arXiv subjects

Ulrich Aschauer

Publications and source records attributed to Ulrich Aschauer.

At least 19 recordsLinked to original sources

arXiv2025

Multiferroicity and 180$^\circ$ domain switching in LaFeO$_3$ via Antisite Defects

Materials with coexisting and coupled ferroelectric and magnetic orders are rare. Here we show, using density functional theory calculations, that inducing Fe$_\mathrm{La}$ antisites into non-ferroelectric and antiferromagnetic LaFeO$_3$ renders the material at the same time ferroelectric and ferrimagnetic. Even more excitingly, we observe a direct coupling between the ferroelectric and ferrimagnetic polarization, the latter being switchable by the former. While on average the magnetic moments of antisites would cancel, we envision that preparing defective LaFeO$_3$ under simultaneous electric and magnetic fields will lead to a net magnetic moment due to magnetic domain reconfiguration. Moreover, ferroelectric switching under a static magnetic field can lead to 180$^\circ$ switching of the antiferromagnetic order in LaFeO$_3$.

cond-mat.mtrl-sci↗

arXiv2024

Spin Excitations of High Spin Iron(II) in Metal-Organic Chains on Metal and Superconductor

Many-body interactions in metal-organic frameworks are fundamental for emergent quantum physics. Unlike their solution counterpart, magnetization at surfaces in low-dimensional analogues is strongly influenced by magnetic anisotropy induced by the substrate and still not well understood. Here, we use on-surface coordination chemistry to synthesize on Ag(111) and superconducting Pb(111) an iron-based spin chain by using pyrene-4,5,9,10-tetraone precursors as ligands. Using low-temperature scanning probe microscopy, we compare their structures and low-energy spin excitations of coordinated Fe atoms with high S = 2 spin-state. Although the chain and coordination centers are identical on both substrates, the long-range spin-spin coupling due to a superexchange through the ligand observed on Ag is absent on Pb(111). We ascribe this reduction of spin-spin interactions on Pb to the depletion of electronic states around the Fermi level in the Pb(111) superconductor as compared to silver.

cond-mat.mtrl-sci↗

arXiv2024

Ferrimagnetism induced by thermal vibrations in oxygen-deficient manganite heterostructures

Super-exchange most often leads to antiferromagnetim in transition-metal perovskite oxides, yet ferromagnetism or ferrimagnetism would be preferred for many applications, for example in data storage. While alloying, epitaxial strain and defects were shown to lead to ferromagnetism, engineering this magnetic order remains a challenge. We propose, based on density functional theory calculations, a novel route to defect-engineer ferrimagnetism, which is based on preferential displacements of oxygen vacancies due to finite temperature vibrations. This mechanism has an unusual temperature dependence, as it is absent at 0K, strengthens with increasing temperature before vanishing once oxygen vacancies disorder, giving it a unique experimentally detectable signature.

cond-mat.mtrl-sci↗

arXiv2023

Gate-tunable topological superconductivity in a supramolecular electron spin lattice

Topological superconductivity emerges in chains or arrays of magnetic atoms coupled to a superconductor. However, the external controllability of such systems with gate voltages is detrimental for their future implementation in a topological quantum computer. Here we showcase the supramolecular assembly of radical molecules on Pb(111), whose discharge is controlled by the tip of a scanning tunneling microscope. Charged molecules carry a spin-1/2 state, as confirmed by observing Yu-Shiba-Rusinov in-gap states by tunneling spectroscopy at millikelvin temperature. Low energy modes are localized at island boundaries with a long decay towards the interior, whose spectral signature is consistent with Majorana zero modes protected by mirror symmetry. Our results open up a vast playground for the synthesis of gate-tunable organic topological superconductors.

cond-mat.supr-con↗

arXiv2023

Observation of Antiferroelectric Domain Walls in a Uniaxial Hyperferroelectric

Ferroelectric domain walls are a rich source of emergent electronic properties and unusual polar order. Recent studies showed that the configuration of ferroelectric walls can go well beyond the conventional Ising-type structure. N\'eel-, Bloch-, and vortex-like polar patterns have been observed, displaying strong similarities with the spin textures at magnetic domain walls. Here, we report the discovery of antiferroelectric domain walls in the uniaxial ferroelectric Pb$_{5}$Ge$_{3}$O$_{11}$. We resolve highly mobile domain walls with an alternating displacement of Pb atoms, resulting in a cyclic 180$^{\circ}$ flip of dipole direction within the wall. Density functional theory calculations reveal that Pb$_{5}$Ge$_{3}$O$_{11}$ is hyperferroelectric, allowing the system to overcome the depolarization fields that usually suppress antiparallel ordering of dipoles along the longitudinal direction. Interestingly, the antiferroelectric walls observed under the electron beam are energetically more costly than basic head-to-head or tail-to-tail walls. The results suggest a new type of excited domain-wall state, expanding previous studies on ferroelectric domain walls into the realm of antiferroic phenomena.

cond-mat.mtrl-sci↗

arXiv2023

Combined theoretical and experimental study of the Moir\'e dislocation network at the SrTiO$_3$-(La,Sr)(Al,Ta)O$_3$ interface

Recently a highly ordered Moir\'e dislocation lattice was identified at the interface between a \ce{SrTiO3} (STO) thin film and the (LaAlO$_3$)$_{0.3}$(Sr$_2$TaAlO$_6$)$_{0.7}$ (LSAT) substrate. A fundamental understanding of the local ionic and electronic structure around the dislocation cores is crucial to further engineer the properties of these complex multifunctional heterostructures. Here we combine experimental characterization via analytical scanning transmission electron microscopy with results of molecular dynamics and density functional theory calculations to gain insights into the structure and defect chemistry of these dislocation arrays. Our results show that these dislocations lead to undercoordinated Ta/Al cations at the dislocation core, where oxygen vacancies can easily be formed, further facilitated by the presence of cation vacancies. The reduced Ti$^{3+}$ observed experimentally at the dislocations by electron energy-loss spectroscopy are a consequence of both the structure of the dislocation itself, as well as of the electron-doping due to oxygen vacancy formation. Finally, the experimentally observed Ti diffusion into LSAT around the dislocation core occurs only together with cation-vacancy formation in LSAT or Ta diffusion into STO.

cond-mat.mtrl-sci↗

arXiv2023

Conversion of La$_2$Ti$_2$O$_7$ to LaTiO$_2$N via Ammonolysis: An ab-initio Investigation

Perovskite oxynitrides are, due to their reduced band gap compared to oxides, promising materials for photocatalytic applications. They are most commonly synthesized from {110} layered Carpy-Galy (A$_2$B$_2$O$_7$}) perovskites via thermal ammonolysis, i.e. the exposure to a flow of ammonia at elevated temperature. The conversion of the layered oxide to the non-layered oxynitride must involve a complex combination of nitrogen incorporation, oxygen removal and ultimately structural transition by elimination of the interlayer shear plane. Despite the process being commonly used, little is known about the microscopic mechanisms and hence factors that could ease the conversion. Here we aim to derive such insights via density functional theory calculations of the defect chemistry of the oxide and the oxynitride as well as the oxide's surface chemistry. Our results point to the crucial role of surface oxygen vacancies in forming clusters of NH$_3$ decomposition products and in incorporating N, most favorably substitutionally at the anion site. N then spontaneously diffuses away from the surface, more easily parallel to the surface and in interlayer regions, while diffusion perpendicular to the interlayer plane is somewhat slower. Once incorporation and diffusion lead to a local N concentration of about 70% of the stoichiometric oxynitride composition, the nitridated oxide spontaneously transforms to a nitrogen-deficient oxynitride.

cond-mat.mtrl-sci↗

arXiv2022

Polygonal tessellations as predictive models of molecular monolayers

Molecular self-assembly plays a very important role in various aspects of technology as well as in biological systems. Governed by the covalent, hydrogen or van der Waals interactions - self-assembly of alike molecules results in a large variety of complex patterns even in two dimensions (2D). Prediction of pattern formation for 2D molecular networks is extremely important, though very challenging, and so far, relied on computationally involved approaches such as density functional theory, classical molecular dynamics, Monte Carlo, or machine learning. Such methods, however, do not guarantee that all possible patterns will be considered and often rely on intuition. Here we introduce a much simpler, though rigorous, hierarchical geometric model founded on the mean-field theory of 2D polygonal tessellations to predict extended network patterns based on molecular-level information. Based on graph theory, this approach yields pattern classification and pattern prediction within well-defined ranges. When applied to existing experimental data, our model provides an entirely new view of self-assembled molecular patterns, leading to interesting predictions on admissible patterns and potential additional phases. While developed for hydrogen-bonded systems, an extension to covalently bonded graphene-derived materials or 3D structures such as fullerenes is possible, significantly opening the range of potential future applications.

cond-mat.mtrl-sci↗

arXiv2022

Energy dissipation from confined states in nanoporous molecular networks

Crystalline nanoporous molecular networks are assembled on the Ag(111) surface, where the pores confine electrons originating from the surface state of the metal. Depending on the pore sizes and their coupling, an antibonding level is shifted upwards by 0.1 to 0.3 eV as measured by scanning tunneling microscopy. On molecular sites, a down-shifted bonding state is observed, which is occupied under equilibrium conditions. Low-temperature force spectroscopy reveals energy dissipation peaks and jumps of frequency shifts at bias voltages, which are related to the confined states. The dissipation maps show delocalization on the supra-molecular assembly and a weak distance-dependence of the dissipation peaks. These observations indicate that two-dimensional arrays of coupled quantum dots are formed, which are quantitatively characterized by their quantum capacitances and resonant tunneling rates. Our work provides a method for studying the capacitive and dissipative response of quantum materials with nanomechanical oscillators.

cond-mat.mtrl-sci↗

arXiv2022

Photochemical Anisotropy and Direction-dependent Optical Absorption in Semiconductors

Photochemical reactions on semiconductors are anisotropic, since they occur with different rates on surfaces of different orientation. Understanding the origin of this anisotropy is crucial to engineering more efficient photocatalysts. In this work, we use hybrid density functional theory (DFT) to identify the surfaces associated with the largest number of photo-generated carriers in different semiconductors. For each material we create a spherical heat map of the probability of optical transitions at different wave vectors. These maps allow to identify the directions associated with the majority of the photo-generated carriers and can thus be used to make predictions about the most reactive surfaces for photochemical applications. Results indicate that it is generally possible to correlate the heat maps with the anisotropy of the bands observed in conventional band-structure plots, as previously suggested. However, we also demonstrate that conventional bands-structure plots do not always provide all the informations and that taking into account the contribution of all possible transitions weighted by their transition dipole moments is crucial to obtain a complete picture.

cond-mat.mtrl-sci↗

arXiv2022

Proximity-Induced Superconductivity in Atomically Precise Nanographene

Obtaining a robust superconducting state in atomically precise nanographene (NG) structures by proximity to a superconductor could foster the discovery of topological superconductivity in graphene. On-surface synthesis of such NGs has been achieved on noble metals or metal oxides, however, it is still absent on superconductors. Here, we present a synthetic method to induce superconductivity to polymeric chains and NGs adsorbed on the superconducting Nb(110) substrate covered by thin Ag films. Using atomic force microscopy at low-temperature, we characterize the chemical structure of each sub-product formed on the superconducting Ag layer. Scanning tunneling spectroscopy further allows us to elucidate electronic properties of these nanostructures, which consistently show a superconducting gap. We foresee our approach to become a promising platform for exploring the interplay between carbon magnetism and superconductivity at the fundamental level.

cond-mat.supr-con↗

arXiv2021

Interplay between polarization, strain and defect-pairs in Fe-doped SrMnO$_{3-δ}$

Defect chemistry, strain, and structural, magnetic and electronic degrees of freedom constitute a rich space for the design of functional properties in transition metal oxides. Here, we show that it is possible to engineer polarity and ferroelectricity in non-polar perovskite oxides via polar defect pairs formed by anion vacancies coupled to substitutional cations. We use a self-consistent site-dependent DFT+$U$ approach that accounts for local structural and chemical changes upon defect creation and which is crucial to reconcile predictions with the available experimental data. Our results for Fe-doped oxygen-deficient SrMnO$_3$ show that substitutional Fe and oxygen vacancies can promote polarity due to an off-center displacement of the defect charge resulting in a net electric dipole moment, which polarizes the lattice in the defect neighborhood. The formation of these defects and the resulting polarization can be tuned by epitaxial strain, resulting in enhanced polarization also for strain values lower than the ones necessary to induce a polar phase transition in undoped SrMnO$_3$. For high enough defect concentrations, these defect dipoles couple in a parallel fashion, thus enabling defect- and strain-based engineering of ferroelectricity in SrMnO$_3$.

cond-mat.mtrl-sci↗

arXiv2021

Ferroelectricity promoted by cation/anion divacancies in SrMnO$_3$

We investigate the effect of polar Sr-O vacancy pairs on the electric polarization of SrMnO$_3$ (SMO) thin films using density functional theory (DFT) calculations. This is motivated by indications that ferroelectricity in complex oxides can be engineered by epitaxial strain but also \textit{via} the defect chemistry. Our results suggest that intrinsic doping by cation and anion divacancies can induce a local polarization in unstrained non-polar SMO thin films and that a ferroelectric state can be stabilized below the critical strain of the stoichiometric material. This polarity is promoted by the electric dipole associated with the defect pair and its coupling to the atomic relaxations upon defect formation that polarize a region around the defect. This suggests that polar defect pairs affect the strain-dependent ferroelectricity in semiconducting antiferromagnetic SMO. For metallic ferromagnetic SMO we find a much weaker coupling between the defect dipole and the polarization due to much stronger electronic screening. Coupling of defect-pair dipoles at high enough concentrations along with their switchable orientation thus makes them a promising route to affect the ferroelectric transition in complex transition metal oxide thin films.

cond-mat.mtrl-sci↗

arXiv2021

Interactions of Tris with rutile surfaces and consequences for in vitro bioactivity testing

Tris(hydroxymethyl)aminomethane (Tris) has been used as the buffer in bioactivity testing for over two decades and has become a standard choice for the scientific community. While it is believed to be non-interacting, the extent of its interactions with titanium oxide surfaces has not been systematically studied. Here, we use experimental (zeta potential measurements) and computational (molecular dynamics) approaches to evaluate the interaction of Tris with a rutile surface and how it affects the adsorption of other molecules relevant in biomedical in vitro testing. We show that the interaction of Tris with the rutile surface is strong and significantly affects the interaction of other organic residues with the surface. These strong interactions are compounded by the Tris concentration in the in vitro testing protocol which is much higher compared to other components. Our findings indicate that the kinetics observed in in vitro tests will be strongly influenced by the presence of Tris as a buffering agent when compared to the natural CO2 buffer in blood. These results reveal that considering the so-far neglected active role of Tris in in vitro testing is critically needed and that in vitro protocols using CO2 partial pressure as the buffering agent should yield more reliable results.

physics.med-ph↗

arXiv2021

Importance of surface oxygen vacancies for ultrafast hot carrier relaxation and transport in Cu$_2$O

Cu$_2$O has appealing properties as an electrode for photo-electrochemical water splitting, yet its practical performance is severely limited by inefficient charge extraction at the interface. Using hybrid DFT calculations, we investigate carrier capture processes by oxygen vacancies (V$_\mathrm{O}$) in the experimentally observed ($\sqrt{3} \times \sqrt{3}$)R30$^{\circ}$ reconstruction of the dominant (111) surface. Our results show that these V$_\mathrm{O}$ are doubly ionized and that associated defects states strongly suppress electron transport. In particular, the excited electronic state of a singly charged V$_\mathrm{O}$ plays a crucial role in the non-radiative electron capture process with a capture coefficient of about 10$^{-9}$~cm$^3$/s and a lifetime of 0.04~ps, explaining the experimentally observed ultrafast carrier relaxation. These results highlight that engineering the surface V$_\mathrm{O}$ chemistry will be a crucial step in optimizing Cu$_2$O for photoelectrode applications.

cond-mat.mtrl-sci↗

arXiv2021

Surface and interface effects in oxygen deficient SrMnO$_3$ thin films grown on SrTiO$_3$

Complex oxide functionality, such as ferroelectricity, magnetism or superconductivity is often achieved in epitaxial thin-film geometries. Oxygen vacancies tend to be the dominant type of defect in these materials but a fundamental understanding of their stability and electronic structure has so far mostly been established in the bulk or strained bulk, neglecting interfaces and surfaces present in a thin-film geometry. We investigate here, via density functional theory calculations, oxygen vacancies in the model system of a SrMnO$_3$ (SMO) thin film grown on a SrTiO$_3$ (STO) (001) substrate. Structural and electronic differences compared to bulk SMO result mainly from undercoordination at the film surface. The changed crystal field leads to a depletion of subsurface valence-band states and transfer of this charge to surface Mn atoms, both of which strongly affect the defect chemistry in the film. The result is a strong preference of oxygen vacancies in the surface region compared to deeper layers. Finally, for metastable oxygen vacancies in the substrate, we predict a spatial separation of the defect from its excess charge, the latter being accommodated in the film but close to the substrate boundary. These results show that surface and interface effects lead to significant differences in stability and electronic structure of oxygen vacancies in thin-film geometries compared to the (strained) bulk.

cond-mat.mtrl-sci↗

arXiv2020

Suitability of $β$-Mn$_2$V$_2$O$_7$/$β$-Cu$_2$V$_2$O$_7$ solid solutions for photocatalytic water-splitting

The pyrovanadates $β$-Mn$_2$V$_2$O$_7$ and $β$-Cu$_2$V$_2$O$_7$ were previously investigated as photoanode materials for water splitting. Neither of them, however, was found to be sufficiently active. In this work we predict the properties of solid solutions of these two structurally similar pyrovanadates via density functional theory calculations to explore the suitability of their band structure for water splitting and to assess their ease of synthesis. We predict that substitution of up to 20\% Cu or Mn into $β$-Mn$_2$V$_2$O$_7$ and $β$-Mn$_2$V$_2$O$_7$ respectively leads to a narrowing of the band gap, which in the former case is experimentally confirmed by UV-vis spectroscopy. Calculations for solid solutions in the intermediate composition range, however, yield nearly constant band gaps. Moreover, we predict solid-solutions with higher substitution levels to be increasingly difficult to synthesize, implying that solid solutions with low substitution levels are most relevant in terms of band gaps and ease of synthesis.

cond-mat.mtrl-sci↗

arXiv2020

Giant Grüneisen parameter in a strain-tuned superconducting quantum paraelectric: A consequence of the vanishing ferroelectric phonon energy

Superconductivity and ferroelectricity are typically incompatible because the former needs free carriers, but the latter is usually suppressed by free carriers, unless their concentration is low. In the case of strontium titanate with low carrier concentration, unconventional superconductivity and ferroelectricity were shown to be correlated. Here, we report theoretically and experimentally evaluated Grüneisen parameters whose divergence under tensile stress indicates that the dominant phonon mode that enhances the superconducting order is the ferroelectric transverse soft-mode. This finding rules out all other phonon modes as the main contributors to the enhanced superconductivity in strained strontium titanate. This methodology shown here can be applied to many other quantum materials.

cond-mat.supr-con↗