CN100465345C - Surface plasmon crystal and preparation method thereof - Google Patents
Surface plasmon crystal and preparation method thereof Download PDFInfo
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- CN100465345C CN100465345C CNB2006100394780A CN200610039478A CN100465345C CN 100465345 C CN100465345 C CN 100465345C CN B2006100394780 A CNB2006100394780 A CN B2006100394780A CN 200610039478 A CN200610039478 A CN 200610039478A CN 100465345 C CN100465345 C CN 100465345C
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Abstract
The invention discloses the surface phasmon crystal and preparing method, comprising two-dimensional sequence square dielectric microsphere underlay and metal hemisphere shell membrane under underlay. The metal hemisphere shells are connected with each other, forming the bidimensional cycle ordered structure metal film possessing micropore array. The method comprises the following steps: arraying the sub-micron/micrometer dielectric microsphere to form ordered bidimensional microsphere array; settling metal nanometer particle on bidimensional microsphere with physics vapor deposition method, until forming the continuous metal hemisphere film. The invention has the advantages of novel style structure, adjustable crystal structure parameter, controlling cycle and simple technology.
Description
One, technical field
The present invention relates to a kind of metal nano material and preparation method thereof, particularly a kind of surface plasmon crystal and preparation method thereof.
Two, background technology
Metal nano material and ordered structure thereof, since its abundant physical connotation with and have direct and potential using value at aspects such as photonics, electronics, catalysis, biomedicine, drug delivery, and obtained extensive concern both domestic and external and research.Experiment shows that factors such as the shape of metal nanoparticle, size and component are determining their physics and chemical property.For example, under electromagnetic effect, metal nanoparticle and produce collective oscillation by the unbound electron of its ordered structure surface of forming forms surface phasmon (surface plasmons).Surface etc. between primitive coupling and excite the efficient of many two-phonon process is significantly improved.Surface phasmon can be widely used in fields such as photoelectronics and bio-science.Being coupled as between surface phasmon and the incident light has sub-wavelength periodic structure planar metal thin-film material (being referred to as planar surface etc. from the primitive crystal) and given peculiar optical characteristics, this specific character has been subjected to the extensive concern of scientific circles, such as handling at quantum information, superhigh precision lithography, and aspect such as surface Raman enhancement effect.So the technology of preparing of development of new metal nano ordered structural material, and can realize that its structural parameter are controlled, be very important meaning to following this type of material in the application of different field.
Existing preparations etc. generally at first are to adopt physical deposition techniques to deposit layer of metal film on smooth substrate from the primitive crystal technology, adopt technology micro-processing technologies such as photoetching, reactive ion beam etching (RIBE), focused ion beam, electron-beam direct writing that metallic membrane is carried out preferred property ground then and remove, thereby form medium/metal separation surface with modulated structure.Though these technology have bigger degree of freedom aspect structure control, the equipment of these technology has high input, complex technical process, makes that the preparation cycle of sample is long, cost is high.Though above-mentioned listed part technology can be modulated yardstick with space structure and is reduced to below the submicron, however in the reality in order to obtain the ordered structure of nanometer or deep-submicron yardstick, these masks or inscription technology still are subjected to very big challenge.
Three, summary of the invention
1, goal of the invention: the purpose of this invention is to provide that a kind of preparation technology is simple, cost is low, the surface plasmon crystal of superior performance and preparation method thereof.
2, technical scheme: surface plasmon crystal of the present invention is characterized in that: it is made up of two-dimension periodic ordered arrangement and isometrical medium microsphere substrate that is in contact with one another and the metal hemisphere shell membrane that is deposited on the substrate surface.
The diameter of described medium microsphere substrate is 200nm～10 μ m, and size dispersion is less than 5%, and its material is silicon-dioxide or polystyrene or at the isometrical microballoon of corresponding optical band transparent medium.
Described medium microsphere substrate planar is in contact with one another and forms two-dimentional hexagonal or two-dimension square dot matrix.
Cover the microwell array that metal hemisphere shell membrane on the microsphere surface has sequential 2 D, the material of metal hemisphere shell membrane can be gold and silver, platinum, aluminium, copper, chromium or the little metallic substance of nickel photoabsorption, and place, the summit thickness of metal film on the medium microsphere substrate surface is between 15nm～150nm.
The preparation method of surface plasmon crystal of the present invention is characterized in that: this method may further comprise the steps:
(1) by self-assembling technique (for example, patent ZL031319890) or other technology, submicron/micron medium microsphere is arranged in the two-dimentional micro-sphere array of high-sequential, be in contact with one another between the microballoon;
(2) utilize physical gas-phase deposite method,, be increased to until the deposition of microsphere surface and make metallic particles form successive metal hemisphere shell membrane at medium microsphere surface deposition metal nanoparticle.
In step (2), said physical gas-phase deposite method is high vacuum coating method, metal fever evaporation coating method, magnetically controlled sputter method, pulsed laser deposition method or Atomic layer deposition method.
Surface plasma crystal of the present invention is a kind of medium/metal interface system with modulated structure, wherein metallic membrane has trilateral micropore oldered array, and metallic film is along with the oldered array periodic undulations of being made up of medium microsphere forms accurate 3-dimensional metal network structure.
3, beneficial effect: compare with existing preparation surface plasmon crystal technology, the present invention has following outstanding advantage: (1) is not high to equipment requirements, and preparation technology is simple, and is with low cost.(2) can prepare large-area surface plasmon crystal, this will satisfy this type of material in the demand of using future in enormous quantities.(3) etc. depend on the grain size of the medium microsphere of its substrate from the primitive crystalline cycle, thereby, can easily space structure be modulated yardstick and be controlled at below the sub-wavelength by selecting the medium microsphere of appropriate size for use.(4) grade of utilizing the preparation of this method is from the primitive crystal, and its primitive is made up of the metal hemispherical Shell on medium microsphere and surface thereof, and making the transmission reinforcing effect of the existing surface plasmon crystal in the past of its optical property has optical properties such as its distinctive chromatic dispersion again.
Four, description of drawings
Fig. 1 is by the isometrical medium microsphere that is in contact with one another and be deposited on the structural representation of the surface plasmon crystal that its lip-deep metal hemispherical Shell forms.
Fig. 2 is being substrate by the isometrical silicon dioxide microsphere two-dimensional array that is in contact with one another, and the electron scanning micrograph of the surface plasmon crystal of being made up of the metal hemispherical Shell.
Fig. 3 is after removing the silicon dioxide microsphere array, the electron scanning micrograph of the metal book film of being made up of interconnective metal hemispherical Shell.
Five, embodiment
Embodiment 1: this example is selected monodisperse silica microspheres for use, and the silicon dioxide microsphere diameter is 1580nm.At first adopt by the surface tension in the microchannel (referring to the microballoon self-organizing technique, patent ZL 03 1 31989.0), microballoon is arranged in hexagonal close-packed array.Adopt high vacuum ar-ion beam sputtering method then, at microsphere surface deposition one deck gold film, the deposition of gold grain is controlled at and makes that golden shell summit thickness is 25nm.Owing to all be capped a hemispheric gold nano shell at each silicon dioxide microsphere, interconnect thereby form hemispheric shell metallic, thereby form by the isometrical silicon dioxide microsphere that is in contact with one another and be deposited on the surface plasmon crystal that its lip-deep golden hemispherical Shell is formed.
Embodiment 2: present embodiment is substantially the same with embodiment 1, is 20mm but the target target of selecting for use is a diameter, the circular silver bullion of thickness about 2mm.Therefore formed by the isometrical silicon dioxide microsphere that is in contact with one another and be deposited on the surface plasmon crystal that its lip-deep silver-colored hemispherical Shell is formed, physical gas-phase deposite method is a metal fever evaporation coating method.
Embodiment 3: present embodiment is substantially the same with embodiment 1, but select polystyrene microsphere sequential 2 D array for use as the medium microsphere array of substrate, obtained by the isometrical polystyrene microsphere that is in contact with one another and be deposited on the surface plasmon crystal that its lip-deep chromium hemispherical Shell is formed, place, summit thickness of metal film on the medium microsphere substrate surface is 150nm, and physical gas-phase deposite method is the pulsed laser deposition method.
Embodiment 4: present embodiment is substantially the same with embodiment 1, but selects polystyrene microsphere sequential 2 D square lattice array for use as the medium microsphere array of substrate, and the diameter of medium microsphere substrate is 10 μ m, and size dispersion is less than 5%.Obtained by the isometrical polystyrene microsphere that is in contact with one another and be deposited on the surface plasmon crystal that its lip-deep platinum hemispherical Shell is formed, place, summit thickness of metal film on the medium microsphere substrate surface is 15nm, and physical gas-phase deposite method is an Atomic layer deposition method.
Embodiment 5: present embodiment is substantially the same with embodiment 1, but selects isometrical microballoon at corresponding optical band transparent medium for use as the medium microsphere array of substrate.Microballoon sequential 2 D square lattice array, the diameter of medium microsphere substrate is 10 μ m, size dispersion is less than 5%.The material that is deposited on its lip-deep metallic substance and is metal hemisphere shell membrane can be aluminium or the little metallic substance of photoabsorption such as copper or chromium or nickel, place, summit thickness of metal film on the medium microsphere substrate surface is 100nm, and physical gas-phase deposite method is the high vacuum coating method.
Claims (9)
1, a kind of surface plasmon crystal is characterized in that: isometrical medium microsphere substrate that it is arranged and be in contact with one another by sequential 2 D and the metal hemisphere shell membrane that is deposited on the substrate surface are formed; The diameter of described medium microsphere substrate is 200nm～10 μ m.
2, a kind of surface plasmon crystal according to claim 1 is characterized in that: the material of described medium microsphere substrate is a silicon-dioxide, or polystyrene.
3, a kind of surface plasmon crystal according to claim 1 is characterized in that: the material of described medium microsphere substrate is at the transparent dielectric material of the optical band of surface plasmon crystal work.
4, a kind of surface plasmon crystal according to claim 1 is characterized in that: described medium microsphere substrate planar is in contact with one another and forms two-dimentional hexagonal or two-dimension square dot matrix.
5, a kind of surface plasmon crystal according to claim 1 is characterized in that: cover the microwell array that metal hemisphere shell membrane on the microsphere surface has sequential 2 D.
6, a kind of according to claim 1 or 5 surface plasmon crystal is characterized in that: the material of metal hemisphere shell membrane is a gold, or silver, or aluminium, or platinum, or copper, or chromium, or the nickel metallic substance.
7, a kind of surface plasmon crystal according to claim 1 is characterized in that: place, the summit thickness of metal film on the medium microsphere substrate surface is between 15nm～150nm.
8, a kind of preparation method of surface plasmon crystal is characterized in that: this method may further comprise the steps:
(1) medium microsphere is arranged in the two-dimentional micro-sphere array of high-sequential, is in contact with one another between the microballoon; The diameter of described medium microsphere is 200nm～10 μ m;
(2) utilize physical gas-phase deposite method,, be increased to until the deposition of microsphere surface and make metallic particles form successive metal hemisphere shell membrane at medium microsphere surface deposition metal nanoparticle.
9, the preparation method of surface plasmon crystal according to claim 8, it is characterized in that: in step (2), said physical gas-phase deposite method is high vacuum coating method, metal fever evaporation coating method, magnetically controlled sputter method, pulsed laser deposition method or Atomic layer deposition method.
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| CN101620290B (en) * | 2008-06-30 | 2012-03-07 | 中华映管股份有限公司 | Color light guide plate and liquid crystal display device |
| EP2403973B1 (en) * | 2009-03-05 | 2015-05-06 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Methods for producing highly ordered arrays of nanoholes in metallic films |
| US9132445B2 (en) | 2009-03-05 | 2015-09-15 | Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. | Highly ordered arrays of nanoholes in metallic films and methods for producing the same |
| CN101551330B (en) * | 2009-05-15 | 2010-12-08 | 南京大学 | Surface plasmon crystal transducer and preparation method thereof |
| KR101272052B1 (en) * | 2009-12-18 | 2013-06-05 | 엘지디스플레이 주식회사 | Method of fabricating color filter using surface plasmon and method of fabricating liquid crystal display device |
| CN101814562B (en) * | 2010-04-21 | 2013-05-29 | 哈尔滨工业大学 | LED with two-dimensional photonic crystals |
| CN104192789B (en) * | 2014-08-25 | 2016-04-20 | 华中科技大学 | A kind of nano/micron gold film and preparation method thereof |
| CN105714290A (en) * | 2016-02-03 | 2016-06-29 | 陕西科技大学 | Preparation method for low-angle dependence high-saturation blue SiO2 colloidal crystal film |
| CN105671550A (en) * | 2016-02-03 | 2016-06-15 | 陕西科技大学 | Preparation method of SiO2 colloidal crystal rainbow film with adjustable saturation degree |
| CN105714291A (en) * | 2016-02-03 | 2016-06-29 | 陕西科技大学 | Preparation method for SiO2 colloidal crystal rainbow film with gorgeous colors |
| CN106958006A (en) * | 2017-04-10 | 2017-07-18 | 江西科技师范大学 | Multicomponent alloy not close arranges the preparation method of spherical nanoparticle array |
| CN108004590A (en) * | 2017-12-12 | 2018-05-08 | 中国工程物理研究院激光聚变研究中心 | Nano-porous surface plasmon crystal and preparation method thereof |
| CN110146485B (en) * | 2019-05-23 | 2021-08-31 | 中国科学院合肥物质科学研究院 | Gold triangular pit array material and preparation method and application thereof |
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