Near Band Edge excitation in 2D materials by Transmission Electron Microscopy

International audienc

Distinguishing different stackings in layered materials via luminescence spectroscopy

Despite its simple crystal structure, layered boron nitride features a surprisingly complex variety of phonon-assisted luminescence peaks. We present a combined experimental and theoretical study on ultraviolet-light emission in hexagonal and rhombohedral bulk boron nitride crystals. Emission spectra of high-quality samples are measured via cathodoluminescence spectroscopy, displaying characteristic differences between the two polytypes. These differences are explained using a fully first-principles computational technique that takes into account radiative emission from ``indirect'', finite-momentum, excitons via coupling to finite-momentum phonons. We show that the differences in peak positions, number of peaks and relative intensities can be qualitatively and quantitatively explained, once a full integration over all relevant momenta of excitons and phonons is performed.Comment: Main: 6 pages and 4 figures, Supplementary: 6 pages and 7 figure

Confinement of Dyes inside Boron Nitride Nanotubes: Photostable and Shifted Fluorescence down to the Near Infrared

Fluorescence is ubiquitous in life science and used in many fields of research ranging from ecology to medicine. Among the most common fluorogenic compounds, dyes are being exploited in bioimaging for their outstanding optical properties from UV down to the near IR (NIR). However, dye molecules are often toxic to living organisms and photodegradable, which limits the time window for in vivo experiments. Here, it is demonstrated that organic dye molecules are passivated and photostable when they are encapsulated inside a boron nitride nanotube (dyes@BNNT). The results show that the BNNTs drive an aggregation of the encapsulated dyes, which induces a redshifted fluorescence from visible to NIR‐II. The fluorescence remains strong and stable, exempt of bleaching and blinking, over a time scale longer than that of free dyes by more than 104. This passivation also reduces the toxicity of the dyes and induces exceptional chemical robustness, even in harsh conditions. These properties are highlighted in bioimaging where the dyes@BNNT nanohybrids are used as fluorescent nanoprobes for in vivo monitoring of Daphnia Pulex microorganisms and for diffusion tracking on human hepatoblastoma cells with two‐photon imaging

Distinguishing Different Stackings in Layered Materials via Luminescence Spectroscopy

peer reviewedDespite its simple crystal structure, layered boron nitride features a surprisingly complex variety of phonon-assisted luminescence peaks. We present a combined experimental and theoretical study on ultraviolet-light emission in hexagonal and rhombohedral bulk boron nitride crystals. Emission spectra of high-quality samples are measured via cathodoluminescence spectroscopy, displaying characteristic differences between the two polytypes. These differences are explained using a fully first-principles computational technique that takes into account radiative emission from “indirect,” finite-momentum excitons via coupling to finite-momentum phonons.We show that the differences in peak positions, number of peaks, and relative intensities can be qualitatively and quantitatively explained, once a full integration over all relevant momenta of excitons and phonons is performed

Exciton-exciton annihilation in hBN

Known as a prominent recombination path at high excitation densities, exciton-exciton annihilation (EEA) is evidenced in bulk hexagonal boron nitride (hBN) by cathodoluminescence at low temperature. Thanks to a careful tune of the the exciton density by varying either the current or the focus of the incident electron beam, we could estimate an EEA rate of 2$\times$10$^{-6}$ cm$^{3}$.s$^{-1}$ at $T=10$ K, the highest reported so far for a bulk semiconductor. Expected to be even stronger in nanotubes or atomic layers, EEA probablly contributes to the luminescence quenching observed in low-dimensionality BN materials

Angular resolved electron energy loss spectroscopy in hexagonal boron nitride

Electron energy loss spectra have been measured on hexagonal boron nitride single crystals employing a novel electron energy loss spectroscopic set-up composed by an electron microscope equipped with a monochromator and an in-column filter. This set-up provides high-quality energy-loss spectra and allows also for the imaging of energy-filtered diffraction patterns. These two acquisition modes provide complementary pieces of information, offering a global view of excitations in reciprocal space. As an example of the capabilities of the method we show how easily the core loss spectra at the $K$ edges of boron and nitrogen can be measured and imaged. Low losses associated to interband and/or plasmon excitations are also measured. This energy range allows us to illustrate that our method provides results of quality comparable to those obtained from non resonant X-ray inelastic scattering, but with advantageous specificities such as an enhanced sensitivity at low q and a much higher simplicity and versatility that makes it well adapted to the study of two-dimensional materials and related heterostructures. Finally, by comparing theoretical calculations against our measures, we are able to relate the range of applicability of ab initio calculations to the anisotropy of the sample and assess the level of approximation required for a proper simulation of our acquisition method

Angle-resolved electron energy loss spectroscopy in hexagonal boron nitride

International audienceElectron energy loss spectra were measured on hexagonal boron nitride single crystals employing an electron energy loss spectroscopic setup composed of an electron microscope equipped with a monochromator and an in-column filter. This setup provides high-quality energy-loss spectra and allows also for the imaging of energy-filtered diffraction patterns. These two acquisition modes provide complementary pieces of information, offering a global view of excitations in reciprocal space. As an example of the capabilities of the method we show how easily the core loss spectra at the K edges of boron and nitrogen can be measured and imaged. Low losses associated with interband and/or plasmon excitations are also measured. This energy range allows us to illustrate that our method provides results whose quality is comparable to that obtained from nonresonant x-ray inelastic scattering but with advantageous specificities such as an enhanced sensitivity at low q and a much greater simplicity and versatility that make it well adapted to the study of two-dimensional materials and related heterostructures. Finally, by comparing theoretical calculations to our measures, we are able to relate the range of applicability of ab initio calculations to the anisotropy of the sample and assess the level of approximation required for a proper simulation of our acquisition method

Dimensionality effects on the luminescence properties of hBN

International audienc

Exciton-exciton annihilation in hBN

Known as a prominent recombination path at high excitation densities, exciton-exciton annihilation (EEA) is evidenced in bulk hexagonal boron nitride (hBN) by cathodoluminescence at low temperature. Thanks to a careful tune of the the exciton density by varying either the current or the focus of the incident electron beam, we could estimate an EEA rate of 2$\times$10$^{-6}$ cm$^{3}$.s$^{-1}$ at $T=10$ K, the highest reported so far for a bulk semiconductor. Expected to be even stronger in nanotubes or atomic layers, EEA probablly contributes to the luminescence quenching observed in low-dimensionality BN materials

Dyes@BNNT Nanohybrids for Photostable Fluorescence Imaging

C. Allard, R. Nascimento F. Fossard, L. Schué, E. Flahaut, A. Loiseau, P. Desjardins, R. Martel, E. Gaufrès (2019): Dyes@BNNT Nanohybrids for Photostable Fluorescence Imaging. ChemRxiv. Preprint. Fluorescence is ubiquitous in life science and used in broad fields of research going from ecology to medicine. Among the most common fluorogenic compounds, dyes are being exploited in bioimaging for their outstanding optical properties across a broad range of wavelengths from the UV to the near-IR. However, dye molecules are often toxic to living organisms and photodegradable, giving limited time windows for in vivo monitoring. By encapsulating organic dyes inside a boron nitride nanotube (dyes@BNNT), we achieve a passivation of the dyes against photodegradation and chemical reaction. The dyes@BNNT nanohybrids contain aggregated and ordered dyes exhibiting strong photoluminescence with signal remaining stable and exempt of blinking over a time scale of more than 104 compared to free dyes. Our results also suggest reduced toxicity and exceptional chemical robustness even in harsh environments. The use of these 1D dyes@BNNT nanohybrids as fluorescence nanoprobes in bio-imaging is highlighted with in-vivo monitoring experiments on living Daphnia Pulex. File list (2) download file view on ChemRxiv [email protected] (1.53 MiB) download file view on ChemRxiv Supp for Mol@BNNT .pdf (3.54 MiB