Beata Kardynal

Switching asymmetries in closely coupled magnetic nanostructure arrays

Cobalt nanostructures (220 and 300 nm×275 nm×30 nm) were fabricated using electron beam lithography into ordered, close proximity (170 nm) arrays. Domain configurations with accompanying hysteresis loops were measured using off-axis electron holography. Measurements were compared to solutions of the Landau–Lifshitz–Gilbert equations. Both exhibit switching asymmetries due to strong intercell coupling and the presence of a field normal to the cell surface. Magnetic domain configurations during switching depended strongly on the initial conditions, as well as the direction of the perpendicular field relative to the in-plane hysteresis-field direction.

Understanding the effect of surface chemistry on charge generation and transport in poly (3-hexylthiophene)/CdSe hybrid solar cells.

For hybrid solar cells, interfacial chemistry is one of the most critical factors for good device performance. We have demonstrated that the size of the surface ligands and the dispersion of nanoparticles in the solvent and in the polymer are important criteria in obtaining optimized device performance. The size of the ligands will affect the charge transport at the particle/particle and particle/polymer interfaces and the chemical structures of the ligands will determine their compatibility with the solvent and polymer. Hence other than pyridine, 2-thiophenemethylamine also showed good potential as ligand replacement for poly(3-hexylthiophene)/CdSe hybrid solar cells. With the right ligand combination, we have shown that the power conversion efficiency improved by a factor of 6 after ligand exchange.

In situ transmission electron microscopy of light-induced photocatalytic reactions

Transmission electron microscopy (TEM) makes it possible to obtain insight into the structure, composition and reactivity of photocatalysts, which are of fundamental interest for sustainable energy research. Such insight can be used for further material optimization. Here, we combine conventional TEM analysis of photocatalysts with environmental TEM (ETEM) and photoactivation using light. Two novel types of TEM specimen holder that enable in situ illumination are developed to study light-induced phenomena in photoactive materials, systems and photocatalysts at the nanoscale under working conditions. The technological development of the holders is described and two representative photo-induced phenomena are studied: the photodegradation of Cu₂O and the photodeposition of Pt onto a GaN:ZnO photocatalyst.

Effect of Zinc Incorporation on the Performance of Red Light Emitting InP Core Nanocrystals

This report presents a systematic study on the effect of zinc (Zn) carboxylate precursor on the structural and optical properties of red light emitting InP nanocrystals (NCs). NC cores were assessed using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), energy-dispersive X-ray spectroscopy (EDX), and high-resolution transmission electron microscopy (HRTEM). When moderate Zn:In ratios in the reaction pot were used, the incorporation of Zn in InP was insufficient to change the crystal structure or band gap of the NCs, but photoluminescence quantum yield (PLQY) increased dramatically compared with pure InP NCs. Zn was found to incorporate mostly in the phosphate layer on the NCs. PL, PLQY, and time-resolved PL (TRPL) show that Zn carboxylates added to the precursors during NC cores facilitate the synthesis of high-quality InP NCs by suppressing nonradiative and sub-band-gap recombination, and the effect is visible also after a ZnS shell is grown on the cores.

Finite element simulations of electrostatic dopant potentials in thin semiconductor specimens for electron holography

Two-dimensional finite element simulations of electrostatic dopant potentials in parallel-sided semiconductor specimens that contain p-n junctions are used to assess the effect of the electrical state of the surface of a thin specimen on projected potentials measured using off-axis electron holography in the transmission electron microscope. For a specimen that is constrained to have an equipotential surface, the simulations show that the step in the projected potential across a p-n junction is always lower than would be predicted from the properties of the bulk device, but is relatively insensitive to the value of the surface state energy, especially for thicker specimens and higher dopant concentrations. The depletion width measured from the projected potential, however, has a complicated dependence on specimen thickness. The results of the simulations are of broader interest for understanding the influence of surfaces and interfaces on electrostatic potentials in nanoscale semiconductor devices.

Quasi 2D electronic states with high spin-polarization in centrosymmetric MoS2 bulk crystals.

Time reversal dictates that nonmagnetic, centrosymmetric crystals cannot be spin-polarized as a whole. However, it has been recently shown that the electronic structure in these crystals can in fact show regions of high spin-polarization, as long as it is probed locally in real and in reciprocal space. In this article we present the first observation of this type of compensated polarization in MoS2 bulk crystals. Using spin- and angle-resolved photoemission spectroscopy (ARPES), we directly observed a spin-polarization of more than 65% for distinct valleys in the electronic band structure. By additionally evaluating the probing depth of our method, we find that these valence band states at the point in the Brillouin zone are close to fully polarized for the individual atomic trilayers of MoS2, which is confirmed by our density functional theory calculations. Furthermore, we show that this spin-layer locking leads to the observation of highly spin-polarized bands in ARPES since these states are almost completely confined within two dimensions. Our findings prove that these highly desired properties of MoS2 can be accessed without thinning it down to the monolayer limit.

Engineering of optical and electronic band gaps in transition metal dichalcogenide monolayers through external dielectric screening

In order to fully exploit the potential of transition metal dichalcogenide monolayers (TMD-MLs), the well-controlled creation of atomically sharp lateral heterojunctions within these materials is highly desirable. A promising approach to create such heterojunctions is the local modulation of the electronic structure of an intrinsic TMD-ML via dielectric screening induced by its surrounding materials. For the realization of this non-invasive approach, an in-depth understanding of such dielectric effects is required. We report on the modulations of excitonic transitions in TMD-MLs through the effect of dielectric environments including low-k and high-k dielectric materials. We present absolute tuning ranges as large as 37 meV for the optical band gaps of WSe 2 and MoSe 2 MLs and relative tuning ranges on the order of 30% for the binding energies of neutral excitons in WSe 2 MLs. The findings suggest the possibility to reduce the electronic band gap of WSe 2 MLs by 120 meV, paving the way towards dielectrically defined lateral heterojunctions.

The role of ion exchange in the passivation of In(Zn)P nanocrystals with ZnS.

We have investigated the chemical state of In(Zn)P/ZnS core/shell nanocrystals (NCs) for color conversion applications using hard X-ray absorption spectroscopy (XAS) and photoluminescence excitation (PLE). Analyses of the edge energies as well as the X-ray absorption fine structure (XAFS) reveal that the Zn2+ ions from ZnS remain in the shell while the S2− ions penetrate into the core at an early stage of the ZnS deposition. It is further demonstrated that for short growth times, the ZnS shell coverage on the core was incomplete, whereas the coverage improved gradually as the shell deposition time increased. Together with evidence from PLE spectra, where there is a strong indication of the presence of P vacancies, this suggests that the core-shell interface in the In(Zn)P/ZnS NCs are subject to substantial atomic exchanges and detailed models for the shell structure beyond simple layer coverage are needed. This substantial atomic exchange is very likely to be the reason for the improved photoluminescence behavior of the core-shell particles compare to In(Zn)P-only NCs as S can passivate the NCs surfaces.

Quantitative measurement of mean inner potential and specimen thickness from high-resolution off-axis electron holograms of ultra-thin layered WSe2

The phase and amplitude of the electron wavefunction that has passed through ultra-thin flakes of WSe2 is measured from high-resolution off-axis electron holograms. Both the experimental measurements and corresponding computer simulations are used to show that, as a result of dynamical diffraction, the spatially averaged phase does not increase linearly with specimen thickness close to an [001] zone axis orientation even when the specimen has a thickness of only a few layers. It is then not possible to infer the local specimen thickness of the WSe2 from either the phase or the amplitude alone. Instead, we show that the combined analysis of phase and amplitude from experimental measurements and simulations allows an accurate determination of the local specimen thickness. The relationship between phase and projected potential is shown to be approximately linear for extremely thin specimens that are tilted by several degrees in certain directions from the [001] zone axis. A knowledge of the specimen thickness then allows the electrostatic potential to be determined from the measured phase. By using this combined approach, we determine a value for the mean inner potential of WSe2 of 18.9±0.8V, which is 12% lower than the value calculated from neutral atom scattering factors.

Quantitative Agreement between Electron-Optical Phase Images of WSe2 and Simulations Based on Electrostatic Potentials that Include Bonding Effects

The quantitative analysis of electron-optical phase images recorded using off-axis electron holography often relies on the use of computer simulations of electron propagation through a sample. However, simulations that make use of the independent atom approximation are known to overestimate experimental phase shifts by approximately 10%, as they neglect bonding effects. Here, we compare experimental and simulated phase images for few-layer WSe_{2}. We show that a combination of pseudopotentials and all-electron density functional theory calculations can be used to obtain accurate mean electron phases, as well as improved atomic-resolution spatial distribution of the electron phase. The comparison demonstrates a perfect contrast match between experimental and simulated atomic-resolution phase images for a sample of precisely known thickness. The low computational cost of this approach makes it suitable for the analysis of large electronic systems, including defects, substitutional atoms, and material interfaces.The quantitative analysis of electron-optical phase images recorded using off-axis electron holography often relies on the use of computer simulations of electron propagation through a sample. However, simulations that make use of the independent atom approximation are known to overestimate experimental phase shifts by approximately 10%, as they neglect bonding effects. Here, we compare experimental and simulated phase images for few-layer WSe2 . We show that a combination of pseudopotentials and all-electron density functional theory calculations can be used to obtain accurate mean electron phases, as well as improved atomic-resolution spatial distribution of the electron phase. The comparison demonstrates a perfect contrast match between experimental and simulated atomic-resolution phase images for a sample of precisely know thickness. The low computational cost of this approach makes it suitable for the analysis of large electronic systems, including defects, substitutional atoms and material interfaces.