CN1219222C - Periodic metal/dielectric structural photon crystal with three-dimensional band gap and preparing mehtod thereof - Google Patents
Periodic metal/dielectric structural photon crystal with three-dimensional band gap and preparing mehtod thereof Download PDFInfo
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Abstract
The present invention relates to periodic metal/dielectric structure photonic crystal with a three-dimensional photonic band gap. Metal/dielectric composite dielectric balls are arranged in a close packing mode, and an inner core of each composite dielectric ball is a spherical metal granule, the outer layer of each composite dielectric ball is a dielectric coating layer, or the inner core of each composite dielectric ball is a supporting ball made of organic materials or inorganic materials, the middle interlayer is a metal ball housing, and the outer layer is a dielectric coating layer. The present invention is a three-dimensional structure formed from metal and dielectric composite dielectric balls. The present invention can not only obtain the three-dimensional photonic crystal with a full band gap but also can omit various complexities in the preparation process, and the present invention can not cause other difficulties on preparation.
Description
One, technical field
The present invention relates to the three-dimensional periodic metal/dielectric structure photon crystal material of full band gap, especially adopts the full band gap photonic crystal and the relevant preparation method of the close pile structure of metal/dielectric material complex media ball formation.
Two, background of invention
Some nearest discoveries allow people's special concern is a kind of and are referred to as the phenomenon of " photon band gap ", name to claim it is because its generation and the so-called electronics " energy gap " in the semiconductor are closely similar.We are referred to as photonic crystal to the structured material with such characteristic part below.
Although the application of 1-D photon crystal has long time, the idea of design and preparation two and three dimensions photonic crystal still just has before nearly more than ten years.Because this class formation has many potential application, people are increasing to its interest.Photonic crystal has been used in such as in the devices such as semiconductor laser, solar cell, high-quality resonator cavity and color filter.
Because its these special natures, people are used in the ultrahigh frequency circuit to it and are operated in some devices of millimere-wave band recently.Photonic crystal can also be made the substrate of antenna system, and this is outstanding example in the nearest relevant application.In this type antenna,, from the complete peripherad air of all electromagnetic waves that antenna sends, launch owing to barrier effect makes as the photonic crystal of substrate so as long as the frequency of operation of antenna and the band gap frequency of photonic crystal are complementary.
The energy gap of photonic crystal and centre wavelength depend on the period of change yardstick of specific inductive capacity, the contrast and the dielectric material arrangement mode therein of specific inductive capacity.
Although simple relatively on the 2 D photon crystal preparation technology, and many application are arranged, in the application facet of similar antenna, three-D photon crystal is more suitable.Say that generally the radiation of antenna is to three-dimensional.If therefore adopt full band gap photonic crystal to surround, then can stop any electromagnetic radiation to be passed in the total space; Therefore three-D photon crystal becomes an effective comprehensive catoptron.
The existing invention technology of three-D photon crystal has had several.Mainly concentrate on and adopt the micro-processing technology aspect.Existing invention one: " optical reflection structure, preparation and the means of communication " (United States Patent (USP), the patent No.: 5,172,267), this is first patent about photonic crystal (China invites the person Yabonolovitch) in the world.Figure 1A has not only shown the principal character of this patent, also comprises relevant preparation process.The mask of the two-dimentional circular hole dot matrix of a regular distribution covers on the lump-shaped media.Little processing by has in succession obtained along the pipeline of different specific directions.For little process operation, can adopt and bore sky, photoetching or ion beam lithography.This is the pipeline that has obtained a distributed in three dimensions through the result of processing slightly.By choosing suitable physical parameter (specific inductive capacity of initial medium block) and geometrical characteristic parameter (distance between the diameter of mask mesopore, the adjacent hole), just can obtain three-dimensional full band gap photonic crystal.
Clearly, because along three different directions, making the quite complicated existing invention two of preparation method here: Ekmel OZBAY etc. describe second type three-dimensional band gap photonic crystal entirely, these borings (see United States Patent (USP): 5,406,573).The photonic crystal structure that this patent proposed is similar to a pile " garden wood ": one deck medium post is side by side piled up layer by layer, and the sensing of the medium post of adjacent layer is vertical mutually.
Figure 1B has summarized the main feature of Fig. 2 in this patent.All here medium posts all are parallel to reference planes; Be in the medium post in one deck and then be parallel to each other; Then vertical mutually between the adjacent layer.Being in the distance between two the adjacent medium axis of a cylinder hearts in one deck is grating constant, then when considering to point to the adjacent two layers medium post of x (y) direction, the translation of half grating constant is arranged between them.In other words, the mode of this accumulation is to repeat once every four layers.
Similar with the situation of front, obtain the photonic crystal of the full band gap of this three-dimensional, for the medium post that constitutes photonic crystal, not only material has appropriate physics (specific inductive capacity) character, and its structure (diameter of medium post, between spacing) also will satisfy certain requirement, and the latter has determined the volume of medium post in whole space to occupy ratio.The details of relevant this respect is referring to this patent.
Compare with prior art one, this structure that this patent proposes is simpler, because just these medium posts are in layer banked out, is similar to heap garden wood here.Existing work shows: even if can prepare such medium post, the efficient that they is arranged in such three-dimensional structure also is low-down.
Existing technology one and two all involves micro-processing technology.When full band gap was in visible or near infrared spectrum district, grating constant required about 1 micron, and under these circumstances, micro-machined difficulty is very big.Simultaneously, because employing is micro-processing method, the efficient that obtain bulk or large-area photonic crystal is very low.
Prior art three: this is that the ordered structure (being called colloidal crystal) that the monodispersed colloid micro ball of a kind of employing (what generally adopt is silicon dioxide or polystyrene microsphere) obtains by process of self-organization is a template, in its space, fill the dielectric material of high index of refraction, remove template by the method for physics (calcining) or chemistry (corrosion) then, referring to " On-chip natural assembly of silicon photonic band gap crystals " Y.A.Vlasov, X.-Z.Bo, J.C.Sturm, and D.J.Norris, Nature, 414 (2001) 289.。If the packing material refractive index is enough big, there is full band gap in the three-dimensional porous medium that then obtains at last, sees Fig. 1 C.The advantage of template method is that technology is simple, and cost is low, can obtain large-area photonic crystal.Shortcoming is need be in the filling of carrying out medium in the space.When the size of ball during in micron dimension, the size in space makes and realizes that in such nanometer space complete filling has sizable difficulty in nanometer scale.
Three, summary of the invention:
The present invention seeks to: propose a kind of cycle metal/dielectric structure photonic crystal and preparation method with three-dimensional photon band gap, the distinctive high-level efficiency of structure itself, and simplify the preparation process of photonic crystal greatly, reduce the preparation cost of photonic crystal, and can obtain the photonic crystal of full band gap.
The present invention proposes the three-dimensional structure of a kind of metal, dielectric material, and it has simple structure and preparation method concurrently and is easy to advantage, structure itself have a distinctive high-level efficiency.
The object of the invention realizes like this: the cycle metal/dielectric structure photonic crystal with three-dimensional photon band gap, metal/dielectric material complex media ball is arranged according to close heap mode at three dimensions, the kernel of complex media ball is the spherical metal particle, skin is the dielectric integument, and Metal Ball diameter (d) satisfies with the ratio of complex media bulb diameter (D): d/D＞0.91.Close heap mode is arranged and is comprised modal face-centered cubic, the close pile structure of hexagonal.The complex media ball is by spherical metal particle outer wrapping layer of even dielectric material; Or be that kernel, metal spherical shell are constituted as the outer wrapping layer by interlayer with the dielectric spherical shell by the colloidal medium ball.
Metal/dielectric type photonic crystal of the present invention during to the penetration depth of metal material, substitutes solid metal ball with the metal sandwich spherical shell at the big sub-electromagnetic wave of thickness of metal spherical shell, and the full band gap of the photonic crystal that is obtained is identical.Because the difficulty of solid metal ball preparation on micron or the submicron-scale, adopt the metal spherical shell, not only reduced the difficulty in the photonic crystal preparation greatly, also, these microballoons provide convenience for being assembled into three-dimensional structure, more make the quality of photonic crystal reduce greatly, thereby can obtain the three-dimensional full band gap photonic crystal of lightweight.
With different in the prior art be, support the medium ball of kernel as the metal spherical shell, its physical property (for example specific inductive capacity) does not influence the character of the full band gap of photonic crystal of the present invention; In order to make the quality of photonic crystal low as much as possible, support kernel and can adopt organic material.
Outer field spherical shell material then adopts inorganic material, like this after being assembled into three-dimensional structure, and " neck " that can adopt method for annealing to make that formation is connected between the adjacent ball, thus make total more firm.
The metal/dielectric composite medium ball of photonic crystal elementary cell among the present invention, its typical a kind of be colloidal spheres be kernel, middle with the metal material spherical shell be interlayer, the three-decker complex media ball that forms as the outermost integument with dielectric material.
The present invention adopts the complex media ball to arrange according to close heap form in the space, and this is a kind of the most stable, space structure of easy formation; Adopt the support kernel of colloidal spheres, and kernel selects organic material for use, can alleviate the quality of crystal like this and don't influence the width and the position of the full band gap of photonic crystal as the metal spherical shell;
Interlayer metal spherical shell among the present invention in the complex media ball, metal can be materials such as gold, silver, copper, aluminium.Its thickness is greater than the penetration depth of electromagnetic wave in the respective tones district.Is tens nanometer at the near-infrared region electromagnetic wave to the penetration depth of metal good conductor, and in wavelength longer infrared or millimeter wave, superhigh frequency band, its penetration depth is littler;
The external diameter of the Metal Ball of complex media ball (shell) and dielectric are wrapped up suitably choosing of shell thickness among the present invention, can make the full band gap of prepared three-D photon crystal be in given wavelength coverage;
The preparation method of the full band gap photonic crystal among the present invention is: above-mentioned metal/dielectric composite medium ball is arranged according to close heap mode, the size of Metal Ball (shell) and dielectric integument thickness meet above-mentioned requirements, and Metal Ball or metal spherical shell diameter (d) satisfy with the ratio of complex media bulb diameter (D): d/D＞0.91.。
By diameter, metal sandwich shell thickness, the specific inductive capacity of dielectric integument and suitably choosing of thickness, can prepare the given full band gap three-D photon crystal of wavelength coverage to complex media ball kernel.
Characteristics of the present invention are: this is a kind of three-dimensional structure that is made of metal, dielectric composite medium ball; The present invention can not only can access the three-D photon crystal of full band gap as above-mentioned invention, and has exempted all complicacy in the preparation process above-mentioned, also can not bring the difficulty in other the preparation.
Four, description of drawings:
Figure 1A to Fig. 1 C is the technology of preparing of existing three kinds of full band gap photonic crystals of three-dimensional.
Fig. 2 is the side schematic view of three-D photon crystal of the present invention.
Fig. 3 A is kernel with the Metal Ball, is the inner structure synoptic diagram of the shell structurre complex media ball of integument formation with the dielectric material for the present invention; Fig. 3 B is that corresponding photonic crystal inside is in the complex media ball cross sectional representation in one deck; Fig. 3 C is for being in adjacent complex media ball detail section synoptic diagram in one deck.
Fig. 4 A is that kernel, metal spherical shell are that interlayer, dielectric material are the inner structure synoptic diagram of the complex media ball of integument for the present invention adopts with the dielectric sphere: Fig. 4 B is the solid matter structure of 4A, and Fig. 4 C is for being in adjacent complex media ball detail section synoptic diagram in one deck.
Fig. 5 is the energy band diagram that the present invention adopts the photonic crystal of the complex media ball composition shown in Fig. 3 A, and the dash area among the figure is the full band gap of photonic crystal.
Fig. 6 is the energy band diagram that the present invention adopts the photonic crystal of the complex media ball composition shown in Fig. 4 A, and the dash area among the figure is the full band gap of photonic crystal.
The mask 1 of two-dimentional circular hole dot matrix among Figure 1A.Little processing by has in succession obtained the medium pipeline 2 along different specific directions
The photonic crystal structure is similar to a pile " garden wood " among Figure 1B: one deck medium post 3 is side by side piled up layer by layer, and the medium post 3 of adjacent layer is orthogonal.
The colloidal crystal that the last monodispersed colloid micro ball 4 of substrate b, c obtains by process of self-organization among Fig. 1 C is a template, fills the dielectric material 5 of high index of refraction in its space
Among Fig. 2-4 among the figure black be metal 6, grey is a dielectric material 7.Be the spherical shape of standard among the figure, real process and standard ball are little to the performance impact of integral body.
Five, embodiment
The complex media ball that the elementary cell of the three-dimensional full band gap photonic crystal of the present invention is made up of metal and dielectric material.Its inner structure synoptic diagram is seen Fig. 3 A and 4A.
By implementing dielectric coat, obtain the complex media ball shown in Fig. 3 A among the present invention on solid metal ball surface.
Take monodispersed colloidal spheres (for example polystyrene or silicon dioxide) as supporting kernel among the present invention, on the surface at first by existing chemical method: these methods mainly contain: surperficial seed growth technology, referring to S.J.Oldenburg, R.D.Averitt, S.L.Westcott, N.J.Halas, Chem.Phys.Lett.1998,288,243; The surface deposition reaction technology, referring to L.M.Liz-Marz á n, M.Giersig, P.Mulvaney, Langmuir 1996,12, and 4329; The surface chemistry method is handled and the functional group adsorption method, referring to S.L.Westcott, and S.J.Oldenburg, T.R.Lee, N.J.Halas, Langmuir 1998,14, and 5396; And the ultrasonic packaging method of reporting recently, referring to V.G.Pol et al., Langmuir 2002,18, and 3352.After implementing metallic coating, implement dielectric coat on the surface of metal spherical shell, obtain the complex media ball shown in Fig. 4 A.
As the colloidal spheres that supports kernel, silicon dioxide, titania, polystyrene etc. are arranged among the present invention, because its physical property does not influence the optical property of photonic crystal, its material without limits.Dielectric material has silicon dioxide, titania etc.
Choosing of metal material can be gold, silver, copper, aluminium etc. among the present invention.The thickness of betal can is greater than the penetration depth of electromagnetic wave to this metal material.In order to reduce the metal pair absorption of electromagnetic wave, can select to conduct electricity good metal material as integument.
Adopt the photonic crystal of the complex media ball composition shown in Fig. 3 A among the present invention, be kernel with the Metal Ball promptly, be that the full band gap Conditions of shell structurre complex media ball that integument constitutes is with the dielectric material: coating thickness makes the Metal Ball diameter (d) and the ratio of complex media bulb diameter (D) satisfy: d/D＞0.91.
The photonic crystal that adopts the complex media ball shown in Fig. 4 A to form among the present invention promptly is that kernel, metal spherical shell are that interlayer, dielectric material are that the full band gap Conditions of complex media ball of integument is: the external diameter (d of metal spherical shell with the dielectric sphere
2) satisfy with the ratio of the diameter (D) of complex media ball: d
2/ D＞0.91.
The appearance of the full band gap of photonic crystal of the present invention does not have the threshold value requirement to the specific inductive capacity of outermost material.Be wrapped in dielectric layer on the Metal Ball (shell) and can be silicon dioxide, titania etc. nonconducting, in relevant wavelength band transparent dielectric material.
The frequency of visual organ spare work or wavelength coverage are if the magnitude of size more than millimeter of the complex media ball among the present invention then can adopt manual method that they are assembled into three-dimensional structure layer by layer according to close heap mode very easily.
The frequency of visual organ spare work or wavelength coverage, if the size of complex media ball is in micron or sub-micrometer scale among the present invention, then can adopt existing self-assembling technique (for example compression molding techniques, vertical deposition method) or capillary attraction self-assembling technique: the capillary attraction self-assembling technique is to utilize capillary force to drive following suspension to be inhaled into the microchannel; Liquid level top in the microchannel, microballoon self-organization and form orderly arrangement in inside microchannels.
The present invention has adopted by place sept between two smooth (as slide), forms a microchannel identical with sept thickness; End with the microchannel is immersed in the suspension of microballoon then.Its top takes place in water evaporates in the microchannel.For the moisture that is evaporated in the compensating pipe, suspension can be inhaled into from the lower end of microchannel in the pipe, and this has just formed a water movement from the bottom to top, is driving microballoon simultaneously together to tip motions.After microballoon outreached, its motion was restricted.These microballoons finally form close pile structure on the top of microchannel according to the minimum principle of system capacity.Through promptly preparing the single domain crystal of required size behind the reasonable time.Thereby microballoon is assembled into close pile structure.These assemble methods are simple, cost is low, and the efficient height.
The present invention is provided with a book sheet minim channel, and with the capillary attraction in this passage, thereby the microballoon self-organization forms orderly two dimension, 3-dimensional metal/dielectric type photonic crystal in passage.
As an example, Fig. 5 has shown the energy band diagram of the three-D photon crystal that the complex media ball of Fig. 3 A structure constitutes according to hexagonal Mi Dui arrangement (see figure 2).Concrete selection of parameter is: kernel is a spherical silver particles, and radius is 1.36 microns, and skin is the titania integument, and integument thickness is 50 nanometers.The center of full band gap is at λ
0=4.08 microns, normalized centre wavelength is λ
0/ D=1.45, D is the diameter of complex media ball here.Full band gap relative width (ratio of full band gap width and centre frequency) is 39.9%, and this value substantially exceeds the corresponding index of above-mentioned existing invention technology.
As an example, Fig. 6 has shown the energy band diagram of the three-D photon crystal that the complex media ball of Fig. 4 A structure constitutes according to hexagonal Mi Dui arrangement (Fig. 2).Concrete selection of parameter is: kernel is the silicon dioxide colloid microballoon, and radius is 1.3 microns, and interlayer is the ping-pong ball shell, and shell thickness is 60 nanometers, and outermost layer is the titania integument, and integument thickness is 50 nanometers.The center of full band gap is at λ
0=4.08 microns, normalized centre wavelength is λ
0/ D=1.45, D is the diameter of complex media ball here.Full band gap relative width is 40.0%, and the result among this value and Fig. 5 much at one.
The size of complex media ball need be complementary with the central task wavelength of the full band gap of photonic crystal among the present invention.If required relative band gap reaches 40%, then the diameter of complex media ball should be 0 times of D ≈ 0.7 λ of centre wavelength; Metal Ball semidiameter (perhaps metal spherical shell external diameter) satisfies: d
2≈ 0.96D.
The complex media ball piles up the minimum transmissivity that the number of plies depends on to be needed in the photonic crystal of the present invention.In general, 4 to 5 layers just can make that the reflectivity of full band gap region reaches capacity.It among Fig. 2 the synoptic diagram that one of the present invention has the full band gap photonic crystal of the 4 layers of close heap complex media of hexagonal ball.Photonic crystal of the present invention all has high reflection to the electromagnetic wave that wavelength is in the full band gap at three-dimensional any direction.
Technical parameter among the present invention is not limited to institute's specified value in the previous example, and parameter is specifically chosen full bandgap center operation wavelength and the band gap width that depends on photonic crystal.
Claims (9)
1, a kind of cycle metal/dielectric structure photonic crystal with the full band gap of three-dimensional photon, it is characterized in that metal/dielectric material complex media ball is arranged according to close heap mode at three dimensions, the kernel of complex media ball is the spherical metal particle, skin is the dielectric integument, and the Metal Ball diameter d satisfies with the ratio of complex media bulb diameter D: d/D＞0.91.
2, by the described cycle metal/dielectric structure photonic crystal with the full band gap of three-dimensional photon of claim 1, the kernel that it is characterized in that the complex media ball is organic or the fulcrum ball of inorganic material formation, and intermediate course is the metal spherical shell, and skin is the dielectric integument.
3, by the described cycle metal/dielectric structure photonic crystal with the full band gap of three-dimensional photon of claim 2, it is characterized in that with the Metal Ball being kernel, be that the full band gap Conditions of shell structurre complex media ball that integument constitutes is with the dielectric material: coating thickness makes Metal Ball diameter d and the ratio of complex media bulb diameter D satisfy: d/D＞0.91.
4, by the described cycle metal/dielectric structure photonic crystal with the full band gap of three-dimensional photon of claim 3, it is characterized in that with the dielectric sphere being that kernel, metal spherical shell are that interlayer, dielectric material are that the full band gap Conditions of complex media ball of integument is: the outside diameter d of metal sandwich spherical shell satisfies with the ratio of complex media bulb diameter D: d＞0.91D.
5, by claim 2 or 3 described cycle metal/dielectric structure photonic crystals with the full band gap of three-dimensional photon, it is characterized in that choosing of metal material can be gold, silver, copper, aluminium, dielectric material is silicon dioxide, titania, iron oxide, and the thickness of betal can is greater than the penetration depth of electromagnetic wave to this metal material.
6, by claim 1,2 or 3 described cycle metal/dielectric structure photonic crystals with the full band gap of three-dimensional photon, what it is characterized in that complex media ball in the photonic crystal piles up the number of plies at least 4 to 5 layers.
7, the preparation method who has the cycle metal/dielectric structure photonic crystal of the full band gap of three-dimensional photon, it is characterized in that the kernel with the complex media ball is the spherical metal particle, outer kernel for dielectric integument photonic crystal or complex media ball is organic or the fulcrum ball of inorganic material formation, intermediate course is the metal spherical shell, skin is the dielectric integument, photonic crystal is arranged according to close heap mode, dielectric material is the shell structurre complex media ball that integument or coating constitute, and Metal Ball or metal spherical shell diameter d and the ratio of complex media bulb diameter D is satisfied: d/D＞0.91.
8, by the described preparation method of claim 7 with cycle metal/dielectric structure photonic crystal of the full band gap of three-dimensional photon, it is characterized in that: for the complex media ball of size in the above magnitude of millimeter, adopt manual method on a flat substrate, the complex media ball to be formed the hexagonal solid matter, be in contact with one another between the adjacent ball; Place second layer complex media ball according to close heap form thereon then, repeat like this to obtain corresponding metal/dielectric type photonic crystal until the needed number of plies.
9, by the described preparation method of claim 7 with cycle metal/dielectric structure photonic crystal of the full band gap of three-dimensional photon, it is characterized in that: for the complex media ball of size in micron or the following magnitude of sub-micron, adopt the capillary attraction self-assembling method: suspension is inhaled into the microchannel to utilize capillary force to drive down; Liquid level top in the microchannel, microballoon self-organization and form orderly arrangement in inside microchannels, promptly adopted by between two smooth, placing sept, form a microchannel identical with sept thickness, end with the microchannel is immersed in the suspension of microballoon then, its top takes place in water evaporates in the microchannel, and these microballoons finally form close pile structure on the top of microchannel according to the minimum principle of system capacity.
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| CN102798901B (en) * | 2004-07-23 | 2015-01-21 | 加利福尼亚大学董事会 | Metamaterials |
| KR100953578B1 (en) * | 2009-08-05 | 2010-04-21 | 주식회사 나노브릭 | Printing medium, printing method and printing apparatus using photonic crystal characteristics |
| CN102708853B (en) * | 2012-05-15 | 2014-05-28 | 北京交通大学 | Three-dimensional phonon functional material structure comprising resonance units and manufacturing method thereof |
| CN102928898A (en) * | 2012-11-12 | 2013-02-13 | 南京大学 | Ultra wide wave band near-infrared electromagnetic wave absorber |
| EP3188260B1 (en) * | 2015-12-31 | 2020-02-12 | Dow Global Technologies Llc | Nanostructure material structures and methods |
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