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.

Visible Out-of-plane Polarized Luminescence and Electronic Resonance in Black Phosphorus.

Black phosphorus (BP) is unique among layered materials because of its homonuclear lattice and strong structural anisotropy. While recent investigations on few-layer BP have extensively explored the in-plane (a, c) anisotropy, much less attention has been given to the out-of-plane direction (b). Here, the optical response from bulk BP is probed using polarization-resolved photoluminescence (PL), photoluminescence excitation (PLE), and resonant Raman scattering along the zigzag, out-of-plane, and armchair directions. An unexpected b-polarized luminescence emission is detected in the visible, far above the fundamental gap. PLE indicates that this emission is generated through b-polarized excitation at 2.3 eV. The same electronic resonance is observed in resonant Raman with the enhancement of the Ag phonon modes scattering efficiency. These experimental results are fully consistent with DFT calculations of the permittivity tensor elements and demonstrate the remarkable extent to which the anisotropy influences the optical properties and carrier dynamics in black phosphorus.

How high is a MoSe2monolayer?

Transition metal dichalcogenides (TMDCs) have attracted significant attention for optoelectronic, photovoltaic and photoelectrochemical applications. The properties of TMDCs are highly dependent on the number of stacked atomic layers, which is usually counted post-fabrication, using a combination of optical methods and atomic force microscopy height measurements. Here, we use photoluminescence spectroscopy, Raman spectroscopy, and three different AFM methods to demonstrate significant discrepancies in height measurements of exfoliated MoSe2flakes on SiO2depending on the method used. We also highlight the often overlooked effect that electrostatic forces can be misleading when measuring the height of a MoSe2flake using AFM.

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.

Bright Luminescence from Indirect and Strongly Bound Excitons in h-BN.

A quantitative analysis of the excitonic luminescence efficiency in hexagonal boron nitride (h-BN) is carried out by cathodoluminescence in the ultraviolet range and compared with zinc oxide and diamond single crystals. A high quantum yield value of ∼50% is found for h-BN at 10 K comparable to that of direct band-gap semiconductors. This bright luminescence at 215 nm remains stable up to room temperature, evidencing the strongly bound character of excitons in bulk h-BN. Ab initio calculations of the exciton dispersion confirm the indirect nature of the lowest-energy exciton whose binding energy is found equal to 300±50 meV, in agreement with the thermal stability observed in luminescence. The direct exciton is found at a higher energy but very close to the indirect one, which solves the long debated Stokes shift in bulk h-BN.

Dimensionality effects on the luminescence properties of hBN.

Cathodoluminescence (CL) experiments at low temperature have been undertaken on various bulk and exfoliated hexagonal boron nitride (hBN) samples. Different bulk crystals grown from different synthesis methods have been studied. All of them present the same so-called S series in the 5.6-6 eV range, proving its intrinsic character. Luminescence spectra of flakes containing 100 down to 6 layers have been recorded. Strong modifications in the same UV range are observed and discussed within the general framework of 2D exciton properties in lamellar crystals.