Adv 032134

Collective plasmon modes in a compositionally asymmetric nanoparticle dimer
Fuyi Chen, Negash Alemu, and Roy L. Johnston Citation: AIP Advances 1, 032134 (2011); doi: 10.1063/1.3628346 View online: http://dx.doi.org/10.1063/1.3628346 View Table of Contents: http://aipadvances.aip.org/resource/1/AAIDBI/v1/i3 Published by the AIP Publishing LLC.
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AIP ADVANCES 1, 032134 (2011)
Collective plasmon modes in a compositionally asymmetric nanoparticle dimer

Fuyi Chen,1,a Negash Alemu,1 and Roy L. Johnston2,b
1
State Key Laboratory of Solidication Processing, Northwestern Polytechnic University, Xian, 710072, P. R. China 2 School of Chemistry, University of Birmingham, Birmingham, B15 2TT, U. K. (Received 26 May 2011; accepted 28 July 2011; published online 11 August 2011)
The plasmon coupling phenomenon of heterodimers composed of silver, gold and copper nanoparticles of 60 nm in size and spherical in shape were studied theoretically within the scattered eld formulation framework. In-phase dipole coupled -modes were observed for the Ag-Au and Ag-Cu heterodimers, and an antiphase dipole coupled -mode was observed for the Ag-Au heterodimer. These observations agree well with the plasmon hybridization theory. However, quadrupole coupled modes dominate the high energy wavelength range from 357-443 nm in the scattering cross section of the D=60 nm Ag-Au and Ag-Cu heterodimer. We demonstrate for the rst time that collective plasmon modes in a compositionally asymmetric nanoparticle dimer have to be predicted from the dipole-dipole approximation of plasmon hybridization theory together with the interband transition effect of the constitutive metals and the retardation effect of the nanoparticle size. Copyright 2011 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. [doi:10.1063/1.3628346]
I. INTRODUCTION
The optical properties of individual metal nanoparticles are dominated by their localized surface plasmon resonances (LSPR), which are associated with the collective coherent oscillation of conduction electrons in metallic nanostructures.1 The electromagnetic eld surrounding a metallic nanoparticle that has been excited near the plasmon resonance can extend for a considerable distance, and a compelling analogy therefore exists between the plasmon resonance of individual nanoparticles and the wave functions of simple atoms. Similar to the roles of atoms in molecules and solids, metal nanoparticles can assemble to create a diverse range of new plasmonic nanoclusters,2 including dimers,3 trimers,4 quadrumers5 and tetramers,6 etc.7 Each type of plasmonic nanocluster exhibits its own unique set of collective plasmon modes. The simplest description of collective plasmon modes is the dipoledipole interaction during the coupling of two nearby oscillators. For two adjacent metallic spheres a lower-energy resonance corresponds to two longitudinally aligned dipoles giving rise to a strong red-shifted absorption peak in the optical spectrum. For the higher energy resonance the coupled dipoles cancel each other, resulting in a resonance with essentially a zero net dipole moment that does not interact with incident light and does not appear in the optical absorption spectrum of the particle pair. Depending on the nanoparticle size and interparticle distance, higher-order multipoles can also play an important role in collective plasmon modes.8 It is striking that the simplest description of collective plasmon modes, the dipoledipole interaction has resulted in a substantial understanding of a rich array of new electromagnetic
a Email: fuyichen@nwpu.edu.cn b Email: r.l.johnston@bham.ac.uk
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properties, such as subradiant (dark) plasmonic modes,9 Fano resonances,10 optical nanodiodes,11 electromagnetically induced transparency12 and, in particular, the magnetic response,13 which is excited by the antisymmetric plasmonic resonance in various arrays of nanoparticle pairs such as in metal nanostrip dimers,14, 15 nanodisk dimers,16, 17 and metal plate pairs.18, 19 Symmetry breaking in collective plasmon modes can introduce effects that are not present in the symmetrical congurations. Recently, these effects that come from the coupling between the otherwise uncoupled plasmon modes of the system were investigated using compositionally asymmetric nanoparticle dimers.2023 For example, Fano-type absorption line proles were observed in the absorption spectra of the gold nanoparticles because of an interaction between the discrete local plasmon resonance of silver and the interband transition of gold in a D=10 nm Au-Ag heterodimer with an interparticle distance of 3 nm.20 The two plasmonic resonances exhibit a simultaneous shift for the D=30 nm Au-Ag heterodimer, and this is in contrast to the homodimer.21 Anomalous red-shifts of the antibonding modes were observed with respect to the silver local plasmon resonance mode in the scattering spectra of the heterodimer composed of a 30 nm silver and a 40 nm gold nanoparticle, and this was induced by the coupling of silver particle plasmon resonance to the continuum of the interband transitions in gold.22 The Fano resonance has only been induced by the longitudinal component of the heterodimer surface plasmon resonance in a heterodimer composed of a 10 nm silver and a 30 nm gold nanoparticle.23 Despite this intense research, neither the dipolar eigenmodes nor the induced charge conguration of plasmonic resonance have been addressed in these recent heterodimers,2023 which indicates that the interaction between the strongly coupled heterodimer is not as completely understood as in the homodimer. Therefore, a systematic study of the collective plasmon modes in the heterodimer is required, as it may result in a new theoretical paradigm and a host of novel applications. We studied a D=60 nm Ag-Au and a D=60 nm Ag-Cu nanoparticle heterodimer under different interparticle separations (1-15 nm) and variable polarizer angles (0-90 ) as prototype systems. We found that the longitudinal coupling between the nanoparticles shows a strong dependence on the size of the dimer gap in the Ag-Au and Ag-Cu heterodimers. We demonstrate for the rst time that a quadrupole-coupled mode emerges in the Ag-Au heterodimers and dominates the scattering spectra of the Ag-Cu heterodimers. An antiphase dipole-coupled mode was observed with low intensity in the Ag-Au heterodimer; this conguration of two stacked antiphased nanoparticles is known as magnetic resonance, and is essential for the development of negative refractive index materials in the visible region of the spectrum.
II. METHODOLOGY
The extinction spectra and electromagnetic eld distribution of the nanoparticle dimers were calculated using the nite difference time domain (FDTD) method. Three-dimensional vector Maxwell equations in the different nanostructures were solved within the scattered eld formulation framework. The FDTD calculations with a ner grid for the elected distances revealed the plasmon hybridization mode in almost perfect agreement with Mie theory for spheres. The surface charge distributions that were induced on the nanoparticle proles were evaluated using the calculated electromagnetic elds. The dimer was formed by identical spherical nanoparticles whose surfaces are separated by a distances gap, ranging from one half of sphere radius a down to conductive touching with gap=-3 nm. Here, we consider spheres with a diameter of 60 nm. The dielectric functions were described using the tabulated empirical data of Johnson and Christy with a linear interpolation for pure copper, silver and gold.24 The dimer without a substrate was embedded in an air medium surrounded by a perfectly matched layer. The distance was a full wavelength from the nanoparticles to avoid spurious reections and to avoid absorbing the energy of evanescent elds. A total-eld scattered-eld plane wave, which was used for excitation, was inserted on the inside of the perfectly matched layers near the air medium interface. The studied model was discretized by a conformal mesh method with a side length of 0.1 nm in the dimers.
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III. RESULTS AND DISCUSSION A. Ag-Ag nanoparticle homodimer
We start with a simple homodimer and show the calculated scattering spectra of a D=60 nm silver nanoparticle homodimer in vacuum as a function of the polarization angle in Fig. 1(a), including parallel (black curve) and perpendicular (red curve) incident polarization with respect to the dimer axis in Fig. 1(b). These results clearly illustrate that only the longitudinal resonance mode (L) is present in the scattering spectrum when the polarizer is oriented along the interparticle axis and the L-mode results from the longitudinal LSPR coupling of the particle plasmons and displays two distinct peaks. The lower energy peak is present at 464 nm and the higher energy peak is at 357 nm. When the polarizer is oriented perpendicular to the interparticle axis only the transverse resonance mode (T) contribution is observed at 364 nm, because of transverse LSPR coupling. At all the intermediate angular orientations the scattering spectra show L- and Torthogonal modes and a clear isosbestic point is present near 412 nm in the spectrum. In Fig. 1(b), a 60 nm isolated silver nanoparticle shows dipole resonance ( ) at 378 nm. By comparison with the single particle resonance ( ) the lower energy L-mode has a longer wavelength and a stronger intensity and the T-mode is slightly blue shifted and lower in intensity. Figure 1(c) shows the calculated scattering spectra of a D=60 nm silver nanoparticle homodimer in vacuum as a function of interparticle separations under longitudinal polarization. For an interparticle separation larger than 9 nm, only lower energy L-modes are present and observed to red-shift signicantly from 411 nm at a 15 nm gap to 505 nm at a 1 nm gap. For an interparticle separation smaller than 9 nm the scattering peak splits into two well-dened peaks and the higher energy L-mode (at 357 nm in Fig. 1(b)) is spectrally separated from the lower energy L-mode by a pronounced dip. This phenomenon is the result of strong longitudinal SPR coupling, and indicates that the electromagnetic interaction between the nanoparticles is far more signicant for an interparticle separation smaller than 9 nm. These higher energy L-modes have been observed to red-shift slightly with a decrease in the interparticle separation, which agrees with previous studies on nanoparticle dimer arrays.25, 26 Figure 2 shows the electric-eld intensity and the surface charge distribution prole for the Lmode and the T-mode in a D=60 nm silver nanoparticle homodimer. As expected, the electric eld intensity is enhanced at the junction of the Ag-Ag homodimer for both the lower energy and the high energy L-mode; however, the local charges exhibit a dipole-dipole (DD) pattern for the lower energy L-mode (464 nm) and a quadrupole-quadrupole (QQ) pattern for the high energy L-mode (357 nm). For the T-mode at 364 nm the electric eld intensity is localized around the silver nanoparticle, i.e., the nonjunction ends of the Ag-Ag homodimer and the local charges exhibit a dipole-dipole (DD) pattern. For the dipole-dipole L-mode and the dipole-dipole T-mode the charges conned to the same edge of the nanoparticle have the same sign, which indicates that these dipole-dipole modes are in-phase collective plasmon modes. Therefore, the bonding-mode ( ) and antibonding-mode ( *) can be assigned as for the dipole-dipole L-mode and the dipole-dipole T-mode, respectively, from the classication frame of the plasmon hybridization model.27 The quadrupole-quadrupole L-mode is associated with the spectral superposition of higher order longitudinal resonance modes, and its main contribution comes from the quadrupole plasmon resonance of an individual silver particle.25, 26 The collective plasmon modes can also be classied as bright and dark modes for the complex nanostructures that consist of multiple closely spaced nanoparticles or patterned nanoholes. As shown in Fig. 2, the quadrupole-quadrupole L-mode, the dipole-dipole L-mode and the dipoledipole T-mode possess nite net dipole moments, and these plasmonic modes are bright plasmonic modes, which are efciently excited by incident light and are clearly visible in the optical spectrum. The quadrupole-quadrupole L-mode is not bright for an interparticle separation bigger than 9 nm in the homodimer.
B. Ag-Au nanoparticle heterodimer
Dark plasmonic modes possess a zero net dipole moment and do not couple to light, and are therefore not very prominent in optical spectra. To enhance the manifestation of dark plasmonic
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FIG. 1. Scattering spectra for the D=60 nm silver nanoparticle homodimer as a function of the polarization angle with interparticle separations of 3 nm (a). Scattering spectra under longitudinal and transverse polarization with respect to a 60 nm isolated silver nanoparticle (b), and as a function of interparticle separations under a polarizer angle of 0 degrees (c).
modes we introduced compositional asymmetry in the collective plasmon modes, and can therefore discuss the optical properties of a D=60 nm silver and gold nanoparticle heterodimer. In Fig. 3(a) and 3(b) we show the calculated scattering spectra of the Ag-Au nanoparticle heterodimer as a function of the polarization angle (0-90 ) and the two extreme cases for orthogonal polarization, respectively. Following the identication of the L- and T- plasmon modes in homodimers similar mode can be assigned as the Ag-Au heterodimer. Figure 3(a) and 3(b) shows that the Ag-Au heterodimer supports the higher energy L-mode at 410 nm, the lower energy L-mode at 545 nm under longitudinal polarization (0 ), the higher energy T-modes at 373 nm and the lower energy T-mode at 527 nm under transverse polarization (90 ). The primitive or unhybridized mode of
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FIG. 2. Electric near-eld proles and surface charge distributions in a D=60 nm silver nanoparticle homodimer for longitudinal and transverse resonance modes.
the isolated 60 nm silver nanoparticle ( 1 ) and the isolated 60 nm gold nanoparticle ( 2 ) are at 379 and 531 nm, respectively. This result is quite different from the D=60 nm Ag-Ag homodimer, where only two or three bright modes exist. The scattering spectra in Fig. 3(a) and 3(b) show four bright modes at 410 nm (L-mode), 545 nm (L-mode), 373 nm (T-mode) and 527 nm (T-mode). Figure 3(c) shows calculated scattering spectra as a function of interparticle separation under longitudinal polarization for a D=60 nm silver and gold nanoparticle heterodimer. Both the lower energy L-mode at 545 nm and the high energy L-mode at 410 nm were observed to red-shift signicantly with a decrease in the interparticle separation although the high energy L-mode changes from a peak to a at shoulder in the scattering spectra for interparticle separations smaller than 9 nm. The L-mode is a bonding-mode where a large portion of the electric eld experiences a modied dielectric environment and increases with a decrease in interparticle separation. In Figure 4, we calculated the surface charge distribution for four bright modes in a D=60 nm silver and gold nanoparticle heterodimer. The high energy L-mode at 410 nm and the lower energy L-mode at 545 nm, similar to that of the D=60 nm Ag-Ag homodimer, gave an enhanced electric eld intensity at the junction of the dimer and revealed a quadrupole-quadrupole (QQ) mode and a dipole-dipole (DD) mode in the surface charge pattern, respectively. The dipole-dipole L-mode at 545 nm is a bonding-mode ( ) in the plasmon hybridization model like that in the D=60 nm Ag-Ag homodimer. The high energy T-mode at 373 nm and the lower energy T-mode at 527 nm are new collective plasmonic modes for the Au-Ag heterodimer, which exhibits a dipole-quadrupole (DQ) mode and a dipole-dipole (DD) mode in the surface charge pattern. Judging from the signs of the charges conned to the nanoparticle edge the dipole-dipole T-mode at 527 nm is an out-of-phase collective plasmon mode of the individual silver plasmons ( 1 ) and the gold plasmons ( 2 ). It is important to note that the lower energy T-mode at 527 nm, which is an otherwise dark mode in the symmetric dimer, is clearly visible in the optical spectrum in the Au-Ag heterodimer, and can be assigned as a bonding-mode ( ) from the classication frame of the plasmon hybridization model. For the higher energy T-mode at 373 nm the electric eld intensity is localized around the silver nanoparticle of the D=60 nm Ag-Au heterodimer and the surface charge in the Ag nanoparticle exhibits a dipolar pattern while the surface charge in the Au nanoparticle exhibits a quadrupolar
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FIG. 3. Scattering spectra for a heterodimer of a D=60 nm silver and gold nanoparticle heterodimer as a function of the polarization angle with interparticle separations of 3 nm (a). Scattering spectra under longitudinal and transverse polarization with respect to the normalized scattering spectra for a 60 nm isolated silver and gold nanoparticle (b), and as a function of interparticle separations at a polarizer angle of 0 degrees (c).
pattern. The charges conned to the Au nanoparticle have a + sign in the left half-sphere and this is opposite to the Ag neighbor nanoparticle and the - sign in the right half-sphere indicating that the quadrupolar charge pattern in the Au nanoparticle is induced by the electric eld from the nearby Ag nanoparticle. As shown in Figure 4, the quadrupole-quadrupole (QQ) L-mode at 410 nm, the dipole-dipole (DD) L-mode at 545 nm, the dipole-quadrupole (DQ) T-mode at 373 nm and the dipole-dipole (DD) T-mode at 527 nm have a nonzero electric dipole moment and can be excited by an incident plane
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FIG. 4. Electric near-eld proles and surface charge distributions in a D=60 nm sliver and gold nanoparticle heterodimer for longitudinal and transverse resonance modes.
wave. The dipole-dipole (DD) T-mode or the -mode at 527 nm dipole are active, because of the incomplete cancellation of the dipoles of the silver and gold particles in the Au-Ag heterodimer.
C. Ag-Cu nanoparticle heterodimer
As another example of a nanoparticle heterodimer, we obtained the optical properties of a D= 60 nm silver and copper nanoparticle heterodimer. The calculated scattering spectra of the heterodimer are shown in Fig. 5(a) as a function of the polarization angle. The extreme cases for the longitudinal and transverse polarization are plotted in Fig. 5(b). Similar to the 60 nm silver particle homodimer, scattering from the longitudinal polarization has a higher energy L-mode at 443 nm and a lower energy L-mode at 575 nm. Scattering from transverse polarization has a T-mode at 373 nm. Figure 5(c) shows the calculated scattering spectra as a function of interparticle separation under longitudinal polarization for a D=60 nm silver and copper nanoparticle heterodimer. The higher energy L-mode gave a signicant red-shift with a decrease in interparticle separation and it splits into two well-dened scattering peaks for interparticle separations smaller than 2 nm. Lower energy L-modes were clearly observed for interparticle separations smaller than 5 nm and these redshift slightly with a decrease in interparticle separation and they have a lower scattering intensity compared to the higher energy L-mode. Figure 6 shows the electric eld intensity and the surface charge distribution prole for the higher energy L-mode at 443 nm, the lower energy L-mode at 575 nm and the T-mode at 373 nm in a D=60 nm silver and copper nanoparticle heterodimer. As expected, the electric eld intensity is enhanced at the junction of the Ag-Cu heterodimer for the higher energy L-mode and the lower energy L-mode. The surface charge congurations exhibit a dipole-dipole (DD) pattern for the lower energy L-mode and a quadrupole-quadrupole (QQ) pattern for the higher energy L-mode. The charges conned to the same edge of the nanoparticle show the same sign for the lower energy L-mode and the opposite sign for the higher energy L-mode. This indicates that the lower energy L-mode is an in-phase collective plasmonic mode and the higher energy L-mode is an out-of-phase collective plasmonic mode. The lower energy dipole-dipole L-mode for these modes at 575 nm is a bonding-mode ( ) in the classication frame of the plasmon hybridization model. Compared to collective plasmonic modes in the Ag-Au heterodimer the higher energy quadrupole-quadrupole (QQ) L-mode is more prominent in the scattering spectra of the Ag-Cu heterodimer. The Ag-Cu heterodimer supports only one T-mode at 373 nm, which is almost the same as the T-mode at 373 nm in the Ag-Au heterodimer, which is a dipole-quadrupole (DQ)
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FIG. 5. Scattering spectra for a D=60 nm sliver and copper nanoparticle heterodimer as a function of the polarization angle with interparticle separations of 3 nm (a). Scattering spectra under longitudinal and transverse polarization with respect to the normalized scattering spectra for a 60 nm isolated copper nanoparticle (b), and as a function of interparticle separations from 1 nm to 15 nm under a polarizer angle of 0 degrees (c).
collective plasmonic mode. The quadrupole charge pattern in the copper nanoparticle is due to phase retardation effects of the Ag nanoparticles and not from the LSPR coupling of the gold particle plasmons.
D. The dipole-dipole approximation of the plasmon hybridization model
According to the well-established model of plasmon hybridization introduced by Nordlander and Halas,27, 28 it is sufcient to consider a longitudinal or transverse interaction for simple geometries.
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FIG. 6. Electric near-eld proles and surface charge distributions in a D=60 nm silver and copper nanoparticle heterodimer for longitudinal and transverse resonance modes.
FIG. 7. Dipole-dipole interaction model from the rst approximation of the hybridization model. A level scheme of two coupled dipoles are shown where the bright mode is red and the dark mode is black (middle) while the surface charge distributions in the dimer under longitudinal coupling (left) and transverse coupling (right) are also shown.
We set up a dipoledipole interaction model as a rst approximation of the plasmon hybridization model, as shown in Fig. 7, and the collective plasmon modes can be viewed as bonding and antibonding linear combinations of primitive plasmons in molecular orbital theory. The individual nanosphere plasmon modes ( 1 and 2 ) of two interacting metal nanoparticles hybridize either in-phase ( 1 + 2 ) or out-of-phase ( 1 2 ). Under longitudinal polarization the in-phase combination reects a bonding mode and the out-of-phase mode represents an antibonding conguration, respectively denoted and *.29 When the polarization is transverse the in-phase combination is an antibonding mode ( *) and the out-of-phase mode is a bond mode ( ).29
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1. D=60 nm Ag-Ag homodimer
In a D=60 nm Ag-Ag homodimer (Figs. 1 and 2) the low-energy L-mode at 464 nm is a -mode with its electric eld strongly localized at the junction of the dimer and the only T-mode at 364 nm is a *-mode. Both of these modes are bright in-phase modes. However, the antiphase mode was not observed in the Ag-Ag homodimer. These results agree with the dipole-dipole approximation of the plasmon hybridization model where the antiphase mode is spectrally dark, because of the cancellation of the equal but oppositely oriented dipoles on the two particles. Therefore, the homodimer structure under longitudinal polarization supports only a bonding plasmon mode ( ) and the homodimer under transverse polarization supports only an antibonding *-mode. It is important to note that the high-energy L-mode at 357 nm, as observed in the D=60 nm Ag-Ag homodimer, is a quadrupolequadrupole (QQ) mode.
2. D=60 nm Ag-Au heterodimer
In the D=60 nm Ag-Au heterodimer (Figs. 3 and 4), the lower energy L-mode at 545 nm is a bonding -mode and a bright in-phase mode, while the lower energy T-mode at 527 nm is a bonding -mode and an otherwise dark antiphase mode. The high energy L-mode at 410 nm is a bonding quadrupole-quadrupole (QQ) mode and the high energy T-mode at 373 nm is a dipole-quadrupole (DQ) mode. The Ag-Au heterodimer does not support the antibonding *-mode and the *-mode. These are not the expected results, because the heterodimer is expected to support all the bonding and antibonding modes at the same time because of its broken symmetry. This is in striking contrast to previous work on a D=40 nm Ag-Au heterodimer, which show that it is possible to excite all four bonding and antibonding modes through the preparation of compositionally asymmetric dimers.22 While the in-phase *-mode is a bright mode as observed in the D=60 nm Ag-Ag homodimer, the absence of * in the D=60 nm Ag-Au heterodimer is not just due to its antibonding property. The magnitude of the coupling of the anti-bonding mode to external light will depend on the net dimer dipole. The anti-bonding mode has zero dipole moment in homodimer, which does not give rise to a sufciently large cross section to be seen in the extinction spectra. By reducing the symmetry, the anti-bonding mode for a heterodimer has a non-zero dipole moment because of the asymmetry in composition, as in this study. Though it interacts more weakly with light than the bonding dimer mode, the anti-bonding heterodimer mode gains intensity and eventually is seen in the extinction spectra. In this sense, both antiphase * and modes have similar magnitudes of coupling to light. The * and *-modes are absence in the D=60 nm Ag-Au heterodimer. The proposed reason is that the high-energy antibonding *-mode and the *-mode are blue-shifted with respect to the LSPR of the isolated gold nanoparticles ( 2 ), and then they are typically located near the ultraviolet (UV) region, are damped by the interband transitions of the gold nanoparticles, and appear as dark modes in the heterodimer. Theoretically, noble metal nanoparticles (Cu, Ag & Au) attract signicant attention because they can support localized surface plasmon resonances in the ultraviolet, visible, and near-infrared regions of the spectrum depending on internal and external effects. The optical properties of these metal nanoparticles originate not only from the coherent oscillation of conduction electrons but also from optical excitation of an electron from an occupied state in the valence band to an unoccupied state in the conduction band, which is known as an interband transition. In view of this electronic structure theory,1 it is very important to consider the interaction of electronic interband transitions with individual plasmon resonances or coupled plasmon modes. According to the model of plasmon hybridization, there are two plasmon modes under longitudinal polarization, namely a low energy in-phase bonding mode and a high energy out of phase anti-bonding mode. Generally, the low energy bonding mode is located at visible or near infrared wavelengths, while the higher energy anti-bonding mode is positioned near the ultraviolet region. Since the anti-bonding mode shows small net dipole moment, the strength of its interaction with light is also weak and it may be obscured by the interband transitions in the metal. The antiphase -mode in a D=60 nm Ag-Au heterodimer is an important result in this study, because its antisymmetric plasmonic resonance may be used to excite the magnetic response13
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in various arrays of nanoparticle pairs. We conrm that this antiphase mode occurs in Ag-Au heterodimers for a diameter range of 40-60 nm and a separation range of 1-3 nm.
3. D=60 nm Ag-Cu heterodimer
In the D=60 nm Ag-Cu heterodimer (Figs. 5 and 6) the lower energy L-mode at 575 nm is a bonding -mode and a bright in-phase mode, the high energy L-mode at 443 nm is a bonding quadrupole-quadrupole (QQ) mode and the high energy T-mode at 373 nm is a dipole-quadrupole (DQ) mode. The Ag-Cu heterodimer does not support a *-mode, a *-mode or even a -mode as this is not expected for the heterodimer. Similar to the Ag-Au heterodimer, a possible reason is that both the high energy */ *-mode and the low energy -mode are diminished by the interband transitions of copper nanoparticles and appear as dark modes in the heterodimer. The electronic interband transitions of the metals are electronic transitions from the energetically deeper valence band into the conduction band, which forms a steep absorption edge starting at the threshold frequency, where all plasmon resonance diminishes dramatically. The threshold energies are 3.8 eV (326 nm), 2.5 eV (500 nm) and 2.1 eV (590 nm) for pure Ag, pure Au and pure Cu, respectively. By comparing the collective plasmon modes of the 60 nm Ag-Au heterodimer with that of the 60 nm Ag-Cu heterodimer there is tendency that the low interband transition energies of the constitutive metals causes the low energy -mode and the two high energy antibonding modes to be diminished by the interband transitions of the copper nanoparticles, and this causes the lowest energy -mode to be visible in the Ag-Cu heterodimers. Compared to previous studies into the D=40 nm Ag-Au heterodimer,22 the high energy collective plasmon modes are governed by the quadrupole moment in the two 60 nm Ag-Au (Cu) heterodimers from 357-443 nm. Although resonant excitation of larger spherical particles gives rise to broad extinction spectra with signicant contributions from high-order multipole modes, for the silver particle of size D=60 nm in this study the quadrupole absorption components were not able to be isolated form the dipole scattering for Ag-Au (Cu) heterodimers. The proposed reason is a retardation (nite size) effect, which is also found in the larger homodimer, as shown in the quadrupole-quadrupole L-mode in the D=60 nm Ag-Ag homodimer. The retardation effect becomes more apparent in larger nanostructures with respect to the spatial wavelength of the light at the plasmon resonance and the onset of higher ordered multipolar resonance modes strongly inuences and even shadows the position of the anti-bonding resonance. In this study, a quadrupole-coupled mode emerges for the D=60 nm Ag-Au nanoparticle heterodimer at interparticle separations smaller than 9 nm, and it is prominent in the D=60 nm Ag-Cu nanoparticle heterodimer while it has the highest scattering intensity for all the investigated interparticle gap separations and polarizer angles. In general, the optical properties of coupled plasmonic particles can be systematically modeled and studied in to two regimes depending on the overall size of the system. When the size of the hybridized system is smaller than the plasmon wavelength, the coupled plasmonic system can be modeled under the quasi-static (dipole) limit, thus retardation effect can be neglected. However, when the dimension of the coupled system is greater than the incident wavelength the quasistatic approximation is no longer applicable (results in signicant error) because of retardation effects. Therefore, it is desirable to consider retardation, which is the effect of the phase difference between the elds propagating from two different regions of the nanoparticle, during the study of large size coupled plasmons to obtain reasonable and accurate optical properties for the given system. In the quasi-static regime, we get a constant resonant frequency independent of particle dimensions or retardation effects, if the bulk dielectric is used the size effect in the quasi-static regime comes from the dependence of the permittivity on the nanoparticle size because of quantum connement. For nanoparticles which are large in size, as in our case, the quantum connement or size dependence of dielectric coefcients becomes negligible and the role of retardation effect comes to play and higher order multipolar resonance modes begin to be observed. Therefore, the appearance of higher order multipolar modes is due to retardation or nite size effect.
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FIG. 8. Scattering spectra calculated for varying dimer separation and conductive overlap for the silver-gold heterodimer.
E. Effects of conductive contact on the collective plasmon modes
In real experiments, a molecular layer of surfactant molecules used in the self-assemble may actually wet the particle surface. The gap between the heterodimers Au-Ag and Ag-Cu is probably governed by the size of the molecular species and is expected to keep the nanoparticles 2-3 nm apart, however, conductive contact can still occur at localized points, especially if the coating is uneven and considering that the molecules on the nanoparticle surface can rearrange. These issues are especially signicant for correlating simulations with experiments while even high resolution TEM only yields a 2-D projection of 3-D objects, thereby obscuring important topographical and structural details. Figure 8 shows the scattering spectra calculated for varying dimer separation and conductive overlap for the silver-gold heterodimer. The accompanying near-eld plots and surface charge distributions corresponding to selected separation and wavelength points are shown in Figure 9. As the gap decreases from 3 to 0 nm, the spherical nanoparticles begin to make conductive contact at a single point: the 545 nm peak corresponding to the dipole-dipole (DD) coupled plasmon mode splits into two modes, i.e., a DD coupled mode at 554 nm and a new infrared dipole-dipole (DD) coupled mode at the 1128 nm peak, respectively. The 410 nm peak corresponding to the quadrupolequadrupole (QQ) coupled plasmon mode splits into two modes, one red shifts from 410 nm to a quadrupole-quadrupole (QQ) coupled mode at 414 nm, the other blue shifts from 410 nm to a quadrupole-dipole (QD) coupled mode at 384 nm. With increasing conductive overlap from 0 to -3 nm, the infrared dipole-dipole (DD) coupled mode at 1128 nm blue shifts to a dipole nanorod mode at 772 nm and a new coupled mode appears at 364 nm due to retardation effects. However, the dipole-dipole (DD) coupled mode at 554 nm, the high-order multipolar quadrupole -dipole (QD) at 384 nm and quadrupole-quadrupole (QQ) at 414 nm coupled modes disappear in the new scattering spectrum with gap=-3 nm, in part, due to mode decoupling. Figure 9 shows the electric near-eld proles and surface charge distributions in a D= 60 nm sliver-gold nanoparticle heterodimer at selected wavelengths with gap = 3nm, 0 nm and -3 nm. Obviously, oscillations driven by external light in electrically separated particles must respect
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FIG. 9. Electric near-eld proles and the surface charge distributions for neighboring silver and gold spheres with their separation gap=-3 nm, 0 nm and 3 nm, the wavelength corresponding to selected points of Fig. 8. For the dimer with gap= 3 nm, the near-eld maps at = 1288 nm is also calculated before the single point contact to check conductive effects, the near-eld maps at = 410 nm is not plotted here and it is same to the prole in Fig. 4.
charge neutrality within each particle. In the near-eld maps of the dipole-dipole (DD) coupled mode of the Ag-Au dimer with gap= 3 nm at = 1288 nm, the charge pileup in each particle near the gap region has a spatial width along the sphere surface that is compensated by a smooth distribution of the opposite charge along the rest of the sphere surface. Because intraparticle charge neutrality is no longer required when the two particles overlap (i.e. each half of the overlapping dimer can have a net charge), it is expected that the charge buildup at the physical gap of separated particles would neutralize as soon as the gap is diminished. Surprisingly, the charge remains on the edges of the narrow conductive neck, as shown in the Ag-Au dimer with gap= 0 nm at = 1288 nm. The large pileup of induced charge in the interparticle gap gives rise to a physical mode that corresponds to the infrared peak that emerges right after the particles touch at a single point in Fig. 8. For the infrared dipole-dipole (DD) coupled mode at 1128 nm, there is a net electrical charge in each half of the dimer, that is, either silver or gold particle is charged, as illustrated in the lower inset of Fig. 9. This shows that the dominant low-energy modes of non-touching and touching dimers are distinctly different. For non-touching spheres, the lowest-energy dipole-dipole (DD) mode, which arises from coupling between dipole modes of each sphere, is charge neutral in
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FIG. 10. Scattering spectra calculated for varying dimer separation and conductive overlap for the silver-copper heterodimer.
each sphere. For touching spheres, the lowest-energy mode is a true dipolar mode with a net charge on each particle. As shown in the Ag-Au dimer at = 772 nm, when the overlap grows to gap= - 3 nm, the charge in each particle has a smooth distribution along the sphere surface, the charge pileup effect at the narrow conductive neck eventually disappears, and the response again becomes that expected for a single particle. The 1128 nm lowest-energy mode of the single-point-touching dimer transitions into the 772 nm higher energy mode of the overlapping dimer. The charge density plot shows the conductive 772 nm mode resembles the dipole mode of a continuous nanorod having twice the length of the constituent nanospheres, and the near-eld map and charge distribution of the 364 nm mode resembles the dipole mode of an individual silver nanosphere.30 Figure 10 shows the scattering spectra calculated for varying dimer separation and conductive overlap in the silver-copper heterodimer, and their accompanying near-eld maps and the surface charge distributions are similar to the corresponding modes in the silver-gold heterodimer. As the spherical nanoparticles begin to make conductive contact at a single point with gap=0 nm, the 575 nm peak corresponding to the dipole-dipole (DD) coupled plasmon mode splits into two modes, i.e., a dipole-dipole (DD) coupled mode at 438 nm and a new infrared dipole-dipole (DD) coupled mode at the 1123 nm. The 443 nm peak corresponding to the quadrupole-quadrupole (QQ) coupled plasmon mode disappears in the new scattering spectrum with gap=0 nm. With increasing conductive overlap from 0 to -3 nm, the infrared dipole-dipole (DD) coupled mode at 1123 nm blue shifts to a dipole nanorod mode at 762 nm and a new coupled mode emerges at 365 nm due to retardation effects, and the dipole-dipole (DD) coupled mode at 438 nm disappears in the new scattering spectrum with gap=-3 nm. The presence of new plasmon modes due to the conductive contact has been observed in both silver-gold and silver-copper systems approaching toward a single point of contact and the plasmon resonance mode has a similar wavelength around 1223 -1228 nm. As the particles approach closer with gap = -3 nm, the dominant dipolar feature in both metallic system becomes similar with the plasmon resonance around 762-772 nm. However, at a single point of contact, with
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gap = 0 nm, the silver-gold heterodimer exhibits a richer structure of higher-energy modes than the silver-copper heterodimer. The silver-gold heterodimer exhibits three resonance peaks and the silver-copper heterodimer exhibits one resonance peak with two shoulders in the wavelength range 300-650 nm of the scattering spectra.
IV. CONCLUSIONS
In summary, the plasmon-coupling phenomenon of heterodimers composed of silver, gold and copper nanoparticles with a size of 60 nm were studied theoretically using the nite difference time domain method within the outline of the scattered eld formulation. The energies and the line widths of the collective plasmon modes strongly depend on interparticle gap separations and polarization angles. In-phase bonding -modes were observed for the Ag-Au and Ag-Cu heterodimer and an antiphase bonding -mode was observed for the Ag-Au heterodimer, and these are in good agreement with that expected from plasmon hybridization theory. However, the quadrupole-coupled mode dominates the high energy wavelength range from 357-443 nm in the scattering cross section of the D=60 nm Ag-Au and Ag-Cu heterodimer. We demonstrate for the rst time that collective plasmon modes in a compositionally asymmetric nanoparticle dimer like the D=60 nm Ag-Au and Ag-Cu heterodimer cannot simply be predicted using plasmon hybridization theory. The interband transition energies of the constitutive metals and nanoparticle size retardation can overlap spectrally with the antibonding mode from plasmon hybridization, which results in new collective plasmon modes, such as a bonding quadrupole-quadrupole (QQ) mode and a dipole-quadrupole (DQ) mode in the Ag-Au heterodimer. This is a unique phenomenon and has not previously been observed in a compositionally asymmetric nanoparticle dimer.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science Foundation of China (Nos. 50971100 and 50671082), the Research Fund of State Key Laboratory of Solidication Processing (NWPU), China (Grant No. 30-TP-2009), the NPU Foundation for Fundamental Research (No. NPU-FFRZC200931), and the Graduate Starting Seed Fund of Northwestern Polytechnical University (Nos. Z2011002, Z2010011, and Z200915).
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Collective plasmon modes in a compositionally asymmetric nanoparticle dimer

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AIP ADVANCES 1, 032134 (2011)

Collective plasmon modes in a compositionally asymmetric nanoparticle dimer

a Email: fuyichen@nwpu.edu.cn b Email: r.l.johnston@bham.ac.uk

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III. RESULTS AND DISCUSSION A. Ag-Ag nanoparticle homodimer

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D. The dipole-dipole approximation of the plasmon hybridization model

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1. D=60 nm Ag-Ag homodimer

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3. D=60 nm Ag-Cu heterodimer

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E. Effects of conductive contact on the collective plasmon modes

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Chen, Alemu, and Johnston

AIP Advances 1, 032134 (2011)

Chen, Alemu, and Johnston

AIP Advances 1, 032134 (2011)

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