Structural Order of the Molecular Adlayer Impacts the Stability of Nanoparticle-on-Mirror Plasmonic Cavities

Immense field enhancement and nanoscale confinement of light are possible within nanoparticle-on-mirror (NPoM) plasmonic resonators, which enable novel optically activated physical and chemical phenomena and render these nanocavities greatly sensitive to minute structural changes, down to the atomic scale. Although a few of these structural parameters, primarily linked to the nanoparticle and the mirror morphology, have been identified, the impact of molecular assembly and organization of the spacer layer between them has often been left uncharacterized. Here, we experimentally investigate how the complex and reconfigurable nature of a thiol-based self-assembled monolayer (SAM) adsorbed on the mirror surface impacts the optical properties of the NPoMs. We fabricate NPoMs with distinct molecular organizations by controlling the incubation time of the mirror in the thiol solution. Afterward, we investigate the structural changes that occur under laser irradiation by tracking the bonding dipole plasmon mode, while also monitoring Stokes and anti-Stokes Raman scattering from the molecules as a probe of their integrity. First, we find an effective decrease in the SAM height as the laser power increases, compatible with an irreversible change of molecule orientation caused by heating. Second, we observe that the nanocavities prepared with a densely packed and more ordered monolayer of molecules are more prone to changes in their resonance compared to samples with sparser and more disordered SAMs. Our measurements indicate that molecular orientation and packing on the mirror surface play a key role in determining the stability of NPoM structures and hence highlight the under-recognized significance of SAM characterization in the development of NPoM-based applications.

Investigation of photoinduced effects in plasmonic nanocavities

Aqeel Ahmed

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.

EPFL2021

Carbon nanotubes functionalized with dye molecules and metal nanoparticles

Tilman Assmus

Single-walled carbon nanotubes are highly interesting quasi one-dimensional nanostructures. They possess a multitude of fascinating optical, mechanical and electrical properties, which can be even further expanded through appropriate functionalization strategies. This thesis covers a number of functionalization strategies and their effects on the nanotube's optical and electrical properties. The first part deals with the functionalization of carbon nanotubes with dye molecules and the characterization of the functionalized system. Both covalent and noncovalent approaches were investigated with the goal of modifying the nanotubes' photoelectrical properties. Upon excitation with light of the appropriate wavelength, a clear electrical response could be observed on some functionalized individual nanotubes. Depending on the attached dye molecule, the conductivity change is either induced by a light-induced conformational change or by a charge transfer between the nanotube and the excited dye molecule. The perspectives of constructing an optoelectronic nanoswitch based on these effects are discussed. The second part of the thesis addresses carbon nanotubes functionalized by a low density of electrodeposited gold nanoparticles with sizes in the range between 10 and 100nm. In this case, the functionalization is targeted on amplifying the nanotube's Raman response (SERS effect). The novel sample preparation technique developed in this thesis allowed for an investigation of SERS on the level of individual molecule / nanoparticle hybrids. The optical emission spectra of the nanotube-nanoparticle hybrid structure disclosed Raman peaks associated with the nanotubes, which are superimposed on a broad luminescence background originating from the metal particles. Wavelength dependent experiments revealed maximum Raman intensity when both the nanotube and the metal particle are in optical resonance. In well-prepared samples the Raman signals collected over isolated particles exhibited an intensity enhancement by at least one order of magnitude, as compared to bare sections on the same tube, without appreciably interfering with polarization dependent Raman measurements.

EPFL2008

Core-Shell GaAs Nanowire p-n Junctions from Growth to Photovoltaic and Optoelectronic Applications

Carlo Colombo

Semiconductor nanowires (NWs) are filamentary crystals with the diameter ranging from few tens up to few hundreds of nanometers. In the last 15 years, they have been intensively studied for the prospectives that their unique quasi-one dimensional shape offers to both fundamental and applied physics. More recently particular attention has been dedicated to the advantages that their geometry exhibits in the separation and extraction of photo-generated carriers with respect to standard thin film or bulk technologies. The aim of this thesis is the realization and characterization of single GaAs NW photovoltaic and optoelectronic devices. The work starts with the synthesis of radial NWp-n junctions. The core growth has been realized using the Vapor-Liquid-Solid (V LS) mechanism by Molecular Beam Epitaxy (MBE). Differently from the commonly used V LS method, which requires Au particles as a catalyst, we use a self-catalyzed process which avoids potential contaminations. The shell is then overgrown around, switching the growth parameters toward standard thin film conditions. The doping mechanism of such a structure has been deeply investigated, with the purpose of discriminating in which way the dopants get incorporated in the crystal structure. A reproducible technique has been developed to electrically contact the NWs and test their photovoltaic properties. They have been measured under different illumination conditions. Conversion efficiency of about 4.5% have been measured under diffuse illumination at 1.5AM and more information about the uniformity of the junction have been deduced by scanning photo-current measurements. Due to the size comparable with the wavelength of the visible light, NWs exhibit characteristic absorption peaks as a function of the photon energy, often referred as Mie resonances. In order to engineer these resonances we have deposited metal nanoparticles on their facets and studied how the plasmonic excitation of the latter could couple with the NW leaky modes. The results have been analyzed with Finite Difference Frequency Domain (FDFD) simulations. Since GaAs is a direct band-gap material, the same devices have also been tested in a reverse way as light emitting diodes and plasmon generators. Finally some preliminary studies about the effect of axial wurtzite/zincblende polytypism on the electronic properties have been performed.

EPFL2012