Extinction imaging of a single quantum emitter in its bright and dark states

Room temperature detection of single quantum emitters has had a broad impact in fields ranging from biophysics to material science, photophysics, or even quantum optics. These experiments have exclusively relied on the efficient detection of fluorescence. An attractive alternative would be to employ direct absorption, or more correctly expressed "extinction" measurements. Indeed, small nanoparticles have been successfully detected using this scheme in reflection and transmission. Coherent extinction detection of single emitters has also been reported at cryogenic temperatures, but their room temperature implementation has remained a great laboratory challenge owing to the expected weak signal-to-noise ratio. Here we report the first extinction study of a single quantum emitter at ambient condition. We obtain a direct measure for the extinction cross section of a single semiconductor nanocrystal both during and in the absence of fluorescence, for example in the photobleached state or during blinking off-times. Our measurements pave the way for the detection and absorption spectroscopy of single molecules or clusters of atoms even in the quenched state

Single-Photon Imaging and Efficient Coupling to Single Plasmons

We demonstrate strong coupling of single photons emitted by individual molecules at cryogenic and ambient conditions to individual nanoparticles. We provide images obtained both in transmission and reflection, where an efficiency greater than 55% was achieved in converting incident narrow-band photons to plasmon-polaritons (plasmons) of a silver nanoparticle. Our work paves the way to spectroscopy and microscopy of nano-objects with sub-shot noise beams of light and to triggered generation of single plasmons and electrons in a well-controlled manner

A planar dielectric antenna for directional single-photon emission and near-unity collection efficiency

Single emitters have been considered as sources of single photons in various contexts such as cryptography, quantum computation, spectroscopy, and metrology. The success of these applications will crucially rely on the efficient directional emission of photons into well-defined modes. To accomplish a high efficiency, researchers have investigated microcavities at cryogenic temperatures, photonic nanowires, and near-field coupling to metallic nano-antennas. However, despite an impressive progress, the existing realizations substantially fall short of unity collection efficiency. Here we report on a theoretical and experimental study of a dielectric planar antenna, which uses a layered structure for tailoring the angular emission of a single oriented molecule. We demonstrate a collection efficiency of 96% using a microscope objective at room temperature and obtain record detection rates of about 50 MHz. Our scheme is wavelength-insensitive and can be readily extended to other solid-state emitters such as color centers and semiconductor quantum dots

Fluorescent oxide nanoparticles adapted to active tips for near-field optics

We present a new kind of fluorescent oxide nanoparticles with properties well suited to active-tip based near-field optics. These particles with an average diameter in the range 5-10 nm are produced by Low Energy Cluster Beam Deposition (LECBD) from a YAG:Ce3+ target. They are studied by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), classical photoluminescence, cathodoluminescence and near-field scanning optical microscopy (NSOM). Particles of extreme photo-stability as small as 10 nm in size are observed. These emitters are validated as building blocks of active NSOM tips by coating a standard optical tip with a 10 nm thick layer of YAG:Ce3+ particles directly in the LECBD reactor and by subsequently performing NSOM imaging of test surfaces.Comment: Changes made following Referee's comments; added references; one added figure. See story on this article at: http://nanotechweb.org/cws/article/tech/3606

Two-Dimensional Impulsively Stimulated Resonant Raman Spectroscopy of Molecular Excited States

Monitoring the interactions between electronic and vibrational degrees of freedom in molecules is critical to our understanding of their structural dynamics. This is typically hampered by the lack of spectroscopic probes able to detect different energy scales with high temporal and frequency resolution. Coherent Raman spectroscopy can combine the capabilities of multidimensional spectroscopy with structural sensitivity at ultrafast timescales. Here, we develop a three-color-based 2D impulsive stimulated Raman technique that can selectively probe vibrational mode couplings between different active sites in molecules by taking advantage of resonance Raman enhancement. Three temporally delayed pulses generate nuclear wave packets whose evolution reports on the underlying potential energy surface, which we decipher using a diagrammatic approach enabling us to assign the origin of the spectroscopic signatures. We benchmark the method by revealing vibronic couplings in the ultrafast dynamics following photoexcitation of the green fluorescent protein

Two-Dimensional Impulsively Stimulated Resonant Raman Spectroscopy of Molecular Excited States

Monitoring the interactions between electronic and vibrational degrees of freedom in molecules is critical to our understanding of their structural dynamics. This is typically hampered by the lack of spectroscopic probes able to detect different energy scales with high temporal and frequency resolution. Coherent Raman spectroscopy can combine the capabilities of multidimensional spectroscopy with structural sensitivity at ultrafast timescales. Here, we develop a three-color-based 2D impulsive stimulated Raman technique that can selectively probe vibrational mode couplings between different active sites in molecules by taking advantage of resonance Raman enhancement. Three temporally delayed pulses generate nuclear wave packets whose evolution reports on the underlying potential energy surface, which we decipher using a diagrammatic approach enabling us to assign the origin of the spectroscopic signatures. We benchmark the method by revealing vibronic couplings in the ultrafast dynamics following photoexcitation of the green fluorescent protein.C. S. acknowledges financial support by the Royal Commission for the Exhibition of 1851. G. Bat. acknowledges the “Avvio Alla Ricerca 2018” grant by Sapienza Universitá di Roma. T. W. acknowledges the Marie Curie Intra-European Fellowship (PIEF-GA-2013-623651) within the 7th European Community Framework Programme. S. M. gratefully acknowledges the support of the National Science Foundation Grant No. CHE-1663822

Long-range ballistic propagation of carriers in methylammonium lead iodide perovskite thin films

© 2019, The Author(s), under exclusive licence to Springer Nature Limited. The performance of semiconductor devices is fundamentally governed by charge-carrier dynamics within the active materials1–6. Although advances have been made towards understanding these dynamics under steady-state conditions, the importance of non-equilibrium phenomena and their effect on device performances remains elusive7,8. In fact, the ballistic propagation of carriers is generally considered to not contribute to the mechanism of photovoltaics (PVs) and light-emitting diodes, as scattering rapidly disrupts such processes after carrier generation via photon absorption or electric injection9. Here we characterize the spatiotemporal dynamics of carriers immediately after photon absorption in methylammonium lead iodide perovskite films using femtosecond transient absorption microscopy (fs-TAM) with a 10 fs temporal resolution and 10 nm spatial precision. We found that non-equilibrium carriers propagate ballistically over 150 nm within 20 fs of photon absorption. Our results suggest that in a typical perovskite PV device operating under standard conditions, a large fraction of carriers can reach the charge collection layers ballistically. The ballistic transport distance appears to be limited by energetic disorder within the materials, probably due to disorder-induced scattering. This provides a direct route towards optimization of the ballistic transport distance via improvements in materials and by minimizing the energetic disorder. Our observations reveal an unexplored regime of carrier transport in perovskites, which could have important consequences for device performance

Optical detection of single non-absorbing molecules using the surface plasmon of a gold nanorod

Current optical detection schemes for single molecules require light absorption, either to produce fluorescence or direct absorption signals. This severely limits the range of molecules that can be detected, because most molecules are purely refractive. Metal nanoparticles or dielectric resonators detect non-absorbing molecules by a resonance shift in response to a local perturbation of the refractive index, but neither has reached single-protein sensitivity. The most sensitive plasmon sensors to date detect single molecules only when the plasmon shift is amplified by a highly polarizable label or by a localized precipitation reaction on the particle's surface. Without amplification, the sensitivity only allows for the statistical detection of single molecules. Here we demonstrate plasmonic detection of single molecules in realtime, without the need for labeling or amplification. We monitor the plasmon resonance of a single gold nanorod with a sensitive photothermal assay and achieve a ~ 700-fold increase in sensitivity compared to state-of-the-art plasmon sensors. We find that the sensitivity of the sensor is intrinsically limited due to spectral diffusion of the SPR. We believe this is the first optical technique that detects single molecules purely by their refractive index, without any need for photon absorption by the molecule. The small size, bio-compatibility and straightforward surface chemistry of gold nanorods may open the way to the selective and local detection of purely refractive proteins in live cells

A large geometric distortion in the first photointermediate of rhodopsin, determined by double-quantum solid-state NMR

Double-quantum magic-angle-spinning NMR experiments were performed on 11,12-C-13(2)-retinylidene-rhodopsin under illumination at low temperature, in order to characterize torsional angle changes at the C11-C12 photoisomerization site. The sample was illuminated in the NMR rotor at low temperature (similar to 120 K) in order to trap the primary photointermediate, bathorhodopsin. The NMR data are consistent with a strong torsional twist of the HCCH moiety at the isomerization site. Although the HCCH torsional twist was determined to be at least 40A degrees, it was not possible to quantify it more closely. The presence of a strong twist is in agreement with previous Raman observations. The energetic implications of this geometric distortion are discussed

A molecular movie of ultrafast singlet fission

Abstract: The complex dynamics of ultrafast photoinduced reactions are governed by their evolution along vibronically coupled potential energy surfaces. It is now often possible to identify such processes, but a detailed depiction of the crucial nuclear degrees of freedom involved typically remains elusive. Here, combining excited-state time-domain Raman spectroscopy and tree-tensor network state simulations, we construct the full 108-atom molecular movie of ultrafast singlet fission in a pentacene dimer, explicitly treating 252 vibrational modes on 5 electronic states. We assign the tuning and coupling modes, quantifying their relative intensities and contributions, and demonstrate how these modes coherently synchronise to drive the reaction. Our combined experimental and theoretical approach reveals the atomic-scale singlet fission mechanism and can be generalized to other ultrafast photoinduced reactions in complex systems. This will enable mechanistic insight on a detailed structural level, with the ultimate aim to rationally design molecules to maximise the efficiency of photoinduced reactions