Investigation of photoinduced effects in plasmonic nanocavities

Light matter interaction can be boosted by several orders of magnitude by tailoring the photonic environment, thus enabling a wide range of applications. One particular example are plasmonic nanostructures that support localized surface plasmon polariton (LSPP) leading to enhancement and confinement of incident electromagnetic fields. These novel properties provide access to a large number of optically driven effects within matter placed in the vicinity of such nanostructures. In this thesis, we investigate the effects of optical excitation on gold nanostructures in the presence of Raman active molecules. This is accomplished by fabricating nanoparticle on mirror (NPoM) plasmonic nanostructures where a gold nanoparticle is placed at a fixed distance from a smooth gold film using molecular monolayers. As the nanoparticle and mirror are placed only a few nanometers apart, optical excitation leads to formation of hybridized LSPP modes due to coupling between the plasmons within the nanoparticle and the mirror. This plasmonic coupling also results in confinement and subsequent enhancement of the incident light within the gap and is extremely sensitive to structural parameters of the NPoM. The creation of a homogeneous gap between the nanoparticle and mirror is quite challenging due the roughness of the mirror. Moreover, due to the large number of NPoM nanostructures present on the sample it is quite difficult to locate a specific NPoM. To bypass these difficulties atomically smooth and patterned substrates were developed using template stripping combined with conventional photolithography techniques. Next, in order to characterize the optical response of the NPoMs, a custom optical setup was built. The setup was primarily designed to investigate the plasmonic properties of the NPoM using elastic scattering spectroscopy along with surface enhanced Raman scattering (SERS) from the molecules within the gap. The combination of these two techniques was later used to investigate the effect of laser power on the NPoMs. It was discovered that the scattering spectra of the NPoMs changed irreversibly after laser exposure even with a few ÎŒW/ÎŒm2 incident intensities. Moreover, the plasmonic response of the NPoMs fabricated with well organized molecular monolayer changed much faster than the NPoMs prepared with disorganized ones. This phenomenon was also investigated in NPoMs prepared using a dielectric gap layer, by changing the gap conductivity, and by changing the nanoparticle shape. The experimental results combined with simulations suggest a decrease in gap height due to the reorientation of the molecular monolayer under optical excitation.

Physics of optically driven nanojunctions

Philippe Andreas Rölli

Recent years have seen spectacular developments in the domain of nano-optics. Alongside the well-known techniques of super-resolution microscopy progress in nanofabrication has enabled important improvements in the fields of optical imaging and spectroscopy. Nowadays enhancements of specific near-field interactions by nano-antennae/cavities allows the optical readout of single molecule properties in a number of different systems. The observation of normal modes of vibration for example carries essential information on the orientation, link to the interface and environment in which the molecule is embedded. This thesis develops firstly a novel theoretical frame for these vibration-cavity interactions by following the optomechanical formalism, which has proven to be an accurate treatment of a wide variety of mechanical systems interacting with a laser field. By leveraging this framework, we investigate on the one hand several quantum limits. On the other hand, for the parameter space experimentally available and for well-designed cavities, novel regimes of interaction between the collective mode of vibration of an ensemble of molecules and an optical tone seem within reach. In parallel, this thesis experimentally explores one specific realization of such a system. In collaboration with the group of Christophe Galland we constructed the optical setups necessary to interrogate our nanostructures. The class of structures constructed, known as self-assembled nanojunctions or nanoparticles on mirror, reaches confinement of electric fields via plasmonic modes close to its fundamental limit and enables the study of many different mechanical systems whose thickness consist in a single molecule. Along this research we have developed techniques to characterize mechanical, electronic and thermal observables of nanojunctions interacting with an optical field. Our experimental study has enabled the discovery of a novel effect related to the electronic confinement of these quasi-0-dimensional structures. The characteristic photoluminescence of metallic nanostructures is found to consistently blink in nanojunctions akin to other quantum emitters. The mechanisms explaining in detail this blinking remain debatable but the numerous experimental data collected highlight the key role of the interface in the specificities of the blinking observed. This finding opens novel ways to characterize the important and to date ill-described question of the interfaces in nanojunctions. The observed modifications of the nanojunctions optical properties might constitute an interesting step towards the development of a novel class of functional materials ('gap-materials') with enhanced and tailored electro-optical properties. The last part of this thesis considers one technological application for this class of material by conceptually developing a new kind of detector based on the upconversion of an infrared photon to the visible; exploiting thus in a unique way the optical properties of the molecular system. The study of the quantum noises of these detectors highlights two exciting and technologically relevant directions for such devices : at room temperature these systems operate with levels of noise below state of the art devices, at lower temperatures these systems open an unexplored path towards single photon detection in a spectral range where this technology remains unavailable to date.

EPFL2020

Developing luminescent Brownian probes for near-field investigations of the intracellular environment

Flavio Maurizio Mor

Life sciences have a constantly growing need for novel methodological approaches suitable to investigate the intracellular environment with increased temporal and spatial resolutions. Recently, optical near-field probes, such as laser-irradiated pointed metal, uncoated/metal-coated tapered optical fibers, as well as nano-emitters, such as single molecules or nanoparticles, have attracted increasing attention as key components of high-resolution microscopes. In parallel, super-resolution fluorescence microscopy, operating in far-field regime and overcoming the light diffraction limit, has markedly improved imaging resolution. Although both near- and far-field optical approaches drastically improve image resolution, they still represent numerous drawbacks, such as, technical difficulties concerning probe preparation (near-field) or potential damaging through very high light intensities (far-field). The aforementioned shortcomings of high-resolution optical microscopy can be overcome to a great extent by photonic force microscopy (PFM). PFM employs a strongly focused near-infrared (NIR) laser light to hold a dielectric or metallic particle as a local probe. Such an optical trap enables one to ‘cage’ a mesoscopic particle and track its three-dimensional (3D) thermal fluctuations in the surrounding environment, e.g. a viscous liquid. Therefore, besides offering near-field 3D imaging, PFM reports also on other important quantities concerning local mechanical properties, including force and viscosity as well as dynamical properties of the surrounding medium. This additional information is derived from the careful analysis of the jittery motion (so-called Brownian motion) of the trapped single-particle probe that collides with thermally-activated surrounding molecules. In this thesis, we first study in detail the Brownian motion of a single spherical particle that is confined within the harmonic potential of the optical trap. To this end, we optimize the NIR light path and electronic noise floor of our custom-built PFM set-up for detecting and quantifying resonances in the Brownian motion. These resonances arise from the coupling between the hydrodynamic memory and strong strength of the optical trap. Due to the high sensitivity of the short-time dynamics, the size of the particle can be measured by simultaneous fitting of the velocity autocorrelation function and power spectral density of its thermal fluctuations. In order to choose the best-suitable spherical probe for a given experiment in PFM, computational modeling based on a Matlab toolbox is performed. The generalized Lorenz-Mie theory is computed using the T -matrix method for various experimental conditions, including changes in the size and refractive index of the sphere, as well as different laser polarization states. The axial equilibrium position is examined to predict its location compared with the position of the laser focus. Optical forces acting on the sphere are investigated in 3D to highlight, in particular, the limits of the perfectly harmonic potential assumption. These limits are quantified and discussed. Subsequently, we identify different types of inorganic nano/micro-sized particles that can be trapped by the NIR laser of the PFM and used simultaneously as mechanical and near-field light sources. To this end, we take advantage of the visible light emission from single probes confined in the optical trap and excited by the NIR laser light. The emphasis is on particles revealing nonlinear optical properties. In particular, nonlinear optical field enhancement resulting from excitation of surface plasmon resonance (SPR) on trapped gold particles of 200 nm is demonstrated by measuring the emission of that second-harmonic generation (SHG). Furthermore, we show, under optical trapping conditions, SHG emission from single potassium niobate (KNbO3) nano/micro-sized particles. We also report on the multicolor upconversion luminescence (UCL), at the single particle level, for randomly shaped crystals of sodium yttrium fluoride codoped with ytterbium and erbium, NaYF4:Yb,Er (UCC), when they are held in the optical trap. In parallel, 3D Brownian fluctuations of a single trapped particle are quantified. Moreover, luminescence resonance energy transfer (LRET) between a KNbO3 particle or an UCC and molecules of an organic dye (rose bengal) adsorbed on their surface is highlighted and analyzed. Finally, randomly shaped UCCs and hexagonal nanoplates are characterized in detail at the single particle level. The hexagonal β phase in the polycrystalline and monocrystalline crystals is identified, in both randomly and hexagonally shaped particles by electron microscopy. UCL emission from the trapped crystal is quantified in terms of power and found to be dependent on the laser power density, size and shape of the particle as well as its orientation within the trap. Most importantly, the different colors in the UCL spectrum do not vary with the same trend for different orientations of the randomly or hexagonally shaped crystal upon trapping. This suggests the existence of crystalline anisotropy-dependent UCL. Thereby, we should be able to design the best-suited particle probe for LRET experiments with subwavelength resolution.

EPFL2013

Nanoparticle on mirror plasmonic nanostructure for molecular cavity optomechanics

Aqeel Ahmed, Christophe Marcel Georges Galland, Nils Kipfer, Tianqi Zhu

The plasmonic response of gold can be utilized to enhance the incident electromagnetic (EM) field by several orders of magnitude. When a gold nanoparticle is placed in close proximity to a gold film, the incident field can excite a deeply confined plasmon, strongly enhancing the Raman interaction with molecules placed within the gap. Recent theoretical predictions suggest the suitability of such arrangements to optically amplify the internal vibrations of molecules. This paper presents the fabrication and characterization of such plasmonic nanocavities.