Laboratoire de Photonique Quantique et Moléculaire

Conventional optical components rely on gradual phase shifts accumulated during light propagation to shape light beams. New degrees of freedom are attained by introducing abrupt phase changes over the scale of the wavelength. A two-dimensional array of optical resonators with spatially varying phase response and subwavelength separation can imprint such phase discontinuities on propagating light as it traverses the interface between two media. Anomalous reflection and refraction phenomena are observed in this regime in optically thin arrays of metallic antennas on silicon with a linear phase variation along the interface, which are in excellent agreement with generalized laws derived from Fermat's principle. Phase discontinuities provide great flexibility in the design of light beams, as illustrated by the generation of optical vortices through use of planar designer metallic interfaces.

The isolated electronic spin system of the nitrogen-vacancy (NV) centre in diamond offers unique possibilities to be employed as a nanoscale sensor for detection and imaging of weak magnetic fields. Magnetic imaging with nanometric resolution and field detection capabilities in the nanotesla range are enabled by the atomic-size and exceptionally long spin-coherence times of this naturally occurring defect. The exciting perspectives that ensue from these characteristics have triggered vivid experimental activities in the emerging field of 'NV magnetometry'. It is the purpose of this article to review the recent progress in high-sensitivity nanoscale NV magnetometry, generate an overview of the most pertinent results of the last years and highlight perspectives for future developments. We will present the physical principles that allow for magnetic field detection with NV centres and discuss first applications of NV magnetometers that have been demonstrated in the context of nano magnetism, mesoscopic physics and the life sciences.

Wave-particle duality is strikingly illustrated by Wheeler's delayed-choice gedanken experiment, where the configuration of a two-path interferometer is chosen after a single-photon pulse has entered it: Either the interferometer is closed (that is, the two paths are recombined) and the interference is observed, or the interferometer remains open and the path followed by the photon is measured. We report an almost ideal realization of that gedanken experiment with single photons allowing unambiguous which-way measurements. The choice between open and closed configurations, made by a quantum random number generator, is relativistically separated from the entry of the photon into the interferometer.

Nitrogen-vacancy (NV) centers in millimeter-scale diamond samples were produced by irradiation and subsequent annealing under varied conditions. The optical and spin-relaxation properties of these samples were characterized using confocal microscopy, visible and infrared absorption, and optically detected magnetic resonance. The sample with the highest ${\text{NV}}^{\ensuremath{-}}$ concentration, approximately 16 ppm $(2.8\ifmmode\times\else\texttimes\fi{}{10}^{18}\text{ }{\text{cm}}^{\ensuremath{-}3})$, was prepared with no observable traces of neutrally charged vacancy defects. The effective transverse spin-relaxation time for this sample was ${T}_{2}^{\ensuremath{\ast}}=118(48)\text{ }\text{ns}$, predominately limited by residual paramagnetic nitrogen which was determined to have a concentration of 49(7) ppm. Under ideal conditions, the shot-noise limited sensitivity is projected to be $\ensuremath{\sim}150\text{ }\text{fT}/\sqrt{\text{Hz}}$ for a $100\text{ }\ensuremath{\mu}\text{m}$-scale magnetometer based on this sample. Other samples with ${\text{NV}}^{\ensuremath{-}}$ concentrations from 0.007 to 12 ppm and effective relaxation times ranging from 27 to over 291 ns were prepared and characterized.

We report a systematic study of the magnetic field sensitivity of a magnetic sensor consisting of a single nitrogen-vacancy (NV) defect in diamond, by using continuous optically detected electron spin resonance (ESR) spectroscopy. We first investigate the behavior of the ESR contrast and linewidth as a function of the microwave and optical pumping power. The experimental results are in good agreement with a simplified model of the NV defect spin dynamics, leading to an optimized sensitivity around $2\phantom{\rule{4pt}{0ex}}\ensuremath{\mu}$T$/\sqrt{\mathrm{Hz}}$ for a single NV defect in a high-purity diamond crystal grown by chemical vapor deposition. We then demonstrate an enhancement of the magnetic sensitivity by one order of magnitude by using a simple pulsed-ESR scheme. This technique is based on repetitive excitation of the NV defect with a resonant microwave $\ensuremath{\pi}$ pulse followed by an optimized readout laser pulse, allowing to fully eliminate power broadening of the ESR linewidth. The achieved sensitivity is similar to that obtained by using Ramsey-type sequences, which is the optimal magnetic field sensitivity for the detection of a dc magnetic field.

Magnetometry and magnetic imaging with nitrogen-vacancy (NV) defects in\ndiamond rely on the optical detection of electron spin resonance (ESR).\nHowever, this technique is inherently limited to magnetic fields that are weak\nenough to avoid electron spin mixing. Here we focus on the high off-axis\nmagnetic field regime for which spin mixing alters the NV defect spin dynamics.\nWe first study in a quantitative manner the dependence of the NV defect optical\nproperties on the magnetic field vector B. Magnetic-field-dependent\ntime-resolved photoluminescence (PL) measurements are compared to a seven-level\nmodel of the NV defect that accounts for field-induced spin mixing. The model\nreproduces the decreases in (i) ESR contrast, (ii) PL intensity and (iii)\nexcited level lifetime with an increasing off-axis magnetic field. We next\ndemonstrate that those effects can be used to perform all-optical magnetic\nimaging in the high off-axis magnetic field regime. Using a scanning NV defect\nmicroscope, we map the stray field of a magnetic hard disk through both PL and\nfluorescence lifetime imaging. This all-optical method for high magnetic field\nimaging at the nanoscale might be of interest in the field of nanomagnetism,\nwhere samples producing fields in excess of several tens of milliteslas are\ntypical.

We present an approach to describe the phase matching of high harmonics emitted by laser driven atoms in a nonperturbative regime, for which the atomic response displays an intrinsic intensity-dependent phase. We show that the traditional phase-matching conditions involving conservation of wave vectors should be modified by taking into account the gradient of this atomic phase. We investigate various focusing geometries and interpret the numerical results of Sali`eres et al. [Phys. Rev. Lett. 74, 3776 (1995)]. Within the framework of the two-step model, we demonstrate that the gradient of the intensity-dependent phase can be considered as the canonical momentum gained by the electron in the continuum due to acceleration by field-gradient forces, including in particular the ponderomotive force.

Conventional optical components rely on the propagation effect to control the phase and polarization of light beams. One can instead exploit abrupt phase and polarization changes associated with scattered light from optical resonators to control light propagation. In this paper, we discuss the optical responses of anisotropic plasmonic antennas and a new class of planar optical components (“metasurfaces”) based on arrays of these antennas. To demonstrate the versatility of metasurfaces, we show the design and experimental realization of a number of flat optical components: 1) metasurfaces with a constant interfacial phase gradient that deflect light into arbitrary directions; 2) metasurfaces with anisotropic optical responses that create light beams of arbitrary polarization over a wide wavelength range; 3) planar lenses and axicons that generate spherical wavefronts and nondiffracting Bessel beams, respectively; and 4) metasurfaces with spiral phase distributions that create optical vortex beams of well-defined orbital angular momentum.

Diamond nanoparticles (nanodiamonds) have been recently proposed as new labels for cellular imaging. For small nanodiamonds (size <40 nm), resonant laser scattering and Raman scattering cross sections are too small to allow single nanoparticle observation. Nanodiamonds can, however, be rendered photoluminescent with a perfect photostability at room temperature. Such a remarkable property allows easier single-particle tracking over long time scales. In this work, we use photoluminescent nanodiamonds of size <50 nm for intracellular labeling and investigate the mechanism of their uptake by living cells. By blocking selectively different uptake processes, we show that nanodiamonds enter cells mainly by endocytosis, and converging data indicate that it is clathrin-mediated. We also examine nanodiamond intracellular localization in endocytic vesicles using immunofluorescence and transmission electron microscopy. We find a high degree of colocalization between vesicles and the biggest nanoparticles or aggregates, while the smallest particles appear free in the cytosol. Our results pave the way for the use of photoluminescent nanodiamonds in targeted intracellular labeling or biomolecule delivery.

We report on optical spectroscopy (photoluminescence and photoluminescence excitation) on two-dimensional self-organized layers of (C(6)H(5)C(2)H(4)-NH(3))(2)-PbI(4) perovskite. Temperature and excitation power dependance of the optical spectra gives a new insight into the excitonic and the phononic properties of this hybrid organic/inorganic semiconductor. In particular, exciton-phonon interaction is found to be more than one order of magnitude higher than in GaAs QWs. As a result, photoluminescence emission lines have to be interpreted in the framework of a polaron model.

We present a study of the charge state conversion of single nitrogen-vacancy (NV) defects hosted in nanodiamonds (NDs). We first show that the proportion of negatively charged ${\text{NV}}^{\ensuremath{-}}$ defects, with respect to its neutral counterpart ${\text{NV}}^{0}$, decreases with the size of the ND. We then propose a simple model based on a layer of electron traps located at the ND surface which is in good agreement with the recorded statistics. By using thermal oxidation to remove the shell of amorphous carbon around the NDs, we demonstrate a significant increase in the proportion of ${\text{NV}}^{\ensuremath{-}}$ defects in 10 nm NDs. These results are invaluable for further understanding, control, and use of the unique properties of negatively charged NV defects in diamond.

The ability of diamond nanoparticles (nanodiamonds, NDs) to deliver small interfering RNA (siRNA) into Ewing sarcoma cells is investigated with a view to the possibility of in-vivo anticancer nucleic-acid drug delivery. siRNA is adsorbed onto NDs that are coated with cationic polymer. Cell uptake of NDs is demonstrated by taking advantage of the NDs' intrinsic fluorescence from embedded color-center defects. Cell toxicity of these coated NDs is shown to be low. Consistent with the internalization efficacy, a specific inhibition of EWS/Fli-1 gene expression is shown at the mRNA and protein level by the ND-vectorized siRNA in a serum-containing medium.

The introduction, within a π-conjugated donor−acceptor molecule, of an intermediate barrier to electron tunneling and its size scaling and influence on electronic polarization properties have remained so far elusive issues of great potential interest toward the fine-tuning of the linear and nonlinear optical properties of molecular materials. Paracyclophane (pCP) provides a most relevant cornerstone for more elaborate compounds where donor and acceptor substituents are made to interact through a sterically constrained π−π stack. A first attempt in this direction is reported here with the synthesis of a model dipolar 4-(4-dihexylaminostyryl)-16-(4-nitrostyryl)[2.2]paracyclophane and the subsequent experimental and theoretical study of its quadratic nonlinear optical properties. A major outcome of this investigation is the evidence of a significant “through-space” charge transfer as unambiguously designated by the strong departure of the β quadratic hyperpolarizability tensor of the full doubly substituted molecule (60 × 10-30 esu) from the additive β value (18 × 10-30 esu) expected for strictly noninteracting singly substituted pCP moieties. This desired increase of nonlinear efficiency upon substitution is not offset by the usual red-shift of the absorption spectrum which generally curtails application perspectives in more common uninterrupted conjugated chains. The collective nonlinear polarization behavior involving the full end-to-end molecular structure is confirmed by theoretical calculations using the Collective Electron Oscillator (CEO) approach which furthermore indicates a significantly enhanced role of electron−hole pair delocalization in the higher order nonlinear response, compared to the linear polarizability or the static dipole moment.

After the demonstration of the first organic FET in 1986, a new era in the field of electronic began: the era of organic electronics. Although the reported performance of organic transistors is still considerably lower compared to that of silicon transistors, a new market is open for organic devices, where the excellent performance of silicon technology is not required. Several commercial applications for organic electronics have been suggested: organic RFID tags, electronic papers, imagers, sensors, organic LED drivers, etc. The main advantage of organic technologies over silicon technologies is the possibility of making low-cost, large area electronics. The main processes which allow patterning with suitable resolution on a large areas are printing methods. Here we will provide an overview of methods that can be useful in the low-cost production of large area electronics.

Two series of push-pull chromophores built around thiophene-based pi-conjugating spacers rigidified either by covalent bonds or by noncovalent intramolecular interactions have been synthesized and characterized by UV-vis spectroscopy, electric field induced second harmonic generation (EFISH) and differential scanning calorimetry. Comparison of the linear and second-order nonlinear optical properties of chromophores based on a covalently bridged dithienylethylene (DTE) spacer with those of their analogues based on open chain DTE shows that the rigidification of the spacer produces a considerable bathochromic shift of the absorption maximum together with a dramatic enhancement of the molecular quadratic hyperpolarizability (mu beta) which reaches values among the highest reported so far. A second series of NLO-phores has been derived from a 2,2'-bi(3,4-ethylenedioxythiophene) (BEDOT) pi-conjugating spacer. As indicated by X-ray and UV-vis data, rigidification of the spacer originates in that case, from noncovalent intramolecular interactions between sulfur and oxygen atoms. Again, comparison with the parent compounds based on an unsubstituted bithiophene spacer reveals a marked red shift of the absorption maximum and a large enhancement of mu beta. In an attempt to distinguish the contribution of the electronic and geometrical effects of the ethylenedioxy group, a third series of NLO-phores based on 3,4-ethylenedioxythiophene (EDOT) and 3,4-dihexyloxythiophene spacers has been synthesized. Comparison with compounds based on unsubstituted thiophene shows that, despite a red shift of lambda(max), introduction of alkoxy groups leads to a decrease of mu beta. Theoretical calculations indicate that this effect results from a decrease of the dipole moment (mu) caused by the auxiliary electron-donor alkoxy groups on the thiophene ring. In contrast, replacement of BT by BEDOT produces an increase of mu, which associated with the noncovalent rigidification of the BT system accounts for the observed enhancement of mu beta.

We demonstrate quantitative magnetic field mapping with nanoscale resolution, by applying a lock-in technique on the electron spin resonance frequency of a single nitrogen-vacancy defect placed at the apex of an atomic force microscope tip. In addition, we report an all-optical magnetic imaging technique which is sensitive to large off-axis magnetic fields, thus extending the operation range of diamond-based magnetometry. Both techniques are illustrated by using a magnetic hard disk as a test sample. Owing to the non-perturbing and quantitative nature of the magnetic probe, this work should open up numerous perspectives in nanomagnetism and spintronics.

The control of domain walls in magnetic wires underpins an emerging class of spintronic devices. Propagation of these walls in imperfect media requires defects that pin them to be characterized on the nanoscale. Using a magnetic microscope based on a single nitrogen-vacancy (NV) center in diamond, we report domain-wall imaging on a 1-nanometer-thick ferromagnetic nanowire and directly observe Barkhausen jumps between two pinning sites spaced 50 nanometers apart. We further demonstrate in situ laser control of these jumps, which allows us to drag the domain wall along the wire and map the pinning landscape. Our work demonstrates the potential of NV microscopy to study magnetic nano-objects in complex media, whereas controlling domain walls with laser light may find an application in spintronic devices.

Diamond nanoparticles are promising photoluminescent probes for tracking intracellular processes, due to embedded, perfectly photostable color centers. In this work, the spontaneous internalization of such nanoparticles (diameter 25 nm) in HeLa cancer cells is investigated by confocal microscopy and time-resolved techniques. Nanoparticles are observed inside the cell cytoplasm at the single-particle and single-color-center level, assessed by time-correlation intensity measurements. Improvement of the nanoparticle signal-to-noise ratio inside the cell is achieved using a pulsed-excitation laser and time-resolved detection taking advantage of the long radiative lifetime of the color-center excited state as compared to cell autofluorescence. The internalization pathways are also investigated, with endosomal marking and colocalization analyses. The low colocalization ratio observed proves that nanodiamonds are not trapped in endosomes, a promising result in prospect of drug delivery by these nanoparticles. Low cytotoxicity of these nanoparticles in this cell line is also shown.

We report an experimental study of the longitudinal relaxation time (${T}_{1}$) of the electron spin associated with single nitrogen-vacancy (NV) defects hosted in nanodiamonds (NDs). We first show that ${T}_{1}$ decreases over three orders of magnitude when the ND size is reduced from 100 to 10 nm owing to the interaction of the NV electron spin with a bath of paramagnetic centers lying on the ND surface. We next tune the magnetic environment by decorating the ND surface with Gd${}^{3+}$ ions and observe an efficient ${T}_{1}$ quenching, which demonstrates magnetic noise sensing with a single electron spin. We estimate a sensitivity down to $\ensuremath{\approx}14$ electron spins detected within 10 s, using a single NV defect hosted in a 10-nm-size ND. These results pave the way towards ${T}_{1}$-based nanoscale imaging of the spin density in biological samples.

Flipping the switch: A new type of bipyridine-based ligand functionalized by phenyl- and dimethylaminophenyldithienylethene groups allows the preparation of photochromic dipolar zinc(II) complexes. For the first time, efficient on/off photoswitching of the NLO response of metallochromophores is observed. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z704138_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.