RESUMEN
The recent surge of interest in polaritons has prompted fundamental questions about the role of dark states in strong light-matter coupling phenomena. Here, we systematically vary the relative number of dark states by controlling the number of stacked CdSe nanoplatelets confined in a Fabry-Pérot cavity. We find the emission spectrum to change significantly with an increasing number of nanoplatelets, with a gradual shift of the dominant emission intensity from the lower polariton branch to a manifold of dark states. Through accompanying calculations based on a kinetic model, this shift is rationalized by an entropic trapping of excitations by the dark state manifold, while a weak dark state dispersion due to local disorder explains their nonzero emission. Our results point toward the relevance of the dark state concentration to the optical and dynamical properties of cavity-embedded quantum emitters with ramifications for Bose-Einstein condensate formation, polariton lasing, polariton-based quantum transduction schemes, and polariton chemistry.
RESUMEN
Most photochemistry occurs in the regime of weak light-matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light-matter interactions between an optical field and multiple molecules lead to collective hybrid light-matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. The effect of strong light-matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light-matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.
RESUMEN
Two-dimensional (2D) materials have attracted attention for quantum information science due to their ability to host single-photon emitters (SPEs). Although the properties of atomically thin materials are highly sensitive to surface modification, chemical functionalization remains unexplored in the design and control of 2D material SPEs. Here, we report a chemomechanical approach to modify SPEs in monolayer WSe2 through the synergistic combination of localized mechanical strain and noncovalent surface functionalization with aryl diazonium chemistry. Following the deposition of an aryl oligomer adlayer, the spectrally complex defect-related emission of strained monolayer WSe2 is simplified into spectrally isolated SPEs with high single-photon purity. Density functional theory calculations reveal energetic alignment between WSe2 defect states and adsorbed aryl oligomer energy levels, thus providing insight into the observed chemomechanically modified quantum emission. By revealing conditions under which chemical functionalization tunes SPEs, this work broadens the parameter space for controlling quantum emission in 2D materials.
RESUMEN
Direct top-down nanopatterning of semiconductors is a powerful tool for engineering properties of optoelectronic devices. Translating this approach to two-dimensional semiconductors such as monolayer transition metal dichalcogenides (TMDs) is challenging because of both the small scales required for confinement and the degradation of electronic and optical properties caused by high-energy and high-dose electron radiation used for high-resolution top-down direct electron beam patterning. We show that encapsulating a TMD monolayer with hexagonal boron nitride preserves the narrow exciton linewidths and emission intensity typical in such heterostructures after electron beam lithography, allowing direct patterning of functional optical monolayer nanostructures on scales of a few tens of nanometers. We leverage this fabrication method to study size-dependent effects on nanodot arrays of MoS2 and MoSe2 as well as laterally confined electrical transport devices, demonstrating the potential of top-down lithography for nanoscale TMD optoelectronics.
RESUMEN
Selective breaking of degenerate energy levels is a well-known tool for coherent manipulation of spin states. Though most simply achieved with magnetic fields, polarization-sensitive optical methods provide high-speed alternatives. Exploiting the optical selection rules of transition metal dichalcogenide monolayers, the optical Stark effect allows for ultrafast manipulation of valley-coherent excitons. Compared to excitons in these materials, microcavity exciton-polaritons offer a promising alternative for valley manipulation, with longer lifetimes, enhanced valley coherence, and operation across wider temperature ranges. Here, we show valley-selective control of polariton energies in WS2 using the optical Stark effect, extending coherent valley manipulation to the hybrid light-matter regime. Ultrafast pump-probe measurements reveal polariton spectra with strong polarization contrast originating from valley-selective energy shifts. This demonstration of valley degeneracy breaking at picosecond timescales establishes a method for coherent control of valley phenomena in exciton-polaritons.