Intrinsic luminescence blinking from plasmonic nanojunctions

Plasmonic nanojunctions, consisting of adjacent metal structures with nanometre gaps, can support localised plasmon resonances that boost light matter interactions and concentrate electromagnetic fields at the nanoscale. In this regime, the optical response of the system is governed by poorly understood dynamical phenomena at the frontier between the bulk, molecular and atomic scales. Here, we report ubiquitous spectral fluctuations in the intrinsic light emission from photo-excited gold nanojunctions, which we attribute to the light-induced formation of domain boundaries and quantum-confined emitters inside the noble metal. Our data suggest that photoexcited carriers and gold adatom - molecule interactions play key roles in triggering luminescence blinking. Surprisingly, this internal restructuring of the metal has no measurable impact on the Raman signal and scattering spectrum of the plasmonic cavity. Our findings demonstrate that metal luminescence offers a valuable proxy to investigate atomic fluctuations in plasmonic cavities, complementary to other optical and electrical techniques.

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

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

Investigation of photoinduced effects in plasmonic nanocavities

Aqeel Ahmed

EPFL2021

Carbon nanotubes functionalized with dye molecules and metal nanoparticles

Tilman Assmus

EPFL2008