arXiv subjects

Bettina V. Lotsch

Publications and source records attributed to Bettina V. Lotsch.

At least 19 recordsLinked to original sources

arXiv2025

Anomalous Sodium Insertion in Highly Oriented Graphite: Thermodynamics, Kinetics and Evidence for Two-Sided Intercalation

The difficult intercalation of sodium (Na) into graphite is studied by systematic and long-time investigations (of up to 2 years) using highly oriented pyrolytic graphite (HOPG). By studying chemical insertion of solid, liquid and gaseous Na at low and high temperatures (LT, HT) as well as using electrochemical insertion at 25 degree Celsius into uncoated and coated HOPG, it became clear that insertion equilibrium requires HT. On decreasing chemical intercalation temperature from HT (500 degree Celsius) to LT (25 degree Celsius), thermodynamic control was found to change to diffusion control and finally to interfacial control. For the electrochemical insertion, coating (TiO2) proved advisable (to avoid co-intercalation) and efficient in reducing the interfacial resistance. Measured saturation values were found to be not higher than about 1 mol %. Towards room temperature higher equilibrium values cannot be excluded but would in view of the very low driving force kinetically be very difficult to reach. The reversible cell voltage of the saturated composition (versus alkali metal) is distinctly lower than for the analogous cells using lithium (Li) or potassium (K). Detailed transmission electron microscopy (TEM) studies reveal the unexpected fact that at HT Na predominantly enters HOPG in the form of two-sided intercalation sandwiching carbon layers (bilayers), while at LT more highly aggregated layers appear to a comparable degree, accompanied with the formation of higher-dimensional crystal imperfections. The reasons for this peculiar feature and the non-monotonic thermodynamics in the sequence Li-Na-K-Rb-Cs are discussed not only from an energetic but also from an entropic point of view.

cond-mat.mtrl-sci↗

arXiv2025

Identifying the Origin of Thermal Modulation of Exchange Bias in MnPS3/Fe3GeTe2 van der Waals Heterostructures

The exchange bias phenomenon, inherent in exchange-coupled ferromagnetic and antiferromagnetic systems, has intrigued researchers for decades. Van der Waals materials, with their layered structure, provide an optimal platform for probing such physical phenomena. However, achieving a facile and effective means to manipulate exchange bias in van der Waals heterostructures remains challenging. In this study, we investigate the origin of exchange bias in MnPS3/Fe3GeTe2 van der Waals heterostructures. Our work demonstrates a method to modulate unidirectional exchange anisotropy, achieving an unprecedented nearly 1000% variation through simple thermal cycling. Despite the compensated interfacial spin configuration of MnPS3, magneto-transport measurements reveal a huge 170 mT exchange bias at 5 K, one of the largest observed in van der Waals antiferromagnet-ferromagnet interfaces. This substantial magnitude of the exchange bias is linked to an anomalous weak ferromagnetic ordering in MnPS3 below 40 K. On the other hand, the tunability of exchange bias during thermal cycling is ascribed to the modified arrangement of interfacial atoms and changes in the vdW gap during field cooling. Our findings highlight a robust and easily adjustable exchange bias in van der Waals antiferromagnetic/ferromagnetic heterostructures, presenting a straightforward approach to enhance other interface-related spintronic phenomena for practical applications. A detailed study of the interface reveals migration of atoms between the layers, leading to the formation of amorphous region on either side of the van der Waals gap, underscoring the importance of precise characterization of interfaces in van der Waals heterostructures, which are often presumed to have pristine interfaces.

cond-mat.mtrl-sci↗

arXiv2025

Kinetics and direct imaging of electrochemically formed palladium hydride for efficient hydrogen evolution reaction

Active and reliable electrocatalysts are fundamental to renewable energy technologies. PdCoO2 has recently been recognized as a promising catalyst template for the hydrogen evolution reaction (HER) in acidic media thanks to the formation of active PdHx. In this article, we monitor the transformation of single PdCoO2 particles during HER, and confirm their almost complete transformation to PdHx with sub-millimeter depths and cracks throughout the particles. Using operando mass spectrometry, Co dissolution is observed under reductive potentials, leading to PdHx formation, whereas the dissolution partial current is found to be 0.1 % of the HER current. The formation of PdHx is confirmed through secondary ion mass spectrometry and quantitatively analyzed by atom probe tomography, enabled by isotope labelling of hydrogen using heavy water. Despite dry storage and high vacuum during sample preparations, an overall composition of PdD0.28 is measured for the PdHx sample, with separation between alpha- (D-poor) and beta- (D-rich) PdHx phases. The PdHx phase formed on PdCoO2 particles is stable for a wide electrochemical potential window, until Pd dissolution is observed at open circuit potentials. Our findings highlight the critical role of a templated growth method in obtaining stabilized PdHx, enabling efficient HER without the commonly slow activation processes observed in Pd. This offers insights into the design of more efficient electrocatalysts for renewable energy technologies.

physics.chem-ph↗

arXiv2024

Noncollinear electric dipoles in a polar, chiral phase of CsSnBr$_3$ perovskite

Polar and chiral crystal symmetries confer a variety of potentially useful functionalities upon solids by coupling otherwise noninteracting mechanical, electronic, optical, and magnetic degrees of freedom. We describe two unstudied phases of the 3D perovskite, CsSnBr$_3$, which emerge below 85 K due to the formation of Sn(II) lone pairs and their interaction with extant octahedral tilts. Phase II (77 K<$T$<85 K, space group $P2_1/m$) exhibits ferroaxial order driven by a noncollinear pattern of lone pair-driven distortions within the plane normal to the unique octahedral tilt axis, preserving the inversion symmetry observed at higher temperatures. Phase I ($T$<77 K, space group $P2_1$) additionally exhibits ferroelectric order due to distortions along the unique tilt axis, breaking both inversion and mirror symmetries. This polar and chiral phase exhibits second harmonic generation from the bulk and a large, intrinsic polarization$-$electrostriction coefficient along the polar axis ($Q_{22}\approx$1.1 m$^4$ C$^{-2}$), resulting in acute negative thermal expansion ($α_V=-9\times10^{-5}$ K$^{-1}$) through the onset of spontaneous polarization. The unprecedented structures of phases I and II were predicted by recursively following harmonic phonon instabilities to generate a tree of candidate structures and subsequently corroborated by synchrotron X-ray powder diffraction and polarized Raman and $^{81}$Br nuclear quadrupole resonance spectroscopies. Relativistic electronic structure scenarios compatible with reported photoluminescence measurements are discussed. Together, the polar symmetry, small bandgap, large spin-orbit splitting of Sn 5$p$ orbitals, and predicted strain sensitivity of the symmetry-breaking distortions suggest bulk samples and epitaxial films of CsSnBr$_3$ or its neighboring solid solutions as strong candidates for bulk Rashba effects.

cond-mat.mtrl-sci↗

arXiv2023

Resonant Inelastic X-ray Scattering from Electronic Excitations in $α$-RuCl$_3$ Nanolayers

We present Ru $L_3$-edge resonant inelastic x-ray scattering (RIXS) measurements of spin-orbit and d-d excitations in exfoliated nanolayers of the Kitaev spin-liquid candidate RuCl$_3$. Whereas the spin-orbit excitations are independent of thickness, we observe a pronounced red-shift and broadening of the d-d excitations in layers with thickness below $\sim$7 nm. Aided by model calculations, we attribute these effects to distortions of the RuCl$_6$ octahedra near the surface. Our study paves the way towards RIXS investigations of electronic excitations in various other 2D materials and heterostructures.

cond-mat.str-el↗

arXiv2023

Designing Covalent Organic Framework-based Light-driven Microswimmers towards Intraocular Theranostic Applications

Even micromachines with tailored functionalities enable targeted therapeutic applications in biological environments, their controlled motion in biological media and drug delivery functions usually require sophisticated designs and complex propulsion apparatuses for practical applications. Covalent organic frameworks (COFs), new chemically versatile and nanoporous materials, offer microscale multi-purpose solutions, which are not explored in light-driven micromachines. We describe and compare two different types of COFs, uniformly spherical TABP-PDA-COF sub-micron particles and texturally highly nanoporous, irregular, micron-sized TpAzo-COF particles as light-driven microrobots. They can be used as highly efficient visible-light-driven drug carriers in aqueous ionic and cellular media, even in intraocular fluids. Their absorption ranging down to red light enables phototaxis even in deeper biological media and the organic nature of COFs enables their biocompatibility. The inherently porous structure with ~2.5 nm structural pores, and large surface areas allow for targeted and efficient drug loading even for insoluble drugs and peptides, which can be released on demand. Also, indocyanine green (ICG) dye loading in the pores enables photoacoustic imaging or optical coherence tomography and hyperthermia in operando conditions. The real-time visualization of the drug-loaded COF microswimmers enables new insights into the function of porous organic micromachines, which will be useful to solve various drug delivery problems.

physics.bio-ph↗

arXiv2022

Dissolution and Recrystallization Behavior of Li3PS4 in Different Organic Solvents

Solid state batteries can be built based on thiophosphate electrolytes such as beta-Li3PS4. For the preparation of these electrolytes, various solvent-based routes have been reported. For recycling of end-of-life solid state batteries based on such thiophosphates, we consider the development of dissolution and recrystallization strategies for the recovery of the model compound beta-Li3PS4. We show that recrystallization can only be performed in polar, slightly protic solvents such as N-methylformamide (NMF). The recrystallization is comprehensively studied, showing that it proceeds via an intermediate phase with composition Li3PS4*2NMF, which is structurally characterized. This phase has a high resistivity for the transport of lithium ions and must be removed in order to obtain a recrystallized product with a conductivity similar to the pristine material. Moreover, the recrystallization from solution results in an increase of the amorphous phase fraction next to crystalline beta-Li3PS4, which results in a decrease of the activation energy to 0.2 eV compared to 0.38 eV for the pristine phase.

cond-mat.mtrl-sci↗

arXiv2022

An Integrated Solar Battery based on a Charge Storing 2D Carbon Nitride

Solar batteries capable of harvesting sunlight and storing solar energy present an attractive vista to transition our energy infrastructure into a sustainable future. We present an integrated, fully earth-abundant solar battery design based on a bifunctional (light absorbing and charge storing) carbon nitride (K-PHI) photoanode, combined with all-organic hole transfer and storage materials. An internal ladder-type hole transfer cascade via a hole transport layer is used to shuttle the photogenerated holes to the PEDOT:PSS cathode. This concept differs from previous designs such as light-assisted battery schemes or photocapacitors and allows charging with only light or light-assisted during electrical charging and discharging, thus substantially increasing the energy output of the cell. Compared to battery operation in the dark, light-assisted (dis)charging increases charge output by 243 %, thereby increasing the electric coulombic efficiency from 68.3 % in the dark to 231 %, leading to energy improvements of 94.1 % under illumination.

cond-mat.mtrl-sci↗

arXiv2021

Photo-memristive sensing with charge storing 2D carbon nitrides

We report the charge storing 2D carbon nitride potassium poly(heptazine imide), K-PHI, as a direct memristive (bio)sensing platform. Memristive devices have the potential to innovate current (bio)electronic systems such as photo-electrochemical sensors by incorporating new sensing capabilities including non-invasive, wireless remote and time-delayed (memory) readout. We demonstrate a direct photomemristive sensing platform that capitalizes on K PHI's visible light bandgap, large oxidation potential and intrinsic optoionic light energy storage properties. Our system simultaneously enables analyte concentration information storage as well as potentiometric, impedimetric and coulo-metric readouts on the same material, with no additional reagents required. Utilizing the light-induced charge storage function of K-PHI, we demonstrate analyte sensing via charge accumulation and present various methods to write/erase this information from the material. Additionally, fully wireless colorimetric and fluorometric detection of the charged state of K-PHI is demonstrated and could facilitate its use as particle-based in-situ sensing probe. The various readout options of the K PHI's response enable us to adapt the sensitivities and dynamic ranges without modifying the sensor. We demonstrate these features using glucose as an example analyte over a wide range of concentrations (50 $μ$M to 50 mM). Moreover, due to the strong oxidative power of K-PHI, this sensing platform is able to detect a large variety of organic or biologically relevant analytes. Since PHI is easily synthesized, based on earth abundant precursors, biocompatible, chemically robust and responsive to visible light, we anticipate that the sensing platform presented herein opens up novel memristive and neuromorphic functions.

physics.app-ph↗

arXiv2021

Biocompatible carbon nitride-based light-driven microswimmer propulsion in biological and ionic media with responsive on-demand drug delivery

We propose two-dimensional organic poly(heptazine imide) (PHI) carbon nitride microparticles as light-driven microswimmers in various ionic and biological media. Their demonstrated high-speed (15-23 $μ$m/s) swimming in multi-component ionic solutions with concentrations up to 1 M and without dedicated fuels is unprecedented, overcoming one of the bottlenecks of previous light-driven microswimmers. Such high ion tolerance is attributed to a favorable interplay between the particle's textural and structural nanoporosity and optoionic properties, facilitating ionic interactions in solutions with high salinity. Biocompatibility of the microswimmers is validated by cell viability tests with three different cell types and primary cells. The nanopores of the swimmers are loaded with a model cancer drug, doxorubicin (DOX), in high (185%) loading efficiency without passive release. Controlled drug release is reported in different pH conditions and can be triggered on-demand also by illumination. Light-triggered, boosted release of DOX and its active degradation products is demonstrated in oxygen-poor conditions using the intrinsic, environmentally sensitive and light-induced charge storage properties of PHI, which could enable future theranostic applications in oxygen-deprived tumor regions. These organic PHI microswimmers simultaneously solve the current light-driven microswimmer challenges of high ion tolerance, fuel-free high-speed propulsion in biological media, biocompatibility and controlled on-demand cargo release towards their biomedical, environmental and other potential future applications.

cond-mat.soft↗

arXiv2020

Relaxed current matching requirements in highly luminescent perovskite tandem solar cells and their fundamental efficiency limits

Here we use time-resolved and steady-state optical spectroscopy on state-of-the-art low- and high-bandgap perovskite films for tandems to quantify intrinsic recombination rates and absorption coefficients. We apply these data to calculate the limiting efficiency of perovskite-silicon and all-perovskite two-terminal tandems employing currently available bandgap materials as 42.0 % and 40.8 % respectively. By including luminescence coupling between sub-cells, i.e. the re-emission of photons from the high-bandgap sub-cell and their absorption in the low-bandgap sub-cell, we reveal the stringent need for current matching is relaxed when the high-bandgap sub-cell is a luminescent perovskite compared to calculations that do not consider luminescence coupling. We show luminescence coupling becomes important in all-perovskite tandems when charge carrier trapping rates are < 10$^{6}$ s$^{-1}$ (corresponding to carrier lifetimes longer than 1 $μ$s at low excitation densities) in the high-bandgap sub-cell, which is lowered to 10$^{5}$ s$^{-1}$ in the better-bandgap-matched perovskite-silicon cells. We demonstrate luminescence coupling endows greater flexibility in both sub-cell thicknesses, increased tolerance to different spectral conditions and a reduction in the total thickness of light absorbing layers. To maximally exploit luminescence coupling we reveal a key design rule for luminescent perovskite-based tandems: the high-bandgap sub-cell should always have the higher short-circuit current. Importantly, this can be achieved by reducing the bandgap or increasing the thickness in the high-bandgap sub-cell with minimal reduction in efficiency, thus allowing for wider, unstable bandgap compositions (>1.7 eV) to be avoided. Finally, we experimentally visualise luminescence coupling in an all-perovskite tandem device stack through cross-section luminescence images.

cond-mat.mtrl-sci↗

arXiv2019

Rational Strain Engineering in Delafossite Oxides for Highly Efficient Hydrogen Evolution Catalysis in Acidic Media

The rational design of hydrogen evolution reaction (HER) electrocatalysts which are competitive with platinum is an outstanding challenge to make power-to-gas technologies economically viable. Here, we introduce the delafossites PdCrO$_2$, PdCoO$_2$ and PtCoO$_2$ as a new family of electrocatalysts for the HER in acidic media. We show that in PdCoO$_2$ the inherently strained Pd metal sublattice acts as a pseudomorphic template for the growth of a strained (by +2.3%) Pd rich capping layer under reductive conditions. The surface modification continuously improves the electrocatalytic activity by simultaneously increasing the exchange current density j$_0$ from 2 to 5 mA/cm$^2_{geo}$ and by reducing the Tafel slope down to 38 mV/decade, leading to overpotentials $η_{10}$ < 15 mV for 10 mA/cm$^2_{geo}$, superior to bulk platinum. The greatly improved activity is attributed to the in-situ stabilization of a $β$-palladium hydride phase with drastically enhanced surface catalytic properties with respect to pure or nanostructured palladium. These findings illustrate how operando induced electrodissolution can be used as a top-down design concept for rational surface and property engineering through the strain-stabilized formation of catalytically active phases.

physics.chem-ph↗

arXiv2017

Surface floating 2D bands in layered nonsymmorphic semimetals: ZrSiS and related compounds

In this work, we present a model of the surface states of nonsymmorphic semimetals. These are derived from surface mass terms that lift the high degeneracy imposed in the band structure by the nonsymmorphic bulk symmetries. Reflecting the reduced symmetry at the surface, the bulk bands are strongly modified. This leads to the creation of two-dimensional floating bands, which are distinct from Shockley states, quantum well states or topologically protected surface states. We focus on the layered semimetal ZrSiS to clarify the origin of its surface states. We demonstrate an excellent agreement between DFT calculations and ARPES measurements and present an effective four-band model in which similar surface bands appear. Finally, we emphasize the role of the surface chemical potential by comparing the surface density of states in samples with and without potassium coating. Our findings can be extended to related compounds and generalized to other crystals with nonsymmorphic symmetries.

cond-mat.mtrl-sci↗

arXiv2017

Tunable Weyl and Dirac states in the nonsymmorphic compound $\rm\mathbf{CeSbTe}$

Recent interest in topological semimetals has lead to the proposal of many new topological phases that can be realized in real materials. Next to Dirac and Weyl systems, these include more exotic phases based on manifold band degeneracies in the bulk electronic structure. The exotic states in topological semimetals are usually protected by some sort of crystal symmetry and the introduction of magnetic order can influence these states by breaking time reversal symmetry. Here we show that we can realize a rich variety of different topological semimetal states in a single material, $\rm CeSbTe$. This compound can exhibit different types of magnetic order that can be accessed easily by applying a small field. It allows, therefore, for tuning the electronic structure and can drive it through a manifold of topologically distinct phases, such as the first nonsymmorphic magnetic topological material with an eight-fold band crossing at a high symmetry point. Our experimental results are backed by a full magnetic group theory analysis and ab initio calculations. This discovery introduces a realistic and promising platform for studying the interplay of magnetism and topology.

cond-mat.mtrl-sci↗

arXiv2016

Non-symmorphic band degeneracy at the Fermi level in ZrSiTe

Non-symmorphic materials have recently been predicted to exhibit many different exotic features in their electronic structures. These originate from forced band degeneracies caused by the non-symmorphic symmetry, which not only creates the possibility to realize Dirac semimetals, but also recently resulted in the prediction of novel quasiparticles beyond the usual Dirac, Weyl or Majorana fermions, which can only exist in the solid state. Experimental realization of non-symmorphic materials that have the Fermi level located at the degenerate point is difficult, however, due to the requirement of an odd band filling. In order to investigate the effect of forced band degeneracies on the transport behavior, a material that has such a degeneracy at or close to the Fermi level is desired. Here, we show with angular resolved photoemission experiments supported by density functional calculations, that ZrSiTe hosts several fourfold degenerate Dirac crossings at the X point, resulting from non-symmorphic symmetry. These crossings form a Dirac line node along XR, which is located almost directly at the Fermi level and shows almost no dispersion in energy. ZrSiTe is thus the first real material that allows for transport measurements investigating Dirac fermions that originate from non-symmorphic symmetry.

cond-mat.mtrl-sci↗

arXiv2016

Towards rational design of carbon nitride photocatalysts: Identification of cyanamide "defects" as catalytically relevant sites

The heptazine-based polymer melon (also known as graphitic carbon nitride, g-C3N4), is a promising photocatalyst for hydrogen evolution. Nonetheless, attempts to improve its inherently low activity are rarely based on rational approaches due to a lack of fundamental understanding of its mechanistic operation. Here, we employ molecular heptazine-based model catalysts to identify the cyanamide moiety as a photocatalytically relevant "defect". We exploit this knowledge for the rational design of a carbon nitride polymer populated with cyanamide groups, yielding a material with 12- and 16-times the hydrogen evolution rate and apparent quantum efficiency (400 nm), respectively, compared to the benchmark melon. Computational modelling and material characterization suggest this moiety improves co-ordination (and, in turn, charge transfer kinetics) to the platinum co-catalyst and enhances the separation of the photo-generated charge carriers. The demonstrated knowledge transfer for rational catalyst design presented here provides the conceptual framework for engineering high performance heptazine-based photocatalysts.

cond-mat.mtrl-sci↗

arXiv2016

Magnetic properties of restacked 2D spin $\frac{1}{2}$ honeycomb RuCl$_3$ nanosheets

Spin $\frac{1}{2}$ honeycomb materials have gained substantial interest due to their exotic magnetism and possible application in quantum computing. However, in all current materials out-of-plane interactions are interfering with the in-plane order, hence a true 2D magnetic honeycomb system is still of demand. Here, we report the exfoliation of the magnetic semiconductor $α$-RuCl$_3$ into the first halide monolayers and the magnetic characterization of the spin $\frac{1}{2}$ honeycomb arrangement of turbostratically stacked RuCl$_3$ monolayers. The exfoliation is based on a reductive lithiation/hydration approach, which gives rise to a loss of cooperative magnetism due to the disruption of the spin $\frac{1}{2}$ state by electron injection into the layers. After an oxidative treatment, cooperative magnetism similar to the bulk is restored. The oxidized pellets of restacked single layers feature a magnetic transition at T$_N$ = 7 K in the in-plane direction, while the magnetic properties in the out-of-plane direction vastly differ from bulk $α$-RuCl$_3$. The macroscopic pellets of RuCl$_3$ therefore behave like a stack of monolayers without any symmetry relation in the stacking direction. The deliberate introduction of turbostratic disorder to manipulate the spin structure of RuCl$_3$ is of interest for research in frustrated magnetism and complex magnetic order as predicted by the Kitaev-Heisenberg model.

cond-mat.mtrl-sci↗

arXiv2015

Dirac Cone Protected by Non-Symmorphic Symmetry and 3D Dirac Line Node in ZrSiS

Materials harboring exotic quasiparticles, such as Dirac and Weyl fermions\cite{xu2015discovery,borisenko2015time,weng2015weyl,xu2015observation}, have garnered much attention from the physics and material science communities. These fermions are massless and, in some materials, have shown exceptional physical properties such as ultrahigh mobility and extremely large magnetoresistances \cite{liang2015ultrahigh,ali2014large,du2015unsaturated,shekhar2015large}. Recently, new materials have been predicted to exist which exhibit line nodes of Dirac cones \cite{PhysRevLett.115.036806,xie2015new,burkov2011topological,rhim2015landau}. Here, we show with angle resolved photoemission studies supported by \textit{ab initio} calculations that the highly stable, non-toxic and earth-abundant material, ZrSiS, has an electronic band structure that hosts several Dirac cones which form a Fermi surface with a diamond-shaped line of Dirac nodes. We also experimentally show, for the first time, that the square Si lattice in ZrSiS is an excellent template for realizing the new types of 2D Dirac cones recently predicted by Young and Kane \cite{young2015dirac} and image an unforseen surface state that arises close to the 2D Dirac cone. Finally, we find that the energy range of the linearly dispersed bands is as high as 2\,eV above and below the Fermi level; much larger than of any known Dirac material so far. This makes ZrSiS a very promising candidate to study the exotic behavior of Dirac electrons, or Weyl fermions if a magnetic field is applied, as well as the properties of lines of Dirac nodes

cond-mat.mtrl-sci↗