The study of optical phenomena related to the strong electromagnetic response of noble metals (silver (Ag) and gold (Au) being most popular) over the last couple of decades has led to the emergence of a fast growing research area called plasmonics named after 'surface plasmons' which are electron density waves that propagate along the interface of a metal and a dielectric medium. Surface plasmons are formed by the coupling of light to the electrons on the metal surface subject to the fulfillment of certain physical conditions and they are bound to the metal surface. Depending on whether the metallic medium is a continuous film or a structure having dimensions less than or comparable to the wavelength of the exciting light, propagating or localized surface plasmons can be excited. The structure can be either a hole or an arbitrary pattern in a metal film, or a metallic particle. An array of subwavelength structures can behave as an effective homogeneous medium to incident light and this is the basis of a new class of media known as metamaterials. Metallic metamaterials enable one to engineer the electromagnetic response to  incident light and provide unconventional optical properties like negative refractive index as one prominent example. Metamaterials exhibiting negative index (also called negative index materials (NIMs)) open the door for super resolution imaging  and development of invisibility cloaks. However, the only problem affecting the utilization of plasmonic media to their fullest potential is the intrinsic loss of the metal, and it becomes a major issue especially at visible-near infrared (NIR) frequencies. The frequency of the surface plasmon is the same as that of the exciting light but its wavelength could be as short as that of X-rays. This property allows light of a given optical frequency to be conned into very small volumes via subwave lengthmetallic structures, that can be used to develop ecient sensors, solar cells, antennas and ultrasensitive molecular detectors to name a few applications. Also, interaction of surface plasmons excited in two or more metallic subwavelength structures in close proximity inuences the far-eld optical properties of the overall coupled system. Some eects of plasmonic interaction in certain coupled particles include polarization conversion, optical activity and transmission spectra mimicking electromagnetically-induced transparency (EIT) as observed in gas based atomicsy stems. In this thesis, we mainly focus on the optical properties of square arrays of certain plasmonic structures popularly researched in the last decade. The structures considered are as follows: (1) subwavelength holes of a composite hole-shape providing superior near-eld enhancement such as two intersecting circles (called' double hole') in an optically thick Au/Ag lm, (2) double layer shnets, (3) subwavelength U-shaped particles and (4) rectangular bars. The entire work is based on electromagnetic simulations using time and frequency domain methods. Au/Ag lms with periodic subwavelength holes provide extraordinarily high transmission of light at certain wavelengths much larger than the dimension of the perforations or holes. The spectral positions of the maxima depend on the shape of the hole and the intra-hole medium, thereby making such lms function as a refractive index sensor in the transmission mode. The sensing performance of the double-hole geometry is analyzed in detail and compared to rectangular holes. Fishnet metamaterials are highly preferred when it comes to constructing a NIM at optical frequencies. A shnet design that theoretically oers a negative refractive index with least losses at telecommunication wavelengths (1.4 1.5 microns) is presented. U-shaped subwavelength metallic particles, in particular single-slit split-ring resonators (SSRRs), provide a large negative response to the magnetic eld of light at a specic resonance frequency. The spectral positions of the structural resonances of the U-shaped particle can be found from its array far field transmission spectrum at normal incidence. An effort is made to clarify our understanding of these resonances with the help of localized surface plasmon modes excited in the overall particle. From an application point of view, it is found that a planar square array of SSRRs eectively functions as an optical half-wave waveplate at the main resonance frequency by creating a polarization in transmission that is orthogonal to that of incident light. A similar waveplate eect can be obtained purely by exploiting the near-eld interaction of dierently oriented neighbouring SSRRs. The physical reasons behind polarization conversion in dierent SSRR-array systems are discussed. A rectangular metallic bar having its dipolar resonance in the visible-NIR is called a nanoantenna, owing to its physical length in the order of nanometers. The excitation of localized surface plasmons, metal dispersion and the geometry of the rectangular nanoantenna make an analytical estimation of the physical length of the antenna from the desired dipolar resonance dicult. A practical map of simulated resonance values corresponding to a variation in geometrical parameters of Au bar is presented. A square array of a coupled plasmonic system comprising of three nanoantennas provides a net transmission response that mimicks the EIT effect. The high transmission spectral window possesses a peculiar dispersion profile that enables light with frequencies in that region to be slowed down. Two popular designs of such plasmonic EIT systems are numerically characterized and compared. / <p>QC 20121017</p>

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21333号 / 理博第4429号 / 新制||理||1636(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 寺西 利治, 教授 倉田 博基, 教授 時任 宣博 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Artificial photosynthesis is used to harvest solar energy and store it in the form of chemical bonds. The system of interest in this study does this by splitting water into hydrogen and oxygen gas through a plasmon assisted process, collective oscillations from free electron gas. This is a renewable way to store energy that could be used as an alternative to fossil based fuel. In this study, a small part of this photo catalytic system is studied, namely the interaction between plasmonically active silver nanoparticles (Ag NPs) transferring photo-excited electrons via a linker molecule, 4-aminobenzoic acid (pABA). The pABA linker molecule transfers charge from the Ag surface to a semiconductor and a catalyst performing the water splitting. The pABA can bind in different ways onto the Ag-surface and the aim of this study is to examine which bond is strongest and which best enables charge transfer. To this purpose three systems where simulated quantum mechanically using a supercomputer. The total free energy of the systems was computed and compared. Out of the three studied binding sites, the hollow-site bond (pABA binding to three silver atoms) was found to have the lowest energy, meaningit's the strongest of the possible bonds. Additionally it was found that the band gap (the energy needed to transfer charge) for the pABA decreased when bound to the Ag-surface. The hollow-site bound pABA also had the smallest band gap, meaning it requires the least energy to transfer a charge and should therefore be the best bond fitted for the photo catalytic system. / Artificiell fotosyntes används för att absorbera solenergi och förvara den i formen av kemiska bindningar. Systemet som används i denna studie gör detta genom att splittra vatten till vätgas och syrgas genom en plasmon assisterad process. Detta är ett förnyelsebart sätt att förvara energi och kan användas som ett alternativ till fossila bränslen. I denna studie studeras en liten del utav detta fotokatalytiska system nämligen interaktionen där plasmonaktiva silvernanopartiklar (Ag NPs) överför foto-exciterade elektroner genom molekyllänken 4-aminobensoesyra (pABA). Molekyllänken pABA överför laddning från silverytan till en halvledare och en katalys som utför splittringen av vattnet. pABA kan binda på olika sätt tillen silveryta och denna studie syftar till att undersöka vilken utav bindningarna som är starkast och vilken som effektivast överför laddning. För att göra detta simulerades tre system kvantmekaniskt med hjälp av en superdator, ett system för varje sorts bindning. Den totala fria energin av systemen beräknades och jämfördes. Av de tre undersökta bindningarna hadehollow-site bindningen (pABA som binder till tre silveratomer) längst energi, vilket betyder att det är den starkaste av bindningarna. Utöver detta så visade det sig att bandgapet (energin som krävs för att överföra laddning) minskade för pABA när den var bunden till Ag-ytan. Hollow-site bundet pABA hade även minst bandgap, vilket betyder att den kräver minst energi för att överföra laddning och är därmed den mest effektiva bindningen för det fotokatalytiska systemet.

We have developed a general theory of the plasmonic enhancement of many-body phenomena resulting in a closed expression for the surface plasmon-dressed Coulomb interaction. It is shown that this interaction has a resonant nature. We have also demonstrated that renormalized interaction is a long-ranged interaction whose intensity is considerably increased compared to bare Coulomb interaction over the entire region near the plasmonic nanostructure. We illustrate this theory by re-deriving the mirror charge potential near a metal sphere as well as the quasistatic potential behind the so-called perfect lens at the surface plasmon (SP) frequency. The dressed interaction for an important example of a metal–dielectric nanoshell is also explicitly calculated and analyzed. The renormalization and plasmonic enhancement of the Coulomb interaction is a universal effect, which affects a wide range of many-body phenomena in the vicinity of metal nanostructures: chemical reactions, scattering between charge carriers, exciton formation, Auger recombination, carrier multiplication, etc. We have described the nanoplasmonic-enhanced Förster resonant energy transfer (FRET) between quantum dots near a metal nanoshell. It is shown that this process is very efficient near high-aspect-ratio nanoshells. We have also obtained a general expression for the force exerted by an electromagnetic field on an extended polarizable object. This expression is applicable to a wide range of situations important for nanotechnology. Most importantly, this result is of fundamental importance for processes involving interaction of nanoplasmonic fields with metal electrons. Using the obtained expression for the force, we have described a giant surface-plasmoninduced drag-effect rectification (SPIDER), which exists under conditions of the extreme nanoplasmonic confinement. Under realistic conditions in nanowires, this giant SPIDER generates rectified THz potential differences up to 10 V and extremely strong electric fields up to 10^5-10^6 V/cm. It can serve as a powerful nanoscale source of THz radiation. The giant SPIDER opens up a new field of ultraintense THz nanooptics with wide potential applications in nanotechnology and nanoscience, including microelectronics, nanoplasmonics, and biomedicine. Additionally, the SPIDER is an ultrafast effect whose bandwidth for nanometric wires is 20 THz, which allows for detection of femtosecond pulses on the nanoscale.