Luiz H. G. Tizei

Bright UV Single Photon Emission at Point Defects in h-BN

To date, quantum sources in the ultraviolet (UV) spectral region have been obtained only in semiconductor quantum dots. Color centers in wide bandgap materials may represent a more effective alternative. However, the quest for UV quantum emitters in bulk crystals faces the difficulty of combining an efficient UV excitation/detection optical setup with the capability of addressing individual color centers in potentially highly defective materials. In this work we overcome this limit by employing an original experimental setup coupling cathodoluminescence within a scanning transmission electron microscope to a Hanbury-Brown-Twiss intensity interferometer. We identify a new extremely bright UV single photon emitter (4.1 eV) in hexagonal boron nitride. Hyperspectral cathodoluminescence maps show a high spatial localization of the emission (∼80 nm) and a typical zero-phonon line plus phonon replica spectroscopic signature, indicating a point defect origin, most likely carbon substitutional at nitrogen sites. An additional nonsingle-photon broad emission may appear in the same spectral region, which can be attributed to intrinsic defects related to electron irradiation.

Spectrally and spatially resolved cathodoluminescence of nanodiamonds: local variations of the NV 0 emission properties

Here we report the spectrally and spatially resolved cathodoluminescence of diamond nanoparticles using focused fast electron beams in a transmission electron microscope. We demonstrate the possibility of quickly detecting various individual colour centres of different kinds on wide areas (several micrometres square) contained in nanoparticles separated by subwavelength distances. Among them, nanoparticles containing one or more neutral nitrogen-vacancy (NV(0)) intensity maxima have been seen, attributable to individual emitters. Thanks to a spatial resolution which is solely limited by charge carrier diffusion in the case of a fast electron (80 keV) setup, the spectra of two individual NV(0) emitters separated by 80 nm inside a nanoparticle have been spatially discerned. A shift of the zero phonon line (ZPL) between the two emitters, which we attribute to internal stress, is shown to arise even within the same nanoparticle. Detailed emission spectra (ZPL, phonon lines and Huang-Rhys factor, directly linked to the relaxation energy of the colour centre) in 51 individual NV(0) centres have been measured in 39 particles. The ZPL and Huang-Rhys factor are found to be measurably dispersed, while the phonon energies keep constant.

Exciton Mapping at Subwavelength Scales in Two-Dimensional Materials

Spatially resolved electron-energy-loss spectroscopy (EELS) is performed at diffuse interfaces between MoS2 and MoSe2 single layers. With a monochromated electron source (20 meV) we successfully probe excitons near the interface by obtaining the low loss spectra at the nanometer scale. The exciton maps clearly show variations even with a 10 nm separation between measurements; consequently, the optical band gap can be measured with nanometer-scale resolution, which is 50 times smaller than the wavelength of the emitted photons. By performing core-loss EELS at the same regions, we observe that variations in the excitonic signature follow the chemical composition. The exciton peaks are observed to be broader at interfaces and heterogeneous regions, possibly due to interface roughness and alloying effects. Moreover, we do not observe shifts of the exciton peak across the interface, possibly because the interface width is not much larger than the exciton Bohr radius.

Nanometric Resolved Luminescence in h-BN Flakes: Excitons and Stacking Order

Romain Bourrellier, Michele Amato, 2 Luiz Henrique Galvão Tizei, Christine Giorgetti, Alexandre Gloter, Malcolm I. Heggie, Katia March, Odile Stéphan, Lucia Reining, Mathieu Kociak, and Alberto Zobelli ∗ Laboratoire de Physique des Solides, Univ. Paris-Sud, CNRS UMR 8502, F-91405, Orsay, France Laboratoire des Solides Irradiés, Ecole Polytechnique, Route de Saclay, F-91128 Palaiseau and European Theoretical Spectroscopy Facility (ETSF), France Department of Chemistry, University of Surrey, Guildford GU2 7XH, United Kingdom

Spontaneous periodic diameter oscillations in InP nanowires: the role of interface instabilities.

We have observed that thin InP nanowires generated by vapor-liquid-solid growth display spontaneous periodic diameter oscillations when large group III supersaturations are used. Diameter variations are associated with a large number of stacking faults and crystallographic phase changes(wurtzite/zinc-blende); also the axial distance between oscillations depends on the indium precursor flow used during the run. We attribute the morphology changes to a substantial deformation of the triple phase line (vapor-liquid-solid) at the catalyst nanoparticle edge originated from multistep nucleation during growth. The deformation alters the mechanical force balance acting on the nanoparticle during growth in such a way that the particle displaces from the nanowire top and wets the nanowire sidewall. Subsequently, as catalytic growth occurs at the sidewall, the associated increase in diameter will eventually push the NP back to its original wire-top position until the onset of a new instability at the triple phase line.

Kinetic effects in InP nanowire growth and stacking fault formation: the role of interface roughening.

InP nanowire polytypic growth was thoroughly studied using electron microscopy techniques as a function of the In precursor flow. The dominant InP crystal structure is wurtzite, and growth parameters determine the density of stacking faults (SF) and zinc blende segments along the nanowires (NWs). Our results show that SF formation in InP NWs cannot be univocally attributed to the droplet supersaturation, if we assume this variable to be proportional to the ex situ In atomic concentration at the catalyst particle. An imbalance between this concentration and the axial growth rate was detected for growth conditions associated with larger SF densities along the NWs, suggesting a different route of precursor incorporation at the triple phase line in that case. The formation of SFs can be further enhanced by varying the In supply during growth and is suppressed for small diameter NWs grown under the same conditions. We attribute the observed behaviors to kinetically driven roughening of the semiconductor/metal interface. The consequent deformation of the triple phase line increases the probability of a phase change at the growth interface in an effort to reach local minima of system interface and surface energy.

Enhanced Eshelby twist on thin Wurtzite InP nanowires and measurement of local crystal rotation.

We have performed a detailed study of the lattice distortions of InP wurtzite nanowires containing an axial screw dislocation. Eshelby predicted that this kind of system should show a crystal rotation due to the dislocation induced torque. We have measured the twisting rate and the dislocation Burgers vector on individual wires, revealing that nanowires with a 10-nm radius have a twist up to 100% larger than estimated from elasticity theory. The strain induced by the deformation has a Mexican-hat-like geometry, which may create a tube-like potential well for carriers.

III―V semiconductor nanowire growth: does arsenic diffuse through the metal nanoparticle catalyst?

The synthesis of III-V semiconductor nanowires (NWs) is based on the delivery of atoms from a vapor phase to a catalytic metal nanoparticle (NP). Although there has been extensive work on such systems, the incorporation pathways of group V atoms remain an open issue. Here, we have performed a detailed structural and chemical analysis of the catalyst NP in NWs where we switch the V atomic element during growth (heterostructured InP/InAs/InP NWs). Our experimental results indicate a group V pathway where these atoms actually diffuse through the catalytic NP by formation of a stable phase containing As under growth conditions. We have observed distinct NW growth behavior within a narrow temperature range (30 degrees C) suggesting a transition between vapor-liquid-solid and vapor-solid-solid growth modes.

Structure and local chemical properties of boron-terminated tetravacancies in hexagonal boron nitride.

Imaging and spectroscopy performed in a low-voltage scanning transmission electron microscope are used to characterize the structure and chemical properties of boron-terminated tetravacancies in hexagonal boron nitride. We confirm earlier theoretical predictions about the structure of these defects and identify new features in the electron energy-loss spectra of B atoms using high resolution chemical maps, highlighting differences between these areas and pristine sample regions. We correlate our experimental data with calculations which help explain our observations.

Postsynthesis of h‐BN/Graphene Heterostructures Inside a STEM

Combinations of 2D materials with different physical properties can form heterostructures with modified electrical, mechanical, magnetic, and optical properties. The direct observation of a lateral heterostructure synthesis is reported by epitaxial in‐plane graphene growth from the step‐edge of hexagonal BN (h‐BN) within a scanning transmission electron microscope chamber. Residual hydrocarbon in the chamber is the carbon source. The growth interface between h‐BN and graphene is atomically identified as largely N–C bonds. This postgrowth method can form graphene nanoribbons connecting two h‐BN domains with different twisting angles, as well as isolated carbon islands with arbitrary shapes embedded in the h‐BN layer. The electronic properties of the vertically stacked h‐BN/graphene heterostructures are investigated by electron energy‐loss spectroscopy (EELS). Low‐loss EELS analysis of the dielectric response suggests a robust coupling effect between the graphene and h‐BN layers.