Mönch - Light Collection / Injection for STEM

The structural and optical properties of axial GaN/InGaN/GaN nanowire heterostructures with high InN molar fractions grown by molecular beam epitaxy have been studied at the nanoscale by a combination of electron microscopy, extended x-ray absorption fine structure and nano-cathodoluminescence techniques. InN molar fractions up to 50% have been successfully incorporated without extended defects, as evidence of nanowire potentialities for practical device realisation in such a composition range. Taking advantage of the N-polarity of the self-nucleated GaN NWs grown by molecular beam epitaxy on Si(111), the N-polar InGaN stability temperature diagram has been experimentally determined and found to extend to a higher temperature than its metal-polar counterpart. Furthermore, annealing of GaN-capped InGaN NWs up to 800 °C has been found to result in a 20 times increase of photoluminescence intensity, which is assigned to point defect curing.

We report on a detailed study of the intensity dependent optical properties of individual GaN/AlN quantum disks (QDisks) embedded into GaN nanowires (NW). The structural and optical properties of the QDisks were probed by high spatial resolution cathodoluminescence (CL) in a scanning transmission electron microscope (STEM). By exciting the QDisks with a nanometric electron beam at currents spanning over three orders of magnitude, strong nonlinearities (energy shifts) in the light emission are observed. In particular, we find that the amount of energy shift depends on the emission rate and on the QDisk morphology (size, position along the NW and shell thickness). For thick QDisks (>4 nm), the QDisk emission energy is observed to blueshift with the increase of the emission intensity. This is interpreted as a consequence of the increase of carriers density excited by the incident electron beam inside the QDisks, which screens the internal electric field and thus reduces the quantum confined Stark effect (QCSE) present in these QDisks. For thinner QDisks $\left(<3\mathrm{nm}\right)$, the blueshift is almost absent in agreement with the negligible QCSE at such sizes. For QDisks of intermediate sizes there exists a current threshold above which the energy shifts, marking the transition from unscreened to partially screened QCSE. From the threshold value we estimate the lifetime in the unscreened regime. These observations suggest that, counterintuitively, electrons of high energy can behave ultimately as single electron-hole pair generators. In addition, when we increase the current from 1 to 10 pA the light emission efficiency drops by more than one order of magnitude. This reduction of the emission efficiency is a manifestation of the “efficiency droop” as observed in nitride-based 2D light emitting diodes, a phenomenon tentatively attributed to the Auger effect.

Ultra-fast transmission electron microscopy (UTEM) combines sub-picosecond time-resolution with the versatility of TEM spectroscopies. It allows one to study the dynamics of materials properties combining complementary techniques. However, until now, time-resolved cathodoluminescence, which is expected to give access to the optical properties dynamics, was still unavailable in a UTEM. In this paper, we report time-resolved cathodoluminescence measurements in an ultrafast transmission electron microscope. We measured lifetime maps, with a 12 nm spatial resolution and sub-nanoseconds resolution, of nano-diamonds with a high density of NV center. This study paves the way to new applications of UTEM and to correlative studies of optically active nanostructures.

Structural, electronic, and chemical nanoscale modifications of transition metal dichalcogenide monolayers alter their optical properties, including the generation of single photon emitters. A key missing element for complete control is a direct spatial correlation of optical response to nanoscale modifications, due to the large gap in spatial resolution between optical spectroscopy and nanometer resolved techniques, such as transmission electron microscopy or scanning tunneling microscopy. Here, we bridge this gap by obtaining nanometer resolved optical properties using electron spectroscopy, specifically electron energy loss spectroscopy (EELS) for absorption and cathodoluminescence (CL) for emission, which were directly correlated to chemical and structural information. In an h-BN/WS2/h-BN heterostructure, we observe local modulation of the trion (X−) emission due to tens of nanometer wide dielectric patches, while the exciton, XA, does not follow the same modulation. Trion emission also increases in regions where charge accumulation occurs, close to the carbon film supporting the heterostructures. Finally, localized exciton emission (L) detection is not correlated to strain variations above 1 %, suggesting point defects might be involved in their formations.

The influence of four substrates [thin Si₃N₄, few-layer graphene (FLG), thin h–BN, and monolayer h–BN] on plasmon resonances of metallic nanoparticles was studied using electron energy loss spectroscopy. The h–BN monolayer is an excellent substrate for the study of plasmonic particles due to its large bandgap, negligible charging under electron irradiation, and negligible influence on the plasmon resonance full width at half maximum and peak positions. These effects were evidenced in experiments with gold nanotriangles focusing on dipolar modes. Nanotriangles on h–BN exhibit the lowest influence from the substrate compared to Si₃N₄ and FLG. In a dataset containing 23 triangles of similar sizes, the dipolar mode was found to have smaller redshifts, sharper peak widths, and higher resonance quality factors on h–BN, showing that it has nearly no effect on the plasmon absorption properties, provided that it is free from carbon contamination. However, light emission (cathodoluminescence) decreases as a function of electron irradiation for triangles on h–BN, even though the electron energy loss signal stays unchanged. This indicates the creation of non-radiative decay channels.

Conical metallic tapers represent an intriguing subclass of metallic nanostructures, as their plasmonic properties show interesting characteristics in strong correlation to their geometrical properties. This is important for possible applications such as in the field of scanning optical microscopy, as favourable plasmonic resonance behaviour can be tailored by optimizing structural parameters like surface roughness or opening angle. Here, we review our recent studies, where single-crystalline gold tapers were investigated experimentally by means of electron energy-loss and cathodoluminescence spectroscopy techniques inside electron microscopes, supported by theoretical finite-difference time-domain calculations. Through the study of tapers with various opening angles, the underlying resonance mechanisms are discussed.

In this tutorial review, we present the use of electron energy loss spectroscopy (EELS) and cathodoluminescence (CL) spectroscopy for surface plasmon mapping within metallic nanoparticles. We put a special emphasis on particles that are much smaller than the wavelength of visible light. We start by introducing the concept of surface plasmons, keeping the formalism as simple as possible by focusing on the quasi-static approximation. We then make a link between optical cross-sections, EELS and CL probabilities, and the surface plasmons' physical properties. A short survey of simulation tools is given. We then present typical experimental set-ups and describe some problems frequently encountered with spectrometers. Experimental conditions for improved signal to noise ratio are discussed. Analysis techniques are discussed, especially those related to the spectral imaging mode, which is extremely useful in EELS and CL experiments. Finally, the specific range of applications of EELS and CL with respect to other nano-optic techniques is discussed, as well as the strengths and weaknesses of EELS as compared with CL.