Optical properties of ZnFe2O4 nanoparticles and Fe-decorated inversion domain boundaries in ZnO.

The maximum efficiency of solar cells utilizing a single layer for photovoltaic conversion is given by the single junction Shockley-Queisser limit. In tandem solar cells, a stack of materials with different band gaps contribute to the conversion, enabling tandem cells to exceed the single junction Shockley-Queisser limit. An intriguing variant of this approach is to embed semiconducting nanoparticles in a transparent conducting oxide (TCO) solar cell front contact. This alternative route would enhance the functionality of the TCO layer, allowing it to participate directly in photovoltaic conversion via photon absorption and charge carrier generation in the nanoparticles. Here, we demonstrate the functionalization of ZnO through incorporation of either ZnFe2O4 spinel nanoparticles (NPs) or inversion domain boundaries (IDBs) decorated by Fe. Diffuse reflectance spectroscopy and electron energy loss spectroscopy show that samples containing spinel particles and samples containing IDBs decorated by Fe both display enhanced absorption in the visible range at around 2.0 and 2.6 eV. This striking functional similarity was attributed to the local structural similarity around Fe-ions in spinel ZnFe2O4 and at Fe-decorated basal IDBs. Hence, functional properties of the ZnFe2O4 arise already for the two-dimensional basal IDBs, from which these planar defects behave like two-dimensional spinel-like inclusions in ZnO. Cathodoluminescence spectra reveal an increased luminescence around the band edge of spinel ZnFe2O4 when measuring on the spinel ZnFe2O4 NPs embedded in ZnO, whereas spectra from Fe-decorated IDBs could be deconvoluted into luminescence contributions from bulk ZnO and bulk ZnFe2O4.

Formation and functionalization of Ge-nanoparticles in ZnO.

Semiconductor nanocrystals are often proposed as a viable route to improve solar energy conversion in photovoltaics and photoelectrochemical systems. Embedding the nanocrystals in, e.g. a transparent and conducting electrode of a solar cell will promote the photon absorption and subsequent transfer of the generated charge carriers from the nanocrystal, and thereby enhance the function of the electrode. This can be accomplished by embedding a semiconducting nanocrystal with a small bandgap in a transparent conducting oxide (TCO), which is commonly utilized as electrode in new generation solar cells. Here, we demonstrate the incorporation, formation, and functionalization of germanium (Ge) nanocrystals in zinc oxide utilizing ion implantation, where post implantation annealing at 800 °C results in diamond cubic Ge nanocrystals with sizes between 2 and 20 nm. Photoluminecence spectra show a distinct emission around 0.7 eV arising from the Ge nanocrystals, and with additional emission features up to 1.15 eV due to quantum confinement, demonstrating a novel functionalization and tunability of the TCO electrode.

Strain Modulation of Si Vacancy Emission from SiC Micro- and Nanoparticles.

Single-photon emitting point defects in semiconductors have emerged as strong candidates for future quantum technology devices. In the present work, we exploit crystalline particles to investigate relevant defect localizations, emission shifting, and waveguiding. Specifically, emission from 6H-SiC micro- and nanoparticles ranging from 100 nm to 5 µm in size is collected using cathodoluminescence (CL), and we monitor signals attributed to the Si vacancy (VSi) as a function of its location. Clear shifts in the emission wavelength are found for emitters localized in the particle center and at the edges. By comparing spatial CL maps with strain analysis carried out in transmission electron microscopy, we attribute the emission shifts to compressive strain of 2-3% along the particle a-direction. Thus, embedding VSi qubit defects within SiC nanoparticles offers an interesting and versatile opportunity to tune single-photon emission energies while simultaneously ensuring ease of addressability via a self-assembled SiC nanoparticle matrix.

The heterogeneous nucleation of threading dislocations on partial dislocations in III-nitride epilayers.

III-nitride compound semiconductors are breakthrough materials regarding device applications. However, their heterostructures suffer from very high threading dislocation (TD) densities that impair several aspects of their performance. The physical mechanisms leading to TD nucleation in these materials are still not fully elucidated. An overlooked but apparently important mechanism is their heterogeneous nucleation on domains of basal stacking faults (BSFs). Based on experimental observations by transmission electron microscopy, we present a concise model of this phenomenon occurring in III-nitride alloy heterostructures. Such domains comprise overlapping intrinsic I1 BSFs with parallel translation vectors. Overlapping of two BSFs annihilates most of the local elastic strain of their delimiting partial dislocations. What remains combines to yield partial dislocations that are always of screw character. As a result, TD nucleation becomes geometrically necessary, as well as energetically favorable, due to the coexistence of crystallographically equivalent prismatic facets surrounding the BSF domain. The presented model explains all observed BSF domain morphologies, and constitutes a physical mechanism that provides insight regarding dislocation nucleation in wurtzite-structured alloy epilayers.

Reply to Comment on 'Nanoscale mapping of optical band gaps using monochromated electron energy loss spectroscopy'.

We respond to the comment by Thomas Walther and reaffirm the findings of our original article.

Nanoscale mapping of optical band gaps using monochromated electron energy loss spectroscopy.

Using monochromated electron energy loss spectroscopy in a probe-corrected scanning transmission electron microscope we demonstrate band gap mapping in ZnO/ZnCdO thin films with a spatial resolution below 10 nm and spectral precision of 20 meV.

Dielectric response of pentagonal defects in multilayer graphene nano-cones.

The dielectric response of pentagonal defects in multilayer graphene nano-cones has been studied by electron energy loss spectroscopy and ab initio simulations. At the cone apex, a strong modification of the dielectric response is observed below the energy of the π plasmon resonance. This is attributed to π → π* interband transitions induced by topology-specific resonant π bonding states as well as π*-σ* hybridization. It is concluded that pentagonal defects strongly affect the local electronic structure in such a way that multi-walled graphene nano-cones should show great promise as field emitters.

The influence of exact exchange corrections in van der Waals layered narrow bandgap black phosphorus.

We study the electronic structure of black phosphorus by combining state-of-the-art density functional theory, multiple scattering calculations and electron energy loss spectroscopy. The hybrid functionals HSE03 and PBE0 are tested to investigate whether they give an improved description compared to the more traditional PZ-LDA and PBE-GGA functionals. These calculations are compared with investigations of the conduction band using electron energy loss spectroscopy and calculations based on the real-space multiple scattering approach, and previous determinations of the bandgap. The hybrid functional HSE03 gives an improved correspondence with these experiments. Comparisons of the calculated valence band with previous XPS studies yield acceptable agreement for the traditional functionals, while the results from the hybrid functionals are less satisfactory, since the hybrid functionals overestimate the valence band width significantly.

Comparison of the electronic structure of a thermoelectric skutterudite before and after adding rattlers: an electron energy loss study.

Skutterudites, with rattler atoms introduced in voids in the crystal unit cell, are promising thermoelectric materials. We modify the binary skutterudite with atomic content Co(8)P(24) in the cubic crystal unit cell by adding La as rattlers in all available voids and replacing Co by Fe to maintain charge balance, resulting in La(2)Fe(8)P(24). The intention is to leave the electronic structure unaltered while decreasing the thermal conductivity due to the presence of the rattlers. We compare the electronic structure of these two compounds by studying the L-edges of P and of the transition elements Co and Fe using electron energy loss spectroscopy (EELS). Our studies of the transition metal white lines show that the 3d electron count is similar for Co and Fe in these compounds. As elemental Fe has one electron less than Co, this supports the notion that each La atom donates three electrons. The L-edges of P in these two skutterudites are quite similar, signalling only minor differences in electronic structure. This is in reasonable agreement with density functional theory (DFT) calculations, and with our multiple scattering FEFF calculations of the near edge structure. However, our experimental plasmon energies and dielectric functions deviate considerably from predictions based on DFT calculations.

A quantitative study of valence electron transfer in the skutterudite compound CoP(3) by combining x-ray induced Auger and photoelectron spectroscopy.

We use the sum of the ionization and Auger energy, the so-called Auger parameter, measured from the x-ray photoelectron spectrum, to study the valence electron distribution in the skutterudite CoP(3). The electron transfer between Co and P was estimated using models relating changes in Auger parameter values to charge transfer. It was found that each P atom gains 0.24 e(-), and considering the unit formula CoP(3) this is equivalent to a donation of 0.72 e(-) per Co atom. This is in agreement with a recent electron energy-loss spectroscopy study, which indicates a charge transfer of 0.77 e(-)/atom from Co to P.