact.
  • the heterojunction is deposited on an indium tin oxide film having a thickness of 500 nm, and an indium tin oxide film is connected to the platinum electrode by a wire to form a photoanode and a photocathode, respectively.
  • the excitation light source is vertically irradiated on the surface of the indium tin oxide film supporting the heterojunction, the surface plasmon effect of the silver nanorod is excited, and the generated "hot electron" passes over the Schott between the silver nanorod and the alumina nanorod.
  • the base barrier is injected into the alumina nanorods to realize effective separation of the photogenerated electron hole pairs, and the generated electrons are transported along the wires to the platinum electrode to realize hydrogen reduction by the reduction reaction, and the remaining holes are oxidized to decompose water to generate oxygen. To achieve photocatalytic decomposition of water to produce hydrogen.
  • Step 1 Preparation of single crystal, density-controlled semiconductor seed crystals
  • a certain amount of silver nanorod solution was uniformly coated on a clean metal zinc substrate and naturally dried in the air to obtain a uniformly distributed silver nanorod structure.
  • 50 ⁇ l of deionized water was uniformly coated on a metal zinc substrate and naturally dried in the air to obtain a zinc oxide seed crystal structure uniformly distributed on the silver nanorods.
  • Step 2 Continued growth of semiconductor seeds
  • the solution method is used to achieve continuous growth.
  • a certain amount of urotropine HMTA, Triton X-100 and acetic acid are weighed separately.
  • Zinc is formulated into a corresponding continuous growth solution. The mixture was heated at a low speed of 60 ° C to dissolve it sufficiently. Stirring was stopped and the metal zinc substrate was placed in the continuous growth solution. Keep this temperature constant for 4 hours. Finally, the substrate is taken out, the surface debris is rinsed out, and it is naturally dried in the air.
  • the one-dimensional surface plasmon micro/nano structure-sparse semiconductor heterojunction and probe molecules constitute an in situ remote sensing Raman optoelectronic integrated device structure including: the excitation light source is a single wavelength of 633 nm The light source; the semiconductor nanostructure array is a tin oxide nano-cone array having a length of 20 ⁇ m, a diameter of 5 ⁇ m, and a pitch of 3000 nm; and the one-dimensional surface plasmon micro-nano structure is a platinum nanorod having a size of 100 ⁇ m.
  • the positional relationship is that the tin oxide nanorod array is located on the side of the platinum nanorod and forms a tight Schottky contact, and Rhodamine 6G is on the surface of the tin oxide nanocone array.
  • Rhodamine 6G is on the surface of the tin oxide nanocone array.
  • Step 1 Preparation of single crystal, density-controlled semiconductor seed crystals
  • platinum nanorod solution A certain amount was uniformly coated on a clean tin metal substrate and naturally dried in the air to obtain a uniformly distributed platinum nanorod structure.
  • 30 ⁇ l of deionized water was uniformly coated on a tin metal substrate and naturally dried in the air to obtain a tin oxide seed crystal structure uniformly distributed on the platinum nanorods.
  • Step 2 Continued growth of semiconductor seeds
  • vapor deposition is used to achieve continuous growth.
  • a certain amount of tin tetrachloride is weighed into a porcelain boat, and the metal tin substrate is placed.
  • high purity N 2 is introduced Into the center of the tube furnace.
  • the temperature of the deposition chamber of the tube furnace was adjusted to 500 ° C, and the reaction was carried out at a constant temperature for 4 h. Finally, it was naturally cooled to room temperature and the sample was taken out.

Abstract

一种表面等离激元-光-电混合传导纳米异质结构及制备方法，该结构包括：激励光源(1)，半导体纳米结构阵列(2)，二维表面等离激元微纳结构(3)，亚波长等离极化激元导波(4)，出射光波(5)，一维表面等离激元微纳结构(6)，导线(7)，金属电极(8)，导电基底(9)，探针分子(10)，原子力显微导电探针(11)和电压源(12)；该方法通过控制金属基底上游离金属离子、空气、水氧实现分布及密度可控的半导体晶种，实现晶种的高度一致化控制，接着通过续生长来严格控制半导体结构的长径比与分布。为研究光与物质相互作用所产生的各种新奇效应提供了新的纳米光学平台。

Description

表面等离激元-光-电混合传导纳米异质结构及制备方法 技术领域
本发明涉及纳米光学、纳米材料和集成光电子器件等领域，特别涉及一种表面等离激元-光-电混合传导纳米异质结构平台及其制备方法。
背景技术
近年来，高度集成化的电子芯片技术推动了电子工业技术的迅猛发展。人们对光学器件技术的集成化充满期待，希望实现光学器件系统和电子器件系统的兼容，构筑功能丰富的光-电子混合芯片系统，推动芯片技术的再次跨越式发展。然而，由于光学衍射极限的存在，光信号仅能被限制在微米尺度范围内传输，导致传统集成光学器件在单元尺寸和系统体积上都无法与高度集成的电子器件比拟。随着表面等离激元学研究的兴起，为光学器件技术集成化的发展提供了新的契机。与传统光波导相比，基于表面等离激元的波导对光的束缚能力更强，支持的模式光斑尺寸更小，从而极大提高了光学器件的集成度。
表面等离激元信号可由光信号激励起来，但是如何有效的将光信号转换为表面等离激元信号，进而实现光信号和表面等离激元信号的高效耦合传输，目前还是一个难题。实验研究表明，单纯利用透镜聚焦激发金属表面等离激元信号的效率仅为不到2％，因此需要引入一些辅助手段提高入射光的波矢，从而提高光波转化为等离激元的效率的方法。迄今为止，这些辅助手段，即可实现光信号和表面等离激元信号相互耦合传输的各种手段主要是分别制造出光波导器件与金属表面等离激元波导器件，并将两种器件相互靠近或焊接在一起，利用近场耦合效应实现光信号和表面等离激元信号的互联传递。或采用微纳加工技术结合薄膜沉积技术制造出介质和金属结构组成的异质结构器件。然而，这些方式制备出的光波导和表面等离激元波导器件在实现信号耦合时必将引入很大的插入损耗。产生损耗的原因包括：光学介质和金属结构的耦合界面处的粗糙度引起的散射损耗、各种镀膜、光刻和刻蚀等纳米加工工艺带来的材料缺陷等引起的波导侧壁散射损耗和端面散射等，无论是光信号还是电信号均无法实现有效传输，大大降低了器件的光学传输效率。此外，在工艺方法上，仍存在工艺复杂、成本高及无法实现大批量制备等瓶颈问题。因此，如何有效实现光-等离激元模式之间的有效低损 耗耦合是当前亟待探索和解决的关键问题。
目前，国际上尚未有人实现直接将等离激元金属微纳结构与半导体光-电混合器件复合，从而实现三种等离激元-光-电耦合的模式。因此，本专利提出了一种表面等离激元-光-电混合传导纳米异质结构平台，通过将单晶的、原子平的等离激元和半导体材料直接复合，利用材料之间有效的晶格匹配，实现了真正意义上的零接触，大大降低了耦合界面处的传输损耗，为研究光与物质相互作用所产生的各种新奇效应提供了新的纳米光学平台。
发明内容
技术问题：本发明的目的是为了克服已有技术的不足之处，提出了一种表面等离激元-光-电混合传导纳米异质结构及制备方法，该方法通过加水轮数来控制晶种的大小和密度，实现晶种的高度一致化控制。并通过续生长来严格控制半导体结构的长径比与分布。该种直接在表面等离激元金属微纳结构上生长疏密可控、长径比可控半导体结构的表面等离激元-光-电混合传导纳米异质结构平台在纳米材料、集成光电子器件领域具有重要应用。
技术方案：本发明的一种表面等离激元-光-电混合传导纳米异质结构包括：激励光源，半导体纳米结构阵列，二维表面等离激元微纳结构，亚波长等离极化激元导波，出射光波，一维表面等离激元微纳结构，导线，金属电极，导电基底，探针分子，原子力显微导电探针和电压源；其中，半导体纳米结构阵列位于二维表面等离激元微纳结构的上表面或位于一维表面等离激元微纳结构的外表面，且形成紧密的肖特基接触，激励光源垂直照射在二维表面等离激元微纳结构的上表面或一维表面等离激元微纳结构的外表面；探针分子位于半导体纳米结构阵列表面，亚波长等离极化激元导波在二维表面等离激元微纳结构或一维表面等离激元微纳结构表面传播，出射光波位于半导体纳米结构阵列尖端；电压源的输出端通过导线与原子力显微导电探针连接，原子力显微导电探针位于半导体纳米结构阵列上；在二维表面等离激元微纳结构中，电压源的输入端通过导线与原子力显微导电探针连接，电压源的输出端通过导线与导电基底连接；在一维表面等离激元微纳结构中，电压源的输入端与导电基底连接，电压源的输出端与金属电极连接。
其中，
所述的二维表面等离激元微纳结构、一维表面等离激元微纳结构，形貌为三 角板、线或多面体的各向异性结构，尺寸为1-1000μm，供选材料为金、银、铜、铝或铂的一维或二维具有表面等离激元效应的金属晶体材料。
所述的导电基底，供选材料为铝、锡、铜、铁或锌等易于与外界水氧发生氧化反应的化学性质活跃的金属材料，由于不同金属与水氧发生化学反应的速率不同，且生成的金属氧化物半导体晶种的物理、化学性质不同，因此可实现半导体晶种在表面等离激元微纳结构的分布密度和形态的精确可控，进而以半导体晶种的优化设计得到后续生长的形貌、结构和功能各异的表面等离激元-光-电混合传导纳米异质结构平台。
所述的半导体纳米结构阵列，其中的半导体纳米结构形貌为纳米棒、纳米锥或纳米管的一维半导体纳米结构，长度为1-1000μm，直径为0.1-1000μm，间距为1-10000nm，或是零维、二维或复杂的螺旋晶体结构；供选材料为氧化锌、二氧化钛或三氧化二铝。
所述的金属电极，供选材料为金、银或铂材料；所述的导电基底，供选材料为氧化铟锡ITO、掺氟氧化锡FTO或石墨等导电载体，厚度为100nm-10000μm。
所述的探针分子，供选材料为罗丹明6G、对巯基苯胺4-ATP或4巯基吡啶4-MPY。
所述的激励光源，为单波长光源或为宽光谱光源，波长范围为300nm-3000nm涵盖紫外到中红外波段。
本发明的表面等离激元-光-电混合传导纳米异质结构的制备方法按照以下步骤：
步骤一：单晶、密度可控的半导体晶种制备
取表面等离激元微纳结构溶液均匀涂敷在干净的金属活性基底上，在空气中自然干燥，得到均匀分布的表面等离激元微纳结构；取去离子水均匀涂敷在金属活性基底上，在空气中自然干燥，得到均匀分布在表面等离激元微纳结构的半导体晶种结构；通过选取具有不同活性的金属活性基底，以及涂覆去离子水的量控制半导体晶种在表面等离激元微纳结构的分布密度和形态；
步骤二：在表面等离激元微纳结构上生长半导体纳米线
采用气相法或溶液法在表面等离激元微纳结构表面以半导体晶种为核，定向生长疏密可控、长径比可调的半导体纳米线，得到由金属和半导体异质结构组构 成的表面等离激元-光-电混合传导纳米异质结构平台；
在气相法中，称取金属盐放入瓷舟内，将上述金属活性基底放入管式炉中央，通入高纯N 2，将管式炉的沉积室温度调到100-700℃，恒温反应0.5-10h，最后自然冷却至室温，得到样品；
在溶液法中，分别称量弱还原剂，表面封盖剂及金属盐配成相应的续生长溶液，低速搅拌加热至60-80℃，使其充分溶解，停止搅拌，将金属活性基底放入续生长溶液中，保持该温度不变，时间持续2-180h，最后将金属活性基底取出，将金属活性基底表面杂物冲洗干净，在空气中自然干燥。
所述表面等离激元-光-电混合传导纳米异质结构分别作为两类集成光电器件的操作方法：第一类是无源一维、二维表面等离激元集成纳米传输平台，可在一维表面等离激元微纳结构、二维表面等离激元微纳结构表面形成亚波长表面等离激元信号传输波导，并以半导体纳米线作为传输光波的光波导，实现表面等离激元信号和光信号的互联，利用密度可控的半导体纳米线阵列2形成的光栅结构提高入射光波矢，增强光信号和表面等离激元信号之间的耦合激励和发射效率，或进一步通过金属颗粒等修饰引入“热点”，形成零维的散射点光源，在表面等离激元-光-电混合传导纳米异质结构平台上构造出具有一定功能的光信号和表面等离激元信号器件和系统；第二类是具有光学增益特性的半导体纳米晶体光源与表面等离激元波导构成的异质集成有源器件，可在一维表面等离激元微纳结构、二维表面等离激元微纳结构边缘形成一维的亚波长散射光源，在纳米尺度下实现等离激元-光-电的有效耦合和能量转换，或利用半导体纳米线所具有的光电转换效应，将入射在半导体纳米线表面的光信号转变成电信号，通过具有导电特性的表面等离激元微纳结构传递电信号，实现表面等离激元-光-电三种信号的片上互联传递。
所述的金属盐，供选材料为三氯化二铝、四氯化锡、硝酸铁或醋酸锌。
所述的弱还原剂溶液，供选材料为抗坏血酸AA、过氧化氢水溶液H 2O 2或乌洛托品HMTA；所述的表面封盖剂，供选材料为聚乙烯亚胺PEI、曲拉通X-100或二－乙基己基琥珀酸酯磺酸钠AOT。
有益效果：本发明与现有的技术相比具有以下的优点：
1、本发明首次提出了表面等离激元-光-电混合传导纳米异质结构平台，为实现表面等离激元、光和电三种信号的混合、互联及低散射损耗传导提供了一种全新的媒介，可广泛用于未来的高密度集成光电器件与系统研制。相比于国际上报道的利用近场耦合、物理接触等方式实现的集成光电器件带来的高损耗、工艺复杂及难以大批量制备等缺陷，该纳米平台不仅有效避免以上问题，还兼具多波长、宽光谱同时激发，低损耗传输，传输方向可延伸到多个维度等优势。同时，还可将CMOS工艺的电子芯片技术直接与该纳米平台互联，实现光电复用，起到强大的信息处理功能。
2、基于传统镀膜技术和微纳图形加工技术研制的等离激元金属-半导体光电器件具有晶体质量差、界面缺陷多，导致其光学损耗大等问题。本发明提出了一种表面等离激元-半导体异质结结构，以原子平的表面等离激元微纳结构作为加工平台生长长径比可控的一维单晶半导体纳米结构，避免了杂质缺陷、表面粗糙等问题，实现单晶对单晶的晶格匹配，大大降低了表面与界面损耗，可实现纳米尺寸下对光的有效耦合、传递和谐振。
3、本发明提出了一种新型疏密可调、分布可控的半导体晶种的制备方法。基于传统的蒸镀、磁控溅射以及化学还原等合成晶种的方法，得到的基于半导体尺寸、形貌、分布均不可控等问题。本发明通过调节水、氧、温度及金属基底提供的游离态金属离子实现半导体晶种密度与分布的严格可控，是对现有在表面等离激元微纳结构上可控生长半导体晶种工艺的突破。且该种构造晶种方法普遍适用于后续化学方法续生长一维半导体纳米结构，实用性大大提高。
4、由于在一般情况下，表面等离激元波的波矢量大于光波的波矢量，所以不可能直接用光波激发出表面等离激元波，即不满足波矢匹配条件。传统的实现波矢匹配的方式诸如棱镜耦合、光栅耦合以及近场耦合等需要引入额外的特殊结构，在增大了器件的体积的同时，在耦合界面处的粗糙度引起的散射损耗、纳米加工工艺带来的材料缺陷等引起的波导侧壁散射损耗和端面散射等，导致光信号和电信号均无法实现有效传输，本发明以密度可控的半导体纳米线阵列形成的光栅结构作为散射中心，可极大提高入射光的波矢，增强光信号和表面等离激元信号之间的耦合激励和发射效率，通过将单晶的、原子平的等离激元和半导体材料 直接复合，利用材料之间有效的晶格匹配，大大降低了耦合界面处的传输损耗，器件的内量子效率得到大幅提高，从而可高效的实现表面等离激元-光-电三种信号的片上互联传递。
附图说明
图1是二维表面等离激元微纳结构-稀疏型半导体混合集成纳米平台结构等离激元-光学信号传输图。
图2是二维表面等离激元微纳结构-稀疏型半导体混合集成纳米平台结构等离激元-电学信号传输及采集图。
图3二维表面等离激元微纳结构-稀疏型半导体混合集成纳米平台结构扫面电子显微镜SEM图。
图4是二维表面等离激元微纳结构-密集型半导体混合集成纳米平台结构等离激元-电学信号传输及采集图。
图5是二维表面等离激元微纳结构-密集型半导体混合集成纳米平台结构等离激元-光学信号传输图。
图6是二维表面等离激元微纳结构-密集型半导体混合集成纳米平台结构扫描电子显微镜SEM图。
图7是一维表面等离激元微纳结构-密集型半导体异质结与金属电极构成的等离激元-光-电异质集成光催化反应装置。
图8是一维表面等离激元微纳结构-稀疏型半导体异质结与探针分子构成的原位遥感拉曼光电集成器件。
图中有：激励光源1，半导体纳米结构阵列2，二维表面等离激元微纳结构3，亚波长等离极化激元导波4，出射光波5，一维表面等离激元微纳结构6，导线7，金属电极8，导电基底9，探针分子10，AFM导电探针11，电压源12。
具体实施方式
本发明提出了一种表面等离激元-光-电混合传导纳米异质结构，该结构包括：激励光源，半导体纳米结构阵列，二维表面等离激元微纳结构，亚波长等离极化激元导波，出射光波，一维表面等离激元微纳结构，导线，金属电极，导电基底，探针分子，原子力显微导电探针和电压源。其位置关系为，半导体纳米结构阵列在二维表面等离激元微纳结构或一维表面等离激元微纳结构的上表面或侧面，且 形成紧密的肖特基接触，激励光垂直照射在二维表面等离激元微纳结构或一维表面等离激元微纳结构的上表面或侧面，探针分子在半导体纳米结构阵列表面，亚波长等离极化激元导波在二维表面等离激元微纳结构或一维表面等离激元微纳结构表面传播，出射光波位于半导体纳米结构阵列尖端，导线与导电基底或金属电极或原子力显微导电探针或电压源相连，原子力显微导电探针位于半导体纳米结构阵列上。
所述表面等离激元-光-电混合传导纳米异质结构平台，制备方法按照以下步骤：
步骤一：单晶、密度可控的半导体晶种制备
取一定量的表面等离激元微纳结构溶液均匀涂敷在干净的金属活性基底上，在空气中自然干燥，得到均匀分布的表面等离激元微纳结构。取一定量的去离子水均匀涂敷在金属活性基底上，在空气中自然干燥，得到均匀分布在表面等离激元微纳结构的半导体晶种结构。通过选取具有不同活性的金属活性基底，以及涂覆去离子水的量控制半导体晶种在表面等离激元微纳结构的分布密度和形态。
步骤二：在表面等离激元微纳结构上生长半导体纳米线
采用气相法或溶液法在表面等离激元微纳结构表面以半导体晶种为核，定向生长疏密可控、长径比可调的半导体纳米线，得到由金属和半导体异质结构组构成的表面等离激元-光-电混合传导纳米异质结构平台。在气相法中，称取一定量的金属盐放入瓷舟内，将上述金属活性基底放入管式炉中央，通入高纯N 2。将管式炉的沉积室温度调到100-700℃，恒温反应0.5-10h。最后自然冷却至室温，得到样品。
在溶液法中，分别称量一定量的弱还原剂，表面封盖剂及金属盐配成相应的续生长溶液。低速搅拌加热至60-80℃，使其充分溶解。停止搅拌，将金属活性基底放入续生长溶液中。保持该温度不变，时间持续2-180h。最后将金属活性基底取出，将金属活性基底表面杂物冲洗干净，在空气中自然干燥。
所述表面等离激元-光-电混合传导纳米异质结构平台分别作为两类集成光电器件的操作方法：第一类是无源一维、二维等离激元集成纳米传输平台，可在一维表面等离激元微纳结构、二维表面等离激元微纳结构表面形成亚波长表面等离激元信号传输波导，并以半导体纳米线作为传输光波的光波导，实现表面等离 激元信号和光信号的互联，利用密度可控的半导体纳米线阵列形成的光栅结构提高入射光波矢，增强光信号和表面等离激元信号之间的耦合激励和发射效率，或进一步通过金属颗粒等修饰引入“热点”，形成零维的散射点光源，在表面等离激元-光-电混合传导纳米异质结构平台上构造出具有一定功能的光信号和表面等离激元信号器件和系统；第二类是具有光学增益特性的半导体纳米晶体光源与表面等离激元波导构成的异质集成有源器件，可在一维等离激元微纳结构、二维等离激元微纳结构边缘形成一维的亚波长散射光源，在纳米尺度下实现等离激元-光-电的有效耦合和能量转换，或利用半导体纳米线所具有的光电转换效应，将入射在半导体纳米线表面的光信号转变成电信号，通过具有导电特性的表面等离激元微纳结构传递电信号，实现表面等离激元-光-电三种信号的片上互联传递。
所述的表面等离激元微纳结构，形貌为三角板、线或多面体等各向异性结构，尺寸为1-1000μm，供选材料为金、银、铜、铝或铂等一维或二维具有表面等离激元效应的金属晶体材料。
所述的金属活性基底，供选材料为铝、锡、铜、铁或锌等易于与外界水氧发生氧化反应的化学性质活跃的金属材料，由于不同金属与水氧发生化学反应的速率不同，且生成的金属氧化物半导体晶种的物理、化学性质不同，因此可实现半导体晶种在表面等离激元微纳结构的分布密度和形态的精确可控，进而以半导体晶种的优化设计得到后续生长的形貌、结构和功能各异的表面等离激元-光-电混合传导纳米异质结构平台。
所述的半导体纳米结构，形貌为纳米棒、纳米锥或纳米管等一维半导体纳米结构，长度为1-1000μm，直径为0.1-1000μm，间距为1-10000nm，也可是其他零维、二维或复杂的螺旋晶体结构。供选材料为氧化锌、二氧化钛或三氧化二铝等能带结构各异的半导体材料。
所述的去离子水的量为0-1000μl，加水的轮次为0-15次。
所述的金属盐，供选材料为三氯化二铝、四氯化锡、硝酸铁或醋酸锌等金属元素与半导体纳米结构晶种中金属元素所一致的金属盐。弱还原剂溶液，供选材料为抗坏血酸AA、过氧化氢水溶液H 2O 2或乌洛托品HMTA等还原性较弱的试剂。表面封盖剂，供选材料为聚乙烯亚胺PEI、曲拉通X-100或二－乙基己基琥珀酸酯磺酸钠AOT等能够促使半导体纳米结构沿特定方向生长的封盖剂。
所述的金属电极，供选材料为金、银或铂等金属材料；所述的导电基底，供选材料为氧化铟锡ITO、掺氟氧化锡FTO或石墨等导电载体，厚度为100nm-10000μm。
所述的探针分子，供选材料为罗丹明6G、对巯基苯胺4-ATP或4巯基吡啶4-MPY等常用拉曼探针分子。
所述的激励光源，可为单波长光源或为宽光谱光源，波长范围为300nm-3000nm涵盖紫外到中红外波段。
下面通过具体实施例和对比例进一步说明本发明：
实施例1：如图1-3所示，该二维表面等离激元微纳结构-稀疏型半导体混合集成纳米平台包括：激励光源为波长为532nm的单波长光源；半导体纳米结构阵列为氧化锌纳米锥阵列，长度为10μm，直径为1μm，间距为1000nm；二维表面等离激元微纳结构为银三角板，尺寸为30μm。其位置关系为，氧化锌纳米锥阵列位于银三角板的侧面，且形成紧密的肖特基接触。当激励光源垂直照射在银三角板的侧面时，激励起沿银三角板表面传播的亚波长等离极化激元导波，该导波在氧化锌纳米锥阵列尖端再次转变为出射光波，实现光-等离激元-光模式转变。由于光路可逆性，该过程可逆向实现。与此同时，在银三角板与氧化锌纳米锥阵列界面处，由于肖特基势垒的存在，由金属等离激元激发的高能光生电子(即“热电子”)将越过该势垒，有效的实现电子空穴对的分离，在外加通电电路作用下，实现电子的定向传输和搜集，实现光-等离激元-电模式转变。因此，该平台可作为光-等离激元-电混合集成纳米平台。
为得到图1-3所示结构，按照以下步骤制备：
步骤一：单晶、密度可控的半导体晶种制备
取一定量的银三角板溶液均匀涂敷在干净的活性金属基底上，在空气中自然干燥，得到均匀分布的银三角板纳米结构。取100μl的去离子水均匀涂敷在活性金属基底上，在空气中自然干燥，得到均匀分布在银三角板上的半导体晶种结构。
步骤二：半导体晶种的续生长
为生长疏密可控、长径比可调的氧化锌纳米线，采用气相沉积法实现续生长，在气相法中，称取一定量的硝酸锌放入瓷舟内，将金属锌基底放入管式炉中央，通入高纯N 2。将管式炉的沉积室温度调到300℃，恒温反应2h。最后自然冷却 至室温，将样品取出。
实施例2：如图4-6所示，该二维表面等离激元微纳结构-密集型半导体混合集成纳米平台结构包括：激励光源为波长为785nm的单波长光源；半导体纳米结构阵列为氧化锌纳米棒阵列，长度为1μm，直径为0.5μm，间距为1nm；二维表面等离激元微纳结构为银三角板，尺寸为10μm。其位置关系为，氧化锌纳米棒阵列位于银三角板的表面和侧面，且形成紧密的肖特基接触。当激励光源垂直照射在银三角板的侧面时，由于波矢匹配，激励起沿银三角板表面传播的亚波长等离极化激元导波，该导波在银三角板表面上的氧化锌纳米棒阵列尖端再次转变为出射光波，实现光-等离激元-光模式转变。由于光路可逆性，该过程可逆向实现。与此同时，在银三角板与氧化锌纳米棒阵列界面处，由于肖特基势垒的存在，由金属等离激元激发的高能光生电子(即“热电子”)将越过该势垒，有效的实现电子空穴对的分离，在外加通电电路作用下，实现电子的定向传输和搜集，实现光-等离激元-电模式转变。因此，该平台可作为光-等离激元-电混合集成纳米平台。
为得到图4-6所示结构，按照以下步骤制备：
步骤一：单晶、密度可控的半导体晶种制备
取一定量的银三角板溶液均匀涂敷在干净的活性金属基底上，在空气中自然干燥，得到均匀分布的银三角板纳米结构。取200μl的去离子水均匀涂敷在活性金属基底上，在空气中自然干燥，得到均匀分布在银三角板上的氧化锌晶种结构。
步骤二：半导体晶种的续生长
为生长疏密可控、长径比可调的半导体纳米线，采用溶液法实现续生长，在溶液法中，分别称量一定量的抗坏血酸AA、聚乙烯亚胺PEI及氧化锌配成相应的续生长溶液。低速搅拌加热80℃，使其充分溶解。停止搅拌，将活性金属基底放入续生长溶液中。保持该温度不变，时间持续8h。最后将基底取出，将表面杂物冲洗干净，在空气中自然干燥。
实施例3：如图7所示，一维表面等离激元微纳结构-密集型半导体异质结与金属电极构成的等离激元-光-电异质集成光催化反应装置结构包括：激励光源为400nm-2000nm的宽光谱光源；半导体纳米结构阵列为氧化锌纳米棒阵列，长度为2μm，直径为1μm，间距为100nm；一维表面等离激元微纳结构为银 纳米棒，尺寸为80μm。其位置关系为，氧化锌纳米棒阵列位于银纳米棒的侧面，且形成紧密的肖特基接触。该异质结沉积在厚度为500nm的氧化铟锡薄膜上，利用导线将氧化铟锡薄膜与铂电极连接起来，分别形成光阳极和光阴极。当激励光源垂直照射在负载异质结的氧化铟锡薄膜表面时，激励银纳米棒的表面等离激元效应，产生的“热电子”越过银纳米棒与氧化铝纳米棒之间的肖特基势垒，注入至氧化铝纳米棒中，实现光生电子空穴对的有效分离，产生的电子沿导线传输至铂电极，实现还原反应制氢，留下的空穴发生氧化反应分解水产生氧气，实现光催化分解水制氢。
为得到图7所示结构，按照以下步骤制备：
步骤一：单晶、密度可控的半导体晶种制备
取一定量的银纳米棒溶液均匀涂敷在干净的金属锌基底上，在空气中自然干燥，得到均匀分布的银纳米棒结构。取50μl的去离子水均匀涂敷在金属锌基底上，在空气中自然干燥，得到均匀分布在银纳米棒上的氧化锌晶种结构。
步骤二：半导体晶种的续生长
为生长疏密可控、长径比可调的氧化锌纳米线，采用溶液法实现续生长，在溶液法中，分别称量一定量的乌洛托品HMTA、曲拉通X-100及醋酸锌配成相应的续生长溶液。低速搅拌加热60℃，使其充分溶解。停止搅拌，将金属锌基底放入续生长溶液中。保持该温度不变，时间持续4h。最后将基底取出，将表面杂物冲洗干净，在空气中自然干燥。
实施4：如图8所示，一维表面等离激元微纳结构-稀疏型半导体异质结与探针分子构成的原位遥感拉曼光电集成器件结构包括：激励光源为633nm的单波长光源；半导体纳米结构阵列为氧化锡纳米锥阵列，长度为20μm，直径为5μm，间距为3000nm；一维表面等离激元微纳结构为铂纳米棒，尺寸为100μm。其位置关系为，氧化锡纳米棒阵列位于铂纳米棒的侧面，且形成紧密的肖特基接触，罗丹明6G在氧化锡纳米锥阵列表面。当激励光垂直照射在铂纳米棒的一端时，激励起沿铂纳米棒径向传播的亚波长等离极化激元导波，该亚波长传导波与氧化锡纳米锥阵列表面的罗丹明6G作用，转化为出射光波信号，被探测器接收，实现原位遥感拉曼信号检测。
为得到图8所示结构，按照以下步骤制备：
步骤一：单晶、密度可控的半导体晶种制备
取一定量的铂纳米棒溶液均匀涂敷在干净的金属锡基底上，在空气中自然干燥，得到均匀分布的铂纳米棒结构。取30μl的去离子水均匀涂敷在金属锡基底上，在空气中自然干燥，得到均匀分布在铂纳米棒上的氧化锡晶种结构。
步骤二：半导体晶种的续生长
为生长疏密可控、长径比可调的半导体纳米线，采用气相沉积法实现续生长，在气相法中，称取一定量的四氯化锡放入瓷舟内，将金属锡基底放入管式炉中央，通入高纯N 2。将管式炉的沉积室温度调到500℃，恒温反应4h。最后自然冷却至室温，将样品取出。
另外，本领域技术人员还可在本发明精神内作其它变化，当然这些依据本发明精神所作的变化，都应包含在本发明所要求保护的范围内。

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  1. 一种表面等离激元-光-电混合传导纳米异质结构，其特征在于该结构包括：激励光源(1)，半导体纳米结构阵列(2)，二维表面等离激元微纳结构(3)，亚波长等离极化激元导波(4)，出射光波(5)，一维表面等离激元微纳结构(6)，导线(7)，金属电极(8)，导电基底(9)，探针分子(10)，原子力显微导电探针(11)和电压源(12)；其中，半导体纳米结构阵列(2)位于二维表面等离激元微纳结构(3)的上表面或位于一维表面等离激元微纳结构(6)的外表面，且形成紧密的肖特基接触，激励光源(1)垂直照射在二维表面等离激元微纳结构(3)的上表面或一维表面等离激元微纳结构(6)的外表面；探针分子(10)位于半导体纳米结构阵列(2)表面，亚波长等离极化激元导波(4)在二维表面等离激元微纳结构(3)或一维表面等离激元微纳结构(6)表面传播，出射光波(5)位于半导体纳米结构阵列(2)尖端；在二维表面等离激元微纳结构中，电压源(12)的输入端通过导线(7)与原子力显微导电探针(11)连接，电压源(12)的输出端通过导线(7)与导电基底(9)连接；在一维表面等离激元微纳结构中，电压源(12)的输入端与导电基底(9)连接，电压源(12)的输出端与金属电极(8)连接。
  2. 如权利要求1所述的表面等离激元-光-电混合传导纳米异质结构，其特征在于，所述的二维表面等离激元微纳结构(3)、一维表面等离激元微纳结构(6)，形貌为三角板、线或多面体的各向异性结构，尺寸为1-1000μm，供选材料为金、银、铜、铝或铂的一维或二维具有表面等离激元效应的金属晶体材料。
  3. 如权利要求1所述的表面等离激元-光-电混合传导纳米异质结构，其特征在于，所述的导电基底(9)，供选材料为铝、锡、铜、铁或锌。
  4. 如权利要求1所述的表面等离激元-光-电混合传导纳米异质结构，其特征在于，所述的半导体纳米结构阵列(2)，其中的半导体纳米结构形貌为纳米棒、纳米锥或纳米管的一维半导体纳米结构，长度为1-1000μm，直径为0.1-1000μm，间距为1-10000nm，或是零维、二维或复杂的螺旋晶体结构；供选材料为氧化锌、二氧化钛或三氧化二铝。
  5. 如权利要求1所述的表面等离激元-光-电混合传导纳米异质结构，其特 征在于，所述的金属电极(8)，供选材料为金、银或铂材料；所述的导电基底(9)，供选材料为氧化铟锡ITO、掺氟氧化锡FTO或石墨等导电载体，厚度为100nm-10000μm。
  6. 如权利要求1所述的表面等离激元-光-电混合传导纳米异质结构，其特征在于，所述的探针分子(10)，供选材料为罗丹明6G、对巯基苯胺4-ATP或4巯基吡啶4-MPY。
  7. 如权利要求1所述的表面等离激元-光-电混合传导纳米异质结构，其特征在于，所述的激励光源(1)，为单波长光源或为宽光谱光源，波长范围为300nm-3000nm涵盖紫外到中红外波段。
  8. 一种如权利要求1所述的表面等离激元-光-电混合传导纳米异质结构的制备方法，其特征在于，所述表面等离激元-光-电混合传导纳米异质结构的制备方法按照以下步骤：
    步骤一：单晶、密度可控的半导体晶种制备
    取表面等离激元微纳结构溶液均匀涂敷在干净的金属活性基底上，在空气中自然干燥，得到均匀分布的表面等离激元微纳结构；取去离子水均匀涂敷在金属活性基底上，在空气中自然干燥，得到均匀分布在表面等离激元微纳结构的半导体晶种结构；通过选取具有不同活性的金属活性基底，以及涂覆去离子水的量控制半导体晶种在表面等离激元微纳结构的分布密度和形态；
    步骤二：在表面等离激元微纳结构上生长半导体纳米线
    采用气相法或溶液法在表面等离激元微纳结构表面以半导体晶种为核，定向生长疏密可控、长径比可调的半导体纳米线，得到由金属和半导体异质结构组构成的表面等离激元-光-电混合传导纳米异质结构平台；
    在气相法中，称取金属盐放入瓷舟内，将上述金属活性基底放入管式炉中央，通入高纯N 2，将管式炉的沉积室温度调到100-700℃，恒温反应0.5-10h，最后自然冷却至室温，得到样品；
    在溶液法中，分别称量弱还原剂，表面封盖剂及金属盐配成相应的续生长溶液，低速搅拌加热至60-80℃，使其充分溶解，停止搅拌，将金属活性基底放入续生长溶液中，保持该温度不变，时间持续2-180h，最后将金属活性基底取出，将金属活性基底表面杂物冲洗干净，在空气中自然干燥。
  9. 如权利要求8所述的表面等离激元-光-电混合传导纳米异质结构，其特征在于，所述的金属盐，供选材料为三氯化二铝、四氯化锡、硝酸铁或醋酸锌。
  10. 如权利要求8所述的表面等离激元-光-电混合传导纳米异质结构，其特征在于，所述的弱还原剂溶液，供选材料为抗坏血酸AA、过氧化氢水溶液H 2O 2或乌洛托品HMTA；所述的表面封盖剂，供选材料为聚乙烯亚胺PEI、曲拉通X-100或二－乙基己基琥珀酸酯磺酸钠AOT。
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