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WO2019169746A1 - 表面等离激元-半导体异质结谐振光电器件及其制备方法 - Google Patents

表面等离激元-半导体异质结谐振光电器件及其制备方法 Download PDF

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WO2019169746A1
WO2019169746A1 PCT/CN2018/088734 CN2018088734W WO2019169746A1 WO 2019169746 A1 WO2019169746 A1 WO 2019169746A1 CN 2018088734 W CN2018088734 W CN 2018088734W WO 2019169746 A1 WO2019169746 A1 WO 2019169746A1
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surface plasmon
semiconductor
nanostructure
crystal
solution
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张彤
王善江
张晓阳
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Southeast University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
    • H10F77/143—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies comprising quantum structures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H10F30/21—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H10F30/21—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation
    • H10F30/22—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes
    • H10F30/222—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes the potential barrier being a PN heterojunction
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
    • H10F77/147—Shapes of bodies
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
    • H10F77/148—Shapes of potential barriers

Definitions

  • the invention relates to the field of nano materials and integrated optical devices, in particular to a surface plasmon-semiconductor heterojunction resonant photovoltaic device and a preparation method thereof.
  • Surface plasmons have significant near-field local enhancement characteristics and can be used as a "nano-antenna" to greatly promote local light intensity.
  • the adjustable resonant spectrum of the ultraviolet to mid-infrared band is achieved by changing the geometry, material, size and environmental medium of the nanostructure itself.
  • Purcell pointed out that by properly constructing a specific cavity, the waveguide structure regulates the density of states of the electromagnetic field around the material, and thus controls the spontaneous emission probability of the material. This effect is called the Purcell effect. Based on this effect, in order to effectively increase the quantum efficiency of the semiconductor material, the high density of states and the small mode volume will contribute to obtaining a larger Purcell coefficient.
  • the plasmon effect and the Purcell effect can be effectively combined, that is, the radiation frequency corresponding to the semiconductor material is close to the resonance frequency of the plasmon, the quantum efficiency of the semiconductor photovoltaic device will be significantly improved. The utilization rate of energy will be greatly improved.
  • the object of the present invention is to overcome the deficiencies of the prior art and to propose a surface plasmon-semiconductor heterojunction resonant optoelectronic device which chemically binds a specific metal crystal plane and passes through a composite Semiconductor seed crystals and their continued growth to strictly achieve a semiconductor structure with a controlled density, aspect ratio, and orientation.
  • a variety of active and passive surface plasmon optoelectronic devices can be realized by regulating the heterogeneous integrated structure process, and have important applications in the field of nano materials and integrated optoelectronic devices.
  • a surface plasmon-semiconductor heterojunction resonant optoelectronic device of the present invention comprises: surface plasmon nanostructure, surface ligand molecule, surface plasmon crystal plane structure, semiconductor nanostructure seed crystal And one-dimensional semiconductor nanostructures; wherein the surface ligand molecules are modified on the surface plasmon nanostructures, the surface plasmon crystal plane structure is bound to the surface ligand molecules, and the semiconductor nanostructure seed crystals are located on the surface.
  • the one-dimensional semiconductor nanostructure is located on the semiconductor nanostructure seed crystal, and each part forms a close contact.
  • the surface plasmon nanostructure is an anisotropic crystal material having a triangular plate, a line or a decahedron, and has a major axis of 10 to 10000 nm, or an isotropic crystal material of a spherical or symmetric polyhedron, and has a size of 10-3000nm.
  • the surface plasmon nanostructure, the candidate material is a metal material having surface plasmon effect such as gold, silver, copper, aluminum or platinum;
  • the surface ligand molecule is selected from the group consisting of cetyltrimethylammonium bromide CTAB, polyvinylpyrrolidone PVP or mercaptopropionic acid MPA.
  • the surface plasmon crystal plane structure is an anisotropic material having a triangular plate, a cone or a cube, and has a size of 1-10 nm.
  • the surface plasmon crystal structure is a small-sized metal nanostructure consistent with the material used for the surface plasmon nanostructure.
  • the semiconductor nanostructure seed crystal has a shape of a sphere, a cone or a rod and has a size of 1-10 nm, and the alternative material is zinc oxide, aluminum oxide or cuprous oxide.
  • the one-dimensional semiconductor nanostructure has a one-dimensional nanostructure with a shape of a rod, a cone or a tube, and has a size of 10 nm to 10000 nm.
  • the material to be selected is a large-sized metal micro/nano structure conforming to the material used for the semiconductor nanostructure seed crystal.
  • the method for preparing a surface plasmon-semiconductor heterojunction resonant photovoltaic device of the present invention comprises the following steps:
  • Step 1 Specific surface plasmon crystal structure
  • a solution of a surface ligand molecule having a concentration of 0.01-1 Mol/L is added to the solution a, and the surface ligand molecule is adsorbed on the specific crystal face of the surface plasmon nanostructure due to the crystal face selectivity.
  • a surface plasmon crystal structure aqueous solution having a concentration of 0.001-0.1 Mol/L is added to the solution b, and stirred to make the surface plasmon crystal structure and the surface of the surface plasmon nanostructure specific crystal plane.
  • the body molecules form a close contact in the form of a covalent bond, multiple centrifugation water washing, redispersing the precipitate in deionized water to obtain a solution c;
  • a metal salt aqueous solution having a concentration of 0.001-0.1 Mol/L, a 0.001-0.1 Mol/L weak reducing agent aqueous solution, and a surface covering having a concentration of 0.01-0.1 Mol/L are successively added to the solution d.
  • the aqueous solution is reacted at 60 ° C - 90 ° C for 1-18 h; the water is washed by repeated centrifugation, and the precipitate is redispersed in deionized water to obtain a final surface plasmon-semiconductor heterojunction.
  • the surface plasmon-semiconductor heterojunction resonant optoelectronic device works by: when the excitation light is incident on the surface of the surface plasmon nanostructure 1, based on the surface plasmon effect, the surface plasmon Nanostructure 1 concentrates light in the sub-wavelength range to form resonance enhancement. This resonance enhancement has wavelength selectivity. The position and band width of the resonance absorption peak are related to the morphology, size and environmental medium of the surface plasmon nanostructure 1. . Immediately thereafter, the resulting surface plasmon wave will be excited into a one-dimensional semiconductor nanostructure 5 waveguide in close contact with the surface plasmon nanostructure 1 to form an directional distribution of the optical signal.
  • the excitation light can be irradiated into the one-dimensional semiconductor nanostructure 5 waveguide having the photoelectric effect, and can be conducted and concentrated in the surface plasmon nanostructure 1 by photoluminescence, and the excitation is excited. Separation.
  • the plasmon can be used to realize a nano-heat source based on plasmon photothermal effect, a photoluminescence-enhanced nano laser, and a photocatalytic reaction carrier based on the "hot electron" effect.
  • the metal salt solution is selected from the group consisting of a metal salt such as zinc acetate, aluminum trichloride or copper nitrate and a metal element in a semiconductor nanostructure seed crystal; a weak reducing agent solution, the material to be selected is Ascorbic acid AA, aqueous hydrogen peroxide solution H 2 O 2 or urotropine HMTA; surface capping agent, available as polyethyleneimine PEI, Triton X-100 or di-ethylhexyl succinate sulfonic acid A capping agent such as sodium AOT that promotes the growth of semiconductor nanostructures in a one-dimensional direction.
  • a metal salt such as zinc acetate, aluminum trichloride or copper nitrate and a metal element in a semiconductor nanostructure seed crystal
  • a weak reducing agent solution the material to be selected is Ascorbic acid AA, aqueous hydrogen peroxide solution H 2 O 2 or urotropine HMTA
  • surface capping agent available as polyethyleneimine
  • the present invention has the following advantages over the prior art:
  • the present invention proposes a novel method for mass-producing a heterostructure of a nanoresonance mechanism.
  • a semiconductor nanostructure growth with adjustable aspect ratio and density can be realized.
  • the non-core-shell structure can simultaneously realize the direct coupling of the local surface plasmon LSPR effect and the optical mode, and avoid the traditional techniques such as welding, assembly, binding and other technical means.
  • the interface loss By controlling the crystal plane structure, a series of heterojunctions with different shapes, structures and orientations can be grown, which can be used to construct various passive and active optoelectronic devices such as nano-antennas, nano-heat sources and surface plasmon lasers.
  • the present invention proposes a surface plasmon-semiconductor heterojunction resonant optoelectronic device structure which can be designed in multiple dimensions compared to conventional semiconductor optoelectronic devices, which will be single crystal, atomic
  • the flat one-dimensional semiconductor nanostructure and the surface plasmon nanostructure realize direct composite, avoiding the high loss problem caused by surface defects and interface roughness, and the near field height caused by the surface plasmon effect.
  • the advantages of local enhancement and response spectrum are adjustable, and the quantum efficiency of the device is greatly improved by optimizing the structure of the semiconductor material.
  • the structure can simultaneously realize surface mode conversion of surface plasmon-light or light-surface plasmons, and realize high-performance, low-cost integrated nano-optics.
  • the present invention proposes a novel crystal face construction method, which utilizes the surface-specific adsorption characteristics of surface ligand molecules to achieve adsorption of specific crystal face positions on specific surface plasmon nanostructures, thereby further realizing Binding of added density-controlled metal seeds.
  • the method Compared with the conventional method of constructing crystal faces such as electron beam etching and nano-imprinting, the method has the advantages of low process cost and large-volume preparation. And the two are bound in the form of covalent bonds, and the stability is higher.
  • the specific crystal plane constructed by chemical methods is also convenient for subsequent further growth and modification, and has simple process and strong maneuverability. It is a breakthrough in the existing process of constructing specific crystal faces on surface plasmon nanomaterials.
  • FIG. 1 is a schematic view showing the growth process of a surface plasmon-semiconductor heterojunction resonant photovoltaic device
  • FIG. 2 is a schematic view showing the morphology of surface plasmon nanostructures
  • Figure 3 is a schematic diagram of the surface plasmon-semiconductor heterojunction structure of different morphologies
  • Example 1 A surface plasmon-semiconductor heterojunction resonant photovoltaic device comprising: a surface plasmon nanostructure of silver nano-decahedron having a size of 20 nm; and a surface ligand molecule of hexadecyl three Ammonium methyl bromide CTAB; surface plasmon crystal structure is silver triangle plate, size is 5nm; semiconductor nanostructure seed crystal is zinc oxide; one-dimensional semiconductor nanostructure is zinc oxide nanorod, size is 500nm.
  • the positional relationship is that cetyltrimethylammonium bromide CTAB is modified on the specific face of silver nano-decahedron, and the silver triangle plate is bound to cetyltrimethylammonium bromide CTAB, zinc oxide crystal.
  • the species is located on the surface of the silver triangle plate, and the zinc oxide nanorods are located on the zinc oxide seed crystal, and the parts form a close contact.
  • the preparation method is as follows:
  • Step 1 Specific surface plasmon metal crystal plane structure
  • a silver nano-dodecahedral solution having a concentration of 0.01 Mol/L was taken, washed by multiple centrifugation, and the precipitate was redispersed in deionized water to obtain a solution a; a solution of 0.01 Mol/L of cetyltrimethyl group was added to the solution a.
  • Ammonium methyl bromide CTAB stirred, due to crystal plane selectivity, the molecule will be adsorbed on the specific crystal face of the silver nano-decahedron to obtain solution b.
  • solution c A certain amount of solution c was taken, and a zinc oxide seed solution having a concentration of 0.05 Mol/L was added and stirred for 1 hour, so that the zinc oxide seed crystal adhered to the crystal face of the silver triangle.
  • the water was washed by repeated centrifugation to remove excess zinc oxide seed crystals in the solution, and the precipitate was redispersed in deionized water to obtain a solution d.
  • a zinc acetate solution having a concentration of 0.1 Mol/L, a 0.1 Mol/L ascorbic acid AA solution, and a polyethyleneimine PEI solution having a concentration of 0.1 Mol/L were successively added to the solution d, 90
  • the reaction was carried out at ° C for 2 h.
  • the water was washed several times and the precipitate was redispersed in deionized water to obtain a final silver decahedral-zinc oxide nanorod heterojunction.
  • Example 2 A surface plasmon-semiconductor heterojunction resonant optoelectronic device comprising: a surface plasmon nanostructure of a gold nano-triangular plate having a size of 60 nm; and a surface ligand molecule of polyvinylpyrrolidone PVP; surface plasmon crystal structure is gold nanorod, size is 10nm; semiconductor nanostructure seed crystal is copper oxide; one-dimensional semiconductor nanostructure is copper oxide nano cone, size 1000nm.
  • the positional relationship is that the polyvinylpyrrolidone PVP is modified on a specific crystal plane of the gold nano-horizontal plate, the gold nanorod crystal face is bound to the polyvinylpyrrolidone PVP, and the copper oxide seed crystal is located on the gold nanorod crystal face.
  • the copper oxide nano-cone is located on the copper oxide seed crystal and the parts form a close contact.
  • the preparation method is as follows:
  • Step 1 Specific surface plasmon crystal structure
  • a certain amount of solution c was taken, a copper oxide seed solution having a concentration of 0.1 Mol/L was added, and stirred for 2 hours, so that the copper oxide seed crystal adhered to the crystal face of the gold nanorod.
  • the water was washed several times to remove excess copper oxide seed crystals in the solution, and the precipitate was redispersed in deionized water to obtain a solution d.
  • a copper nitrate solution having a concentration of 0.1 Mol/L, a 0.1 Mol/L hydrogen peroxide solution, and a Triton X-100 solution having a concentration of 1 Mol/L were successively added to the solution d.
  • the reaction was carried out at 80 ° C for 6 h.
  • the water was washed several times and the precipitate was redispersed in deionized water to obtain a final gold triangle-copper oxide nanocone heterojunction.
  • Example 3 A surface plasmon-semiconductor heterojunction resonant optoelectronic device comprising: a surface plasmon nanostructure of platinum nanorods having a size of 80 nm; a surface ligand molecule of mercaptopropionic acid MPA; surface The plasmon crystal structure is a platinum nanocube with a size of 20 nm; the semiconductor nanostructure seed crystal is alumina; and the one-dimensional semiconductor nanostructure is an alumina nanorod with a size of 500 nm.
  • the positional relationship is that the mercaptopropionic acid MPA is modified on the specific crystal plane of the platinum nanorod, the platinum nanocube crystal face is bound to the mercaptopropionic acid MPA, the alumina seed crystal is located on the platinum nanocube crystal face, the alumina nanorod Located on the alumina seed and the parts form a close contact.
  • the preparation method is as follows:
  • Step 1 Specific surface plasmon crystal structure
  • solution c A certain amount of solution c was taken, and a solution of alumina seed crystal having a concentration of 0.1 Mol/L was added and stirred for 1 hour, so that the alumina seed crystal adhered to the crystal face of the platinum nanocube.
  • the aqueous washing was repeated several times to remove excess alumina seed crystals in the solution, and the precipitate was redispersed in deionized water to obtain a solution d.
  • an aluminum trichloride solution having a concentration of 0.1 Mol/L, a 0.1 Mol/L urotropine HMTA solution, and a di-ethyl group having a concentration of 0.1 Mol/L were successively added to the solution d.
  • a sodium hexyl succinate sulfonate AOT solution was reacted at 60 ° C for 15 h. The water was washed several times and the precipitate was redispersed in deionized water to obtain a final platinum nanorod-alumina nanorod heterojunction.

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Abstract

一种表面等离激元-半导体异质结谐振光电器件及其制备方法，其中，表面配体分子（2）修饰在表面等离激元纳米结构（1）上，表面等离激元晶面结构（3）绑定在表面配体分子（2）上，半导体纳米结构晶种（4）位于表面等离激元晶面结构（3）上，一维半导体纳米结构（5、6）位于半导体纳米结构晶种（4）上，且各部分形成紧密的接触。该类异质集成材料在界面处实现了晶格的匹配，大大降低了缺陷、晶面粗糙等带来的损耗，可实现表面等离激元模式与光模式的直接耦合，在纳米激光器、纳米热源、光电探测及光催化领域中具有极大地应用前景。

Description

表面等离激元-半导体异质结谐振光电器件及其制备方法 技术领域
本发明涉及纳米材料领域、集成光学器件领域，特别涉及一种表面等离激元-半导体异质结谐振光电器件及其制备方法。
背景技术
随着半导体理论的不断发展，在追求器件的小型化和集成化的同时，如何构造高量子效率、低成本以及可大批量制备的半导体光电器件是当前人们研究的热点方向，并开辟了一系列新的应用领域。然而，由于半导体纳米材料自身带隙的限制及光生载流子再复合等问题，使得传统的基于半导体材料的光电器件存在响应波长受限、量子效率低等缺陷，导致该类器件在实用性、可靠性以及成本等方面限制了其应用范围和进一步的工业化和市场化。随着表面等离激元学研究的兴起，为该类半导体基光电器件技术的发展提供了新的契机。表面等离激元具有显著的近场局域增强特性，可作为一种“纳米天线”，极大地促进局部的光强密度。通过改变纳米结构本身的几何形状、材质、尺寸及环境介质等因素实现紫外到中红外波段可调的谐振谱。此外，Purcell指出，可通过合理的构造特定的腔，波导结构来调控材料周围电磁场的态密度，进而控制材料的自发辐射几率，该效应称为Purcell效应。基于该效应，为了有效提高半导体材料的量子效率，高态密度和小模体积将有助于获得较大的Purcell系数。因此，如果能将等离激元效应与Purcell效应二者有效结合起来，即将半导体材料对应的辐射频率接近于等离激元的谐振频率，那么将会显著提高该半导体光电器件的量子效率，光能的利用率将大幅提高。
随着半导体加工工艺的的日渐成熟，基于表面等离激元-半导体异质集成的有源、无源光电器件的研究层出不穷，但大多数的制备工艺仅仅通过焊接、绑定、修饰以及组装等方式实现两种不同材料的异质集成。制备工艺复杂，成本高而且周期长，与此同时，以上这些技术手段难以在表面等离激元结构上实现长径比可调、密度可控以及取向可变的半导体材料。不同材料之间的晶面失配也导致形成的异质集成的光电器件存在较高的界面损耗以及诸多的不确定性，器件的实用性及稳定性也需要进一步发掘。
因此，亟需一种高质量、稳定且可大批量制备的高效异质集成光电器件，避免传统构造晶面技术手段带来的“特异性”差(导致极易生成核壳型结构而无法实现光波的传导)，不可控等缺陷，从而实现表面等离激元传统与光模式的直接高效耦合。
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-半导体异质结谐振光电器件，该方法通过化学绑定特定金属晶面，并通过复合半导体晶种及其续生长来严格实现密度、长径比、取向可控的半导体结构。通过调控该种异质集成结构工艺可实现多种有源、无源表面等离激元光电器件，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-半导体异质结谐振光电器件包括：表面等离激元纳米结构，表面配体分子，表面等离激元晶面结构，半导体纳米结构晶种和一维半导体纳米结构；其中，表面配体分子修饰在表面等离激元纳米结构上，表面等离激元晶面结构绑定在表面配体分子上，半导体纳米结构晶种位于表面等离激元晶面结构上，一维半导体纳米结构位于半导体纳米结构晶种上，且各部分形成紧密的接触。
其中，
所述的表面等离激元纳米结构，形貌为三角板、线或十面体的各向异性晶体材料，长轴尺寸为10-10000nm，或为球、对称多面体的各向同性晶体材料，尺寸为10-3000nm。
所述的表面等离激元纳米结构，供选材料为金、银、铜、铝或铂等具有表面等离激元效应的金属材料；
所述的表面配体分子，供选材料为十六烷基三甲基溴化铵CTAB、聚乙烯吡络烷酮PVP或巯基丙酸MPA。
所述的表面等离激元晶面结构，形貌为三角板、锥或立方体的各向异性材料，尺寸为1-10nm。
所述的表面等离激元晶面结构，供选材料为与表面等离激元纳米结构所用材料一致的小尺寸金属纳米结构。
所述的半导体纳米结构晶种，形貌为球、锥或棒，尺寸为1-10nm，供选材料为氧化锌、三氧化二铝或氧化亚铜。
所述的一维半导体纳米结构，形貌为棒、锥或管状的一维纳米结构，尺寸为10nm-10000nm，供选材料为与半导体纳米结构晶种所用材料一致的大尺寸金属微纳结构。
本发明的表面等离激元-半导体异质结谐振光电器件的制备方法包括以下步骤：
步骤一：特定表面等离激元晶面结构构造
取浓度为0.01-1Mol/L的表面等离激元纳米结构水溶液，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液a；
在溶液a中加入浓度为0.01-1Mol/L的表面配体分子水溶液，搅拌，由于晶面选择性，该种表面配体分子将会吸附在表面等离激元纳米结构特定的晶面上，得到溶液b；
在溶液b中加入浓度为0.001-0.1Mol/L的表面等离激元晶面结构水溶液，搅拌，使得该表面等离激元晶面结构与表面等离激元纳米结构特定晶面位置的配体分子以共价键的形式形成紧密接触，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液c；
步骤二：半导体晶种制备及续生长
取所述的溶液c，加入浓度为0.01-0.1Mol/L的半导体晶种水溶液，搅拌1-4h，使得半导体晶种附着在表面等离激元纳米结构特定晶面上；
多次离心水洗，去除溶液中过量的半导体晶种，沉淀重新分散在去离子水中，得到溶液d；
为得到一维半导体纳米结构，在溶液d中先后加入浓度为0.001-0.1Mol/L的金属盐水溶液、0.001-0.1Mol/L弱还原剂水溶液及浓度为0.01-0.1Mol/L的表面封盖剂水溶液，60℃-90℃下反应1-18h；多次离心水洗，将沉淀物重新分散在去离子水中，得到最终的表面等离激元-半导体异质结。
所述一种表面等离激元-半导体异质结谐振光电器件工作方式为：当激励光入射到表面等离激元纳米结构1表面时，基于表面等离激元效应，表面等离激元纳米结构1将光聚集在亚波长范围内形成共振增强，该种共振增强具有波长选择性，共振吸收峰的位置和波段宽度与表面等离激元纳米结构1的形貌、尺寸以及环境介质相关。紧接着，产生的表面等离激元波将激发到与表面等离激元纳米结构1紧密接触的一维半导体纳米结构5波导中，形成光信号的定向分配。该过程 可逆向实现，即可将激励光照射在具有光电效应的一维半导体纳米结构5波导中，以光致发光的方式，传导并汇聚在表面等离激元纳米结构1中，激发其等离激元。最终可利用该等离激元实现基于等离激元光热效应的纳米热源、光致发光增强的纳米激光器以及基于“热电子”效应的光催化反应载体。
其中，所述的金属盐溶液，供选材料为醋酸锌、三氯化铝或硝酸铜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；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一维方向生长的封盖剂。
有益效果：本发明与现有的技术相比具有以下的优点：
1、本发明提出了一种大批量制造纳米谐振机制的异质结构的新方法，通过选择性构造特定金属晶面，实现长径比可控、疏密可调的半导体纳米结构生长。相比于传统的技术手段，该种非核壳型结构，可同时实现局域表面等离激元LSPR效应与光模式的直接耦合，也避免了传统工艺如焊接、组装、绑定等技术手段带来的界面损耗。通过控制晶面结构，可生长一系列不同形貌、结构、取向的异质结，可用于构造纳米天线、纳米热源及表面等离激元激光器等各种无源、有源光电器件。
2、本发明提出了一种表面等离激元-半导体异质结谐振光电器件结构，相比于传统的半导体光电器件，可在多个维度上对该结构进行设计，将单晶的、原子平的一维半导体纳米结构与表面等离激元纳米结构实现直接复合，避免了材料表面缺陷，界面粗糙等原因带来的高损耗问题，同时利用表面等离激元效应带来的近场高度局域增强特性及响应光谱可调等优势，通过优化半导体材料的结构，大大提高了器件的量子效率。该种结构可同时实现表面等离激元-光或光-表面等离激元的模式转换，实现高性能、低成本的集成纳米光学器件。
3、本发明提出了一种新型晶面构造方法，利用表面配体分子具有晶面特异性吸附的特点，实现其在特定表面等离激元纳米结构上特定晶面位置的吸附，从而进一步实现对加入的密度可控的金属晶种的绑定。相比于传统的电子束刻蚀、纳米压印等构造晶面的方法，具有工艺成本低、可大批量制备等特点。且二者以共价键的形式绑定，稳定性更高。此外，利用化学方法构造的特定晶面，也便于后续进行下一步的续生长、修饰等技术手段，工艺简单、可操控性强。是对现有 在表面等离激元纳米材料上构建特定晶面工艺的突破。
附图说明
图1为表面等离激元-半导体异质结谐振光电器件生长过程示意图，
图2为表面等离激元纳米结构形貌示意图，
图3不同形貌表面等离激元-半导体异质结结构示意图，
图中有表面等离激元纳米结构1，纳米十面体11，纳米三角板12，纳米棒13，纳米球14，表面配体分子2，表面等离激元晶面结构3，半导体纳米结构晶种4，一维半导体纳米锥5，一维半导体纳米柱6。
具体实施方式
下面通过具体实施例和对比例进一步说明本发明：
实施例1：一种表面等离激元-半导体异质结谐振光电器件，结构包括：表面等离激元纳米结构为银纳米十面体，尺寸为20nm；表面配体分子为十六烷基三甲基溴化铵CTAB；表面等离激元晶面结构为银三角板，尺寸为5nm；半导体纳米结构晶种为氧化锌；一维半导体纳米结构为氧化锌纳米棒，尺寸为500nm。其位置关系为，十六烷基三甲基溴化铵CTAB修饰在银纳米十面体特定晶面上，银三角板晶面绑定在十六烷基三甲基溴化铵CTAB上，氧化锌晶种位于银三角板晶面上，氧化锌纳米棒位于氧化锌晶种上，且各部分形成紧密的接触。
制备方法按照以下步骤：
步骤一：特定表面等离激元金属晶面结构构造
取浓度为0.01Mol/L的银纳米十面体溶液，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液a；在溶液a中加入浓度为0.01Mol/L的十六烷基三甲基溴化铵CTAB，搅拌，由于晶面选择性，该分子将会吸附在银纳米十面体特定的晶面上，得到溶液b。在溶液b中加入浓度为0.01Mol/L的银三角板晶面，搅拌，使得该三角板晶面被十六烷基三甲基溴化铵CTAB绑定在银纳米十面体特定晶面位置上，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液c。
步骤二：半导体晶种制备及续生长
取一定量的溶液c，加入浓度为0.05Mol/L的氧化锌晶种溶液，搅拌1h，使得氧化锌晶种附着在银三角板晶面上。多次离心水洗，去除溶液中过量的氧化锌晶种，沉淀重新分散在去离子水中，得到溶液d。为得到一维氧化锌纳米棒结构，在溶液d中先后加入浓度为0.1Mol/L的醋酸锌溶液、0.1Mol/L抗坏血酸 AA溶液及浓度为0.1Mol/L的聚乙烯亚胺PEI溶液，90℃下反应2h。多次离心水洗，将沉淀物重新分散在去离子水中，得到最终的银十面体-氧化锌纳米棒异质结。
实施例2：一种表面等离激元-半导体异质结谐振光电器件，结构包括：表面等离激元纳米结构为金纳米三角板，尺寸为60nm；表面配体分子为聚乙烯吡络烷酮PVP；表面等离激元晶面结构为金纳米棒，尺寸为10nm；半导体纳米结构晶种为氧化铜；一维半导体纳米结构为氧化铜纳米锥，尺寸为1000nm。其位置关系为，聚乙烯吡络烷酮PVP修饰在金纳米三角板的特定晶面上，金纳米棒晶面绑定在聚乙烯吡络烷酮PVP上，氧化铜晶种位于金纳米棒晶面上，氧化铜纳米锥位于氧化铜晶种上，且各部分形成紧密的接触。
制备方法按照以下步骤：
步骤一：特定表面等离激元晶面结构构造
取浓度为1Mol/L的金纳米三角板溶液，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液a；在溶液a中加入浓度为0.1Mol/L的聚乙烯吡络烷酮PVP，搅拌，由于晶面选择性，该分子将会吸附在金纳米三角板特定的晶面上，得到溶液b。在溶液b中加入浓度为0.1Mol/L的金纳米棒，搅拌，使得该金纳米棒晶面被聚乙烯吡络烷酮PVP绑定在金纳米三角板特定晶面位置上，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液c。
步骤二：半导体晶种制备及续生长
取一定量的溶液c，加入浓度为0.1Mol/L的氧化铜晶种溶液，搅拌2h，使得氧化铜晶种附着在金纳米棒晶面上。多次离心水洗，去除溶液中过量的氧化铜晶种，沉淀重新分散在去离子水中，得到溶液d。为得到一维氧化铜纳米锥结构，在溶液d中先后加入浓度为0.1Mol/L的硝酸铜溶液、0.1Mol/L过氧化氢溶液及浓度为1Mol/L的曲拉通X-100溶液，80℃下反应6h。多次离心水洗，将沉淀物重新分散在去离子水中，得到最终的金三角板-氧化铜纳米锥异质结。
实施例3：一种表面等离激元-半导体异质结谐振光电器件，结构包括：表面等离激元纳米结构为铂纳米棒，尺寸为80nm；表面配体分子为巯基丙酸MPA；表面等离激元晶面结构为铂纳米立方体，尺寸为20nm；半导体纳米结构晶种为氧化铝；一维半导体纳米结构为氧化铝纳米棒，尺寸为500nm。其位置关系为，巯基丙酸MPA修饰在铂纳米棒的特定晶面上，铂纳米立方体晶面绑定在巯基丙 酸MPA上，氧化铝晶种位于铂纳米立方体晶面上，氧化铝纳米棒位于氧化铝晶种上，且各部分形成紧密的接触。
制备方法按照以下步骤：
步骤一：特定表面等离激元晶面结构构造
取浓度为0.01Mol/L的铂纳米棒溶液，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液a；在溶液a中加入浓度为0.01Mol/L的巯基丙酸MPA，搅拌，由于晶面选择性，该分子将会吸附在铂纳米棒特定的晶面上，得到溶液b。在溶液b中加入浓度为0.1Mol/L的铂纳米立方体晶面结构，搅拌，使得该铂纳米立方体晶面被巯基丙酸MPA绑定在铂纳米棒特定晶面位置上，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液c。
步骤二：半导体晶种制备及续生长
取一定量的溶液c，加入浓度为0.1Mol/L的氧化铝晶种溶液，搅拌1h，使得氧化铝晶种附着在铂纳米立方体晶面上。多次离心水洗，去除溶液中过量的氧化铝晶种，沉淀重新分散在去离子水中，得到溶液d。为得到一维氧化铝棒结构，在溶液d中先后加入浓度为0.1Mol/L的三氯化铝溶液、0.1Mol/L乌洛托品HMTA溶液及浓度为0.1Mol/L的二－乙基己基琥珀酸酯磺酸钠AOT溶液，60℃下反应15h。多次离心水洗，将沉淀物重新分散在去离子水中，得到最终的铂纳米棒-氧化铝纳米棒异质结。
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。

Claims (10)

  1. 一种表面等离激元-半导体异质结谐振光电器件，其特征在于该光电器件包括：表面等离激元纳米结构(1)，表面配体分子(2)，表面等离激元晶面结构(3)，半导体纳米结构晶种(4)和一维半导体纳米结构(5)；其中，表面配体分子(2)修饰在表面等离激元纳米结构(1)上，表面等离激元晶面结构(3)绑定在表面配体分子(1)上，半导体纳米结构晶种(4)位于表面等离激元晶面结构(3)上，一维半导体纳米结构(5)位于半导体纳米结构晶种(4)上，且各部分形成紧密的接触。
  2. 如权利要求1所述的一种表面等离激元-半导体异质结谐振光电器件，其特征在于，所述的表面等离激元纳米结构(1)，形貌为三角板、线或十面体的各向异性晶体材料，长轴尺寸为10-10000nm，或为球、对称多面体的各向同性晶体材料，尺寸为10-3000nm。
  3. 如权利要求1所述的一种表面等离激元-半导体异质结谐振光电器件，其特征在于，所述的表面等离激元纳米结构(1)，供选材料为金、银、铜、铝或铂等具有表面等离激元效应的金属材料；
  4. 如权利要求1所述的一种表面等离激元-半导体异质结谐振光电器件，其特征在于，所述的表面配体分子(2)，供选材料为十六烷基三甲基溴化铵CTAB、聚乙烯吡络烷酮PVP或巯基丙酸MPA。
  5. 如权利要求1所述的一种表面等离激元-半导体异质结谐振光电器件，其特征在于，所述的表面等离激元晶面结构(3)，形貌为三角板、锥或立方体的各向异性材料，尺寸为1-10nm。
  6. 如权利要求1所述的一种表面等离激元-半导体异质结谐振光电器件，其特征在于，所述的表面等离激元晶面结构(3)，供选材料为与表面等离激元纳米结构(1)所用材料一致的小尺寸金属纳米结构。
  7. 如权利要求1所述的一种表面等离激元-半导体异质结谐振光电器件，其特征在于，所述的半导体纳米结构晶种(4)，形貌为球、锥或棒，尺寸为1-10nm，供选材料为氧化锌、三氧化二铝或氧化亚铜。
  8. 如权利要求1或7所述的一种表面等离激元-半导体异质结谐振光电器件，其特征在于，所述的一维半导体纳米结构(5)，形貌为棒、锥或管状的一维纳米 结构，尺寸为10nm-10000nm，供选材料为与半导体纳米结构晶种(4)所用材料一致的大尺寸金属微纳结构。
  9. 一种如权利要求1所述的表面等离激元-半导体异质结谐振光电器件的制备方法，其特征在于，该制备方法按照以下步骤：
    步骤一：特定表面等离激元晶面结构构造
    取浓度为0.01-1Mol/L的表面等离激元纳米结构水溶液，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液a；
    在溶液a中加入浓度为0.01-1Mol/L的表面配体分子水溶液，搅拌，由于晶面选择性，该种表面配体分子将会吸附在表面等离激元纳米结构特定的晶面上，得到溶液b；
    在溶液b中加入浓度为0.001-0.1Mol/L的表面等离激元晶面结构水溶液，搅拌，使得该表面等离激元晶面结构与表面等离激元纳米结构特定晶面位置的配体分子以共价键的形式形成紧密接触，多次离心水洗，将沉淀物重新分散在去离子水中，得到溶液c；
    步骤二：半导体晶种制备及续生长
    取所述的溶液c，加入浓度为0.01-0.1Mol/L的半导体晶种水溶液，搅拌1-4h，使得半导体晶种附着在表面等离激元纳米结构特定晶面上；
    多次离心水洗，去除溶液中过量的半导体晶种，沉淀重新分散在去离子水中，得到溶液d；
    为得到一维半导体纳米结构，在溶液d中先后加入浓度为0.001-0.1Mol/L的金属盐水溶液、0.001-0.1Mol/L弱还原剂水溶液及浓度为0.01-0.1Mol/L的表面封盖剂水溶液，60℃-90℃下反应1-18h；多次离心水洗，将沉淀物重新分散在去离子水中，得到最终的表面等离激元-半导体异质结。
  10. 如权利要求9所述的一种表面等离激元-半导体异质结谐振光电器件的制备方法，其特征在于，所述的金属盐溶液，供选材料为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H2O2或乌洛托品HMTA；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一维方向生长的封盖剂。
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