Laboratoire de Physique et Chimie des Nano-Objets

Most two-dimensional (2D) semiconductors are interesting materials as quantum confinement enhances the Coulomb interaction between carriers, leading to a strong attraction between conduction electrons and valence holes, forming stable excitons and the optical response of 2D semiconductors can be extraordinary. In this Colloquium the progress and open questions in the study of excitons in 2D semiconductors from both the experimental and theoretical perspectives are reviewed.

To optimize the heating properties of magnetic nanoparticles (MNPs) in magnetic hyperthermia applications, it is necessary to calculate the area of their hysteresis loops in an alternating magnetic field. The separation between “relaxation losses” and “hysteresis losses” presented in several articles is artificial and criticized here. The three types of theories suitable for describing hysteresis loops of MNPs are presented and compared to numerical simulations: equilibrium functions, Stoner–Wohlfarth model based theories (SWMBTs), and a linear response theory (LRT) using the Néel–Brown relaxation time. The configuration where the easy axis of the MNPs is aligned with respect to the magnetic field and the configuration of a random orientation of the easy axis are both studied. Suitable formulas to calculate the hysteresis areas of major cycles are deduced from SWMBTs and from numerical simulations; the domain of validity of the analytical formula is explicitly studied. In the case of minor cycles, the hysteresis area calculations are based on the LRT. A perfect agreement between the LRT and numerical simulations of hysteresis loops is obtained. The domain of validity of the LRT is explicitly studied. Formulas are proposed to calculate the hysteresis area at low field that are valid for any anisotropy of the MNP. The magnetic field dependence of the area is studied using numerical simulations: it follows power laws with a large range of exponents. Then analytical expressions derived from the LRT and SWMBTs are used in their domains of validity for a theoretical study of magnetic hyperthermia. It is shown that LRT is only pertinent for MNPs with strong anisotropy and that SWMBTs should be used for weakly anisotropic MNPs. The optimum volume of MNPs for magnetic hyperthermia is derived as a function of material and experimental parameters. Formulas are proposed to allow to the calculation of the optimum volume for any anisotropy. The maximum achievable specific absorption rate (SAR) is calculated as a function of the MNP anisotropy. It is shown that an optimum anisotropy increases the SAR and reduces the detrimental effects of the size distribution of the MNPs. The optimum anisotropy is simple to calculate; it depends only on the magnetic field used in the hyperthermia experiments and the MNP magnetization. The theoretical optimum parameters are compared to those of several magnetic materials. A brief review of experimental results as well as a method to analyze them is proposed. This study helps in the determination of suitable and unsuitable materials for magnetic hyperthermia and provides accurate formulas to analyze experimental data. It is also aimed at providing a better understanding of magnetic hyperthermia to researchers working on this subject.

The support plays an important role for supported metal catalysts by positioning itself as a macromolecular ligand, which conditions the nature of the active site and contributes indirectly but also sometimes directly to the reactivity. Metal species such as nanoparticles, clusters, or single atoms can be deposited on carbon materials for various catalytic reactions. All the carbon materials used as catalyst support constitute a large family of compounds that can vary both at textural and at structural levels. Today, the recent developments of well-controlled synthesis methodologies, advanced characterization techniques, and modeling tools allow one to correlate the relationships between metal/support/reactant at the molecular level. Based on these considerations, in this Review article, we wish to provide some answers to the question “How and why anchoring metal nanoparticles, clusters, or single atoms on carbon materials for catalysis?”. To do this, we will rely on both experimental and theoretical studies. We will first analyze what sites are available on the surface of a carbon support for the anchoring of the active phase. Then, we will describe some important effects in catalysis inherent to the presence of a carbon-type support (metal–support interaction, confinement, spillover, and surface functional group effects). These effects will be commented on by putting into perspective catalytic results obtained in numerous reactions of thermal catalysis, electrocatalysis, or photocatalysis.

Integration of electrochemical capacitors with silicon-based electronics is a major challenge, limiting energy storage on a chip. We describe a wafer-scale process for manufacturing strongly adhering carbide-derived carbon films and interdigitated micro-supercapacitors with embedded titanium carbide current collectors, fully compatible with current microfabrication and silicon-based device technology. Capacitance of those films reaches 410 farads per cubic centimeter/200 millifarads per square centimeter in aqueous electrolyte and 170 farads per cubic centimeter/85 millifarads per square centimeter in organic electrolyte. We also demonstrate preparation of self-supported, mechanically stable, micrometer-thick porous carbon films with a Young's modulus of 14.5 gigapascals, with the possibility of further transfer onto flexible substrates. These materials are interesting for applications in structural energy storage, tribology, and gas separation.

We show that the light-matter interaction in monolayer WSe_{2} is strongly enhanced when the incoming electromagnetic wave is in resonance with the energy of the exciton states of strongly Coulomb bound electron-hole pairs below the electronic band gap. We perform second harmonic generation (SHG) spectroscopy as a function of laser energy and polarization at T=4 K. At the exciton resonance energies we record an enhancement by up to 3 orders of magnitude of the SHG efficiency, due to the unusual combination of electric dipole and magnetic dipole transitions. The energy and parity of the exciton states showing the strong resonance effects are identified in 1- and 2-photon photoluminescence excitation experiments, corroborated by first principles calculations. Targeting the identified exciton states in resonant 2-photon excitation allows us to maximize k-valley coherence and polarization.

Transition-metal dichalcogenides are a class of two-dimensional materials that offer potential for developing flat and flexible transistors and optoelectronics, but their quality is often hindered by traditional methods for depositing these atomically flat materials. An experiment demonstrates a new technique that leads to higher quality crystals and better access to studying their properties.

After about three decades of development, the polyol process is now widely recognized and practised as a unique soft chemical method for the preparation of a large variety of nanoparticles which can be used in important technological fields. It offers many advantages: low cost, ease of use and, very importantly, already proven scalability for industrial applications. Among the different classes of inorganic nanoparticles which can be prepared in liquid polyols, metals were the first reported. This review aims to give a comprehensive account of the strategies used to prepare monometallic nanoparticles and multimetallic materials with tailored size and shape. As regards monometallic materials, while the preparation of noble as well as ferromagnetic metals is now clearly established, the scope of the polyol process has been extended to the preparation of more electropositive metals, such as post-transition metals and semi-metals. The potential of this method is also clearly displayed for the preparation of alloys, intermetallics and core-shell nanostructures with a very large diversity of compositions and architectures.

We have investigated the exciton dynamics in transition metal dichalcogenide monolayers using time-resolved photoluminescence experiments performed with optimized time resolution. For $\mathrm{MoS}{\mathrm{e}}_{2}$ monolayer, we measure ${\ensuremath{\tau}}_{\mathrm{rad}}^{0}=1.8\ifmmode\pm\else\textpm\fi{}0.2\phantom{\rule{0.16em}{0ex}}\mathrm{ps}$ at $T=7\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ that we interpret as the intrinsic radiative recombination time. Similar values are found for $\mathrm{WS}{\mathrm{e}}_{2}$ monolayers. Our detailed analysis suggests the following scenario: at low temperature $(T\ensuremath{\lesssim}50\phantom{\rule{0.16em}{0ex}}\mathrm{K})$, the exciton oscillator strength is so large that the entire light can be emitted before the time required for the establishment of a thermalized exciton distribution. For higher lattice temperatures, the photoluminescence dynamics is characterized by two regimes with very different characteristic times. First the photoluminescence intensity drops drastically with a decay time in the range of the picosecond driven by the escape of excitons from the radiative window due to exciton-phonon interactions. Following this first nonthermal regime, a thermalized exciton population is established gradually yielding longer photoluminescence decay times in the nanosecond range. Both the exciton effective radiative recombination and nonradiative recombination channels including exciton-exciton annihilation control the latter. Finally the temperature dependence of the measured exciton and trion dynamics indicates that the two populations are not in thermodynamical equilibrium.

We use micro-Raman and photoluminescence (PL) spectroscopy at 300 K to investigate the influence of uniaxial tensile strain on the vibrational and optoelectronic properties of monolayer and bilayer MoS${}_{2}$ on a flexible substrate. The initially degenerate ${E}^{\ensuremath{'}}$ monolayer Raman mode is split into a doublet as a direct consequence of the strain applied to MoS${}_{2}$ through Van der Waals coupling at the sample-substrate interface. We observe a strong shift of the direct band gap of 48 meV/(% of strain) for the monolayer and 46 meV/% for the bilayer, whose indirect gap shifts by 86 meV/%. We find a strong decrease of the PL polarization linked to optical valley initialization for both monolayer and bilayer samples, indicating that scattering to the spin-degenerate $\ensuremath{\Gamma}$ valley plays a key role.

We report polarization resolved photoluminescence from monolayer ${\mathrm{MoS}}_{2}$, a two-dimensional, noncentrosymmetric crystal with direct energy gaps at two different valleys in momentum space. The inherent chiral optical selectivity allows exciting one of these valleys, and close to 90$%$ polarized emission at 4 K is observed with 40$%$ polarization remaining at 300 K. The high polarization degree of the emission remains unchanged in transverse magnetic fields up to 9 T indicating robust, selective valley excitation.

Optical interband transitions in monolayer transition metal dichalcogenides such as ${\mathrm{WSe}}_{2}$ and ${\mathrm{MoS}}_{2}$ are governed by chiral selection rules. This allows efficient optical initialization of an electron in a specific K valley in momentum space. Here we probe the valley dynamics in monolayer ${\mathrm{WSe}}_{2}$ by monitoring the emission and polarization dynamics of the well-separated neutral excitons (bound electron-hole pairs) and charged excitons (trions) in photoluminescence. The neutral exciton photoluminescence intensity decay time is about 4 ps, whereas the trion emission occurs over several tens of ps. The trion polarization dynamics shows a partial, fast initial decay within tens of ps before reaching a stable polarization of $\ensuremath{\approx}20%$, for which a typical valley polarization decay time of the order of 1 ns can be inferred.

In monolayer MoS2, optical transitions across the direct band gap are governed by chiral selection rules, allowing optical valley initialization. In time-resolved photoluminescence (PL) experiments, we find that both the polarization and emission dynamics do not change from 4 to 300 K within our time resolution. We measure a high polarization and show that under pulsed excitation the emission polarization significantly decreases with increasing laser power. We find a fast exciton emission decay time on the order of 4 ps. The absence of a clear PL polarization decay within our time resolution suggests that the initially injected polarization dominates the steady-state PL polarization. The observed decrease of the initial polarization with increasing pump photon energy hints at a possible ultrafast intervalley relaxation beyond the experimental ps time resolution. By compensating the temperature-induced change in band gap energy with the excitation laser energy, an emission polarization of 40% is recovered at 300 K, close to the maximum emission polarization for this sample at 4 K.

Abstract Progress in the prediction and optimization of the heating of magnetic nanoparticles in an alternating magnetic field is highly desirable for their application in magnetic hyperthermia. Here, a model system consisting of metallic iron nanoparticles with a size ranging from 5.5 to 28 nm is extensively studied. Their properties depend strongly on their size: behaviors typical of single‐domain particles in the superparamagnetic regime, in the ferromagnetic regime, and of multi‐domain particles are observed. Ferromagnetic single‐domain nanoparticles are the best candidates and display the highest specific losses reported in the literature so far (11.2 ± 1 mJ g −1 ). Measurements are analysed using recently a demonstrated analytical formula and numerical simulations of the hysteresis loops. Several features expected theoretically are observed for the first time experimentally: i) the correlation between the nanoparticle diameter and their coercive field, ii) the correlation between the amplitude of the coercive field and the losses, and iii) the variation of the optimal size with the amplitude of the magnetic field. None of these features are predicted by the linear response theory – generally used to interpret hyperthermia experiments – but are a natural consequence of theories deriving from the Stoner–Wohlfarth model; they also appear clearly in numerical simulations. These results open the path to a more accurate description, prediction, and analysis of magnetic hyperthermia.

The mesoscopic spin system formed by the ${10}^{4}--{10}^{6}$ nuclear spins in a semiconductor quantum dot offers a unique setting for the study of many-body spin physics in the condensed matter. The dynamics of this system and its coupling to electron spins is fundamentally different from its bulk counterpart or the case of individual atoms due to increased fluctuations that result from reduced dimensions. In recent years, the interest in studying quantum-dot nuclear spin systems and their coupling to confined electron spins has been further fueled by its importance for possible quantum information processing applications. The fascinating nonlinear (quantum) dynamics of the coupled electron-nuclear spin system is universal in quantum dot optics and transport. In this article, experimental work performed over the last decade in studying this mesoscopic, coupled electron-nuclear spin system is reviewed. Here a special focus is on how optical addressing of electron spins can be exploited to manipulate and read out the quantum-dot nuclei. Particularly exciting recent developments in applying optical techniques to efficiently establish nonzero mean nuclear spin polarizations and using them to reduce intrinsic nuclear spin fluctuations are discussed. Both results critically influence the preservation of electron-spin coherence in quantum dots. This overall recently gained understanding of the quantum-dot nuclear spin system could enable exciting new research avenues such as experimental observations of spontaneous spin ordering or nonclassical behavior of the nuclear spin bath.

The optical selection rules for interband transitions in WSe_{2}, WS_{2}, and MoSe_{2} transition metal dichalcogenide monolayers are investigated by polarization-resolved photoluminescence experiments with a signal collection from the sample edge. These measurements reveal a strong polarization dependence of the emission lines. We see clear signatures of the emitted light with the electric field oriented perpendicular to the monolayer plane, corresponding to an interband optical transition forbidden at normal incidence used in standard optical spectroscopy measurements. The experimental results are in agreement with the optical selection rules deduced from group theory analysis, highlighting the key role played by the different symmetries of the conduction and valence bands split by the spin-orbit interaction. These studies yield a direct determination of the bright-dark exciton splitting, for which we measure 40±1 meV and 55±2 meV in WSe_{2} and WS_{2} monolayer, respectively.

Abstract The optical properties of transition metal dichalcogenide monolayers are widely dominated by excitons, Coulomb-bound electron–hole pairs. These quasi-particles exhibit giant oscillator strength and give rise to narrow-band, well-pronounced optical transitions, which can be brought into resonance with electromagnetic fields in microcavities and plasmonic nanostructures. Due to the atomic thinness and robustness of the monolayers, their integration in van der Waals heterostructures provides unique opportunities for engineering strong light-matter coupling. We review first results in this emerging field and outline future opportunities and challenges.

In semiconductor physics, many essential optoelectronic material parameters can be experimentally revealed via optical spectroscopy in sufficiently large magnetic fields. For monolayer transition-metal dichalcogenide semiconductors, this field scale is substantial-tens of teslas or more-due to heavy carrier masses and huge exciton binding energies. Here we report absorption spectroscopy of monolayer [Formula: see text], and [Formula: see text] in very high magnetic fields to 91 T. We follow the diamagnetic shifts and valley Zeeman splittings of not only the exciton's [Formula: see text] ground state but also its excited [Formula: see text] Rydberg states. This provides a direct experimental measure of the effective (reduced) exciton masses and dielectric properties. Exciton binding energies, exciton radii, and free-particle bandgaps are also determined. The measured exciton masses are heavier than theoretically predicted, especially for Mo-based monolayers. These results provide essential and quantitative parameters for the rational design of opto-electronic van der Waals heterostructures incorporating 2D semiconductors.

We study the neutral exciton energy spectrum fine structure and its spin dephasing in transition metal dichalcogenides such as ${\mathrm{MoS}}_{2}$. The interaction of the mechanical exciton with its macroscopic longitudinal electric field is taken into account. The splitting between the longitudinal and transverse excitons is calculated by means of the both electrodynamical approach and $\mathbit{k}\ifmmode\cdot\else\textperiodcentered\fi{}\mathbit{p}$ perturbation theory. This long-range exciton exchange interaction can induce valley polarization decay. The estimated exciton spin dephasing time is in the picosecond range, in agreement with available experimental data.

We have experimentally studied the pump-probe Kerr rotation dynamics in ${\mathrm{WSe}}_{2}$ monolayers. This yields a direct measurement of the exciton valley depolarization time ${\ensuremath{\tau}}_{v}$. At $T=4\phantom{\rule{0.28em}{0ex}}\mathrm{K}$, we find ${\ensuremath{\tau}}_{v}\ensuremath{\approx}6$ ps, a fast relaxation time resulting from the strong electron-hole Coulomb exchange interaction in bright excitons. The exciton valley depolarization time decreases significantly when the lattice temperature increases, with ${\ensuremath{\tau}}_{v}$ being as short as 1.5 ps at 125 K. The temperature dependence is well explained by the developed theory, taking into account the exchange interaction and fast exciton scattering time on the short-range potential.

Charged excitons, or ${X}^{\ifmmode\pm\else\textpm\fi{}}$ trions, in monolayer transition-metal dichalcogenides have binding energies of several tens of meV. Together with the neutral exciton ${X}^{0}$ they dominate the emission spectrum at low and elevated temperatures. We use charge-tunable devices based on ${\mathrm{WSe}}_{2}$ monolayers encapsulated in hexagonal boron nitride to investigate the difference in binding energy between ${X}^{+}$ and ${X}^{\ensuremath{-}}$ and the ${X}^{\ensuremath{-}}$ fine structure. We find in the charge-neutral regime, the ${X}^{0}$ emission accompanied at lower energy by a strong peak close to the longitudinal optical (LO) phonon energy. This peak is absent in reflectivity measurements, where only the ${X}^{0}$ and an excited state of the ${X}^{0}$ are visible. In the $n$-doped regime, we find a closer correspondence between emission and reflectivity as the trion transition with a well-resolved fine-structure splitting of 6 meV for ${X}^{\ensuremath{-}}$ is observed. We present a symmetry analysis of the different ${X}^{+}$ and ${X}^{\ensuremath{-}}$ trion states and results of the binding energy calculations. We compare the trion binding energy for the $n$- and $p$-doped regimes with our model calculations for low carrier concentrations. We demonstrate that the splitting between the ${X}^{+}$ and ${X}^{\ensuremath{-}}$ trions as well as the fine structure of the ${X}^{\ensuremath{-}}$ state can be related to the short-range Coulomb-exchange interaction between the charge carriers.