Since the demonstration of negative refraction in microwave frequencies, the need for possible applications in optics has pushed the phenomenon to visible frequencies. Perhaps the most prominent application is the concept of the perfect lens that will break the diffraction limit. So far, negative refraction is realized only in periodic or quasi-periodic structures such as metamaterials and photonic crystals. As the frequency is increased, the wavelength becomes smaller, and thus so does the required unit cell size. This puts a tremendous strain on the design and fabrication of suitable negative refraction materials.
To date, the approaches for negative refraction and all-angle negative refraction in the optical range have required sophisticated structures to be fabricated. Even if made possible, such materials are lossy and typically narrowband.
According to one aspect of the invention, a metamaterial comprises a plurality of metallic nanowires embedded in a dielectric matrix. The metamaterial composite media of the invention provide broadband all-angle negative refraction and flat lens and superlens imaging over a wide range of frequencies including, for example, from deep infrared to ultraviolet frequencies.
For applications in the infrared range, for example, copper and gold nanowires can be used. Metallic semiconductor nanowires can also be used. For applications in the near infrared and visible range, for example, silver nanowires can be used. For applications in the ultraviolet range, for example, free-standing aluminum nanowires are preferably utilized.
The composite anistropic media of the invention includes two surface plasmon resonances (SPR): a longitudinal SPR and a transverse SPR. The longitudinal SPR generally has a longer wavelength than the transverse SPR. The smaller the dielectric constant of the host material, the shorter the longitudinal SPR wavelength.
For wavelengths longer than the longitudinal SPR, the composite medium has a negative group refractive index, which enables flat lens imaging. In certain embodiments, the metamaterials of the invention can be used for superlens and hyperlens imaging.
The loss in the composite media can be tailored by choice of constituent materials, particularly the host medium, and the proportions of materials in the composite media.
The metamaterials of the invention can be fabricated using a variety of processes, including both top-down lithography and bottom-up assembly methods. In general, it is not necessary to have a dielectric matrix. For the bottom-up assembly method, it is normally required to have a dielectric matrix to support the nanowires. Even when the dielectric matrix other than air is necessary, other dielectrics, such as porous silicon, or porous titania, can be used as the matrix.
The embedded nanowires can also be carbon nanotubes, or metallic semiconductors. The metamaterials will be operated in the windows of anomalous dispersion of the nanotubes or nanowires.
If the surface is flat, the metamaterial can be used as a flat lens or a superlens. If the surface is curved, it can be used as a hyperlens.
The metamaterials of the present invention provide new and simpler structures for negative refraction and its application in the infrared and the visible range. The invention further enables negative refraction applications in the ultraviolet range. The present metamaterials are easy to fabricate, and the loss can be easily tailored.
The metamaterials of the invention provide negative refraction and flat lens imaging up to the ultraviolet range, which is of tremendous importance for photolithography applications. Furthermore, the present metamaterials include numerous applications for imaging and sensor systems, can be integrated into optical circuits for telecommunications devices, and can also be useful for bio-sensor applications.
Considering a metal with Re εm<0 embedded in an ambient medium with positive εa. In the long wavelength limit, one has the Bruggeman's EMT:
Here, f is the metal filling ratio, D=measure of the aspect ratio of the metal inclusions, εa=permittivity of the dielectric, εm=permittivity of the wires and εeff=effective permittivity of composite structure. The solution is:
with Δ=f(1+D)(εm−εa)+κDεa−εm. The sign is chosen such that Im εeff>0. For sphere inclusion, one has D=2. For slab inclusion, D=0 and ∞ for the effective permittivity perpendicular and parallel to the slabs, respectively.
For cylindrical inclusions with the cylindrical axis in the z direction, as shown in
εx=εy=εeff(1).
εz=εeff(∞)=fεm+(1−f)εa. (3)
From this expression, one can see that there exists a minimum filling ratio:
fmin=εa/(εa−Reεm) (4)
such that for f>fmin, Reεz<0 and for f>½, Reεx,y<0. If one desires Re εx,y>0 but Re εz<0, one should have Re εm<−εa so that fmin<½. It is noted that for the modeling of real systems, the value of D can be different from those used here.
The physical meaning of fmin is the following. At this filling ratio, which also corresponds to a fixed frequency of wavelength λl since εm is dispersive, the composite medium has Re εz=0, which gives strong absorption of the medium since Imkz will have a peak for any nonzero kx. This frequency corresponds to the longitudinal SPR. For example, for a Drude metal with εm=1−λ2/λp2 and λp the plasmon wavelength, one has λl=λp[1+(f−1−1)εa]1/2. Thus, λl is very sensitive to the filling ratio, f, and the dielectric constant of the host medium εa. This increase of the filling ratio results in a blue-shift of the longitudinal SPR. The smaller the refractive index of the host medium, the shorter the longitudinal SPR λl. High absorption is also expected for frequency at the so-called transverse SPR, which is located around the surface plasmon wavelength λsp (Re εm=−εa) and has a very weak dependence on the filling ratio. For a Drude metal, there is a frequency range λl,+<λ<λl,− with εm(λl,±)=εa{1−2(1−2f)−2±4[f(1−f)]1/2(1−2f)−2} such that Im εx>0, and the medium shows strong absorption. Here εm(λl,+)>−εa and εm(λl,−)<−εa. For f<0.1464, one has λl.−<λl.
For composite media with embedded silver (Ag), gold (Au) and aluminum (Al) nanowires, the effective permittivities and absorption spectra y=ln[(1−R)/T] are calculated and shown in
When the metamaterial has Re εz<0 and Re εx,y>0, this so-called indefinite medium has unusual wave refraction phenomena and can be used for negative refraction (NR) and superlens imaging for incident waves along the nanowire axis. A slab of such material whose surface is along the x axis and surface normal is along the z axis is illustrated schematically in
tan θ=−σ tan φ (5)
Here φ is the angle for the incident group velocity and θ is that for the refracted group velocity (see
Here k0z=√{square root over (k02−kx2)}. At λ>λ1, one has σ>0 for all propagating waves, thus all-angle negative refraction (AANR) can be realized in this medium. For small kx, the EFS can be approximated by kz≅κ−σ0k0zwith σ0=−√{square root over (εx)}/εz>0, and κ=√{square root over (εx)}k0(1−1/εz). A slab of this material with thickness d can be used as a flat lens with the lens equation μ+vν=σ0d. Since a is not a constant, caustics will be present in the image. However, an effective 0<σeff<σ0 can be obtained for this lens. The group refractive index neff is related to σ through neff sin θ=sin φ. One has neff˜−σ−1.
There are two strategies to realize Re εz<0 and Re εx>0. For spherical embedment, the composite medium is isotropic which is generally not suitable for negative refraction if no magnetic material is used. A cylinder or slab inclusion will provide the desired property. For the frequency lower than that of SPR where Re εm=−εa, the cylinder axis should be along the z-direction, as previously discussed. For frequency higher than that of SPR but lower than the plasmon frequency where Re εm=0, the cylinder axis should be in the xy plane. If one considers the cylinder axis to be along the x-axis, then εx=fεm+(1−f)εa and
Since for these frequencies, −εa<Re εm<0, one should have a lower and upper bound for the filling ratio as fmin=½ and fmax=εa/(εa−Re εm), respectively. These structures suffer a drawback that the wave phenomena for negative refraction should be limited to the xz-plane since εy has the same value as εz.
Note that the above metamaterials do not support surface waves. The enhancement of subwavelength imaging resolution is limited. However, if the lens is curved, one can use it as a magnifying hyperlens. The metamaterials can be either metallic nanowires embedded in a dielectric matrix or metallic film with holes filled with dielectrics including air. These media can be used for negative refraction and flat lens imaging in three-dimensional free space. The currently studied multilayered structures for negative refraction, superlens and hyperlens are two-dimensional reductions of theses structures. The filling ratio of f=½ is special for multilayered metal-dielectric structures. At this filling ratio, Re εx and Re εz will always have the opposite signs. This can be utilized to realize a magnifying hyperlens.
Anistropic metamaterials with embedded Au, Ag and Al nanowires can be used for flat lens imaging in the infrared, visible and ultraviolet, respectively. For example, for gold at λ=1.55 μm, one has εm=−104.2+3.59i. Here one can use εa=2.89 for alumina in the infrared and the visible range. With a 5% filling ratio, εz=−2.42+0.19i and εx=3.23+0.001i. Thus, σ0=0.74. The permittivity of gold is taken from Weaver, supra. For this filling ratio, negative refraction and flat lens imaging can be realized for the wavelength λ>1.15 μm. For Ag at λ=833 nm, εm=−33.5+3.14i. A filling ratio f=0.1 of silver in alumina template will have εx=3.826+0.025i and εz=−0.749+0.314i. For this lens, σ0=2.2 and the thickness of the lens can be up to 20 μm. For Al at λ=364.7 nm, εm=−19.42+3.60i. A 12% filling ratio of aluminum in a magnesium fluoride (MgF2) matrix (εa=2.0) gives εx=2.886+0.066i and εz=−0.570+0.432i. A lens made of a flat slab of such medium has σ0=1.88 and can have a maximum thickness of 2.98 μm.
According to another aspect, the metamaterials of the present invention can provide superlens imaging. Referring again to Equation 6, when the material property, σ, is constant, then the phase across the lens Φz=k0z(u+v)+kzd=κd is stationary and an image will be formed without aberration. Here u, v, and d obey the equation u+v=d (see
In the present anisotropic material, σ is angle dependent and not a constant because the EFS is hyperbolic and not elliptic, hence the lens has caustics and the image is not “perfect.” Nevertheless, a high quality image can be formed by the lens with u+ν=σeffd and σeff<σ0. Furthermore, although the nonlocal effect on effective permittivity indicates the limitation of Bruggeman's EMT, it will render the EFS to be more elliptic than hyperbolic. Thus, it can reduce the caustics.
The present composite medium with cylindrical inclusion can be used for NR and superlens imaging in three-dimensional free space for frequencies below the surface plasmon frequency. These metamaterials do not support surface waves. The enhancement of subwavelength imaging resolution is still possible. If the lens is curved, one may be able to use it as a magnifying hyperlens. The currently known multilayered structures for NR, superlens and hyperlens are two-dimensional reductions of these structures. The filling ratio f=½ is special for multilayered metal-dielectric structures. At this filling ratio, Re εx and Re εz will always have the opposite signs. This has been utilized to realize a magnifying hyperlens. Naturally available anisotropic dielectric crystals may be used to achieve NR, but cannot be used for superlens imaging.
Anisotropic metamaterials with embedded Au, Ag and Al nanowires can be used for superlens imaging in the infrared, visible and ultraviolet, respectively. For example, for Al at λ=326.3 nm, εm=−15.468+2.575i, a 10% filling ratio of Al nanowires in air gives εx=1.301+0.010i and εz=−0.647+0.258i. A lens made of a flat slab of such a medium has σ0=1.52 and can have a maximum thickness of 11.9 μm. The imaging effect of a point source of such a medium is shown in
For the propagating waves within the xy plane, NR and superlens imaging can be realized in a finite slab of such an anisotropic medium. In this case, for the P-polarized waves, kx=√{square root over (εz)}√{square root over (k02−kz2/εx)}. For λ>λ1, Re εz<0, a free-suspending slab will support guided waves in the xy plane if √{square root over (Reεx)}>1 and kz>√{square root over (Reεx)}k0. These guided waves are backward waves with Re kx<0. In this geometry, surface waves can be formed, which can lead to subwavelength imaging resolution. There is no need to sandwich this medium by perfect conductor waveguide plates.
For the S polarization, the medium with cylinder inclusion is isotropic with positive effective permittivity. The dispersion is given by kz2=εyk02−kx2. No NR can be realized for this polarization.
There are two strategies to realize Re εz<0 and Re εx>0, depending on the wavelength λ>λsp or λ<λsp. Sphere inclusion will lead to isotropic permittivity. However, cylinder or slab inclusion will provide the desired anisotropy. For λ>λsp, the cylinder axis should be along the z axis, as previously discussed. The slab inclusion can be realized as a metallic grating. In such a case, Re εy,z<0 and Re εx>0. Though loss is low in εx, NR is limited to the xz plane. EMT theory gives a very simple explanation for the broadband AANR in the metallic grating. Furthermore, the EMT is more accurate than the coupled-wave theory. In addition, numerical simulations indicate that AANR does not require the metallic grating to be periodic.
For λp<λ<λsp, indefinite medium can be realized if the cylinder axis is in the xy plane for the cylinder inclusion. If the cylinder axis is along the x axis, εx=εeff(∞) and εy,z=εeff(1). For these wavelengths −εz<Re εm<0, one should have ½<f<εa/(εa−Re εm) high loss will be expected for εx. However, the slab inclusion, which is exemplified by multilayered metal-dielectric structures, will have εy,z<0 and Re εx>0 for −εm/(εa−Re εm)<f<εa/(εa−Re εm) with low loss. For these structures, Bruggeman's EMT may not be very precise to calculate effective permittivity, but the present imaging theory indicates that they are able to focus.
To demonstrate a negative index metamaterial, a versatile bottom-up nanofabrication approach has been used to prepare a high-aspect ratio metal nanowire array embedded in a dielectric aluminum oxide matrix. Such a metal-dielectric nanocomposite structure exhibits both longitudinal and transverse surface plasmon resonance modes in the absorbance as demonstrated in optical transmission measurements. The peak intensity and position of the resonances are found to depend strongly on nanocomposite parameters, incident polarization and incident angle, consistent with modeling results based on the effective medium theory. Negative refraction and superlens imaging can be realized in such structures in either the parallel or perpendicular orientations of the incident radiation with respect to axis of the nanowires. However, specific wavelength regimes are dictated by the position of the plasmon modes. Specifically, for large aspect ratio, e.g., length/diameter ˜103, of the nanowires and small filling factors, e.g., (metal volume)/(dielectric volume) ˜10−1, negative refraction can occur at visible and near-infrared wavelengths. Structures with such parameters are easily constructed using the present nanofabrication approach.
According to one embodiment, the nanowires are synthesized inside nanoporous aluminum oxide films making a uniform array of vertical nanowires arranged parallel to each other. The fabrication method allows for the preparation of nanowires with small diameters (d≦˜10 nm) and large lengths (1>˜2 μm), in effect, nanowires with large aspect ratio (l/d ˜103). The optical absorbance is calculated from transmission measurements. The optical absorbance can be modeled by taking into account the plasmonic interaction between the metal nanowire and the aluminum oxide, where the filling factor of the metal inside the dielectric aluminum oxide and the aspect ratio of the nanowires are the main fitting parameters.
According to one example, nanoporous aluminum oxide templates were first generated by dc anodization of commercially available Al foil in an acidic electrolyte. The pore diameter of the templates can be controlled by adjusting the fabrication parameters—most importantly the acid used and the applied dc voltage. In this example, templates with two different pore diameters were fabricated. Templates with pore diameter ˜12 nm were fabricated by anodization in 15% sulfuric acid at 10V and templates with pore diameter ˜35 nm were fabricated by anodization in 3% oxalic acid at 40V. The pore patterns were quasi-ordered and uniform. The time of anodization was adjusted to produce templates with large thickness (and correspondingly large pore lengths) of ˜4 microns. Below the porous layer was a thin barrier layer of aluminum oxide (-tens of nanometers) followed by the remaining unanodized aluminum. The nanowires were synthesized inside the templates by means of ac electrodeposition (20V, 250 Hz). In the case of Au, an aqueous solution consisting of HAuCl4 (1 g/l) and boric acid (4 g/l) was used as electrolyte. For Ag nanowires, an aqueous solution containing AgNO3 (1 g/l) was used as electrolyte. The unanodized Al layer below the pores was removed in mercuric chloride solution. This leaves behind a dielectric template consisting of embedded Au or Ag nanowires.
Transmission spectra for the nanowires with diameter 12 nm are shown in
The important experimental results are now discussed. For Ag nanowires, the transmission for S-polarized light has a minimum at ˜390 nm, shown in
The corresponding modeling results for the anisotropic permittivity and absorbance are shown in
Similar plasmon resonances are observed for Au nanowires with wire diameter 12±2 nm as shown in
The dielectric matrix can be any-dielectric including, without limitation, alumina, titania, silicon or air. Even when the dielectric matrix other than air is necessary, other dielectrics can also be used as the matrix. That is, one may form metallic nanowires by a self-assembly process in other porous nanotemplates, such as porous silicon, or porous titania. The embedded nanowires can also be carbon nanotubes, or metallic semiconductors. The metamaterials will be operated in the windows of anomalous dispersion of the nanotubes or semiconductor nanowires. For example, one may grow silicon carbide in a porous template. According to our modeling, this metamaterial can be operated at around 11 microns.
In the negative refraction regime, optical devices, such as superlenses can be constructed utilizing such a nanocomposite structure. If the surface of the metamaterial is curved, it can be used as a hyperlens. Finally, it will be apparent that by simply adjusting the fabrication parameters, one can tailor the template parameters to tune the optical properties so that negative refraction is achieved at visible frequencies. In the presently-described fabrication approach one can easily control composite parameters to achieve the desired optical properties. Indeed, it may also be mentioned that these nanocomposite-based structures, due to their thin film nature, are easily compatible with nano- and micro-scale engineering processes making such devices practical.
In conclusion, nanocomposite structures consisting of very high aspect ratio metal nanowires embedded in dielectric have been demonstrated. Detailed transmission studies on such structures reveal the presence of two resonance peaks, the position and peak intensity of which are clearly dependent on the nanocomposite dimensions, filling ratio and the angle of incidence and polarization direction. The results are consistent with a model based on Bruggeman's effective medium theory. The nonlocal effect on the effective permittivity is small and negligible, which is confirmed by a band structure calculation. Though direct laser writing can also be used to obtain nanorod arrays, the simple fabrication approach used in the previously described example is easily amenable to varying wire dimensions, aspect ratio and fill factor to produce structures which can exhibit negative refraction in the visible wavelength regime. Such structures also demonstrate easy compatibility with micro and nanoscale engineering processes making the development of such devices feasible.
Applications for the metamaterials of the present invention include, for example, in imaging devices and waveguide devices in integrated photonics and all-optical circuits in computer chip designs in the telecommunication range. The present metamaterials can also be used to enhance high-resolution photolithography, including up to 193 nm. The present materials can also be valuable in the visible regime for biosensor applications. These metamaterials may also be used to trap light for solar cell application or as transparent electrodes.
While the invention has been described in connection with specific methods and apparatus, those skilled in the art will recognize other equivalents to the specific embodiments herein. It is to be understood that the description is by way of example and not as a limitation to the scope of the invention and these equivalents are intended to be encompassed by the claims set forth below.
This application claims the benefit of U.S. Provisional Application No. 60/961,831, entitled “Anistropic Metal-Dielectric Metamaterials for Broadband All-Angle Negative Refraction and Flat Lens Imaging” filed Jul. 24, 2007, the entire teachings of which are incorporated herein by reference.
This work was supported by the Air Force Research Laboratories, Hanscom through FA8718-06-C-0045 and the National Science Foundation through PHY-0457002.
Number | Date | Country | |
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60961831 | Jul 2007 | US |