Revealing the Band-Edge Exciton Fine Structure of Single InP Nanocrystals.

We investigate the fundamental optical properties of single zinc-blende InP/ZnSe/ZnS nanocrystals (NCs) using frequency- and time-resolved magneto-photoluminescence spectroscopy. At liquid helium temperature, highly resolved spectral fingerprints are obtained and identified as the recombination lines of the three lowest states of the band-edge exciton fine structure. The evolutions of the photoluminescence spectra and decays under magnetic fields show evidence for a ground dark exciton level 0L with zero angular momentum projection along the NC main elongation axis. It lies 300 to 600 µeV below the ±1L bright exciton doublet, which is finely split by the NC shape anisotropy. These spectroscopic findings are well reproduced with a model of exciton fine structure accounting for shape anisotropy of the InP core. Our spectral fingerprints are extremely sensitive to the NC morphologies and unveil highly uniform shapes with prolate deviations of less than 3% from perfect sphericity.

High-resolution optical imaging of single magnetic flux quanta with a solid immersion lens.

Magneto-optical imaging of quantized magnetic flux tubes in superconductors - Abrikosov vortices - is based on Faraday rotation of light polarization within a magneto-optical indicator placed on top of the superconductor. Due to severe aberrations induced by the thick indicator substrate, the spatial resolution of vortices is usually well beyond the optical diffraction limit. Using a high refractive index solid immersion lens placed onto the indicator garnet substrate, we demonstrate wide field optical imaging of single flux quanta in a Niobium film with a resolution better than 600 nm and sub-second acquisition periods, paving the way to high-precision and fast vortex manipulation. Vectorial field simulations are also performed to reproduce and optimize the experimental features of vortex images.

Single-walled carbon nanotube reptation dynamics in submicron sized pores from randomly packed mono-sized colloids.

Studying the Brownian motion of fibers and semi-flexible filaments in porous media is the key to understanding the transport and mechanical properties in a variety of systems. The motion of semi-flexible filaments in gel-like porous media including polymer networks and cell cytoskeleton has been studied theoretically and experimentally, whereas the motion of these materials in packed-colloid porous media, advanced foams, and rock-like systems has not been thoroughly studied. Here we use video microscopy to directly visualize the reptation and transport of intrinsically fluorescent, semiflexible, semiconducting single-walled carbon nanotubes (SWCNTs) in the sub-micron pores of packed colloids as fixed obstacles of packed-colloid porous media. By visualizing the filament motion and Brownian diffusion at different locations in the pore structures, we study how the properties of the environment, like the pore shape and pore structure of the porous media, affect SWCNT mobility. These results show that the porous media structure controls SWCNT reorientation during Brownian diffusion. In packed-colloid pores, SWCNTs diffuse along straight pores and bend across pores; conversely, in gel pores, SWCNTs consistently diffuse into curved pores, displaying a faster parallel motion. In both gel and packed-colloid porous media, SWCNT finite stiffness enhances SWCNT rotational diffusion and prevents jamming, allowing for inter-pore diffusion.

Self-interference 3D super-resolution microscopy for deep tissue investigations.

Fluorescence localization microscopy has achieved near-molecular resolution capable of revealing ultra-structures, with a broad range of applications, especially in cellular biology. However, it remains challenging to attain such resolution in three dimensions and inside biological tissues beyond the first cell layer. Here we introduce SELFI, a framework for 3D single-molecule localization within multicellular specimens and tissues. The approach relies on self-interference generated within the microscope's point spread function (PSF) to simultaneously encode equiphase and intensity fluorescence signals, which together provide the 3D position of an emitter. We combined SELFI with conventional localization microscopy to visualize F-actin 3D filament networks and reveal the spatial distribution of the transcription factor OCT4 in human induced pluripotent stem cells at depths up to 50 µm inside uncleared tissue spheroids. SELFI paves the way to nanoscale investigations of native cellular processes in intact tissues.

On-Demand Optical Generation of Single Flux Quanta.

Superconductors can host quantized magnetic flux tubes surrounded by supercurrents, called Abrikosov vortices. Vortex penetration into a superconducting film is usually limited to its edges and triggered by external magnetic fields or local electrical currents. With a view to novel research directions in quantum computation, the possibility to generate and control single flux quanta in situ is thus challenging. We introduce a far-field optical method to sculpt the magnetic flux or generate permanent single vortices at any desired position in a superconductor. It is based on a fast quench following the absorption of a tightly focused laser pulse that locally heats the superconductor above its critical temperature. We achieve ex-nihilo creation of a single vortex pinned at the center of the hotspot, while its counterpart opposite flux is trapped tens of micrometers away at its boundaries. Our method paves the way to optical operation of Josephson transport with single flux quanta.

The ground exciton state of formamidinium lead bromide perovskite nanocrystals is a singlet dark state.

Lead halide perovskites have emerged as promising new semiconductor materials for high-efficiency photovoltaics, light-emitting applications and quantum optical technologies. Their luminescence properties are governed by the formation and radiative recombination of bound electron-hole pairs known as excitons, whose bright or dark character of the ground state remains unknown and debated. While symmetry analysis predicts a singlet non-emissive ground exciton topped with a bright exciton triplet, it has been predicted that the Rashba effect may reverse the bright and dark level ordering. Here, we provide the direct spectroscopic signature of the dark exciton emission in the low-temperature photoluminescence of single formamidinium lead bromide perovskite nanocrystals under magnetic fields. The dark singlet is located several millielectronvolts below the bright triplet, in fair agreement with an estimation of the long-range electron-hole exchange interaction. Nevertheless, these perovskites display an intense luminescence because of an extremely reduced bright-to-dark phonon-assisted relaxation.

Neutral and Charged Exciton Fine Structure in Single Lead Halide Perovskite Nanocrystals Revealed by Magneto-optical Spectroscopy.

Revealing the crystal structure of lead halide perovskite nanocrystals is essential for the optimization of stability of these emerging materials in applications such as solar cells, photodetectors, and light-emitting devices. We use magneto-photoluminescence spectroscopy of individual perovskite CsPbBr3 nanocrystals as a unique tool to determine their crystal structure, which imprints distinct signatures in the excitonic sublevels of charge complexes at low temperatures. At zero magnetic field, the identification of two classes of photoluminescence spectra, displaying either two or three sublevels in their exciton fine structure, shows evidence for the existence of two crystalline structures, namely tetragonal D4h and orthorhombic D2h phases. Magnetic field shifts, splitting, and coupling of the sublevels provide a determination of the diamagnetic coefficient and valuable information on the exciton g-factor and its anisotropic character. Moreover, this spectroscopic study reveals the optical properties of charged excitons and allows the extraction of the electron and hole g-factors for perovskite systems.

Chemical Cutting of Perovskite Nanowires into Single-Photon Emissive Low-Aspect-Ratio CsPbX3 (X=Cl, Br, I) Nanorods.

Post-synthetic shape-transformation processes provide access to colloidal nanocrystal morphologies that are unattainable by direct synthetic routes. Herein, we report our finding about the ligand-induced fragmentation of CsPbBr3 perovskite nanowires (NWs) into low aspect-ratio CsPbX3 (X=Cl, Br and I) nanorods (NRs) during halide ion exchange reaction with PbX2 -ligand solution. The shape transformation of NWs-to-NRs resulted in an increase of photoluminescence efficiency owing to a decrease of nonradiative decay rates. Importantly, we found that the perovskite NRs exhibit single photon emission as revealed by photon antibunching measurements, while it is not detected in parent NWs. This work not only reports on the quantum light emission of low aspect ratio perovskite NRs, but also expands our current understanding of shape-dependent optical properties of perovskite nanocrystals.

Carrier Multiplication in a Single Semiconductor Nanocrystal.

To confirm the existence of the carrier multiplication (CM) effect and estimate its generation efficiency of multiple excitons in semiconductor nanocrystals (NCs), it is imperative to completely exclude the false contribution of charged excitons from the measured CM signal. Here we place single CdSe NCs above an aluminum film and successfully resolve their UV-excited photoluminescence (PL) time trajectories where the true and false CM signals are contained in the blinking "on" and "off" levels, respectively. By analyzing the PL dynamics of the on-level photons, an average CM efficiency of ∼20.2% can be reliably estimated when the UV photon energy is ∼2.46 times the NC energy gap.

Transport of fibroblast growth factor 2 in the pericellular matrix is controlled by the spatial distribution of its binding sites in heparan sulfate.

The heparan sulfate (HS) chains of proteoglycans are a key regulatory component of the extracellular matrices of animal cells, including the pericellular matrix around the plasma membrane. In these matrices they regulate transport, gradient formation, and effector functions of over 400 proteins central to cell communication. HS from different matrices differs in its selectivity for its protein partners. However, there has been no direct test of how HS in the matrix regulates the transport of its partner proteins. We address this issue by single molecule imaging and tracking in fibroblast pericellular matrix of fibroblast growth factor 2 (FGF2), stoichiometrically labelled with small gold nanoparticles. Transmission electron microscopy and photothermal heterodyne imaging (PHI) show that the spatial distribution of the HS-binding sites for FGF2 in the pericellular matrix is heterogeneous over length scales ranging from 22 nm to several µm. Tracking of individual FGF2 by PHI in the pericellular matrix of living cells demonstrates that they undergo five distinct types of motion. They spend much of their time in confined motion (∼110 nm diameter), but they are not trapped and can escape by simple diffusion, which may be slow, fast, or directed. These substantial translocations (µm) cover distances far greater than the length of a single HS chain. Similar molecular motion persists in fixed cells, where the movement of membrane PGs is impeded. We conclude that FGF2 moves within the pericellular matrix by translocating from one HS-binding site to another. The binding sites on HS chains form non-random, heterogeneous networks. These promote FGF2 confinement or substantial translocation depending on their spatial organisation. We propose that this spatial organisation, coupled to the relative selectivity and the availability of HS-binding sites, determines the transport of FGF2 in matrices. Similar mechanisms are likely to underpin the movement of many other HS-binding effectors.

Spectroscopy of single nanocrystals.

As colloidal semiconductor nanocrystals are developed for a wider range of diverse applications, it becomes more important to gain a deeper understanding of their properties in order to direct synthetic efforts. While most synthetic developments are guided by changes in ensemble properties, certain applications such as those in nano-electronics and nano-photonics rely on properties of nanocrystals at the individual level. For such applications and even for a more detailed understanding of the ensemble behavior, single nanocrystal spectroscopy becomes a vital tool. This review looks at how single nanocrystal spectroscopy has been applied to materials based on modern synthetic techniques and how these studies are elucidating properties that remain hidden at the ensemble level. First, recent theoretical models that are important for understanding many observed phenomena are explored. Then the review highlights new insights into many of the photophysical properties that are of interest in semiconductor nanocrystal materials, such as the ubiquitous spectral instability, magneto-optical identification of the band-edge exciton fine structure, emission from multi-excitons, and the spectroscopic properties of charged nanocrystals that challenge long standing theories on photoluminescence blinking behavior. To date most of the research has been conducted on materials based on cadmium selenide primarily due to its many years of development as a prototypical nanocrystal system. The review ends with a discussion of new materials that would also benefit from a detailed photophysical understanding afforded by single nanocrystal spectroscopy.

State selective pumping reveals spin-relaxation pathways in CdSe quantum dots.

The band-edge exciton in elongated CdSe nanocrystals is composed of an upper and lower manifold associated with heavy and light holes in which the energy separation is sensitive to the nanocrystal shape. Using resonant photoluminescence excitation, we probe the upper heavy hole exciton manifold and find rapid relaxation to the lower light hole manifold on a 5 ps time scale. State selective excitation allows the preparation of single quantum states in this system. We used this to map the hole spin relaxation pathways between the fine structure sublevels, which have energy splittings incommensurate with either optical or acoustic phonon energies. This reveals a hitherto unexpected hole spin-relaxation channel in these materials.

Super-resolution microscopy approaches for live cell imaging.

By delivering optical images with spatial resolutions below the diffraction limit, several super-resolution fluorescence microscopy techniques opened new opportunities to study biological structures with details approaching molecular structure sizes. They have now become methods of choice for imaging proteins and their nanoscale dynamic organizations in live cells. In this mini-review, we describe and compare the main far-field super-resolution approaches that allow studying endogenous or overexpressed proteins in live cells.

Large parallelization of STED nanoscopy using optical lattices.

As a scanning microscope, STimulated Emission Depletion (STED) nanoscopy needs parallelization for fast wide-field imaging. Using well-designed optical lattices for depletion together with wide-field excitation and a fast camera for detection, we achieve large parallelization of STED nanoscopy. Wide field of view super-resolved images are acquired by scanning over a single unit cell of the optical lattice, which can be as small as 290 nm * 290 nm. Optical Lattice STED (OL-STED) imaging is demonstrated with a resolution down to 70 nm at 12.5 frames per second.

Photothermal microscopy: optical detection of small absorbers in scattering environments.

Photothermal microscopy enables detection of nanometer-sized objects solely based on their absorption. This technique allows efficient observation of various nano-objects in scattering media notably gold nanoparticles in cells. The extreme sensitivity of the method and the stability of the signals open numerous applications in spectroscopy, analytical chemistry and bioimaging. This review briefly describes the principle and the main characteristics of photothermal microscopy, with its major advantages and limitations, and exposes the principal applications that have been carried out since its first implementation.

The optical phonon spectrum of CdSe colloidal quantum dots.

The direct coupling of excited electronic states to optical phonons in single CdSe colloidal quantum dots is explored using both photoluminescence emission and excitation spectroscopies. We find a broad optical phonon spectrum associated with a single fine structure state. Multiple peaks in the optical phonon sideband are ascribed to different optical phonon types emanating from both the core and shell layers. A mixed emission process that involves the simultaneous generation of two different types of optical phonon is also observed. In general, rather than a single mode, each designated phonon type is associated with a dispersed family of modes. Narrow optical phonon sidebands, consistent with the dominant LO mode, are observed in some nanocrystals. A linewidth analysis indicates that optical phonon lifetimes are in the 10 picosecond range. We demonstrate the ability to selectively excite a specific band-edge state by directly exciting its LO phonon sideband.

A highly specific gold nanoprobe for live-cell single-molecule imaging.

Single molecule tracking in live cells is the ultimate tool to study subcellular protein dynamics, but it is often limited by the probe size and photostability. Because of these issues, long-term tracking of proteins in confined and crowded environments, such as intracellular spaces, remains challenging. We have developed a novel optical probe consisting of 5 nm gold nanoparticles functionalized with a small fragment of camelid antibodies that recognize widely used green fluorescent proteins (GFPs) with a very high affinity, which we call GFP-nanobodies. These small gold nanoparticles can be detected and tracked using photothermal imaging for arbitrarily long periods of time. Surface and intracellular GFP-proteins were effectively labeled even in very crowded environments such as adhesion sites and cytoskeletal structures both in vitro and in live cell cultures. These nanobody-coated gold nanoparticles are probes with unparalleled capabilities; small size, perfect photostability, high specificity, and versatility afforded by combination with the vast existing library of GFP-tagged proteins.

Giant Quantum Electrodynamic Effects on Single SiV Color Centers in Nanosized Diamonds.

Understanding and mastering quantum electrodynamics phenomena is essential to the development of quantum nanophotonics applications. While tailoring of the local vacuum field has been widely used to tune the luminescence rate and directionality of a quantum emitter, its impact on their transition energies is barely investigated and exploited. Fluorescent defects in nanosized diamonds constitute an attractive nanophotonic platform to investigate the Lamb shift of an emitter embedded in a dielectric nanostructure with high refractive index. Using spectral and time-resolved optical spectroscopy of single SiV defects, we unveil blue shifts (up to 80 meV) of their emission lines, which are interpreted from model calculations as giant Lamb shifts. Moreover, evidence for a positive correlation between their fluorescence decay rates and emission line widths is observed, as a signature of modifications not only of the photonic local density of states but also of the phononic one, as the nanodiamond size is decreased. Correlative light-electron microscopy of single SiVs and their host nanodiamonds further supports these findings. These results make nanodiamond-SiVs promising as optically driven spin qubits and quantum light sources tunable through nanoscale tailoring of vacuum-field fluctuations.

Mechanism of electrolyte-induced brightening in single-wall carbon nanotubes.

While addition of electrolyte to sodium dodecyl sulfate suspensions of single-wall carbon nanotubes has been demonstrated to result in significant brightening of the nanotube photoluminescence (PL), the brightening mechanism has remained unresolved. Here, we probe this mechanism using time-resolved PL decay measurements. We find that PL decay times increase by a factor of 2 on addition of CsCl as the electrolyte. Such an increase directly parallels an observed near-doubling of PL intensity, indicating the brightening results primarily from changes in nonradiative decay rates associated with exciton diffusion to quenching sites. Our findings indicate that a reduced number of these sites results from electrolyte-induced reorientation of the surfactant surface structure that partially removes pockets of water from the tube surface where excitons can dissociate, and thus underscores the contribution of interfacial water in exciton recombination processes.

Single molecule detection of nanomechanical motion.

We investigate theoretically how single molecule spectroscopy techniques can be used to perform fast and high resolution displacement detection and manipulation of nanomechanical oscillators, such as singly clamped carbon nanotubes. We analyze the possibility of real time displacement detection by the luminescence signal and of displacement fluctuations by the degree of second order coherence. Estimates of the electromechanical coupling constant indicate that intriguing regimes of strong backaction between the two-level system of a molecule and the oscillator can be realized.