Optical properties of metallic systems

University of Technology, Sydney. Department of Physics and Advanced Materials, Faculty of Science.The continuous improvement of nanoscale fabrication techniques will ultimately result in a situation where the performance of plasmonic devices is not dependent on engineering defects, but rather on the fundamentally limiting behaviour of the underlying metals. This thesis addresses the following questions: Are silver and gold the best metals for plasmonics? What other materials are available? and finally; Can we design better plasmonic materials? To answer these questions, classical electrodynamics calculations are performed using tabulated dielectric functions from the literature. Starting from a comparison of nanoshells made of various free electron metals, it is shown that the low plasma frequency metals sodium and potassium perform well. However, these metals are not suitable for many common uses of nanoshells. As such, the material choice is extended to all non fgroup metals in the periodic table and a variety of additional geometries are studied, including nanorods, superlenses and a number of guiding structures. It is shown that gold, silver, the alkali metals and aluminium outperform all other metals, each over a range of frequencies and permittivities. None of the reviewed elements performs better than silver and gold. As none of the elements seem to offer any advantage over silver or gold, the search is extended to alternative materials with tabluated dielectric functions. A review of the plasmonic properties of these materials is presented, including alloys, intermetallic compounds , high pressure materials as well as silicides, metallic glasses, and liquid metals. It is discovered that liquid sodium outperforms its solid elemental counterpart. Additionally, several materials with simple crystal structures seem to perform well, but none to the extent of silver or gold. The number of compounds for which tabulated optical constants are available is severely limited. In order to evaluate the performance of a large number of materials, first principles quantum mechanical calculations must be performed. It is shown that the plasmonic performance can be approximately gleened from the relationship between the optical gap and the plasma frequency. However, in order to compare the calculated optical response of materials with experimental data for the elements, the Drude phenomenological scattering rate must be known. Here, for the first time, calculations of the real and imaginary components of the dielectric function including the electron-phonon scattering rate are performed in order to gauge the plasmonic performance of materials with no tabulated optical data. A list of publications associated with this work is presented on page iv

Optical performance and metallic absorption in nanoplasmonic systems

Optical metrics relating to metallic absorption in representative plasmonic systems are surveyed, with a view to developing heuristics for optimizing performance over a range of applications. We use the real part of the permittivity as the independent variable; consider strengths of particle resonances, resolving power of planar lenses, and guiding lengths of planar waveguides; and compare nearly-free-electron metals including Al, Cu, Ag, Au, Li, Na, and K. Whilst the imaginary part of metal permittivity has a strong damping effect, field distribution is equally important and thus factors including geometry, real permittivity and frequency must be considered when selecting a metal. Al performs well at low permittivities (e.g. sphere resonances, superlenses) whereas Au & Ag only perform well at very negative permittivities (shell and rod resonances, LRSPP). The alkali metals perform well overall but present engineering challenges. © 2009 Optical Society of America

Optical properties of intermetallic compounds from first principles calculations: A search for the ideal plasmonic material

First principles calculations have been used to predict the optical properties for a range of intermetallic compounds for which little or no experimental optical data are currently available. Density functional theory combined with the random phase approximation is used to calculate the dielectric functions for these compounds. The aim of this work is to investigate how the band edge and plasma frequency vary with composition in order to identify materials with promising plasmonic properties. Towards this end the intermetallic compounds chosen are composed of elements which on their own have reasonable optical properties for plasmonic applications. The position of the band edge relative to the plasma frequency is most favourable in the simple binary compounds formed from the alkali plus noble metals NaAu, KAu and KAg. In particular, for KAu the band edge and plasma frequency occur at almost the same frequency, and hence the imaginary part of the dielectric function is practically zero for frequencies below the plasma frequency. In addition, the plasma frequency in this compound is at relatively low frequency, promising a material with strong plasmon response in the infrared. © 2009 IOP Publishing Ltd

Search for the ideal lasmonic nanoshell: the effects of surface scattering and alternatives to gold and silver

The optical absorption efficiency of nanospheres and nanoshells of the elements Na, K, Al, Ag, and Au are compared, and the effects of surface scattering, as introduced by the billiard model [Moroz, A. J. Phys. Chem. C 2008, 112 (29), 10641-10652] are discussed. We find that the introduction of surface scattering has comparatively little effect on the optimized absorption efficiency of nanospheres, with the maximum absorption efficiency of K nanospheres falling from 14.7 to 13.3. Conversely, the reduction in absorption efficiency in nanoshells is substantial. This effect is compounded in metals with higher plasma frequency. We show that the high comparative plasma frequencies in silver and gold result in a greatly reduced optimized absorption efficiency when compared to nanoshells in the absence of surface scattering. Whereas sodium and potassium, with low plasma frequencies, are not affected as much. © 2009 American Chemical Society

Universal scaling of local plasmons in chains of metal spheres

The position, width, extinction, and electric field of localized plasmon modes in closely-coupled linear chains of small spheres are investigated. A dipole-like model is presented that separates the universal geometric factors from the specific metal permittivity. An electrostatic surface integral method is used to deduce universal parameters that are confirmed against results for different metals (bulk experimental Ag, Au, Al, K) calculated using retarded vector spherical harmonics and finite elements. The mode permittivity change decays to an asymptote with the number of particles in the chain, and changes dramatically from 1/f3to 1/f 1/2 as the gap fraction (ratio of gap between spheres to their diameter), f, gets smaller. Scattering increases significantly with closer coupling. The mode sharpness, strength and electric field for weakly retarded calculations are consistent with electrostatic predictions once the effect of radiative damping is accounted for. ©2010 Optical Society of America

Plasmonic resonances of closely coupled gold nanosphere chains

The optical properties of an ordered array of gold nanospheres have been calculated using the T-matrix method in the regime where the near-fields of the particles are strongly coupled. The array consists of a one-dimensional chain of spheres of 15 nm diameter where the number of spheres in the chain and interparticle spacing is varied. Calculations have been performed with chains up to 150 particles in length and with an interparticle spacing between 0.5 and 30 nm. Incident light polarized along the axis of the chain (longitudinal) and perpendicular (transverse) to it are considered, and in the latter case for wavevectors along and perpendicular to the chain axis. For fixed chain length the longitudinal plasmon resonance red shifts, relative to the resonance of an isolated sphere, as the interparticle spacing is reduced. The shift in the plasmon resonance does not appear to follow an exponential dependence upon gap size for these extended arrays of particles. The peak shift is inversely proportional to the distance, a result that is consistent with the van der Waals attraction between two spheres at short range, which also varies as 1/d. The transverse plasmon resonance shifts in the opposite direction as the interparticle gap is reduced; this shift is considerably smaller and approaches 500 nm as the gap tends to zero. Increasing the number of particles in the chain for a fixed gap has a similar effect on the longitudinal and transverse plasmon. In this case, however, the longitudinal plasmon tends toward an asymptotic value with increasing chain length, with the asymptotic value determined by the interparticle spacing. Here, the approach to the asymptote is exponential with a characteristic length of approximately two particles, at small interparticle spacings. This approach to an asymptote as the chain length becomes infinite has been verified in a finite element calculation with periodic boundary conditions. © 2009 American Chemical Society

Optimisation of absorption efficiency for varying dielectric spherical nanoparticles

In this paper we compare the optical absorption for nanospheres made from a range of transition and alkali metals from Li (A=3) to Au (A=79). Numerical solutions to Mie theory were used to calculate the absorption efficiency, Q abs, for nanospheres varying in radii between 5 nm and 100 nm in vacuum. We show that, although gold is the most commonly used nanoparticle material, its absorption efficiency at the plasmon resonance is not as strong as materials such as the alkali metals. Of all the materials tried, potassium spheres with a radius of 21 nm have an optimum absorption efficiency of 14.7. In addition we also show that, unlike gold, the wavelength of the plasmon peak in other materials is sensitive to the sphere radius. In potassium the peak position shifts by 100 nm for spheres ranging from 5 nm to 65 nm, the shift is less than 10 nm for gold spheres. © 2006 IEEE

Design Principles for Plasmonic Nanoparticle Devices

For all applications of plasmonics to technology it is required to tailor the resonance to the optical system in question. This chapter gives an understanding of the design considerations for nanoparticles needed to tune the resonance. First the basic concepts of plasmonics are reviewed with a focus on the physics of nanoparticles. An introduction to the finite element method is given with emphasis on the suitability of the method to nanoplasmonic device simulation. The effects of nanoparticle shape on the spectral position and lineshape of the plasmonic resonance are discussed including retardation and surface curvature effects. The most technologically important plasmonic materials are assessed for device applicability and the importance of substrates in light scattering is explained. Finally the application of plasmonic nanoparticles to photovoltaic devices is discussed.Comment: 29 pages, 15 figures, part of an edited book: "Linear and Non-Linear Nanoplasmonics