Pump-Selective Spectral Shaping of the Ultrafast Response in Plasmonic Nanostars

Plasmonic nanostructures are, to date, well-known to offer unique possibilities for the tailoring of light–matter interactions at the nanoscale. Most recently, a new route to ultrafast all-optical modulation has been disclosed by combining the resonant features of plasmonic nanostructures with the giant third-order optical nonlinearity of noble metals regulated by highly energetic (hot) carriers. In this framework, a variety of nanostructures have been designed, with special attention to shapes featuring tips, where extreme and highly sensitive field enhancements (hot spots) can be attained. Here, we report on a broadband pump–probe spectroscopy analysis of an ensemble of spiky star-shaped nanoparticles, exploring both the perturbative and nonperturbative regimes of photoexcitation. The experiments are corroborated by semiclassical numerical simulations of the ultrafast optical response of the sample. We found that the peculiar hot spots supported by the star tips allow one to easily control the spectral shape of the transient optical signal, upon tuning of the pump wavelength. Our results elucidate the ultrafast response of hot electrons in star-shaped nanostructures and contribute to the understanding of the tip-mediated enhanced nonlinearities. This work paves the way to the development of ultrafast all-optical plasmonic modulators for pump-selective spectral shaping

Activated Singlet Exciton Fission in a Semiconducting Polymer

Singlet exciton fission is a spin-allowed process to generate two triplet excitons from a single absorbed photon. This phenomenon offers great potential in organic photovoltaics, but the mechanism remains poorly understood. Most reports to date have addressed intermolecular fission within small-molecular crystals. However, through appropriate chemical design chromophores capable of intramolecular fission can also be produced. Here we directly observe sub-100 fs activated singlet fission in a semiconducting poly­(thienylenevinylene). We demonstrate that fission proceeds directly from the initial 1B_u exciton, contrary to current models that involve the lower-lying 2A_g exciton. In solution, the generated triplet pairs rapidly recombine and decay through the 2A_g state. In films, exciton diffusion breaks this symmetry and we observe long-lived triplets which form charge-transfer states in photovoltaic blends

Panchromatic “Dye-Doped” Polymer Solar Cells: From Femtosecond Energy Relays to Enhanced Photo-Response

There has been phenomenal effort synthesizing new low-band gap polymer hole-conductors which absorb into the near-infrared (NIR), leading to >10% efficient all-organic solar cells. However, organic light absorbers have relatively narrow bandwidths, making it challenging to obtain panchromatic absorption in a single organic semiconductor. Here, we demonstrate that (poly­[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta­[2,1-b;3,4-b0]­dithiophene)-alt-4,7-(2,1,3-benzothiadia-zole)] (PCPDTBT) can be “photo-sensitized” across the whole visible spectrum by “doping” with a visible absorbing dye, the (2,2,7,7-tetrakis­(3-hexyl-5-(7-(4-hexylthiophen-2-yl)­benzo­[c]­[1,2,5]­thiadiazol-4-yl)­thiophen-2-yl)-9,9-spirobifluorene) (spiro-TBT). Through a comprehensive sub-12 femtosecond–nanosecond spectroscopic study, we demonstrate that extremely efficient and fast energy transfer occurs from the photoexcited spiro-TBT to the PCPDTBT, and ultrafast charge injection happens when the system is interfaced with ZnO as a prototypal electron-acceptor compound. The visible photosensitization can be effectively exploited and gives panchromatic photoresponse in prototype polymer/oxide bilayer photovoltaic diodes. This concept can be successfully adopted for tuning and optimizing the light absorption and photoresponse in a broad range of polymeric and hybrid solar cells