arXiv subjects

Marius Grundmann

Publications and source records attributed to Marius Grundmann.

At least 19 recordsLinked to original sources

arXiv2025

Decoupling Composition and Band Gap in $\kappa$-Ga$_2$O$_3$ Heterostructures via STEM-EELS

High-resolution mapping of electronic properties at oxide heterointerfaces remains challenging due to probe delocalization and overlapping signals. In this work, we employ monochromated, probe-corrected scanning transmission electron microscopy combined with electron energy-loss spectroscopy (STEM-EELS) to resolve band gap variations across $\kappa$-Ga$_2$O$_3$-based multilayers with nanometer-scale precision. A custom automated quantitative-based EELS analysis framework enabled automated band gap fitting and visualization, ensuring reproducibility and high spatial resolution. By optimizing acquisition parameters and quantifying inelastic delocalization, we demonstrate reliable extraction of band gap excitations from layers only a few nanometers thick. For heterostructures grown on ITO templates, strain at defect-free interfaces induces a gradual band gap transition from $5.08~\mathrm{eV}$ to $4.28~\mathrm{eV}$ over $\sim 10~\mathrm{nm}$, despite an abrupt compositional change. In contrast, ZnO-based templates introduce structural defects that relieve strain, yielding band gaps consistent with composition. These results establish STEM-EELS as a powerful tool for nanoscale electronic characterization and highlight the dominant role of interfacial strain over composition in governing local band structure.

cond-mat.mtrl-sci↗

arXiv2023

Determination of acoustic phonon anharmonicities via second-order Raman scattering in CuI

We demonstrate the determination of anharmonic acoustic phonon properties via second-order Raman scattering exemplarily on copper iodide single crystals. The origin of multi-phonon features from the second-order Raman spectra was assigned by the support of the calculated 2-phonon density of states. In this way, the temperature dependence of acoustic phonons was determined down to 10\,K. To determine independently the harmonic contributions of respective acoustic phonons, density functional theory (DFT) in quasi-harmonic approximation was used. Finally, the anharmonic contributions were determined. The results are in agreement with earlier publications and extend CuI's determined acoustic phonon properties to lower temperatures with higher accuracy. This approach demonstrates that it is possible to characterize the acoustic anharmonicities via Raman scattering down to zero-temperature renormalization constants of at least 0.1\,cm$^{-1}$.

cond-mat.mtrl-sci↗

arXiv2023

Impact of magnetization and hyperfine field distribution on high magnetoelectric coupling strength in BaTiO$_3$-BiFeO$_3$ multilayers

Understanding the mechanisms of magnetoelectric (ME) coupling within multiferroic structures is paramount from a fundamental as well as an applied point of view. We report here that the magnetoelectric properties, as well as the magnetization, of BaTiO$_3$-BiFeO$_3$ superlattices can be tuned by varying the BiFeO$_3$ layer thickness. The magnetoelectric voltage coefficient ($α_{ME}$) reaches its maximum of 60.2 Vcm$^{-1}$Oe$^{-1}$ at 300 K, one of the highest values reported so far, for a sample with a BiFeO$_3$ thickness of 5 nm and a BaTiO$_3$ thickness of 10 nm. To gain deeper insight into the increased magnetoelectric coupling, and both the local and macroscopic magnetic properties, samples with varying BiFeO$_3$ thicknesses have been investigated. Correlations were established between the hyperfine field (HFF), the magnetoelectric voltage coefficient and the magnetization. The possible mechanisms responsible for the strong magnetoelectric coupling are discussed.

cond-mat.mtrl-sci↗

arXiv2022

Mid- and far-infrared localized surface plasmon resonances in chalcogen-hyperdoped silicon

Plasmonic sensing in the infrared region employs the direct interaction of the vibrational fingerprints of molecules with the plasmonic resonances, creating surface-enhanced sensing platforms that are superior than the traditional spectroscopy. However, the standard noble metals used for plasmonic resonances suffer from high radiative losses as well as fabrication challenges, such as tuning the spectral resonance positions into mid- to far-infrared regions, and the compatibility issue with the existing complementary metal-oxide-semiconductor (CMOS) manufacturing platform. Here, we demonstrate the occurrence of mid-infrared localized surface plasmon resonances (LSPR) in thin Si films hyperdoped with the known deep-level impurity tellurium. We show that the mid-infrared LSPR can be further enhanced and spectrally extended to the far-infrared range by fabricating two-dimensional arrays of micrometer-sized antennas in a Te-hyperdoped Si chip. Since Te-hyperdoped Si can also work as an infrared photodetector, we believe that our results will unlock the route toward the direct integration of plasmonic sensors with the one-chip CMOS platform, greatly advancing the possibility of mass manufacturing of high-performance plasmonic sensing systems.

cond-mat.mtrl-sci↗

arXiv2022

Dielectric function of CuBr$_\mathrm{x}$I$_{1-\mathrm{x}}$ alloy thin films

We study the dielectric function of CuBr$_\mathrm{x}$I$_{1-\mathrm{x}}$ thin film alloys using spectroscopic ellipsometry in the spectral range between 0.7 eV to 6.4 eV, in combination with first-principles calculations based on density functional theory. Through the comparison of theory and experiment, we attribute features in the dielectric function to electronic transitions at specific k-points in the Brillouin zone. The observed bandgap bowing as a function of alloy composition is discussed in terms of different physical and chemical contributions. The band splitting at the top of the valence band due to spin-orbit coupling is found to decrease with increasing Br-concentration, from a value of 660 meV for CuI to 150 meV for CuBr. This result can be understood considering the contribution of copper d-orbitals to the valence band maximum as a function of the alloy composition.

cond-mat.mtrl-sci↗

arXiv2022

Light absorption and emission by defects in doped nickel oxide

Nickel oxide is a versatile p-type semiconducting oxide with many applications in opto-electronic devices, but high doping concentrations are often required to achieve necessary electrical conductivity. In contrast to many other transparent oxide semiconductors, even moderate levels of doping of NiO can lead to significant optical absorption in the visible spectral range, limiting the application range of the material. This correlation has been reported extensively in literature, but its origin has been unknown until now. This work combines experimental data on optical properties from a variety of NiO samples with results from hybrid density functional theory calculations. It shows that strong electron-phonon interaction leads to a significant blue shift (0.6-1 eV) of electronic transitions from the valence band maximum to defect states by light absorption with respect to the thermodynamic charge transition levels. This essentially renders NiO a narrow-gap semiconductor by defect band formation already at moderate doping levels, with strong light absorption for photon energies of approximately 1 eV. The calculations are also shown to be fully consistent with experimental data on defect-related light emission in NiO.

cond-mat.mtrl-sci↗

arXiv2020

Identification of Li$_{\text{Ni}}$ and V$_{\text{Ni}}$ acceptor levels in doped nickel oxide

Nickel oxide, in particular in its doped, semiconducting form, is an important component of several optoelectronic devices. Doping NiO is commonly achieved either by incorporation of lithium, which readily occupies Ni sites substitutionally, producing the Li$_{\text{Ni}}$ acceptor, or by supplying reactive oxygen species during NiO film deposition, which leads to the formation of Ni vacancies (V$_{\mathrm{Ni}}$). However, the energetic position of these acceptors in the NiO band gap has not been experimentally determined until today. In this work, we close this knowledge gap by studying rectifying n$^{++}$p heterojunctions of NiO on top of fluorine-doped tin oxide. These structures show sufficient rectification to perform electric characterization by defect spectroscopic techniques, specifically capacitance-voltage and thermal admittance spectroscopy. Using these methods, the (0/-) charge transition levels are determined to be 190meV and 409meV above the valence band edge for the Li$_{\text{Ni}}$ and the V$_{\text{Ni}}$ acceptor, respectively.

cond-mat.mtrl-sci↗

arXiv2020

SnO/$β$-Ga2O3 vertical $pn$ heterojunction diodes

Vertical $pn$ heterojunction diodes were prepared by plasma-assisted molecular beam epitaxy of unintentionally-doped $p$-type SnO layers with hole concentrations ranging from $p=10^{18}$ to $10^{19}$cm$^{-3}$ on unintentionally-doped $n$-type $β$-Ga$_{2}$O$_{3}$(-201) substrates with an electron concentration of $n=2.0\times10^{17}$cm$^{-3}$. The SnO layers consist of (001)-oriented grains without in-plane expitaxial relation to the substrate. After subsequent contact processing and mesa etching (which drastically reduced the reverse current spreading in the SnO layer and associated high leakage) electrical characterization by current-voltage and capacitance-voltage measurement was performed. The results reveal a type-I band alignment and junction transport by thermionic emission in forward bias. A rectification of $2\times10^{8}$ at $\pm1$V, an ideality factor of 1.16, differential specific on-resistance of 3.9m$Ω\thinspace$cm$^{2}$, and built-in voltage of 0.96V were determined. The $pn$-junction isolation prevented parallel conduction in the highly-conductive Ga$_{2}$O$_{3}$ substrate (sheet resistance $R_{S}\approx3\thinspaceΩ$) during van-der-Pauw Hall measurements of the SnO layer on top ($R_{S}\approx150$k$Ω$, $p\approx2.5\times10^{18}$cm$^{-3}$, Hall mobility $\approx1$cm$^{2}$/Vs). The measured maximum reverse breakdown voltage of the diodes was 66V, corresponding to a peak breakdown field 2.2MV/cm in the Ga$_{2}$O$_{3}$-depletion region. Higher breakdown voltages that are required in high-voltage devices could be achieved by reducing the donor concentration in the $β$-Ga$_{2}$O$_{3}$ to increase the depletion width as well as improving the contact geometry to reduce field crowding.

physics.app-ph↗

arXiv2020

Ultrafast dynamics of hot charge carriers in an oxide semiconductor probed by femtosecond spectroscopic ellipsometry

Many linked processes occur concurrently in strongly excited semiconductors, such as interband and intraband absorption, scattering of electrons and holes by the heated lattice, Pauli blocking, bandgap renormalization and the formation of Mahan excitons. In this work, we disentangle their dynamics and contributions to the optical response of a ZnO thin film. Using broadband pump-probe ellipsometry, we can directly and unambiguously obtain the real and imaginary part of the transient dielectric function which we compare with first-principles simulations. We find interband and excitonic absorption partially blocked and screened by the photo-excited electron occupation of the conduction band and hole occupation of the valence band (absorption bleaching). Exciton absorption turns spectrally narrower upon pumping and sustains the Mott transition, indicating Mahan excitons. Simultaneously, intra-valence-band transitions occur at sub-picosecond time scales after holes scatter to the edge of the Brillouin zone. Our results pave new ways for the understanding of non-equilibrium charge-carrier dynamics in materials by reliably distinguishing between changes in absorption coefficient and refractive index, thereby separating competing processes. This information will help to overcome the limitations of materials for high-power optical devices that owe their properties from dynamics in the ultrafast regime.

cond-mat.mtrl-sci↗

arXiv2020

The nickel vacancy acceptor in NiO: doping beyond thermodynamic equilibrium

This work reports on temperature-induced out-diffusion and concentration decay of the prominent intrinsic point defect VNi (nickel vacancy) in the wide-gap p-type semiconductor nickel oxide (NiO). VNi can easily be introduced into NiO thin films by offering high oxygen partial pressures during film growth, rendering nonstoichiometric semiconducting structures. However, exposure to lower oxygen supply after growth, e.g. in a standard atmosphere, usually leads to a gradual decrease of film conductivity, because the vacancy concentration equilibrates. In this study, we observe this process in situ by performing temperature-dependent measurements of the electrical conductivity on a room temperature-grown NiO film. At a temperature of 420K under exclusion of oxygen, the doping level decreases by a factor of 8 while the associated room temperature dc conductivity drops by six orders of magnitude. At the same time, out-diffusion of the mobile VNi species can be indirectly observed through the occurrence of electrode polarization characteristics.

cond-mat.mtrl-sci↗

arXiv2019

Record-Breaking Magnetoresistance at the Edge of a Microflake of Natural Graphite

Placing several electrodes at the edge of a micrometer-size Sri Lankan natural graphite sample at distances comparable to the size of the internal crystalline regions, we found record values for the change of the resistance with magnetic field. At low temperatures and at $B \sim 21$T the magnetoresistance (MR) reaches $\sim 10^7$%. The MR values exceed by far all earlier reported ones for graphite and they are comparable or even larger (at $T > 50$K) than the largest reported in solids including the Weyl semimetals. The origin of this large MR lies in the existence of highly conducting 2D interfaces aligned parallel to the graphene planes.

cond-mat.str-el↗

arXiv2019

Nickel oxide-based heterostructures with large band offsets

We present research results on the electronic transport in heterostructures based on p-type nickel oxide (NiO) with the n-type oxide semiconductors zinc oxide (ZnO) and cadmium oxide (CdO). NiO is a desirable candidate for application in (opto-)electronic devices. However, because of its small electron affinity, heterojunctions with most n-type oxide semiconductors exhibit conduction and valence band offsets at the heterointerface in excess of 1 eV. ZnO/NiO junctions exhibit a so called type-II band alignment, making electron-hole recombination the only process by which a current can vertically flow through the structure. These heterojunctions are nevertheless shown to be of practical use in efficient optoelectronic devices, as exemplified here by our UV-converting transparent solar cells. These devices, although exhibiting high conversion efficiencies, suffer from two light-activated recombination channels connected to the type-II interface, one of which we identify and analyse in more detail here. Furthermore, CdO/NiO contacts were studied - a heterostructure with even larger band offsets such that a type-III band alignment is achieved. This situation theoretically enables the development of a 2-dimensional electronic system consisting of topologically protected states. We present experiments demonstrating that the CdO/NiO heterostructure indeed hosts a conductive layer absent in both materials when studied separately.

cond-mat.mtrl-sci↗

arXiv2019

Control of Magnetic Order in Spinel ZnFe$_2$O$_4$ Thin Films Through Intrinsic Defect Manipulation

We present a systematic study of the magnetic properties of semiconducting ZnFe$_2$O$_4$ thin films fabricated by pulsed laser deposition at low and high oxygen partial pressure and annealed in oxygen and argon atmosphere, respectively. The magnetic response is enhanced by annealing the films at 250$^{\circ}$C and diminished at annealing temperatures above 300$^{\circ}$C. The initial increase is attributed to the formation of oxygen vacancies after argon treatment, evident by the increase in the low energy absorption at $\sim$ 0.9 eV involving Fe$^{2+}$ cations. The weakened magnetic response is related to a decline in disorder with a cation redistribution toward a normal spinel configuration. The structural renormalization is consistent with the decrease and increase in oscillator strength of respective electronic transitions involving tetrahedrally (at $\sim$ 3.5 eV) and octahedrally (at $\sim$ 5.7 eV) coordinated Fe$^{3+}$ cations.

physics.app-ph↗

arXiv2019

Polaronic inter-acceptor hopping transport in intrinsically doped nickel oxide

In this work, we revisit the issue of the nature of electronic transport in nickel oxide (NiO) and show that the widely used model of free small polaron hopping, initially raised to characterize transport in high-purity samples, is not appropriate for modeling intrinsically doped NiO. Instead, we present extensive evidence, collected by means of temperature- and frequency-dependent measurements of the electrical conductivity $σ$, that the model of polaronic inter-acceptor hopping can be used to consistently explain the electronic conduction process. In this framework, holes are localized to acceptors (Ni vacancies), forming a strongly bound, polaron-like state. They can only move through the film by hopping to a neighboring, at least partially unoccupied, acceptor. This renders the spatial overlap between neighboring polaronic wave functions a highly critical parameter. The signature of this process is the occurrence of two temperature regions of the DC conductivity, separated by about half the Debye temperature $θ_D/2 \approx 200 K$. For $T > θ_D/2$, holes are transferred by phonon-assisted hopping over the potential barrier between two sites, whereas phonon-assisted tunneling through the barrier dominates below that temperature. We also show that the degree of structural and electronic disorder plays a vital role in determining the characteristics of the transport process: high disorder leads to strong energetic broadening of the acceptor states such that hopping to more distant sites may be favored over transfer to nearest neighbors (variable range hopping). The assumption of high binding energies of the charge carriers at VNi is in accordance with the recent paradigm shift regarding the understanding of the electronic structure of NiO: holes doped into NiO couple to Ni 3d spins, thereby occupying deep polaron-like states within the band gap (Zhang-Rice bound doublets).

cond-mat.other↗

arXiv2019

Strain and Band-Gap Engineering in Ge-Sn Alloys via P Doping

Ge with a quasi-direct band gap can be realized by strain engineering, alloying with Sn, or ultrahigh n-type doping. In this work, we use all three approaches together to fabricate direct-band-gap Ge-Sn alloys. The heavily doped n-type Ge-Sn is realized with CMOS-compatible nonequilibrium material processing. P is used to form highly doped n-type Ge-Sn layers and to modify the lattice parameter of P-doped Ge-Sn alloys. The strain engineering in heavily-P-doped Ge-Sn films is confirmed by x-ray diffraction and micro Raman spectroscopy. The change of the band gap in P-doped Ge-Sn alloy as a function of P concentration is theoretically predicted by density functional theory and experimentally verified by near-infrared spectroscopic ellipsometry. According to the shift of the absorption edge, it is shown that for an electron concentration greater than 1x10^20 cm-3 the band-gap renormalization is partially compensated by the Burstein-Moss effect. These results indicate that Ge-based materials have high potential for use in near-infrared optoelectronic devices, fully compatible with CMOS technology.

cond-mat.mtrl-sci↗

arXiv2017

Effect of annealing on the magnetic properties of zinc ferrite thin films

We report on the magnetic properties of zinc ferrite thin film deposited on SrTiO$_3$ single crystal using pulsed laser deposition. X-ray diffraction result indicates the highly oriented single phase growth of the film along with the presence of the strain. In comparison to the bulk antiferromagnetic order, the as-deposited film has been found to exhibit ferrimagnetic ordering with a coercive field of 1140~Oe at 5~K. A broad maximum, at $\approx$105~K, observed in zero-field cooled magnetization curve indicates the wide grain size distribution for the as-deposited film. Reduction in magnetization and blocking temperature has been observed after annealing in both argon as well as oxygen atmospheres, where the variation was found to be dependent on the annealing temperature.

cond-mat.mtrl-sci↗

arXiv2016

Exceptional points in anisotropic planar microcavities

Planar microcavities allow the control and manipulation of spin-polarization, manifested in phenomena like the optical spin Hall effect due to the intrinsic polarization mode splitting. Here, we study a transparent microcavity with broken rotational symmetry, realized by aligning the optical axis of a uniaxial cavity material in the cavity plane. We demonstrate that the in-plane optical anisotropy gives rise to exceptional points in the dispersion relation, which occur pair-wise, are circularly polarized, and are cores of polarization vortices. These exceptional points are a result of the non-Hermitian character of the system, and are in close relationship to singular optical axes in absorptive biaxial systems.

physics.optics↗

arXiv2016

Fundamental absorption edges in heteroepitaxial YBiO$_3$ thin films

The dielectric function of heteroepitaxial YBiO$_3$ grown on $a$-Al$_2$O$_3$ single crystals via pulsed laser deposition is determined in the spectral range from 0.03 eV to 4.5 eV by simultaneous modeling of spectroscopic ellipsometry and optical transmission data of YBiO$_3$ films of different thickness. The (111)-oriented YBiO$_3$ films are nominally unstrained and crystallize in a defective fluorite-type structure with $Fm\bar{3}m$ space group. From the calculated absorption spectrum, a direct electronic bandgap energy of 3.6(1) eV and the signature of an indirect electronic transition around 0.5 eV are obtained. These values provide necessary experimental feedback to previous conflicting electronic band structure calculations predicting either a topologically trivial or non-trivial insulating ground state in YBiO$_3$.

cond-mat.mtrl-sci↗