Multiple metallic-shell nanocylinders for surface-enhanced spectroscopes
© Lu et al; licensee Springer. 2011
Received: 13 September 2010
Accepted: 24 February 2011
Published: 24 February 2011
The optical properties of multiple dielectric-core-gold-shell nanocylinder pairs are investigated by two-dimensional finite difference time domain method. The core-shell cylinders are assumed to be of the same dimension and composition. For normal incidence, the diffraction spectra of multiple cylinder pairs contain the lightning-rod plasmon mode, and the electric field intensity is concentrated in the gap between the nanocylinder pairs in the infrared region. The resonance wavelength and local field enhancement of this plasmon mode can be tuned by varying the pair-distance between the pairs, the gap-distance between the pairs, and the optical constants of the dielectric-core and the surrounding medium. The results show that the multiple core-shell nanocylinder pair contains the plasmon mode same as that of the solid metallic cylinder pairs at the long wavelength part of the spectrum. The large electric field intensity in the infrared region at long wavelength makes multiple core-shell cylinders as ideal candidates for surface-enhanced spectroscopes.
In the emerging field of plasmonics, dielectric-core-metallic-shell nanostructures have attracted much attention. Compared to solid metallic particles, these core-shell nanostructures exhibit highly tunable plasmon modes that can be tuned over an extended wavelength range between visible and near-infrared regions. The variation of the plasmon resonance wavelength is interpreted as originating from the coupling of localized surface plasmon modes at the inner and outer surfaces of the core-shell structure [1, 2]. The dependence of their optical properties on the size, shape, and surrounding medium is an active subject of research, and recent advances in nanofabrication have enabled us to design nanostructures with different shapes and functionalities, such as nanorices , nanorings , and nanoshells .
The most widely used surface-enhanced spectroscopy is surface-enhanced Raman scattering (SERS) [5, 6], where the electric field intensity on the molecule is required to be maximized to enhance the detected signals. Such an enhancement can be very large in the gap region between two closely spaced nanoparticles [7–9]. The Raman enhancement is approximately given by , where is the local electric field near the detected molecule, and is the incident electric field. For core-shell dimmers [10–12], the dramatically enhanced electric field and tunability in the resonant frequency can be obtained by varying the geometrical parameters. The same effect can also be used to enhance infrared signals and is called the surface-enhanced infrared absorption (SEIRA) spectroscopy . This enhancement is not as strong as for Raman spectroscopy in the visible range, but the enhancement factors are still proportional to the square of the electromagnetic field. Originally, the local field enhancement of surface plasmon excitations in plasmonic nanostructures can only be found in the visible and UV regions, which is suitable for SERS. Recently, nanoshell arrays have been found to possess ideal properties as a common substrate for both SERS and SEIRA spectroscopies. The reason for this is that nanoshell arrays can provide large electric field enhancement at the same spatial location in both the visible and infrared regions of the spectrum .
In this article, the plasmon modes of multiple dielectric-core gold-shell cylinder pairs for normal incident light are investigated. The simulation results show that the multiple nanocylinder pairs provide large electromagnetic enhancement in the wide spectral range between visible and infrared regions. The localized surface plasmon excitation occurring in the infrared region in the spectrum is due to the efficient metallic screening effect at low frequency. The infrared plasmon resonance is identified as due to the interactions between the electrons at the outer metallic surfaces of the nanocylinder pairs, which is independent of the electrons at the inner surfaces. The other plasmon modes of multiple nanocylinder pairs are only weakly red-shifted from the individual nanocylinder pair plasmon modes. This analysis shows how to tune the plasmon modes of multiple nanocylinder pairs by varying the pair-distance between the pairs, the gap-distance between the pairs, and the optical constants of the dielectric-core and surrounding medium.
When the number of the cylinder pairs is three, it is found that the lightning-rod effect results in two plasmon modes in the infrared region. One of the two infrared plasmon modes is similar to the open cavity mode of three solid metallic nanocylinder pairs studied by Wu [15, 16]. The strongest electric field enhancement of such a cavity mode exhibits in the gap of the second pair and the open cavity has a linear relation between the resonant wavelength and the radius of nanocylinders. Therefore, the multiple core-shell nanocylinder pair contains the plasmon mode same as that of the solid metallic cylinder pairs at the long wavelength part of the spectrum.
where inc in the subscript means incident fields. In addition, the near-field electric field intensity is the electric field distribution normalized by the incident continuous electric wave. In this simulation, the cylinder is of the same geometry and composition. The inner and outer radii of the dielectric-core-gold-shell nanocylinder are 60 and 80 nm, respectively; the propagating direction of the incident wave is along the axis that connects the nanocylinder pairs, and the polarization of the incident wave is parallel to the axis that connects the two nanocylinders of the pair.
Results and discussion
The other plasmon mode, of approximately 575 nm, corresponds to in-phase symmetric quadrupole-quadrupole plasmon mode. The out-of-phase plasmon mode cannot not be observed in the spectrum. This is because out-of-phase plasmon modes do not contain any the dipole moment, so that external light cannot excite these modes.
The plasmon mode of approximately 690 nm is produced from the interaction between in-phase dipole-dipole mode of the first nanocylinder pair and the in-phase quadrupole-quadrupole mode of the second nanocylinder pair. The other Plasmon mode, of approximately 620 nm, corresponds to two in-phase quadrupole-quadrupole modes oscillating in the out-of-phase way. Therefore, for normal incidence, the plasmon modes of two nanocylinder pairs are composed of the individual nanocylinder pair plasmon mode.
When the incident wavelength increases to 1050 nm, the incident wave cannot penetrate into the nanocylinder. The maximum electric field intensity concentrates in the gap between the nanocylinders, and such a phenomenon is called lightning-rod plasmon mode . When the electric field is completely screened by the metal, no electric field and no induced charges could be found in the inner side of the metallic shell. This plasmon mode is the effect of the coupling of the in-phase dipolar modes formed by the electrons at the outer surfaces of the core-shell nanocylinders. From Figure 3, it can be known that except for this plasmon mode of approximately 1050 nm, other plasmon modes consist of the essential plasmon modes of the core-shell nanocylinder pair. The lightning-rod plasmon mode for a single dielectric-core-gold-shell nanocylinder pairs cannot be observed. This is because for just a single core-shell nanocylinder pair with the outer radius of 80 nm, the resonance wavelength of the in-phase dipolar mode resulted from the outer surfaces does not exist in the infrared region . When two core-shell nanocylinder pairs interact with each other, such a plasmon mode can be observed. The lightning-rod plasmon mode is red-shifted to longer wavelength than those of plasmon modes that are a result from coupling of the individual nanocylinder pair plasmon modes due to the pair-pair interaction.
Figure 4b shows that as pair-distance decreases between the core-shell cylinder pairs, the intensity of the plasmon mode, of approximately 1100 nm, decreases and is red-shifted. The resonance energy shifts to lower energy because the two cylinder pairs oscillate in the out-of-phase way. As the pair-distance decreases, the static coulomb energy also decreases . The interaction between the cylinder pairs gathers the energy flow inside the region between the pairs and this interaction also enhances the backscattering effect . However, the enhancement of the backscattering results in the reduction of the lightning-rod effect because the amount of the incident energy flow concentrating in the gap of the nanocylinder pair decreases.
The two nanocylinder pairs with different dielectric constants of dielectric cores are also simulated as shown in Figure 4c. The figure shows that as the refractive index of the dielectric core increases, the resonance energy of the plasmon modes reduces, except for the lightning-rod plasmon mode. This is because for the core-shell nanocylinder pairs, lightning-rod plasmon mode is only the result of the electrons at the outer surface of the nanocylinders. A large real permittivity of the dielectric core results in an efficient screening and thus results in a redshift of the plasmon energies [26, 27]. The resonance energy of other plasmon modes associated with the electrons of the inner surface of the nanocylinders can be decreased by increasing the refractive index of the dielectric core. Similarly, as the refractive index of the surrounding medium is increased as shown in Figure 4d, the resonance energy of all the plasmon modes will decrease. This is because all the plasmon modes are dependent on the electrons at the outer surface of the nanocylinders.
From the simulation results discussed, one can understand how to control the lightening mode and other plasmon modes which are resulted from the interaction between the individual core-shell nanocylinders in the multiple nanocylinder pairs. Multiple nanocylinder pairs can provide the enhancement of the electric field intensity on the gap between the nanocylinder pair in the spectra from the visible to the infrared region. Therefore, they efficiently combine two SERS and SEIRA substrates on a single substrate.
In conclusion, the plasmonic properties of multiple nanocylinder pairs are investigated by the FDTD method. The interaction between the dipolar mode of the nanocylinder results in the lightning-rod plasmon mode in the infrared region. The interaction between the essential plasmon modes was due to a single core-shell nanocylinder pair that resulted in other plasmon modes of multiple nanocylinder pairs. One can systematically control the strength and resonance energy of these plasmon modes by varying the pair-distance between the pairs, the gap-distance between the pair, the optical constant of the dielectric-core, and the surrounding medium. The multiple core-shell nanocylinder pair contains the plasmon mode same as that of the solid metallic cylinder pairs at the long wavelength part of the spectrum due to metallic screening effect. In particular, one of the lightning plasmon modes in three core-shell cylinder pairs is similar to the cavity mode confined by three solid cylinder pairs. Therefore, the core-shell nanocylinder pairs possess an ideal property that can enhance the electric field intensity at the same spatial positions in the wide wavelength range between the visible and the infrared regions.
finite difference time domain
surface-enhanced infrared absorption
surface-enhanced Raman scattering.
- Wang H, Brandl DW, Le F, Nordlander P, Halas NJ: Nanorice: A Hybrid Plasmonic Nanostructure". Nano Lett 2006, 6: 827. 10.1021/nl060209wView Article
- Aizpurua J, Hanarp P, Sutherland DS, Kall M, Bryant GW, Garcia de Abajp FJ: "Optical properties of gold nanorings". Phys Rev Lett 2004, 90: 057401. 10.1103/PhysRevLett.90.057401View Article
- Oldenburg SJ, Jackson JB, Wescott SL, Halas NJ: "Infrared extinction properties of gold nanoshells". Appl Phys Lett 1999, 75: 2897. 10.1063/1.125183View Article
- Prodan E, Radloff C, Halas NJ, Norlander P: "A Hybridization Model for the Plasmon Response of Complex Nanostructures". Science 2003, 302: 419. 10.1126/science.1089171View Article
- Ushioda S, Sasaki Y: "Raman scattering mediated by surface-plasmon polariton resonance". Phys Rev B 1983, 27: 1401. 10.1103/PhysRevB.27.1401View Article
- Lee PC, Meisel D: "Adsorption and Surface-Enhanced Raman of Dyes on Silver and Gold Sol". J Phys Chem 1982, 86: 3391. 10.1021/j100214a025View Article
- Xu H, Bjerneld EJ, Käll M, Börjesson L: "Spectroscopy of Single Hemoglobin Molecules by Surface Enhanced Raman Scattering". Phys Rev Lett 1999, 83: 4357. 10.1103/PhysRevLett.83.4357View Article
- Xu H, Aizpurua J, Käll M, Apell P: "Electromagnetic contributions to single-molecule sensitivity in surface-enhanced Raman scattering". Phys Rev E 2000, 62: 4318. 10.1103/PhysRevE.62.4318View Article
- Xu H, Käll M: " Enhanced plasmon coupling in crossed dielectric/metal nanowire composite geometries and applications to surface-enhanced Raman spectroscopy". ChemPhysChem 2003, 4: 1001. 10.1002/cphc.200200544View Article
- Prokes SM, Glembocki OJ, Rendell RW, Ancona MG: "Enhanced plasmon coupling in crossed dielectric/metal nanowire composite geometries and applications to surface-enhanced Raman spectroscopy". Appl Phys Lett 2007, 90: 093105. 10.1063/1.2709996View Article
- Zhao K, Xu H, Gu B, Zhang Z: "One-dimensional arrays of nanoshell dimers for single molecule spectroscopy via surface-enhanced Raman scattering". J Chem Phys 2006, 125: 081102. 10.1063/1.2229204View Article
- Xu H: "Theoretical study of coated spherical metallic nanoparticles for single molecule surface-enhanced spectroscopy". Appl Phys Lett 2004, 85: 5980. 10.1063/1.1833570View Article
- Kundu J, Le F, Nordlander P, Halas NJ: "Surface enhanced infrared absorption (SEIRA) spectroscopy on nanoshell aggregate substrates". Chem Phys Lett 2008, 452: 115. 10.1016/j.cplett.2007.12.042View Article
- Lassiter JB, Aizpurua J, Hernandez LI, Brandl DW, Romero I, Lal S, Hafner JH, Nordlander P, Halas NJ: "Close encounters between two nanoshells". Nano Lett 2008, 8: 1212. 10.1021/nl080271oView Article
- Ng MY, Liu WC: "Local-field confinement Local-field confinement in three-pair arrays of metallic nanocylinders". Opt Express 2006, 14: 4505. 10.1364/OE.14.004504View Article
- Ng MY, Liu WC: "Local field enhancement of asymmetric metallic nanocylinder pairs". J Korean Phys Soc 2005, 47: 135.
- Yousif HA, Mattis RE, Kozminski K: "Light scattering at oblique incidence on two coaxial cylinders". Appl Opt 1994, 9: 4012.
- Lu JY, Chang YH: "Implementation of an efficient dielectric function into the finite difference time domain method for simulating the coupling between localized surface plasmons of nanostructures ". Superlattices Microstruct 2010, 47: 60. 10.1016/j.spmi.2009.07.017View Article
- Johnson PB, Christy RW: "Optical constants of the noble metals ". Phys Rev B 1972, 6: 4370. 10.1103/PhysRevB.6.4370View Article
- Yang P, Liou KN: "Finite-difference time domain method for light scattering by small ice crystals in three-dimensional space". J Opt Soc Am 1996, 13: 2072. 10.1364/JOSAA.13.002072View Article
- Radloff C, Halas NJ: "Plasmonic Response of Concentric Nanoshells". Nano Lett 2004, 4: 1323. 10.1021/nl049597xView Article
- Lu JY, Chao HY, Wu JC, Wei SY, Chang YH, Chen SC: "Retardation-effect-induced plasmon modes in a silica-core gold-shell nanocylinder pair". Physica E 2010, 42: 2583. 10.1016/j.physe.2009.12.010View Article
- Le F, Brandl DW, Urzhumov YA, Wang H, Kundu J, Halas NJ, Aizpurua J, Nordlander P: "Metallic nanoparticle arrays: a common substrate for both surface-enhanced Raman scattering and surface-enhanced infrared absorption". ACS Nano 2008, 2: 707. 10.1021/nn800047eView Article
- Lu JY, Chang YH: "The lightning-rod mode in a core shell nanocylinder dimer". Opt Commun 2010, 283: 2627. 10.1016/j.optcom.2010.02.025View Article
- She HY, Li LW, Chua SJ, Ewe WB, Martin OJF, Mosig JR: "Enhanced Backscattering by Multiple NanoCylinders Illuminated by TE Plane Wave". J Appl Phys 2008, 104: 064310. 10.1063/1.2975214View Article
- Wang H, Tam F, Grady NK, Halas NJ: "Cu nanoshells: Effects of interband transitions on the nanoparticle plasmon resonance". J Phys Chem B 2005, 109: 18218. 10.1021/jp053863tView Article
- Prodan E, Lee A, Norlander P: "The effect of a dielectric core and embedding medium on the polarizability of metallic nanoshells". Chem Phys Lett 2002, 360: 325. 10.1016/S0009-2614(02)00850-3View Article
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