The Multipole Description of Complex Plasmonic Nanostructures

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The Multipole Description of Complex Plasmonic Nanostructures The Multipole Description of Complex Plasmonic Nanostructures Dissertation zur Erlangung des akademischen Grades doctor rerum naturalium (Dr. rer. nat.) vorgelegt dem Rat der Physikalisch-Astronomischen Fakultät der Friedrich-Schiller-Universität Jena von Dipl.-Phys. Jörg Petschulat geboren am 12.02.1981 in Zwickau. Gutachter / Referees: 1. Prof. Thomas Pertsch (Friedrich-Schiller-Universität Jena) 2. Prof. Kurt Busch (Universität Karlsruhe) 3. Prof. Olivier J. F. Martin (Ecole Polytechnique Federale De Lausanne) Tag der Disputation / Day of defense: 12.04.2011 For Nadja and Mathilde. Contents 1 Introduction 3 2 Theoretical and experimental basics 8 2.1 Theory . .8 2.1.1 Averaging microscopic Maxwell’s equations - the role of multipole moments8 2.1.2 Multipole radiation . 18 2.1.3 Localized plasmon polaritons . 21 2.1.4 Propagating plasmon polaritons . 26 2.1.5 Rigorous numerical methods . 31 2.2 Experimental . 37 2.2.1 Far-field spectroscopy . 38 3 Electric dipole excitations in metal nanostructures 40 3.1 Optical properties of dipole nanoantennas . 40 3.1.1 Near-field enhancement . 40 3.1.2 Polarization dependence . 45 3.2 Combining localized dipole and propagating surface plasmon modes . 49 3.2.1 Doubly resonant nanoantenna arrays . 49 3.2.2 Surface-Enhanced Raman Scattering . 56 3.2.3 Application of doubly resonant nanoantenna arrays to Surface-Enhanced Raman Scattering . 59 4 Higher-order multipole properties of optical metamaterials 63 4.1 Linear optical properties . 63 4.1.1 Cut-Wire metamolecule . 63 4.1.2 Split-Ring Resonator metamolecule and planar modifications enabling asymmetric transmission . 70 4.2 Nonlinear optical properties . 76 4.2.1 Multipole nonlinearity - Second-harmonic generation . 77 4.2.2 Comparison with other nonlinear approaches . 85 4.3 Scattering patterns of isolated metamolecules . 88 4.3.1 Multipole decomposition of the scattered field . 88 4.3.2 Origin dependence for the multipole expansion . 94 5 Summary and perspective 97 1 6 Zusammenfassung II 7 Curriculum Vitae VI 8 Bibliography XI 9 List of Figures XXVI 2 1 Introduction The peculiarities of the interaction of light with confined metal inclusions have been of interest for a long time. The most prominent examples are the coloring effects achieved by certain noble metals included in windows in churches1. The theoretical description of such effects has been performed by G. Mie [Mie08]. Furthermore, the theoretical prediction of bound elec- tromagnetic modes at metal dielectric interfaces by R. H. Ritchie [Rit57] comprises another important milestone. In the following decades many interesting applications have been inves- tigated, e.g., extra-ordinary transmission of light through metal films perforated with holes of sub-wavelength dimensions [ELG+98, BDE03]. During the last years, the subject of light-matter interaction with metal objects of sub- wavelength size has been experienced further interest [BFL+07, Ram05, Sha07]. The reasons for this development are manyfold. On one side the fabrication processes have been contin- uously improved due to the growing demands for smaller circuit sizes in the semiconductor industry. Among other fabrication schemes, mostly top-down approaches2, such as electron beam lithography, have successfully been applied to realize highly reproducible structures covering large areas. Thus, versatile fabrication methods have been established to provide structures with feature sizes far below the wavelength of optical radiation. On the other side, the classical electrodynamic description of light-matter interaction with arbitrarily-shaped ob- jects got enriched by the exploration and application of powerful numerical techniques. These methods allow the verification of experimental findings in the same manner as new effects can be predicted and finally observed in application-oriented realizations of specific structures. Moreover, the numerical methods are valuable tools to bridge the gap between the physics, taking place at the scale of nanometers, and the macroscopic observation. The dramatical developments in these two fields provided the optimal breeding ground for the emerging field of metamaterials. Eventually, everything that was required to launch this topic was a physical idea. Exactly this idea was presented in the work of J. B. Pendry in 1999 [PHRS99]. He proposed the concept of artificial materials, i.e., metamaterials3, that are composed of sub-wavelength structures, acting similarly as atoms and molecules do in ordinary matter. These structures were termed metamolecules and have in common that their dimensions are much smaller than the wavelength of the impinging radiation. Thus, in a simplified picture, the illumination cannot resolve the structural details and behaves like in an effective medium with propagation 1The Lycurcus Cup, exposed in the British museum in London, is a frequently referred example for its different color appearance depending on the illumination conditions. 2The term top-down accounts for fabrication schemes for which the entire structure is created starting from a predefined arrangement, e.g., a stack of layers, that is finally processed, typically by electron or ion beam lithography. Differently, bottom-up approaches denote schemes that are starting with entities at a smaller scale than the final structure. Examples are chemical synthesis of gold spheres and other self-organized fabrication schemes. 3The term metamaterial originates from the greek word "meta" which can be translated by "beyond". Hence, the expression metamaterials should account for materials beyond the capabilities of natural matter. 3 properties dictated by the elementary metamolecules. These metamolecules, similar to ordi- nary matter, predominantly interact with electromagnetic waves by their carriers. In contrast to ordinary matter, for which the carrier dynamics is determined by the atomic assembly of the respective element, the carrier dynamics can be tailored by the geometry of the meta- molecules in metamaterials. Due to their high electron density and mobility, noble metals such as gold or silver are typically selected as composite materials for metamolecules. The associated resonant carrier excitations are so-called localized surface plasmon-polaritons that can be controlled by adjusting the shape and the composition of the metamolecule. As it may be anticipated from the terminology, such excitations are located at the surface of the respective metamolecule, due to the limited penetration depth in the metal on the one side and an evanescent decay in the ambient dielectric medium on the other side. Furthermore, they are hybrid excitations, since the electron dynamics (plasmon) induces an electric field (polariton) and vice versa. With these considerations it becomes clear that a resonance in the carrier dynamics is accompanied with a resonant and thus enhanced local electromagnetic field in the vicinity of the structure. In contrast to the research associated with metamaterials, localized surface plasmon-polari- tons have been known for a long time. A famous and fundamental theoretical description related to such resonances is the work published by G. Mie [Mie08] which has been already mentioned above. Although Mie did not use the terminology of localized surface plasmon- polaritons, he developed a rigorous electrodynamic formalism to solve the scattering problem of electromagnetic waves at isolated spheres with arbitrary diameter and composition. With this approach he was able to predict the resonances occurring in the scattering spectra of colloidal gold solutions. These resonances have been observed in the form of coloring effects mentioned in the beginning. Hence, the physics of metal structures with sub-wavelength dimensions has been known for decades and was subject of intense investigations. The dramatic new feature of structures that are typically investigated in the field of metamaterials is the possibility to additionally create a magnetic response besides the electrical one. Exactly this intriguing difference can be considered as the major achievement during the last years, since metamaterials can exhibit optical magnetism, i.e., magnetic light-matter interaction at optical frequencies [PHRS99]. Such an effective magnetic response has never been observed in natural matter before and opens the gate to alter both, the magnetic and the electric properties for light propagation by structured materials with an unprecedented diversity. Among other famous works which investigated a potential magnetic response there is one publication that is of particular importance in the field of metamaterials. This work has been presented by V. G. Veselago [Ves68, Boa11] who theoretically investigated what impact a potential magnetic response would have early in 1968. As the most important consequence, Veselago considered the case of a negative refractive index [Ves68]. However, only in combi- nation with the structures and the concepts proposed by Pendry, realizations of such effects became feasible [BdWPA10, DWSL07, SCC+05, VZZ+08]. Although the ability to create a magnetic response in addition to the electrical seems to 4 be only an incremental development, the consequences of such an apparently slight change are enormous. For instance, the resolution limit of E. Abbe [Abb73], which is approximately one half of the irradiating wavelength, can be circumvented by perfect lenses [Pen00, SE06, JAN06]. Recently, much smaller details have been resolved with the use of metamaterials [LLX+07, SHD07]. Finally, the fascinating concept of cloaking
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