Measuring the orientation of a single CdSe/CdS nanocrystal at the end of a near-field tip for the realization of a versatile active SNOM probe.

The orientation of a CdSe/CdS nanocrystal attached at the end of a scanning near field optical microscope (SNOM) tip is analyzed by its coupling with a flat gold layer. The Purcell factors for a set of distances to the gold surface are measured after a NC is caught by a SNOM tip. These measurements are compared with the modeling of the emission of a 2D dipole on a gold layer taking into account the layer of polymer serving as a glue for the NC. The 2D dipole is perpendicular to the c-axis of the NC, which is the growth axis. The behavior of the Purcell factor as a function of the distance to the gold layer depends on the angle made by this axis and the surface. The adjustment of the experimental results and the modelization gives the orientation of the NC at the end of the SNOM tip. Different orientations of the c-axis are determined.

Ultrafast exciton dynamics in 2D in-plane hetero-nanostructures: delocalization and charge transfer.

In this article we study the ultrafast dynamics of excitons and charge carriers photogenerated in two-dimensional in-plane heterostructures, namely, CdSe-CdTe nanoplatelets. We combine transient absorption and two-dimensional electronic spectroscopy to study charge transfer and delocalization from a few tens of femtoseconds to several nanoseconds. In contrast with spherical nanocrystals, the relative alignment of the electron and hole states of CdSe and CdTe in thin 2D nanoplatelets does not lead to a type-II heterostructure. Following the excitation in CdSe or CdTe materials, the electron preferentially delocalises instantaneously over the whole heterostructure. In addition, depending on the crown material (CdTe versus CdTeSe), the hole transfers either to trap states or to the crown, within a few hundreds of femtoseconds. We conclude that the photoluminescence band, at lower energy than the CdSe and CdTe first exciton transition, does not result from the recombination of the charge carriers at the charge transfer state but involves localised hole states.

Morphology-induced phonon spectra of CdSe/CdS nanoplatelets: core/shell vs. core-crown.

Recently developed two-dimensional colloidal semiconductor nanocrystals, or nanoplatelets (NPLs), extend the palette of solution-processable free-standing 2D nanomaterials of high performance. Growing CdSe and CdS parts subsequently in either side-by-side or stacked manner results in core-crown or core/shell structures, respectively. Both kinds of heterogeneous NPLs find efficient applications and represent interesting materials to study the electronic and lattice excitations and interaction between them under strong one-directional confinement. Here, we investigated by Raman and infrared spectroscopy the phonon spectra and electron-phonon coupling in CdSe/CdS core/shell and core-crown NPLs. A number of distinct spectral features of the two NPL morphologies are observed, which are further modified by tuning the laser excitation energy Eexc between in- and off-resonant conditions. The general difference is the larger number of phonon modes in core/shell NPLs and their spectral shifts with increasing shell thickness, as well as with Eexc. This behaviour is explained by strong mutual influence of the core and shell and formation of combined phonon modes. In the core-crown structure, the CdSe and CdS modes preserve more independent behaviour with only interface modes forming the phonon overtones with phonons of the core.

Engineering the Charge Transfer in all 2D Graphene-Nanoplatelets Heterostructure Photodetectors.

Two dimensional layered (i.e. van der Waals) heterostructures open up great prospects, especially in photodetector applications. In this context, the control of the charge transfer between the constituting layers is of crucial importance. Compared to bulk or 0D system, 2D materials are characterized by a large exciton binding energy (0.1-1 eV) which considerably affects the magnitude of the charge transfer. Here we investigate a model system made from colloidal 2D CdSe nanoplatelets and epitaxial graphene in a phototransistor configuration. We demonstrate that using a heterostructured layered material, we can tune the magnitude and the direction (i.e. electron or hole) of the charge transfer. We further evidence that graphene functionalization by nanocrystals only leads to a limited change in the magnitude of the 1/f noise. These results draw some new directions to design van der Waals heterostructures with enhanced optoelectronic properties.

Unraveling the time cross correlations of an emitter switching between two states with the same fluorescence intensity.

The autocorrelation function of the fluorescence intensity of a nanoemitter is measured with the standard Hanbury-Brown and Twiss setup. Time-tagging of the photodetection events during all the experiment has opened new possibilities in terms of post-selection techniques that enable to go beyond the blinking and antibunching characterization. Here, we first present a new method developed to investigate in detail the antibunching of a fluorophore switching between two emitting states. Even if they exhibit the same fluorescence intensity, their respective amount of antibunching can be measured using the gap between their respective decay rates. The method is then applied to a nanoemitter consisting in a colloidal quantum dot coupled to a plasmonic resonator. The relative quantum efficiency of the charged and neutral biexcitons are determined.

Spectroscopy of colloidal semiconductor core/shell nanoplatelets with high quantum yield.

Free standing two-dimensional materials appear as a novel class of structures. Recently, the first colloidal two-dimensional heterostructures have been synthesized. These core/shell nanoplatelets are the first step toward colloidal quantum wells. Here, we study in detail the spectroscopic properties of this novel generation of colloidal nanoparticles. We show that core/shell CdSe/CdZnS nanoplatelets with 80% quantum yield can be obtained. The emission time trace of single core/shell nanoplatelets exhibits reduced blinking compared to core nanoplatelets with a two level emission time trace. At cryogenic temperatures, these nanoplatelets have a quantum yield close to 100% and a stable emission time trace. A solution of core/shell nanoplatelets has emission spectra with a full width half-maximum close to 20 nm, a value much lower than corresponding spherical or rod-shaped heterostructures. Using single particle spectroscopy, we show that the broadening of the emission spectra upon the shell deposition is not due to dispersity between particles but is related to an intrinsic increased exciton-phonon coupling in the shell. We also demonstrate that optical spectroscopy is a relevant tool to investigate the presence of traps induced by shell deposition. The spectroscopic properties of the core/shell nanoplatelets presented here strongly suggest that this new generation of objects will be an interesting alternative to spherical or rod-shaped nanocrystals.

Controlling spontaneous emission with plasmonic optical patch antennas.

We experimentally demonstrate the control of the spontaneous emission rate and the radiation pattern of colloidal quantum dots deterministically positioned in a plasmonic patch antenna. The antenna consists of a thin gold microdisk separated from a planar gold layer by a few tens of nanometers thick dielectric layer. The emitters are shown to radiate through the entire patch antenna in a highly directional and vertical radiation pattern. Strong acceleration of spontaneous emission is observed, depending on the antenna geometry. Considering the double dipole structure of the emitters, this corresponds to a Purcell factor up to 80 for dipoles perpendicular to the disk.

Thermal activation of non-radiative Auger recombination in charged colloidal nanocrystals.

Applications of semiconductor nanocrystals such as biomarkers and light-emitting optoelectronic devices require that their fluorescence quantum yield be close to 100%. However, such quantum yields have not been obtained yet, in part, because non-radiative Auger recombination in charged nanocrystals could not be suppressed completely. Here, we synthesize colloidal core/thick-shell CdSe/CdS nanocrystals with 100% quantum yield and completely quenched Auger processes at low temperatures, although the nanocrystals are negatively photocharged. Single particle and ensemble spectroscopy in the temperature range 30-300 K shows that the non-radiative Auger recombination is thermally activated around 200 K. Experimental results are well described by a model suggesting a temperature-dependent delocalization of one of the trion electrons from the CdSe core and enhanced Auger recombination at the abrupt CdS outer surface. These results point to a route for the design of core/shell structures with 100% quantum yield at room temperature.

Colloidal nanoplatelets with two-dimensional electronic structure.

The syntheses of strongly anisotropic nanocrystals with one dimension much smaller than the two others, such as nanoplatelets, are still greatly underdeveloped. Here, we demonstrate the formation of atomically flat quasi-two-dimensional colloidal CdSe, CdS and CdTe nanoplatelets with well-defined thicknesses ranging from 4 to 11 monolayers. These nanoplatelets have the electronic properties of two-dimensional quantum wells formed by molecular beam epitaxy, and their thickness-dependent absorption and emission spectra are described very well within an eight-band Pidgeon-Brown model. They present an extremely narrow emission spectrum with full-width at half-maximum less than 40 meV at room temperature. The radiative fluorescent lifetime measured in CdSe nanoplatelets decreases with temperature, reaching 1 ns at 6 K, two orders of magnitude less than for spherical CdSe nanoparticles. This makes the nanoplatelets the fastest colloidal fluorescent emitters and strongly suggests that they show a giant oscillator strength transition.

Continuous transition from 3D to 1D confinement observed during the formation of CdSe nanoplatelets.

We study the formation of colloidal CdSe nanoplatelets using both tansmission electron microscopy (TEM) and spectroscopic analysis. We show that the platelets form by continuous lateral extension of small (<2 nm) nanocrystal CdSe seeds. The nanoplatelet thickness is fixed by the seed dimension and remains constant during the platelet formation. The nanoplatelet lateral dimensions can be tuned using additional precursor injection. Absorption and fluorescence analysis of the CdSe nanoplatelets as they continuously extend laterally confirms a continuous transition from 3D to 1D confined nanoparticles. The formation of the CdSe platelets is found to be similar for different platelet thicknesses that we control with a precision of one CdSe monolayer.

Bright and grey states in CdSe-CdS nanocrystals exhibiting strongly reduced blinking.

When compared to standard colloidal nanocrystals, individual CdSe-CdS core-shell nanocrystals with thick shells exhibit strongly reduced blinking. Analyzing the photon statistics and lifetime of the on state, we first demonstrate that bright periods correspond to single photon emission with a fluorescence quantum efficiency of the monoexcitonic state greater than 95%. We also show that low intensity emitting periods are not dark but correspond to a grey state, with a fluorescence quantum efficiency of 19%. From these measurements, we deduce the radiative lifetime (45 ns) and the Auger lifetime (10.5 ns) of the grey state.

[Quantum dots in oncological surgery: the future for surgical margin status]. / Quantum dots en chirurgie oncologique : un rôle d'avenir pour le marquage des berges d'exérèse?

Quantum dots (QDs) are semi-conductor nanocrystals that emit fluorescence on excitation with a light source. They have excellent optical properties, including high brightness and resistance to photobleaching. Their spectroscopic properties can be modulated by many factors. Recent progress in developing QDs enable us to control the size, shape and surface functionality of nanoparticles for potential application in cancer imaging. QDs with near-infrared emission could be applied to identify sentinel lymph-node. Conjugation of QDs with biomolecules could be used to target tumors in vivo. This article reviewed recent developments and issues in nanotechnology with a particular focus on applications to the surgery.

Full-field optical sectioning and three-dimensional localization of fluorescent particles using focal plane modulation.

We present a technique for imaging fluorescent particles based on the axial modulation of the objective's focal plane position. This technique provides full-field optical sectioning and can be used to localize the fluorophores in three dimensions. We describe the technique and apply it to image 200 nm diameter fluorescent beads immobilized in a gel. We show that full-field optical sectioning is obtained and that the beads are localized with a precision of 10 nm in the transverse plane and 14 nm in the axial direction.

Dynamics of DNA-protein interaction deduced from in vitro DNA evolution.

We report the first experimental study of the dynamics of in vitro evolution of DNA. Starting from a random pool of DNA sequences, we used cycles of selection (binding to the lac repressor protein), amplification, and mutations to evolve to a unique DNA sequence, the lac operator. Statistical analysis of the DNA sequences obtained during the cycles of evolution shows that the DNA bases are selected at different rates. The rates of selection provide a quantitative measure of the interaction of the DNA bases with the protein during the complex formation. A model reproduces the evolution dynamics of the DNA population but cannot give the fine structure of the DNA-protein interaction.

Single-mismatch detection using gold-quenched fluorescent oligonucleotides.

Here we describe a hybrid material composed of a single-stranded DNA (ssDNA) molecule, a 1.4 nm diameter gold nanoparticle, and a fluorophore that is highly quenched by the nanoparticle through a distance-dependent process. The fluorescence of this hybrid molecule increases by a factor of as much as several thousand as it binds to a complementary ssDNA. We show that this composite molecule is a different type of molecular beacon with a sensitivity enhanced up to 100-fold. In competitive hybridization assays, the ability to detect single mismatch is eightfold greater with this probe than with other molecular beacons.

Geometrical models of the renewal of the epidermis.

We give a review of the different models developed recently that describe the renewal of the epidermis. These models, based on concepts borrowed from statistical mechanics, geometry and topology, shed new light on the understanding of the organization and the dynamics of the system. We discuss in detail a topological model of the dynamics of the inner-most layer of the epidermis: the basal layer.

The renewal of the epidermis: a topological mechanism.

Using a topological approach, we study the dynamics of the basement membrane of the mammalian epidermis when basal cells detach or divide. A theoretical characterization of the steady state of the tissue, in very good agreement with experimental data, includes for the first time the division and the disappearance of cells in a two-dimensional random cellular structure. We predict a strong correlation between the size of the attachment of basal cells to the basement membrane and their biological behavior (division or detachment). This suggests that the main factor determining the fate of basal cells, and thus controlling the renewal of the epidermis, is the cells' surface tension and adhesion.

The stationary state of epithelia.

A tissue is a geometrical, space-filling, random cellular network; it remains in this steady state while individual cells divide. Cell division is a local, elementary topological transformation which establishes statistical equilibrium of the structure. We describe the physical conditions to maintain stationary the epidermis (of mammals or of the cucumber), in spite of the fact that cells constantly divide and die. Specifically, we study the statistical equilibrium of the basal layer, a corrugated surface filled with cells, constituting a two-dimensional topological froth. Cells divide and detach from the basal layer, and these two topological transformations are responsible for the stationary state of the epidermis. The topological froth is capable of responding rapidly and locally to external constraints, and is a good illustration of the plasticity of random cellular networks. Statistical equilibrium is controlled by entropy, both as a measure of disorder and as information, and is characterized by observable relations between average cell shapes and sizes. The technique can be applied to any random cellular network in dynamical equilibrium. Mitosis as the dominating topological transformation and the fact that the distribution of cell shapes is very narrow are the only inputs specific to biology.