Plasmonic metamolecules have received much interest in the last years because they can produce a wide spectrum of different hybrid optical resonances. Most of the configurations presented so far, however, considered planar resonators lying on a dielectric substrate. This typically yields high damping and radiative losses, which severely limit the performance of the system. Here we show that these limits can be overcome by considering a 3D arrangement made from slanted nanorod dimers extruding from a silver baseplate. This configuration mimics an out-of-plane split ring resonator capable of a strong near-field interaction at the terminations and a strong diffractive coupling with nearby nanostructures. Compared to the corresponding planar counterparts, higher values of electric and magnetic fields are found (about a factor 10 and a factor 3, respectively). High-quality-factor resonances (Q ≈ 390) are produced in the mid-IR as a result of the efficient excitation of collective modes in dimer arrays.
Plasmonic metamolecules have received much interest in the last years because they can produce a wide spectrum of different hybrid optical resonances. Most of the configurations presented so far, however, considered planar resonators lying on a dielectric substrate. This typically yields high damping and radiative losses, which severely limit the performance of the system. Here we show that these limits can be overcome by considering a 3D arrangement made from slanted nanorod dimers extruding from a silver baseplate. This configuration mimics an out-of-plane split ring resonator capable of a strong near-field interaction at the terminations and a strong diffractive coupling with nearby nanostructures. Compared to the corresponding planar counterparts, higher values of electric and magnetic fields are found (about a factor 10 and a factor 3, respectively). High-quality-factor resonances (Q ≈ 390) are produced in the mid-IR as a result of the efficient excitation of collective modes in dimer arrays.
Entities:
Keywords:
3D metamolecule; 3D split ring; Fano lattice resonance; electromagnetic field enhancement; hollow nanoantenna; plasmon hybridization
The past decade has seen an ever growing interest in plasmonic resonators
as building blocks of numerous and variegated nanophotonics components,[1−3] ranging from optical biosensors[4] to metasurfaces,[5] from optical tweezers[6] to nanolasers.[7] The first pioneering
studies on isolated nanoparticles and nanorods highlighted the enhancements
of scattering and electric field produced by these structures, thanks
to localized surface plasmon resonances.[8] Later on it has been realized that by combining two or more resonators
into near-field-interacting multiplets, usually referred to as metamolecules,[9] a wide range of hybrid plasmonic resonances can
be obtained,[10−15] often classified as bright or dark modes,[15−17] depending on
their excitability by far-field illumination. Broadly speaking, the
excitation of bright hybrid modes may lead to huge electric[18−20] and magnetic[21] field enhancements, taking
advantage of nanometric gaps between the coupled resonators. On the
other hand, the indirect excitation of dark modes can give rise to
higher quality-factor resonances.[19,22−25] In addition, the coherent diffractive coupling between isolated
metamolecules can produce collective phenomena, which may dramatically
amplify or inhibit the overall optical features.[22,23,26−29]Currently, most of the
contributions on the subject focused on planar nanoresonators, namely
with small aspect ratios, because these configurations are compatible
with standard fabrication techniques.[30] However, a number of severe limitations have been pointed out for
planar structures.[31−35] Dipole resonators oscillating parallel to the substrate interface
scatter most of the power in out-of-plane directions.[31] This determines a poor and anisotropic diffractive coupling
between antennas with consequently relatively low collective resonance
quality factors. Another well-known issue is the strong influence
exerted by the presence of a high refractive index substrate on the
optical properties of planar nanoantenna arrays.[27,32−35] It has been shown that a progressive increase of the dielectric
asymmetry of the system affects both the isolated resonator properties,
red-shifting and broadening the resonances,[34,35] and the collective modes of the systems, which can be dramatically
reduced or even completely suppressed.[27,32−35] Although index matching techniques can be adopted,[27] these may create nontrivial problems in practical applications
of the resonant arrays, such as sensing.The additional degree
of freedom provided by the third spatial dimension may help to overcome
these limitations. Going in this direction, first achievements were
obtained by considering arrays of single vertical nanorods protruding
normally to the substrate plane.[31,36−40] However, analogously to the case of horizontal resonators, the most
interesting phenomena are found when two or more 3D nanostructures
are coupled together by near-field interaction, combining the advantages
offered by tridimensionality with the variegate hybrid resonance scenarios
produced by near-field coupling. For example, the simplest near field
coupling can be achieved by pairing two vertical and parallel nanorods
(dimer). Upon pairing, the plasmonic resonance characterizing the
isolated vertical antenna splits up into two hybrid modes, respectively
symmetric and antisymmetric in charge distribution, often referred
to as antibonding and bonding, respectively.[10] However, as we shall show, in this side-by-side vertical configuration,
only the antibonding mode turns out to be accessible by far-field
illumination, whereas the bonding one remains dark, similar to the
case of side-by-side planar nanorod dimers.[10] In order to make the bonding mode accessible to far-field illumination
more complex spatial arrangements have to be considered.Here
we propose the plasmonic dimer layout depicted in Figure a. It consists of a pair of
high-aspect-ratio slanted silver nanorods supported by a silver baseplate
and separated by a nanometric gap (details on the geometrical parameters
are reported in the figure caption). The advantage of considering
such an exotic configuration is manifold. The rods are efficiently
near-field coupled by means of the nanometric gap separation between
their terminations. We will show that both bonding and antibonding
modes become bright and then excitable by far-field illumination.
The excitation of both modes is proved to be independent of each other
and tunable as a function of different geometrical parameters, thus
enabling interesting spectral engineering opportunities. In addition,
thanks to the quadrupolar nature of the bonding resonance, a high
magnetic field enhancement can be produced in the area subtended by
the metamolecule, which actually can be viewed as a slanted 3D split-ring
resonator.[41] Finally, dimers are arranged
in regular arrays in order to promote diffracting far-field couplings
that are intrinsically much more efficient than those achievable in
2D planar configuration. In fact vertical resonators, unlike planar
ones, mainly scatter light in directions parallel to the substrate
surface thus redirecting light toward the neighbor dimers and increasing
the fraction of coupled light.[36]
Figure 1
(a) Scheme
of slanted silver nanorod dimer on silver substrate. In the most general
case, these nanorods are characterized by a nonzero tilt angle, α,
and by a nonzero angle β between the rods planes. (b) Scanning
electron microscope images of the fabricated structures. (c) Experimental
reflectances of arrays of single tilted rods (black), pairs of touching
tilted rods (namely gap g = 0, red line) and rod
dimers with gap g = 100 nm (blue). Right insets report
SEM images of the three cases. Geometrical parameters are α
= 30°, β = 90°, h = 1.8 μm,
and p = 4.5 μm. Nonpolarized light impinges
at 25° along the scattering plane depicted in the left inset.
The impinging angle is kept fixed for all of the experimental and
simulative results presented in the paper. (d) Energy splitting of
the isolated tilted rod resonance upon dimerization, and schematic
representation of real and image charge distribution at resonances
with corresponding exciting electric field orientations.
Periodic arrays of slanted nanorod dimers were fabricated by means
of a recently presented technique relying on low energy secondary
electrons emitted during the process of focused ion beam milling.[42,43] A SEM picture showing an example of fabricated nanorod dimer is
reported in Figure b. Fabrication details are already described elsewhere[42,43] and here reported in the Supporting Information 1. The final structures consist of hollow metal nanotubes with a
diameter of 160 nm and silver wall thickness of 30 nm while their
length can range from hundreds of nanometers to several microns.(a) Scheme
of slanted silver nanorod dimer on silver substrate. In the most general
case, these nanorods are characterized by a nonzero tilt angle, α,
and by a nonzero angle β between the rods planes. (b) Scanning
electron microscope images of the fabricated structures. (c) Experimental
reflectances of arrays of single tilted rods (black), pairs of touching
tilted rods (namely gap g = 0, red line) and rod
dimers with gap g = 100 nm (blue). Right insets report
SEM images of the three cases. Geometrical parameters are α
= 30°, β = 90°, h = 1.8 μm,
and p = 4.5 μm. Nonpolarized light impinges
at 25° along the scattering plane depicted in the left inset.
The impinging angle is kept fixed for all of the experimental and
simulative results presented in the paper. (d) Energy splitting of
the isolated tilted rod resonance upon dimerization, and schematic
representation of real and image charge distribution at resonances
with corresponding exciting electric field orientations.In Figure c, we compare the experimental reflectance of a slanted dimer
array (blue line) with that one of an array of single tilted rods
(black line). In the same plot, we report also the reflectance of
a slanted dimer with rods connected at the extremity, namely gap g = 0 nm (red line). The presented measurements were performed
by Fourier transform infrared spectroscopy, carried out with a commercial
micro-FTIR (ThermoFisher iS50) in the spectral range of 5–15
μm. Nonpolarized illumination impinges at fixed impinging angle
of 25° and scattering plane parallel to one of the rods (red
dashed line in left inset of Figure c). As is seen, the single reflectance dip observed
in the case of single rod array splits up into two in the case of
dimer array with nonzero gap. The lower energy dip, in particular,
is closely related to the presence of the gap. In fact, when the gap
is reduced to zero (connected rods) we observed just a single resonance
(red curve), which spectrally matches the higher energy dip observed
for the separated dimer arrays, while the lower energy dip disappears.The metallic baseplate plays a crucial role in determining the
observed optical properties of these structures, which can be interpreted
by means of the method of images,[44] considering
the baseplate to be a perfectly conducting surface. Charges and currents
located in the substrate rearrange themselves in a mirror-like way,
that is, the metallic baseplate can be replaced with a mirror image
of the resonator, endowed with opposite surface charge distribution.
The dip found in the case of the single rod arrays can thus be viewed
as the fundamental dipolar resonance of an equivalent free-standing
rod with double length,[44] as schematically
depicted in Figure d. Similarly, it can be easily realized that two resonances are expected
for the rod dimers, corresponding to the two possible oscillation
modes of real and image charges (Figure d). This closely resembles the case of side-by-side
planar nanorod dimers, widely discussed in literature,[10] with the difference that here the dipole moments
are aligned vertically. The two observed experimental dips correspond
to the excitation of the bonding and antibonding modes,[10] the former being at lower energy with antisymmetric
charge distribution (antiparallel electric dipole moments), and the
latter being at higher energy with symmetric charge distribution (parallel
electric dipole moments).Scattering simulations of an isolated slanted
nanorods dimer with same geometrical parameters as in Figure . (a) Solid lines are the scattering
cross sections (CS) in the three illumination conditions sketched
in the insets, while the blue dashed line is the absorption CS corresponding
to the blue solid scattering CS. Values are normalized to the geometrical
CS. Insets on the left show the E fields at peak wavelengths in two cross sections of the structures.
Field values are normalized to the impinging light amplitude and saturated
to arbitrary values to better evidence their distribution. (b) Scattering
far-field patterns at resonant wavelengths. (c) Scattering cross-section
spectra for different tilting angles α of the dimers and illumination
condition as sketched in the inset (for TM and TE polarized light
as indicated by the arrows).To verify this interpretation, we performed electromagnetic
finite elements simulations (COMSOL Multiphysics software[45]) of an isolated slanted rod dimer in order to
separate the near-field intradimer coupling effects from the interdimer
coupling ones. The rods were modeled as slanted silver cylinders with
sharp edge terminations. We verified that the effect of nonzero edge
curvature radii on the optical behavior is negligible (see Supporting Information 2). Results in case of
a dimer with the same geometrical parameters of the fabricated sample
(see Figure caption)
are reported in Figure . The blue solid curve in Figure a represents the calculated scattering cross section
in case of a transverse magnetic (TM)-polarized plane wave impinging
at 25° with scattering plane parallel to one of the two rodss
(as schematized in the inset). We clearly observe two peaks, which
correspond to the excitation of the two resonances, antibonding (shorter
wavelength) and bonding (larger wavelength). This can be readily verified
by inspecting the z-component of the electric field at resonances
(Figure a, insets).
Figure 2
Scattering simulations of an isolated slanted
nanorods dimer with same geometrical parameters as in Figure . (a) Solid lines are the scattering
cross sections (CS) in the three illumination conditions sketched
in the insets, while the blue dashed line is the absorption CS corresponding
to the blue solid scattering CS. Values are normalized to the geometrical
CS. Insets on the left show the E fields at peak wavelengths in two cross sections of the structures.
Field values are normalized to the impinging light amplitude and saturated
to arbitrary values to better evidence their distribution. (b) Scattering
far-field patterns at resonant wavelengths. (c) Scattering cross-section
spectra for different tilting angles α of the dimers and illumination
condition as sketched in the inset (for TM and TE polarized light
as indicated by the arrows).
A further check of the resonances interpretation is provided by
looking at the scattering far-field patterns at resonances, reported
in Figure b. For the
antibonding resonance, we find a doughnut-shaped emission pattern
with maximum isotropic emission in all directions parallel to the
metal baseplate. This is compatible with a dipolar-like emission with
dipole moment oriented in the z-direction.[44,46] As anticipated, this effect strongly improves the far-field diffractive
coupling because light impinging on a dimer is redirected toward its
neighbors. In fact, it can be noticed that the antibonding peak in
the scattering cross section of isolated dimer (Figure a) is much broader than the corresponding
reflectance dip in Figure c (blue line). This is due to array effects that substantially
modify the antibonding-resonance properties. Conversely, at bonding
resonance (Figure c) the emission pattern has two maxima in the direction connecting
the two rods, which is very similar to the far-field produced by a
pair of closely spaced vertical dipole emitters with π-phase
shift between each other.[44,46] In such a case, as
we shall see, array effects only weakly affect the position and the
width of the resonance.It is worth to underline that in the
proposed nanorods arrangement both the bonding and antibonding modes
are bright for suitable far-field excitation. As a matter of fact,
the antibonding mode is excited in the presence of an impinging electric
field having a nonzero z-component. On the other
hand, the bonding mode is excited by a nonzero electric field component
in the direction parallel to the dimer interaxis. To evidence this
aspect, we report the simulations in the case of impinging light wave
vector parallel to the symmetry plane of the dimer and consider TM
and transverse electric (TE) polarized light impinging (see corresponding
insets in Figure a).
The scattering cross sections for these two illumination conditions
are reported in Figure a (green and red lines). Clearly, it is possible to selectively excite
either the antibonding resonance with TM polarization or the bonding
resonance with TE polarization.Beside the illumination conditions,
it is also important to notice that the access to the bonding resonance
is made possible thanks to the particular slanted geometry. The tilt
angle α of the rods introduces a horizontal component in the
electronic oscillation, which enables coupling with the corresponding
exciting electric field projection. This is demonstrated in Figure c, where the scattering
cross sections for different tilting angles α are reported for
TM and TE polarized illumination. As presented in these plots, the
bonding resonance is absent in the case of α = 0 and gradually
appears with increasing α. Interestingly, the spectral location
of the antibonding resonance remains almost unaltered, and this is
the first evidence of how this resonance is only slightly dependent
on geometrical details of the dimer. A similar behavior is found when
varying the angle of aperture β between the two rods (see Supporting Information 3 for more details).While the scattering cross section presents two peaks of comparable
intensity, by looking at the absorption cross section in Figure a (blue dashed line)
a much more pronounced peak is observed in correspondence of the bonding
resonance. This is correlated to a strong field enhancement (FE) at
the rods terminations and within the gap. We address in detail this
feature of the bonding resonance by considering the case of coplanar
slanted nanorods, namely α = 30°, β = 180°,
and TE polarized light impinging with scattering plane parallel to
the dimer symmetry plane (Figure a, inset). This is the optimal condition for bonding
mode excitation, because the projection of the geometry along the
impinging field is maximized (see Supporting Information 3). All other geometrical parameters are as in Figure and in particular we consider
a 100 nm wide gap. In Figure a, the red line reports the electric FE spectrum at the center
of the gap in the case of TE polarized impinging light, exciting thus
the bonding mode. A maximum enhancement of 150 is predicted for the
electric field amplitude. To better evidence the extent of the FE
in this configuration, we consider as references a planar nanorod
dimer on silicon substrate with same gap width and metal cross sectional
area (Figure c), and
a single vertical nanorod on silver substrate (Figure e). The illumination of the two structures
is schematized in the figures. In both cases, the nanorod lengths
have been tuned in order to produce the fundamental resonance at the
same wavelength as the slanted dimer antibonding oscillation. The
black dashed and solid lines in Figure a report respectively the FE at the gap center of the
planar dimer, and the FE calculated 50 nm above the vertical rod termination
(see Figure a, inset).
As can be seen, the FE predicted for the tilted dimer largely exceeds
those calculated in the two reference structures. In particular, it
is 1 order of magnitude higher than in case of planar dimer. The electric
FE maps at resonant wavelengths in vertical cross sections, Figure b,c,e, further highlight
the very different performances of the three architectures. A maximum
electric FE of 310 is calculated at a distance of 10 nm from the rod
edge. It is interesting to further compare the FEs of the bonding
resonance of the slanted dimer with that one at antibonding resonance.
The green solid line in Figure a represents the FE in case of antibonding resonance, calculated
50 nm above one of the antenna edges, while Figure e reports the corresponding FE map at the
resonant wavelength. As can be expected, the FE in this case is comparable
to the one obtained for the single straight rod and thus much lower
than for the bonding resonance.
Figure 3
Comparison of electric (a–e) and
magnetic (f–i) properties of the slanted nanorod dimer with
reference structures. The slanted dimer geometry and illumination
considered are depicted in (a), left inset. It has the same geometrical
parameters as in Figure except for β = 180°. (a) Comparison of electric FEs spectra
for the structures (b–e). Fields are taken in representative
positions, as schematized in the legend. The red curve denotes the
field at the gap center of the slanted dimer for TE-polarized illumination
and scattering plane as depicted in the inset. The green curve is
the FE for the same structure with TM-polarized illumination and calculated
50 nm above the antenna terminations. The solid black line is the
FE in case of vertical antenna on silver substrate, calculated 50
nm above the antenna edge; the black dashed line is the FE at the
center of a planar dimer antenna on silicon substrate with gap size
of 100 nm. (f) Comparison of the maximum magnetic FE for the slanted
dimer bonding resonance (red line) with the maximum FEs in case of
a planar silver antenna on 70 nm thick silicon layer on a silver substrate.
Field maxima are calculated over the respective spatial regions shaded
with red in the schematics. (g) Surface current distributions (white
arrows and color map) and magnetic field in the middle plane (green
arrows) for the slanted dimer at bonding resonance. (h,i) Magnetic
FE maps at resonant wavelengths. The lengths of the reference structures
considered (c,e,i) have been tuned in order to resonate at the same
wavelength of the slanted antenna bonding resonance. They are 1800
nm for (c), 2450 nm for (e), and 1700 nm for (i).
Comparison of electric (a–e) and
magnetic (f–i) properties of the slanted nanorod dimer with
reference structures. The slanted dimer geometry and illumination
considered are depicted in (a), left inset. It has the same geometrical
parameters as in Figure except for β = 180°. (a) Comparison of electric FEs spectra
for the structures (b–e). Fields are taken in representative
positions, as schematized in the legend. The red curve denotes the
field at the gap center of the slanted dimer for TE-polarized illumination
and scattering plane as depicted in the inset. The green curve is
the FE for the same structure with TM-polarized illumination and calculated
50 nm above the antenna terminations. The solid black line is the
FE in case of vertical antenna on silver substrate, calculated 50
nm above the antenna edge; the black dashed line is the FE at the
center of a planar dimer antenna on silicon substrate with gap size
of 100 nm. (f) Comparison of the maximum magnetic FE for the slanted
dimer bonding resonance (red line) with the maximum FEs in case of
a planar silver antenna on 70 nm thick silicon layer on a silver substrate.
Field maxima are calculated over the respective spatial regions shaded
with red in the schematics. (g) Surface current distributions (white
arrows and color map) and magnetic field in the middle plane (green
arrows) for the slanted dimer at bonding resonance. (h,i) Magnetic
FE maps at resonant wavelengths. The lengths of the reference structures
considered (c,e,i) have been tuned in order to resonate at the same
wavelength of the slanted antenna bonding resonance. They are 1800
nm for (c), 2450 nm for (e), and 1700 nm for (i).Beside the strong electric field localization in the gap
region, we notice that our structure is expected to create also a
high magnetic field in the area subtended by the nanorods. In fact,
owing to the conductive substrate connecting the two rods, at bonding
resonance an oscillating loop current is produced, analogous to those
observed in split-ring resonators.[41] This
is shown in Figure g, where the local surface current density (white arrows and colormap)
and the resulting magnetic field in the midplane (green arrows) are
visualized (see also the Supporting Information Movie). As can be seen, the resonant dimer can then be viewed as
a magnetic dipole with magnetic dipole moment parallel to the baseplate
surface. In Figure f, the red solid line reports the maximum magnetic FE calculated
in the dimer cross section as a function of wavelength, while the
magnetic FE map at resonance is reported in Figure h. As it can be expected, the strongest H field is found close to the antenna regions presenting the
highest surface charge currents, namely at the antenna basements (compare
with Figure g). Magnetic
FE values as high as 90 are obtained. To assess the magnetic performance
of the structure, we consider one of the most studied magnetic nanoantenna
configurations, namely a planar nanorod on a dielectric-coated metallic
substrate (Figure i).[47] We assume here the dielectric to
be silicon. Geometrical details of the simulated structure are reported
in Figure caption.
By illuminating this antenna with normally impinging light polarized
along the antenna axis it is possible to excite a magnetic resonance,
thanks to the mirror symmetry provided by the metal substrate.[47] At resonance, a high magnetic field is obtained
in the silicon region between antenna and substrate. In Figure f, the black dashed and solid
black lines report respectively the maximum magnetic field in the
silicon layer and in the air superstrate as a function of wavelength,
while the field distribution at resonance is reported in Figure i. As shown in Figure f, the slanted nanorod
dimer provides a higher magnetic FE, which reaches a factor of 3 when
the maximum magnetic field in air is considered for the planar dimer.While the most interesting properties of the bonding resonance
concern field enhancements, the antibonding is interesting from the
scattering efficiency point of view, which translates into strong
diffractive coupling between nearby nanorod dimers. As introduced
above, it is important to observe that, because the nanorods scatter
as vertically oriented electric dipoles for both resonances the electric
field scattered in directions parallel to the xy plane
is necessarily polarized along z. The scattered field
is thus optimally oriented for the excitation of the antibonding resonance
in nearby dimers. By contrast, the bonding resonance cannot be diffractively
excited, because it requires an exciting field with a nonzero horizontal
component. Consequently, we expect the antibonding resonance to give
rise to much more pronounced interdimer coupling effects than the
bonding resonance.We study in detail this aspect by scattering
simulations of squared dimer arrays considering the same dimer geometrical
parameters as in the Figure caption with TM polarized illumination and scattering plane
as in Figure c. The
calculated total reflectance as a function of impinging wavelength
and array pitch is reported in Figure a.
Figure 4
(a) Simulated total reflectance of a slanted nanorod dimer
array with illumination condition as in the inset of Figure c, as a function of pitch and
wavelength. Geometrical parameters are the same reported in Figure . The bonding and
antibonding resonant wavelengths of the isolated structures are marked
with horizontal black dashed lines, while Wood–Rayleigh anomalies
are marked with white dashed lines. The insets report the E field maps in two sample
configurations. (b) SEM micrograph of a fabricated sample. (c) Cross
section of the map in (a) corresponding to the green dashed line.
(d,e) Simulated 0th order reflectance (averaged between TE and TM
polarizations) of an array with gap g = 100 nm for
three sample pitches, (d), and of an array with p = 4 μm for some values of gap g, (e). (f),
(g) Corresponding experimental reflectances.
(a) Simulated total reflectance of a slanted nanorod dimer
array with illumination condition as in the inset of Figure c, as a function of pitch and
wavelength. Geometrical parameters are the same reported in Figure . The bonding and
antibonding resonant wavelengths of the isolated structures are marked
with horizontal black dashed lines, while Wood–Rayleigh anomalies
are marked with white dashed lines. The insets report the E field maps in two sample
configurations. (b) SEM micrograph of a fabricated sample. (c) Cross
section of the map in (a) corresponding to the green dashed line.
(d,e) Simulated 0th order reflectance (averaged between TE and TM
polarizations) of an array with gap g = 100 nm for
three sample pitches, (d), and of an array with p = 4 μm for some values of gap g, (e). (f),
(g) Corresponding experimental reflectances.For reference, the spectral locations of the single-dimer
resonances are marked in the map with black dashed lines. A horizontal
resonant region, almost independent of the pitch, is evident in the
map, which is crossed by a number of narrow strongly pitch-dependent
resonances. The E field
maps in two sample configurations (insets of Figure a) reveal that the horizontal resonant region
corresponds to the bonding while the sharp dips are the antibonding
resonance. As expected, owing to the efficient scattering along the
baseplate surface, the antibonding resonance shows a strong pitch
dependence. For a given grating pitch and light impinging angle, the
in-phase superposition of the field scattered by each dimer along
the baseplate surface takes place at specific wavelengths, usually
denoted as Wood–Rayleigh (WR) anomalies.[48] They are marked with white dashed lines in Figure a and are found when the following
equation is satisfiedwith m, n being integers, k = êk0 sin(θ) is the in-plane component of
the impinging light momentum, k0 is the
vacuum light wave vector, G = ê(2π/p) are the reciprocal lattice basis vectors, and p is the pitch of the array both in x-
and y- directions. The spectral overlap of the (n,m) = (1,0) and (0,1) WR anomalies with
the broad single-dimer antibonding resonance produces the sharp Fano-like
dips observed in Figure a (sometimes called surface lattice resonances).[23,26−29,49] Analogous mechanisms of collective
resonance generation have been widely described for horizontal nanorod
arrays.[49] This phenomenon arises because
at WR anomalies one of the diffracted waves travels at a grazing angle
along the surface of the substrate and hence interacts with the nearby
array elements. From the plot reported in Figure c, corresponding to the vertical green dashed
line in Figure a,
we observe that the Fano resonance quality factor can be as large
as 100. By optimizing the grating pitch and illumination conditions,
this value can be further raised up to 390 (see Supporting Information 4), which is almost an order of magnitude
higher than the typical Q-factors reported in case
of horizontal plasmonic nanorod arrays at mid-infrared wavelengths
(of the order of tens).[49−51] Indeed, as already mentioned,
when light impinges on planar nanorods it is mainly back scattered
or transmitted into the substrate, as expected from a classical dipole
that oscillates in the substrate plane and therefore emits out of
the plane (normally to the direction the oscillation). This results
in a relatively poor diffractive coupling efficiency, taking place
only along the direction normal to the planar nanorod axis. By contrast,
the depth of the spectral dips found in 3D resonators evidences the
efficient coupling in this configuration, while the presence of features
along both (0,1) and (1,0) anomalies demonstrates that this coupling
takes place isotropically along the substrate surface.For what
concerns the bonding resonance, we notice in Figure a that the only nontrivial reflectance variations
as a function of the grating
pitch correspond to the crossing points with the antibonding resonances.
In these configurations the scattered field produced by the bonding
resonance can excite the antibonding one, opening a channel of diffractive
coupling between the dimers. Far from the crossing points, as expected,
the bonding reflectance dip does not depend on the grating pitch,
and its spectral location is almost identical to that one of the insulated
dimer. This reveals the inherent intradimer character of this resonance.The different intercoupling behaviors of the two resonances have
been experimentally verified. Figure d,f reports respectively the simulated and measured
reflectance spectra of nanorod arrays with g = 100
nm and different pitches. As can be seen, an excellent agreement between
simulated and measured spectral dip locations is found. It can be
noticed, however, that the experimental bonding resonance dips result
broader and less pronounced than the simulated ones. This effect can
be ascribed to the different sensitivity of the two resonances to
the geometrical details of the unitary cell. At the bonding resonance
in particular, the opposite sign of the charges on the two nanorod
terminations yields a strong capacitive coupling, resulting in a marked
dependence on the gap size. This is shown in Figure e,g, in which we report respectively the
simulated and experimental reflectance for arrays with fixed pitch
of 4 μm and different gaps. As can be expected, the gap dependence
of the resonant wavelength becomes stronger with decreasing of the
gap size due to an increased near field coupling. For larger gap sizes
(>500 nm) the dip stabilizes at a fixed wavelength. The reason
why the bonding dips appear generally broader and shallower than the
simulated ones is explained by considering the experimental fabrication
error in realizing a monodispersed gap size within a nanorod array,
which has, in our case, a variability of ±10 nm. The resulting
reflectance dip is thus an average and is consequently smeared out.By contrast, the antibonding resonance appears almost totally insensitive
to the gap size. Moreover, the grating pitch is experimentally controlled
with a higher precision. This explains the good agreement between
experiment and simulations for the corresponding reflectance dip.Figure , panels d,f
and e,g, shows that we can almost independently tune the spectral
location of the two resonances by tuning different geometrical parameters:
gap size for the bonding resonance and grating pitch for the antibonding
resonance. This can be useful in practical applications of the presented
structure, allowing an easy engineering of the resonant spectrum according
to the particular needs. Furthermore, by properly tuning the parameters
one can spectrally overlap bonding and antibonding resonances, and
the spectral location of the crossing point can itself be tuned.In conclusion, we numerically and experimentally investigated the
optical properties of high-aspect-ratio out-of-plane metallic slanted
nanorod dimers standing on a metallic substrate. The proposed architecture
mimics a 3D split-ring resonator with nanometric gap. We showed that
the tiny gap between the nanorods enables a strong near-field coupling
between the rods, resulting in the splitting of the single rod resonance
into two hybrid dimer modes, bonding and antibonding. The tilt of
the structure on the other hand is shown to be the key feature enabling
the excitation of the bonding resonance of the structure by far-field
illumination. This resonance yields both remarkable electric field
enhancements at the nanorods terminations (a factor 310 calculated
at 10 nm from the nanorods edge) and magnetic-field enhancements at
the nanorod basement (a factor 90). The antibonding resonance, instead,
is characterized by an efficient lateral scattering of light, yielding
a strong interdimer interaction, which is shown to produce high-quality-factor
collective resonances (up to Q = 390). A final valuable
feature of the proposed structure is the possibility to freely tune
the resonance wavelengths as a function of different geometrical parameters
(gap size for the bonding, array pitch for the antibonding resonance).
This property can be particularly important for sensing applications
in which the resonance of the structure has to be tuned to those ones
of the target molecule. In Supporting Information 5, we report experimental evidence that molecules of interest can
be deposited onto the slanted nanorods terminations without damaging
the architecture itself, provided a proper deposition process and/or
a suitable nanorods geometry are chosen.Several interesting
applications can be envisaged for the presented structure. In fact,
the electric and magnetic hot spots as well as the efficient diffractive
interdimer coupling can be smartly associated with other interesting
morphological properties of this full-3D architecture, such as the
hollow cores of the nanorods, which may be exploited as nanochannels
for molecule injection in microfluidic chips, or the presence of a
suspended nanogap, which may enable to study the optical properties
of target molecules placed on its boundary surfaces without any kind
of influence from the substrate This may pave the way to the development
of extremely compact multifunctional biosensing platforms, combining
optical-based functionalities with micro- and nanoparticle trapping,
microfluidics, and electrical probing.[43,52]
Authors: Stefan Linden; Christian Enkrich; Martin Wegener; Jiangfeng Zhou; Thomas Koschny; Costas M Soukoulis Journal: Science Date: 2004-11-19 Impact factor: 47.728
Authors: Francesco De Angelis; Mario Malerba; Maddalena Patrini; Ermanno Miele; Gobind Das; Andrea Toma; Remo Proietti Zaccaria; Enzo Di Fabrizio Journal: Nano Lett Date: 2013-07-09 Impact factor: 11.189
Authors: Vincenzo Giannini; Yan Francescato; Hemmel Amrania; Chris C Phillips; Stefan A Maier Journal: Nano Lett Date: 2011-06-03 Impact factor: 11.189
Authors: Manuela Oliverio; Sara Perotto; Gabriele C Messina; Laura Lovato; Francesco De Angelis Journal: ACS Appl Mater Interfaces Date: 2017-08-24 Impact factor: 9.229
Authors: Xuejing Wang; Jie Jian; Susana Diaz-Amaya; Cindy E Kumah; Ping Lu; Jijie Huang; Daw Gen Lim; Vilas G Pol; Jeffrey P Youngblood; Alexandra Boltasseva; Lia A Stanciu; Deirdre M O'Carroll; Xinghang Zhang; Haiyan Wang Journal: Nanoscale Adv Date: 2018-11-27
Authors: Andrea Jacassi; Angelo Bozzola; Pierfrancesco Zilio; Francesco Tantussi; Francesco De Angelis Journal: Sci Rep Date: 2016-06-27 Impact factor: 4.379